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WO2018092434A1 - Batterie tout solide, dispositif électronique, carte électronique, dispositif vestimentaire et véhicule électrique - Google Patents

Batterie tout solide, dispositif électronique, carte électronique, dispositif vestimentaire et véhicule électrique Download PDF

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Publication number
WO2018092434A1
WO2018092434A1 PCT/JP2017/035527 JP2017035527W WO2018092434A1 WO 2018092434 A1 WO2018092434 A1 WO 2018092434A1 JP 2017035527 W JP2017035527 W JP 2017035527W WO 2018092434 A1 WO2018092434 A1 WO 2018092434A1
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solid
positive electrode
electrode layer
negative electrode
battery
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English (en)
Japanese (ja)
Inventor
圭輔 清水
健史 岸本
鈴木　正光
須藤　業
深澤　宣雄
基一 石原
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/574—Devices or arrangements for the interruption of current
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This technology relates to an all-solid-state battery and an electronic device, an electronic card, a wearable device and an electric vehicle including the same.
  • Patent Document 1 discloses a lithium ion secondary battery having the following configuration.
  • the lithium ion secondary battery is composed of a laminate in which positive electrode current collectors 1 and negative electrode current collectors 2 are alternately laminated via solid electrolyte layers 3.
  • the solid electrolyte layer 3 includes an active material 4 in a matrix made of a solid electrolyte, and the ratio of the volume of the solid electrolyte to the volume of the active material 4 is 90:10 to 65:35.
  • Patent Document 2 discloses an all-solid lithium secondary battery including a positive electrode layer forming material having the following configuration.
  • the positive electrode layer forming material is composed of a positive electrode active material that is at least one of LiCoO 2 and LiNiO 2 and a sulfide-based solid electrolyte material.
  • the average particle diameter of the positive electrode active material is in the range of 1 to 5 ⁇ m, and the volume fraction of the positive electrode active material in the positive electrode layer forming material is in the range of 37 to 42 vol%.
  • An object of the present technology is to provide an all-solid-state battery capable of improving energy density, and an electronic device, an electronic card, a wearable device, and an electric vehicle including the same.
  • a first technique includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer, and at least one of the positive electrode layer and the negative electrode layer includes an active material and an oxide glass. And at least one of oxide glass ceramics, and has an active material volume occupancy of 40 vol% or more.
  • the second technology is an electronic device that receives power from the all-solid-state battery of the first technology.
  • the third technology is an electronic card that receives power from the all-solid-state battery of the first technology.
  • the fourth technology is a wearable device that receives power from the all-solid-state battery of the first technology.
  • the fifth technology includes the all-solid-state battery according to the first technology, a conversion device that receives power from the all-solid-state battery and converts the power into driving force of the vehicle, and information processing related to vehicle control based on information about the all-solid-state battery. It is an electric vehicle which has a control device which performs.
  • This technology can improve the energy density of all solid state batteries.
  • FIG. 1 is a perspective view showing an overall configuration of a smart watch. It is a perspective view which shows a part of internal structure of the band type electronic device as an application example of this technique. It is a block diagram which shows the circuit structure of a band type electronic device. It is sectional drawing for demonstrating the meandering state of a flexible circuit board. It is a perspective view which shows the state by which a battery is arrange
  • FIG. 25A is a conceptual diagram of a third example of the image display device.
  • FIG. 25B is a schematic cross-sectional view showing an enlarged part of the reflective volume hologram diffraction grating.
  • FIG. 25B is a schematic cross-sectional view showing an enlarged part of the reflective volume hologram diffraction grating.
  • FIG. 4th example of an image display apparatus It is a schematic diagram showing roughly an example of composition of a hybrid vehicle which adopts a series hybrid system to which this art is applied. It is the schematic which shows the electrical storage system for houses to which this technique was applied.
  • Embodiments of the present technology will be described in the following order. 1 1st Embodiment (example of all-solid-state battery) 2 Second Embodiment (Example of all-solid battery) 3 Third Embodiment (Example of All Solid State Battery) 4 Application examples
  • the battery according to the first embodiment of the present technology is a so-called bulk type all-solid battery, and as illustrated in FIG. 1, a solid electrolyte layer 11 and a positive electrode layer provided on one main surface of the solid electrolyte layer 11. 12 and a negative electrode layer 13 provided on the other main surface of the solid electrolyte layer 11.
  • This battery is a secondary battery obtained by repeatedly receiving and transferring Li, which is an electrode reactant, and may be a lithium ion secondary battery in which the capacity of the negative electrode is obtained by occlusion and release of lithium ions, It may be a lithium metal secondary battery in which the capacity of the negative electrode is obtained by precipitation dissolution of lithium metal.
  • the battery according to the first embodiment has a volume energy density of 400 wh / L or more in a battery volume of 5 cc or less.
  • the battery according to the first embodiment has a volume energy density of 150 wh / kg or more in a battery volume of 5 cc or less.
  • the battery volume is not limited to 5 cc or less, and may be 5 cc or more.
  • energy density when both volume energy density and weight energy density are meant, they are simply referred to as “energy density”.
  • volume energy density [wh / L] (rated capacity [Ah] ⁇ rated voltage [V]) / battery volume [L]
  • the battery volume is obtained in the same manner as the battery volume calculation method described above. However, as a unit of the volume of the battery, [L] is used instead of [cc].
  • Weight energy density [wh / kg] (rated capacity [Ah] ⁇ rated voltage [V]) / battery weight [kg]
  • the solid electrolyte layer 11 includes one kind or two or more kinds of solid electrolytes.
  • the solid electrolyte is at least one of an oxide glass and an oxide glass ceramic that are lithium ion conductors, and is preferably an oxide glass ceramic from the viewpoint of improving lithium ion conductivity.
  • Oxide glass and oxide glass ceramics have high stability with respect to the atmosphere (moisture), so that an exterior material such as an aluminum laminate film can be omitted. When the exterior material is omitted, the energy density of the battery can be further improved.
  • the solid electrolyte layer 11 is, for example, a fired body of a green sheet (hereinafter referred to as “solid electrolyte green sheet”) as a solid electrolyte layer precursor.
  • the glass means a crystallographically amorphous material such as halo observed in X-ray diffraction or electron beam diffraction.
  • Glass ceramics refers to a crystallographic mixture of amorphous and crystalline materials, such as peaks and halos observed in X-ray diffraction, electron beam diffraction, and the like.
  • the lithium ion conductivity of the solid electrolyte is preferably 10 ⁇ 7 S / cm or more from the viewpoint of improving battery performance.
  • the ionic conductivity is a value obtained by the AC impedance method as follows. First, a sample is prepared by forming electrodes made of gold (Au) on both surfaces of the solid electrolyte layer 11. Next, AC impedance measurement (frequency: 10 +6 Hz to 10 ⁇ 1 Hz, voltage: 100 mV, 1000 mV) is performed on the sample at room temperature (25 ° C.) using an impedance measuring device (manufactured by Toyo Technica). -Create a call plot. Subsequently, ionic conductivity is obtained from this Cole-Cole plot.
  • the solid electrolyte contained in the solid electrolyte layer 11 is sintered.
  • the sintering temperature of the oxide glass and the oxide glass ceramic that is a solid electrolyte is preferably 550 ° C. or lower, more preferably 300 ° C. or higher and 550 ° C. or lower, and even more preferably 300 ° C. or higher and 500 ° C. or lower.
  • the carbon material is prevented from being burned out in the firing step (sintering step), so that the carbon material can be used as the negative electrode active material. Therefore, the energy density of the battery can be further improved.
  • the positive electrode layer 12 contains a conductive agent
  • a carbon material can be used as the conductive agent. Therefore, a good electron conduction path can be formed in the positive electrode layer 12, and the conductivity of the positive electrode layer 12 can be improved.
  • the negative electrode layer 13 includes a conductive agent, a carbon material can be used as the conductive agent, so that the conductivity of the negative electrode layer 13 can be improved.
  • the sintering temperature is 550 ° C. or lower, it is possible to suppress the formation of by-products such as a passive state due to the reaction between the solid electrolyte and the electrode active material in the firing step (sintering step). Accordingly, it is possible to suppress a decrease in battery characteristics. Further, when the firing temperature is as low as 550 ° C. or less, the range of selection of the type of electrode active material is widened, so that the degree of freedom in battery design can be improved.
  • a general organic binder such as an acrylic resin contained in the electrode precursor and / or the solid electrolyte layer precursor is burned off in the firing step (sintering step). Can be made.
  • Oxide glass and oxide glass ceramics preferably have a sintering temperature of 550 ° C. or lower, a high heat shrinkage rate, and high fluidity. This is because the following effects can be obtained. That is, the reaction between the solid electrolyte layer 11 and the positive electrode layer 12 and the reaction between the solid electrolyte layer 11 and the negative electrode layer 13 can be suppressed. Further, good interfaces are formed between the positive electrode layer 12 and the solid electrolyte layer 11, and between the negative electrode layer 13 and the solid electrolyte layer 11, and between the positive electrode layer 12 and the solid electrolyte layer 11, and between the negative electrode layer 13 and the solid electrolyte. The interface resistance between the layers 11 can be reduced.
  • oxide glass and oxide glass ceramic at least one of Ge (germanium), Si (silicon), B (boron), and P (phosphorus), Li (lithium), and O (oxygen) Those containing Si, B, Li and O are more preferable. Specifically, at least one of germanium oxide (GeO 2 ), silicon oxide (SiO 2 ), boron oxide (B 2 O 3 ) and phosphorus oxide (P 2 O 5 ), and lithium oxide (Li 2 O). ) Are preferred, and those containing SiO 2 , B 2 O 3 and Li 2 O are more preferred. As described above, the oxide glass and oxide glass ceramic containing at least one of Ge, Si, B, and P, Li, and O have a sintering temperature of 300 ° C. or higher and 550 ° C. or lower, Since it has a high heat shrinkage ratio and is rich in fluidity, it is advantageous from the viewpoint of reducing interfacial resistance and improving the energy density of the battery.
  • the content of Li 2 O is preferably 20 mol% or more and 75 mol% or less, more preferably 30 mol% or more and 75 mol% or less, still more preferably 40 mol% or more and 75 mol% or less, from the viewpoint of lowering the sintering temperature of the solid electrolyte. Especially preferably, they are 50 mol% or more and 75 mol% or less.
  • the content of the GeO 2 is preferably less greater 80 mol% than 0 mol%.
  • the content of the SiO 2 is preferably from greater than 0 mol% 70 mol%.
  • the content of the B 2 O 3 is preferably not more than greater than 0 mol% 60 mol%.
  • the content of the P 2 O 5 is preferably from greater than 0 mol% 50 mol%.
  • the content of each oxide is the content of each oxide in the solid electrolyte, and specifically, one or more of GeO 2 , SiO 2 , B 2 O 3 and P 2 O 5 ,
  • the ratio of the content (mol) of each oxide to the total amount (mol) with Li 2 O is shown as a percentage (mol%).
  • the content of each oxide can be measured using inductively coupled plasma emission spectroscopy (ICP-AES) or the like.
  • the solid electrolyte may further contain an additive element as necessary.
  • an additive element for example, Na (sodium), Mg (magnesium), Al (aluminum), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese) ), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ga (gallium), Se (selenium), Rb (rubidium), S (sulfur), Y (yttrium) ), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium), Ba (vanadium), Hf (hafnium) ), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum), Nd (ne
  • the positive electrode layer 12 is a positive electrode active material layer containing one or more kinds of positive electrode active materials and one or more kinds of solid electrolytes.
  • the solid electrolyte may have a function as a binder.
  • the positive electrode layer 12 may further contain a conductive agent as necessary.
  • the positive electrode layer 12 is, for example, a fired body of a green sheet (hereinafter referred to as “positive electrode green sheet”) as a positive electrode layer precursor.
  • the positive electrode active material includes, for example, a positive electrode material capable of occluding and releasing lithium ions that are electrode reactants.
  • the positive electrode material is preferably a lithium-containing compound or the like from the viewpoint of obtaining a high energy density, but is not limited thereto.
  • This lithium-containing compound is, for example, a composite oxide (lithium transition metal composite oxide) containing lithium and a transition metal element as constituent elements, or a phosphate compound (lithium transition metal) containing lithium and a transition metal element as constituent elements. Phosphate compounds).
  • the transition metal element is preferably one or more of Co, Ni, Mn, and Fe.
  • the lithium transition metal composite oxide is represented by, for example, Li x M1O 2 or Li y M2O 4 . More specifically, for example, the lithium transition metal composite oxide is LiCoO 2 , LiNiO 2 , LiVO 2 , LiCrO 2, or LiMn 2 O 4 . Further, the lithium transition metal phosphate compound is represented by, for example, Li z M3PO 4 . More specifically, for example, the lithium transition metal phosphate compound is LiFePO 4 or LiCoPO 4 . However, M1 to M3 are one or more transition metal elements, and the values of x to z are arbitrary.
  • the positive electrode active material may be, for example, an oxide, disulfide, chalcogenide, or conductive polymer.
  • the oxide include titanium oxide, vanadium oxide, and manganese dioxide.
  • the disulfide include titanium disulfide and molybdenum sulfide.
  • An example of the chalcogenide is niobium selenide.
  • the conductive polymer include disulfide, polypyrrole, polyaniline, polythiophene, polyparastyrene, polyacetylene, and polyacene.
  • the solid electrolyte is the same as that included in the solid electrolyte layer 11 described above.
  • the composition (material) or composition ratio of the solid electrolyte contained in the solid electrolyte layer 11 and the positive electrode layer 12 may be the same or different.
  • the solid electrolyte is preferably at least one of oxide glass and oxide glass ceramics having a sintering temperature of 550 ° C. or less, a high thermal shrinkage rate, and excellent fluidity.
  • oxide glass and oxide glass ceramics having a sintering temperature of 550 ° C. or less, a high thermal shrinkage rate, and excellent fluidity.
  • the conductive agent is, for example, at least one of a carbon material, a metal, a metal oxide, a conductive polymer, and the like.
  • a carbon material for example, graphite, carbon fiber, carbon black, carbon nanotube, or the like can be used.
  • carbon fiber for example, vapor growth carbon fiber (VGCF) can be used.
  • VGCF vapor growth carbon fiber
  • carbon black acetylene black, Ketjen black, etc.
  • the carbon nanotube for example, a multi-wall carbon nanotube (MWCNT) such as a single wall carbon nanotube (SWCNT) or a double wall carbon nanotube (DWCNT) can be used.
  • MWCNT multi-wall carbon nanotube
  • SWCNT single wall carbon nanotube
  • DWCNT double wall carbon nanotube
  • Ni powder can be used.
  • SnO 2 can be used as the metal oxide.
  • the conductive polymer for example, substituted or unsubstituted polyaniline, polypyrrole, polythiophene, and one or two (co) polymers selected from these can be used.
  • the conductive agent may be any material having conductivity, and is not limited to the above example.
  • the negative electrode layer 13 is a negative electrode active material layer containing one or more types of negative electrode active materials and one or more types of solid electrolytes.
  • the solid electrolyte may have a function as a binder.
  • the negative electrode layer 13 may further contain a conductive agent as necessary.
  • the negative electrode layer 13 is, for example, a fired body of a green sheet (hereinafter referred to as “negative electrode green sheet”) as a negative electrode layer precursor.
  • the negative electrode active material includes, for example, a negative electrode material capable of occluding and releasing lithium ions that are electrode reactants.
  • the negative electrode material is preferably a carbon material or a metal-based material from the viewpoint of obtaining a high energy density, but is not limited thereto.
  • Examples of the carbon material include graphitizable carbon, non-graphitizable carbon, graphite, mesocarbon microbeads (MCMB), and highly oriented graphite (HOPG).
  • the metal-based material is a material containing, for example, a metal element or a metalloid element capable of forming an alloy with lithium as a constituent element.
  • the metal materials are Si (silicon), Sn (tin), Al (aluminum), In (indium), Mg (magnesium), B (boron), Ga (gallium), Ge (germanium). ), Pb (lead), Bi (bismuth), Cd (cadmium), Ag (silver), Zn (zinc), Hf (hafnium), Zr (zirconium), Y (yttrium), Pd (palladium) or Pt (platinum) ) And the like, any one kind or two or more kinds of alloys or compounds.
  • the simple substance is not limited to 100% purity, and may contain a small amount of impurities.
  • the alloy or compound include SiB 4 , TiSi 2 , SiC, Si 3 N 4 , SiO v (0 ⁇ v ⁇ 2), LiSiO, SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSnO, Mg 2. Sn etc. are mentioned.
  • the metal-based material may be a lithium-containing compound or lithium metal (lithium simple substance).
  • the lithium-containing compound is a composite oxide (lithium transition metal composite oxide) containing lithium and a transition metal element as constituent elements. Examples of this composite oxide include Li 4 Ti 5 O 12 .
  • the solid electrolyte is the same as that included in the solid electrolyte layer 11 described above.
  • the composition (material) or composition ratio of the solid electrolyte contained in the solid electrolyte layer 11 and the negative electrode layer 13 may be the same or different.
  • the solid electrolyte is preferably at least one of oxide glass and oxide glass ceramics having a sintering temperature of 550 ° C. or less, a high thermal shrinkage rate, and excellent fluidity.
  • a carbon material can be used as the negative electrode active material, the volume occupancy of the negative electrode active material in the negative electrode layer 13 and the mass ratio of the negative electrode active material in the negative electrode layer 13 are improved, and the negative electrode active material / solid Interfacial resistance between electrolytes can be reduced.
  • the conductive agent is the same as the conductive agent in the positive electrode layer 12 described above.
  • At least one of the volume occupation ratio of the positive electrode active material in the positive electrode layer 12 and the volume occupation ratio of the negative electrode active material in the negative electrode layer 13 is 40 vol% or more, preferably 50 vol% or more, more preferably 60 vol% or more. is there.
  • the energy density of the battery can be improved. From the viewpoint of improving the energy density, it is preferable that both the volume occupancy of the positive electrode active material in the positive electrode layer 12 and the volume occupancy of the negative electrode active material in the negative electrode layer 13 are in the above numerical ranges.
  • the upper limit of at least one of the volume occupancy of the positive electrode active material in the positive electrode layer 12 and the volume occupancy of the negative electrode active material in the negative electrode layer 13 is preferably 90 vol% or less. If the volume occupancy of the positive electrode active material in the positive electrode layer 12 exceeds 90 vol%, the volume occupancy of the solid electrolyte in the positive electrode layer 12 may decrease, and the strength of the positive electrode layer 12 may decrease. Moreover, when the volume occupation ratio of the negative electrode active material in the negative electrode layer 13 exceeds 90 vol%, the volume occupation ratio of the solid electrolyte in the negative electrode layer 13 may be decreased, and the strength of the negative electrode layer 13 may be decreased. is there.
  • both the volume occupation ratio of the positive electrode active material in the positive electrode layer 12 and the volume occupation ratio of the negative electrode active material in the negative electrode layer 13 are 90 vol. % Or less is preferable.
  • the volume occupancy of the positive electrode active material of the positive electrode layer 12 is a value determined as follows. First, after the battery is completely discharged, the following process is performed at 10 points randomly selected from the battery. First, a cross section of the battery is prepared by ion milling, and the procedure of photographing the cross section SEM image of the positive electrode layer 12 at 5000 kV at 5 kV is repeated to obtain a three-dimensional SEM image. Thereafter, the volume occupation ratio of the positive electrode active material in a 5 ⁇ m ⁇ 5 ⁇ m cube is obtained from the acquired three-dimensional SEM image. Next, the volume occupancy of the positive electrode active material in the cube obtained at 10 points as described above is simply averaged (arithmetic average) to obtain the volume occupancy (vol%) of the positive electrode layer 12.
  • the volume occupancy of the negative electrode active material in the negative electrode layer 13 is obtained by the same calculation method as the volume occupancy of the positive electrode active material in the positive electrode layer 12 described above.
  • the ratio of the total volume of the positive electrode layer 12 and the negative electrode layer 13 to the battery volume is preferably 50 vol% or more, more preferably 60 vol% or more, and even more preferably 70 vol% or more. When the ratio is 50 vol% or more, the energy density of the battery can be further improved.
  • the ratio of the total volume of the positive electrode layer 12 and the negative electrode layer 13 to the battery volume is preferably 95% or less, more preferably 90 vol% or less. When the ratio exceeds 95 vol%, the thickness of the solid electrolyte layer 11 becomes too thin, and it may be difficult to form the solid electrolyte layer 11 with a green sheet.
  • the ratio of the total volume of the positive electrode layer 12 and the negative electrode layer 13 to the battery volume is a value obtained as follows. First, the battery volume is determined in the same manner as the battery volume calculation method described above. However, the unit of the volume of the battery is [m 3 ] instead of [cc].
  • Ratio [vol%] (volume of positive electrode layer 12 [m 3 ] + volume of negative electrode layer 13 [m 3 ]) / volume of battery [m 3 ]
  • the ratio of the sum of the average thicknesses of the positive electrode layer 12 and the negative electrode layer 13 to the average thickness of the battery is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. When the ratio is 70% or more, the energy density of the battery can be further improved.
  • the ratio of the sum of the average thicknesses of the positive electrode layer 12 and the negative electrode layer 13 to the average thickness of the battery is preferably 95% or less, more preferably 90% or less. When the ratio exceeds 95%, the thickness of the solid electrolyte layer 11 becomes too thin, and it may be difficult to form the solid electrolyte layer 11 with a green sheet.
  • Mass ratio of positive electrode active material in positive electrode layer, mass ratio of negative electrode active material in negative electrode At least one of the mass ratio of the positive electrode active material in the positive electrode layer 12 and the mass ratio of the negative electrode active material in the negative electrode layer 13 is 70% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more. . When at least one of the mass ratios is 70% by mass or more, the energy density of the battery can be improved. From the viewpoint of improving the energy density, it is preferable that both the mass ratio of the positive electrode active material in the positive electrode layer 12 and the mass ratio of the negative electrode active material in the negative electrode layer 13 are in the above numerical ranges.
  • the upper limit of the mass ratio of the positive electrode active material in the positive electrode layer 12 is preferably 97% by mass or less. When the mass ratio of the positive electrode active material in the positive electrode layer 12 exceeds 97% by mass, the mass ratio of the solid electrolyte in the positive electrode layer 12 may decrease, and the strength of the positive electrode layer 12 may decrease. Moreover, it is preferable that the upper limit of the mass ratio of the negative electrode active material in the negative electrode layer 13 is 90 mass% or less. When the mass ratio of the negative electrode active material in the negative electrode layer 13 exceeds 90% by mass, the mass ratio of the solid electrolyte in the negative electrode layer 13 may decrease, and the strength of the negative electrode layer 13 may decrease.
  • lithium ions released from the positive electrode layer 12 are taken into the negative electrode layer 13 through the solid electrolyte layer 11, and at the time of discharging, lithium ions released from the negative electrode layer 13 are solid. It is taken into the positive electrode layer 12 through the electrolyte layer 11.
  • This manufacturing method includes a step of forming a positive electrode layer precursor, a negative electrode layer precursor, and a solid electrolyte layer precursor, and a step of laminating and firing these precursors.
  • a positive electrode green sheet as a positive electrode layer precursor is formed as follows. First, a positive electrode active material, a solid electrolyte, an organic binder, and a conductive agent as necessary are mixed to prepare a positive electrode mixture powder. Then, the mixture powder is dispersed in a solvent, A slurry as a composition for forming a positive electrode green sheet is obtained. In addition, in order to improve the dispersibility of the mixture powder, the dispersion may be performed in several times.
  • the organic binder for example, an acrylic resin can be used.
  • the solvent is not particularly limited as long as it can disperse the positive electrode mixture powder, but is preferably one that burns away in a temperature range lower than the firing temperature of the positive electrode green sheet.
  • the solvent include lower alcohols having 4 or less carbon atoms such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, t-butanol, ethylene glycol, propylene glycol (1,3-propanediol), 1, Aliphatic glycols such as 3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, ketones such as methyl ethyl ketone, dimethylethylamine Amines such as alicyclic alcohols such as terpineol can be used alone or in admixture of
  • the slurry may be filtered with a filter to remove foreign matters in the slurry.
  • the slurry layer is formed by uniformly applying or printing the slurry on the surface of the support substrate.
  • a polymer resin film such as polyethylene terephthalate (PET) can be used.
  • PET polyethylene terephthalate
  • a coating method or the like can be used, but is not particularly limited thereto.
  • a printing method for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method, and the like can be used, but the invention is not particularly limited thereto.
  • the composition imparting releasability include a paint containing a binder as a main component and added with wax or fluorine, or a silicone resin.
  • a positive electrode green sheet is formed on the surface of the support substrate by drying the slurry layer.
  • the drying method include natural drying, blow drying with hot air, heating drying with infrared rays or far infrared rays, vacuum drying, and the like. These drying methods may be used alone or in combination of two or more.
  • a negative electrode green sheet as a negative electrode layer precursor is formed as follows. First, a negative electrode active material, a solid electrolyte, an organic binder, and a conductive agent as necessary are mixed to prepare a negative electrode mixture powder. Then, the mixture powder is dispersed in a solvent, A slurry as a composition for forming a negative electrode green sheet is obtained. Except for using this slurry, the negative electrode green sheet is obtained in the same manner as in the “positive electrode layer precursor forming step” described above.
  • a solid electrolyte green sheet as a solid electrolyte layer precursor is formed as follows. First, a solid electrolyte and an organic binder are mixed to prepare an electrolyte mixture powder, and then the mixture powder is dispersed in a solvent to obtain a slurry as a solid electrolyte green sheet forming composition. . A solid electrolyte green sheet is obtained in the same manner as in the “positive electrode layer precursor forming step” except that this slurry is used.
  • a battery is manufactured as follows. First, each green sheet is cut into a predetermined size and shape. Next, a positive electrode green sheet and a negative electrode green sheet are laminated so as to sandwich the solid electrolyte green sheet to form a laminate. In addition, when the green sheet on each support substrate is thick enough to handle the green sheet alone, after peeling each green sheet from the support substrate with tweezers, for example, on the SUS substrate, a negative electrode, a solid electrolyte Then, pressure bonding and lamination are performed in the order of the positive electrode.
  • the green sheet on the support substrate is pressure-bonded on the SUS substrate so that the green sheet and the substrate face each other, and then only the support substrate is peeled off from the SUS substrate.
  • the laminate is heated, and the laminate is pressed so that pressure is applied at least in the thickness direction of the laminate.
  • the organic binder contained in each green sheet constituting the laminate is melted, and the green sheets constituting the laminate are brought into close contact with each other.
  • Specific methods for pressing the laminate while heating include, for example, a hot press method, a warm isostatic press (WIP) method, and the like.
  • WIP warm isostatic press
  • the solid electrolyte contained in the positive electrode green sheet, the negative electrode green sheet, and the solid electrolyte green sheet is at least one of oxide glass and oxide glass ceramics before the firing step.
  • the oxide glass and the oxide glass ceramic have a sintering temperature of 550 ° C. or lower, a high heat shrinkage rate, and a high fluidity.
  • the firing temperature of the laminate is not less than the sintering temperature of the solid electrolyte, preferably not less than the sintering temperature of the solid electrolyte and not more than 550 ° C., more preferably not less than the sintering temperature of the solid electrolyte and not more than 500 ° C.
  • the sintering temperature of a solid electrolyte means the sintering temperature of the solid electrolyte, when there is one kind of solid electrolyte contained in the laminate.
  • it means the lowest one among the sintering temperatures of those solid electrolytes.
  • the firing temperature of the laminate is equal to or higher than the sintering temperature of the solid electrolyte, the sintering of the solid electrolyte proceeds, so that the lithium ion conductivity of the positive electrode layer 12, the negative electrode layer 13, and the solid electrolyte layer 11 can be improved. Further, the strength of the positive electrode layer 12, the negative electrode layer 13, and the solid electrolyte layer 11 can be increased.
  • the reason why the firing temperature of the laminate is 550 ° C. or lower or 500 ° C. or lower is the same as the reason why the sintering temperature of the solid electrolyte is 550 ° C. or lower or 500 ° C. or lower.
  • the oxide glass may be changed to an oxide glass ceramic in the firing step.
  • the target battery is obtained.
  • At least one of the positive electrode layer 12 and the negative electrode layer 13 has a volume occupation ratio of the active material of 40 vol% or more. Thereby, the energy density of a battery can be improved.
  • the battery In a general lithium ion secondary battery using an organic electrolyte, the battery is covered with an exterior material such as an aluminum laminate film so that the organic electrolyte does not leak from the battery.
  • an exterior material such as an aluminum laminate film
  • the battery is covered with an exterior material such as an aluminum laminate film in order to prevent moisture from entering. This is because electrolytes such as sulfides have low stability to the atmosphere (water).
  • the energy density of the battery tends to be reduced because the volume of the exterior material and the presence of the seal portion of the exterior material reduce the proportion of the electrode active material in the battery. .
  • the battery according to the first embodiment since at least one of oxide glass and oxide glass ceramic having high stability to the atmosphere (moisture) is used as the solid electrolyte, the aluminum laminate film Etc. can be omitted. Therefore, the energy density of the battery can be improved.
  • the energy density of the battery can be particularly improved.
  • the exterior material such as an aluminum laminate film is omitted.
  • the ratio of the total volume of the positive electrode layer 12 and the negative electrode layer 13 to the battery volume is set to 50 vol% or more.
  • Both the volume occupation ratio of the positive electrode active material in the positive electrode layer 12 and the volume occupation ratio of the negative electrode active material in the negative electrode layer 13 are set to 40 vol% or more.
  • High capacity graphite is used as the negative electrode active material.
  • a solid electrolyte having the following characteristics.
  • An oxide glass electrolyte and an oxide glass ceramic electrolyte that have a sufficiently high heat shrinkage rate and are stable against moisture are used.
  • the ionic conductivity of the solid electrolyte is 10 ⁇ 7 S / cm or more.
  • the sintering temperature of the solid electrolyte is a temperature of 550 ° C. or lower.
  • the battery further includes a positive electrode current collecting layer 14 provided on one main surface of the positive electrode layer 12 and a negative electrode current collecting layer 15 provided on one main surface of the negative electrode layer 13. Also good.
  • the solid electrolyte layer 11 is provided between the other main surface of the positive electrode layer 12 and the other main surface of the negative electrode layer 13.
  • the battery may include only one of the positive electrode current collecting layer 14 and the negative electrode current collecting layer 15.
  • the positive electrode current collecting layer 14 is a metal layer containing, for example, Al, Ni, stainless steel, or the like.
  • the negative electrode current collecting layer 15 is a metal layer containing, for example, Cu or stainless steel.
  • the shape of the metal layer is, for example, a foil shape, a plate shape, or a mesh shape.
  • the positive electrode current collecting layer 14 and the negative electrode current collecting layer 15 may be a green sheet fired body containing conductive particles and a solid electrolyte.
  • the present technology is not limited to this example.
  • the present technology may be applied to a battery using another alkali metal such as Na or K, an alkaline earth metal such as Mg or Ca, or another metal such as Al or Ag as an electrode reactant.
  • the battery may have a bipolar stacked structure.
  • a part of the layers constituting the battery may be a green sheet, and other layers may be directly formed on the green sheet by printing or the like.
  • the positive electrode slurry may be formed by applying or printing the positive electrode slurry on one surface of the solid electrolyte layer precursor or the solid electrolyte layer 11 and then drying the positive electrode slurry.
  • coating or printing a negative electrode slurry to the other surface of the solid electrolyte layer precursor or the solid electrolyte layer 11 you may make it dry and form a negative electrode layer precursor.
  • the positive electrode layer precursor, the negative electrode layer precursor, and the solid electrolyte layer precursor are green sheets.
  • the positive electrode layer precursor, the negative electrode layer precursor, and the solid electrolyte layer are described as examples.
  • the precursor may be a green compact.
  • the positive electrode layer precursor, the negative electrode layer precursor, and the solid electrolyte layer precursor one or two layers of the precursor may be a green sheet, and the rest may be a green compact.
  • the green compact as the positive electrode layer precursor is produced by pressure-molding the positive electrode mixture powder with a press or the like.
  • the green compact as the negative electrode layer precursor is produced by pressure-molding the negative electrode mixture powder with a press or the like.
  • the green compact as the solid electrolyte layer precursor is produced by pressure-molding the electrolyte mixture powder with a press or the like.
  • the positive electrode mixture powder, the negative electrode mixture powder, and the electrolyte mixture powder may not contain an organic binder.
  • the positive electrode layer precursor, the solid electrolyte layer precursor, and the negative electrode layer precursor are laminated and then fired.
  • the positive electrode layer precursor, the solid electrolyte layer precursor, and the negative electrode layer are described.
  • these fired bodies may be laminated to form a laminate.
  • the laminate may not be fired after pressing the laminate, or the laminate may be fired after pressing the laminate as necessary.
  • both the positive electrode layer 12 and the negative electrode layer 13 have been described as an example of a configuration including at least one of oxide glass and oxide glass ceramic as a solid electrolyte. It is not limited to this configuration.
  • one of the positive electrode layer 12 and the negative electrode layer 13 may include at least one of oxide glass and oxide glass ceramic as a solid electrolyte, and the other may include an oxide crystal as a solid electrolyte.
  • both the positive electrode layer 12 and the negative electrode layer 13 are electrodes including a solid electrolyte.
  • at least one of the positive electrode layer 12 and the negative electrode layer 13 includes a solid electrolyte.
  • the electrode which does not contain may be sufficient.
  • the electrode not including the solid electrolyte may be a thin film produced by a vapor deposition method such as a vapor deposition method or a sputtering method.
  • the battery according to the second embodiment of the present technology includes a stacked body 20, a positive electrode terminal 26 ⁇ / b> A that contacts the positive electrode exposed portion and the negative electrode exposed portion exposed from the side surface of the stacked body 20, and the negative electrode And a terminal 26B.
  • the laminate 20 includes a solid electrolyte layer 21, a positive electrode 22 and insulating layers 24 ⁇ / b> A and 24 ⁇ / b> B stacked on one main surface of the solid electrolyte layer 21, and the other of the solid electrolyte layers 21.
  • Negative electrode 23 and insulating layers 25A and 25B stacked on the main surface.
  • the positive electrode 22 includes a positive electrode layer 22A provided on one main surface of the solid electrolyte layer 21, and a positive electrode current collecting layer 22B provided on one main surface of the positive electrode layer 22A.
  • the negative electrode 23 includes a negative electrode layer 23A provided on the other main surface of the solid electrolyte layer 21, and a negative electrode current collecting layer 23B provided on the other main surface of the negative electrode layer 23A.
  • illustration is abbreviate
  • the laminate 20 has a rectangular plate shape, and has a first side surface 20Sa and a second side surface 20Sb facing each other.
  • the side surface of the positive electrode 22 is covered with an insulating layer 24A so that the side surface of the positive electrode 22 is exposed from the first side surface 20Sa side.
  • the side surface of the positive electrode 22 exposed from the first side surface 20Sa is in contact with the positive electrode terminal 26A.
  • the side surface of the negative electrode 23 is covered with an insulating layer 25A so that the side surface of the negative electrode 23 is exposed from the second side surface 20Sb side.
  • the side surface of the negative electrode 23 exposed from the second side surface 20Sb is in contact with the negative electrode terminal 26B.
  • One main surface of the stacked body 20 is covered with an insulating layer 24B, and the other main surface of the stacked body 20 is covered with an insulating layer 25B.
  • the main surfaces of the solid electrolyte layer 21 and the insulating layers 24B and 25B have a rectangular shape having substantially the same size.
  • the main surfaces of the positive electrode 22 and the negative electrode 23 have a rectangular shape having substantially the same size.
  • the sizes of the main surfaces of the positive electrode 22 and the negative electrode 23 are slightly smaller than the sizes of the main surfaces of the solid electrolyte layer 21 and the insulating layers 24B and 25B.
  • the insulating layer 24A When the insulating layer 24A is viewed in a plan view from a direction perpendicular to one main surface of the positive electrode 22, the insulating layer 24A has a U-shape, and the solid electrolyte layer 21 covers three of the side surfaces of the positive electrode 22. And the insulating layer 24B.
  • One main surface of the positive electrode 22 and the insulating layer 24A has substantially the same height and is covered with the insulating layer 24B.
  • the insulating layer 25A When the insulating layer 25A is viewed in a plan view from a direction perpendicular to the other main surface of the negative electrode 23, the insulating layer 25A has a U shape, and the solid electrolyte layer covers the three side surfaces of the side surfaces of the negative electrode 23. 21 and the peripheral portion of the main surface of the insulating layer 25B.
  • the other main surfaces of the negative electrode 23 and the insulating layer 25A have substantially the same height and are covered with the insulating layer 25B.
  • Solid electrolyte layer, positive electrode layer, negative electrode layer The solid electrolyte layer 21, the positive electrode layer 22A, and the negative electrode layer 23A have the same configuration as the solid electrolyte layer 11, the positive electrode layer 12, and the negative electrode layer 13 in the first embodiment, respectively.
  • the positive electrode current collecting layer 22B and the negative electrode current collecting layer 23B include conductive particles and oxide glass or oxide glass ceramics.
  • the positive electrode current collector layer 22B is, for example, a fired body of a green sheet (hereinafter referred to as “positive electrode current collector green sheet”) as a positive electrode current collector layer precursor.
  • the negative electrode current collecting layer 23B is, for example, a fired body of a green sheet (hereinafter referred to as “negative electrode current collecting green sheet”) as a negative electrode current collecting layer precursor.
  • Examples of the shape of the conductive particles include a spherical shape, an ellipsoidal shape, a needle shape, a plate shape, a scale shape, a tube shape, a wire shape, a rod shape (rod shape), and an indefinite shape. It is not something. Two or more kinds of particles having the above shapes may be used in combination.
  • Conductive particles are conductive inorganic particles.
  • the inorganic particles are at least one of metal particles, metal oxide particles, and carbon particles.
  • the metal is defined to include a semi-metal.
  • the metal particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, lead.
  • metals such as these, or these alloys, etc. are mentioned, It is not limited to this.
  • the metal oxide particles include indium tin oxide (ITO), zinc oxide, indium oxide, antimony-added tin oxide, fluorine-added tin oxide, aluminum-added zinc oxide, gallium-added zinc oxide, silicon-added zinc oxide, and zinc oxide.
  • ITO indium tin oxide
  • zinc oxide zinc oxide
  • indium oxide antimony-added tin oxide
  • fluorine-added tin oxide aluminum-added zinc oxide
  • gallium-added zinc oxide gallium-added zinc oxide
  • silicon-added zinc oxide and zinc oxide.
  • zinc oxide include, but are not limited to, a tin oxide system, an indium oxide-tin oxide system, and a zinc oxide-indium oxide-magnesium oxide system.
  • Examples of the carbon particles include, but are not limited to, carbon black, porous carbon, carbon fiber, fullerene, graphene, carbon nanotube, carbon microcoil, and nanohorn.
  • the oxide glass and the oxide glass ceramic are the same as the oxide glass and the oxide glass ceramic contained in the solid electrolyte layer 21, respectively.
  • the insulating layers 24A, 24B, 25A, and 25B contain insulating particles and oxide glass or oxide glass ceramics.
  • the insulating layers 24A, 24B, 25A, and 25B are, for example, fired bodies of green sheets (hereinafter referred to as “insulating green sheets”) as insulating layer precursors.
  • Examples of the shape of the insulating particles include a spherical shape, an ellipsoidal shape, a needle shape, a plate shape, a scale shape, a tube shape, a wire shape, a rod shape (rod shape), and an indefinite shape. It is not something. Two or more kinds of particles having the above shapes may be used in combination.
  • the insulating particles are inorganic particles having electrical insulating properties.
  • the inorganic particles include aluminum oxide (alumina, Al 2 O 3 ), silicon oxide (silica, SiO 2 ), silicon nitride (SiN), aluminum nitride (AlN), and silicon carbide (silicon carbide, SiC). At least one of the following.
  • the oxide glass and the oxide glass ceramic are the same as the oxide glass and the oxide glass ceramic contained in the solid electrolyte layer 21, respectively.
  • the positive terminal 26A and the negative terminal 26B include conductive particles and oxide glass.
  • the conductive particles are the same as the conductive particles contained in the positive electrode current collector layer 22B and the negative electrode current collector layer 23B described above.
  • First and second insulating green sheets as precursors for the insulating layers 24B and 25B are formed as follows. First, insulating particles, oxide glass or oxide glass ceramic, and an organic binder are mixed to prepare a mixture powder, and then the mixture powder is dispersed in a solvent to form an insulating green sheet. A slurry as a composition for use is obtained. Except for using this slurry, the first and second insulating green sheets are obtained in the same manner as the “positive electrode layer precursor forming step” in the first embodiment.
  • the third and fourth insulating green sheets as precursors of the insulating layers 24B and 25B are obtained in the same manner as the first and second insulating green sheets described above.
  • the thicknesses of the first to fourth insulating green sheets are set according to the desired thickness of the insulating layers 24A, 24B, 25A, and 25B, respectively.
  • a positive current collecting green sheet as a positive current collecting layer precursor is formed as follows. First, conductive particles, oxide glass or oxide glass ceramics, and an organic binder are mixed to prepare a mixture powder, and then the mixture powder is dispersed in a solvent to obtain a positive electrode current collector. A slurry as a green sheet forming composition is obtained. Except for using this slurry, a positive electrode current collector green sheet is obtained in the same manner as in the “positive electrode layer precursor forming step” in the first embodiment.
  • the negative electrode current collecting green sheet as the negative electrode current collecting layer precursor is obtained in the same manner as the above-mentioned “forming step of positive electrode current collecting layer precursor”.
  • a battery is produced as follows. First, the positive electrode green sheet, the negative electrode green sheet, the solid electrolyte green sheet, and the first and second insulating green sheets are punched into a rectangular shape having a predetermined size. Further, the third and fourth insulating green sheets are punched into a U shape having a predetermined size.
  • the first insulating green sheet, the positive electrode current collecting green sheet, the positive electrode green sheet, the solid electrolyte green sheet, the negative electrode green sheet, and the second insulating green sheet punched into a rectangular shape are laminated in this order, and the laminate 20 is stacked.
  • the first insulating green sheet and the solid electrolyte green are disposed so that the positive electrode current collecting green sheet and the positive electrode green sheet side surface are exposed from the first side surface 20Sa side of the laminate 20. It arrange
  • the fourth insulating green sheet and the solid electrolyte green are formed so that the side surfaces of the negative electrode current collecting green sheet and the negative electrode green sheet are exposed from the second side surface 20Sb side of the laminate 20. It arrange
  • the periphery of the stacked body 20 is covered with insulating layers 24A, 24B, 25A, and 25B. Therefore, the safety of the battery can be improved.
  • the insulating layers 24A, 24B, 25A, and 25B have a function of suppressing moisture intrusion into the stacked body 20, the durability of the battery can be improved.
  • the entire side surface of the positive electrode layer 22A may be covered with the insulating layer 24A, and only the positive electrode current collecting layer 22B may be in contact with the positive electrode terminal 26A on the first side surface 20Sa.
  • the entire side surface of the negative electrode layer 23A may be covered with the insulating layer 25A, and only the negative electrode current collecting layer 23B may be in contact with the negative electrode terminal 26B on the second side surface 20Sb.
  • the peripheral edge of the positive electrode layer 22 ⁇ / b> A is preferably located inside the peripheral edge of the negative electrode layer 23 ⁇ / b> A in the in-plane direction of the stacked body 20. This is because the deposition of lithium on the peripheral edge of the negative electrode layer 23A can be suppressed and the safety can be improved.
  • a part of the layers constituting the battery may be a green sheet, and other layers may be directly formed on the green sheet by printing or the like.
  • the positive electrode layer 22A, the positive electrode current collector layer 22B, and the insulating layers 24A and 24B are formed on one main surface of a solid electrolyte green sheet having a predetermined shape by a printing method, and the negative electrode layer 23A and the negative electrode current collector are formed on the other main surface.
  • the layer 23B and the insulating layers 25A and 25B may be formed by a printing method or the like.
  • the battery according to the third embodiment of the present technology is different from the battery according to the second embodiment in that a stacked body 20 ⁇ / b> A is provided instead of the stacked body 20.
  • the same reference numerals are given to the same portions as in the second embodiment.
  • the laminated body 20A includes an insulating layer 24B, a positive electrode 22, a solid electrolyte layer 21, a negative electrode 23C, a solid electrolyte layer 21, a positive electrode 22C, a solid electrolyte layer 21, a negative electrode 23C, a solid electrolyte layer 21, a positive electrode 22, a solid electrolyte layer 21, and a negative electrode.
  • 23 and the insulating layer 25B are stacked in this order.
  • the side surface of the stacked body 20A is covered with insulating layers 24A, 24C, 25A, and 25C. More specifically, the side surfaces of the positive electrodes 22 and 22C are covered with insulating layers 24A and 24C, respectively, so that the side surfaces of the positive electrodes 22 and 22C are exposed from the first side surface 20Sa side. The side surfaces of the positive electrodes 22 and 22C exposed from the first side surface 20Sa are in contact with the positive electrode terminal 26A. The side surfaces of the negative electrodes 23 and 23C are covered with insulating layers 25A and 25C so that the side surfaces of the negative electrodes 23 and 23C are exposed from the second side surface 20Sb side. The side surfaces of the negative electrodes 23 and 23C exposed from the second side surface 20Sb are in contact with the negative electrode terminal 26B.
  • the positive electrode 22C includes a positive electrode current collecting layer 22B, a positive electrode layer 22A provided on one main surface of the positive electrode current collecting layer 22B, and a positive electrode layer 22A provided on the other main surface of the positive electrode current collecting layer 22B.
  • the negative electrode 23 includes a negative electrode current collecting layer 23B, a negative electrode layer 23A provided on one main surface of the negative electrode current collecting layer 23B, and a negative electrode layer 23A provided on the other main surface of the negative electrode current collecting layer 23B.
  • the insulating layers 24C and 25C are the same as the insulating layers 24A and 25A, respectively, except that the insulating layers 24C and 25C have thicknesses that cover the three side surfaces of the positive electrode 22C and the negative electrode 23C.
  • the numerical range of the total volume of the positive electrode layer 22A and the negative electrode layer 23A relative to the battery volume is the same as the “numerical range of the total volume of the positive electrode layer 12 and the negative electrode layer 13 relative to the battery volume” in the first embodiment.
  • the total volume of the positive electrode layer 22A and the negative electrode layer 23A means the total volume of all the positive electrode layers 22A and the negative electrode layers 23A included in the battery.
  • the total volume of positive electrode layers 22A and negative electrode layers 23A Means the sum of the total volume of the n positive electrode layers 22A and the total volume of the m negative electrode layers 23A.
  • the volume of each positive electrode layer 22A and each negative electrode layer 23A is calculated in the same manner as the method for obtaining the volumes of the positive electrode layer 12 and the negative electrode layer 13 described in the first embodiment.
  • the numerical range of the ratio of the total thickness of the positive electrode layer 22A and the negative electrode layer 23A to the average thickness of the battery is “the ratio of the total average thickness of the positive electrode layer 12 and the negative electrode layer 13 to the average thickness of the battery” in the first embodiment. It is the same as “Numerical range of”. However, in the third embodiment, the sum of the average thicknesses of the positive electrode layer 22A and the negative electrode layer 23A means the sum of the average thicknesses of all the positive electrode layers 22A and the negative electrode layers 23A included in the battery.
  • the sum of the average thicknesses of positive electrode layer 22A and negative electrode layer 23A Means the total sum of the average thicknesses of the n positive electrode layers 22A and the average thickness of the m negative electrode layers 23A.
  • the average thickness of each positive electrode layer 22A and each negative electrode layer 23A is calculated in the same manner as the method for obtaining the average thickness of the positive electrode layer 12 and the negative electrode layer 13 described in the first embodiment.
  • the entire side surface of the positive electrode layer 22A may be covered with the insulating layers 24A and 24C, and only the positive electrode current collecting layer 22B may be in contact with the positive electrode terminal 26A on the first side surface 20Sa.
  • the entire side surface of the negative electrode layer 23A may be covered with the insulating layers 25A and 25C, and only the negative electrode current collecting layer 23B may be in contact with the negative electrode terminal 26B on the second side surface 20Sb.
  • the peripheral edge of the positive electrode layer 22A is located inside the peripheral edge of the negative electrode layer 23A in the in-plane direction of the stacked body 20A. This is because the deposition of lithium on the peripheral edge of the negative electrode layer 23A can be suppressed and the safety can be improved.
  • the laminated body 20A may be formed as follows. That is, the first laminated body is formed by forming the positive electrode layer 22A, the positive electrode current collecting layer 22B, and the insulating layer 24C on one main surface of the solid electrolyte green sheet having a predetermined shape by a printing method or the like. Further, the second laminate is formed by forming the negative electrode layer 23A, the negative electrode current collecting layer 23B, and the insulating layer 25C on one main surface of the solid electrolyte green sheet having a predetermined shape by a printing method or the like. The first stacked body and the second stacked body obtained as described above are alternately stacked to form a stacked body 20A.
  • lithium cobaltate (LiCoO 2 ) manufactured by Aldrich as a positive electrode active material and oxide glass (Li 2 O: SiO 2 : B 2 O 3 54: 11: 35 (mol% ratio) as a solid electrolyte )
  • this mixture was mixed with butyl acetate so that the solid content was 30% by mass, and stirred with 5 mm ⁇ zirconia balls for 4 hours to obtain a slurry.
  • this slurry was applied on a release film and dried at 80 ° C. for 10 minutes, thereby forming a green sheet on the release film.
  • the green sheet was punched into a disk shape together with the release film, and then the green sheet was peeled from the release film. Thereby, the positive electrode green sheet as a positive electrode layer precursor was obtained.
  • the negative electrode green sheet as a negative electrode layer precursor was obtained.
  • a laminated body was obtained by laminating a negative electrode green sheet, a solid electrolyte green sheet, and a positive electrode green sheet on the SUS plate in this order, and this laminated body was thermocompression bonded at 100 ° C. for 10 minutes.
  • the laminate was heated at 300 ° C. for 10 hours to remove the acrylic binder, and then sintered at 400 ° C. for 30 minutes.
  • the intended all solid state battery all solid state lithium ion secondary battery
  • Example 1 is the same as Example 1 except that the garnet-type oxide crystal powder (Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 ) is used as the solid electrolyte in the production process of the electrolyte layer precursor, the positive electrode layer precursor, and the negative electrode layer precursor. In the same manner, an all-solid battery was obtained.
  • the garnet-type oxide crystal powder Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12
  • Example 9 to 15 (Preparation process of electrolyte layer precursor, positive electrode layer precursor and negative electrode layer precursor) A solid electrolyte green sheet, a positive electrode green sheet, and a negative electrode green sheet were obtained in the same manner as in Example 1 except that the green sheet was punched into a rectangular shape together with the release film.
  • the green sheet was punched into a rectangular shape together with the release film, and then the green sheet was peeled from the release film. Thereby, the current collection green sheet as a current collection layer precursor was obtained.
  • a U-shaped insulating green sheet is formed in the same manner as the above-described insulating layer precursor manufacturing process except that the coating thickness of the slurry is changed and the green sheet is punched into a U-shape together with the release film. Obtained.
  • a laminate having the configuration shown in FIG. 6 was produced as follows. First, as shown in FIG. 6, after a solid electrolyte green sheet, a positive electrode green sheet, a negative electrode green sheet, a current collecting green sheet, a rectangular and U-shaped insulating green sheet are laminated, a laminate is obtained. The laminate was thermocompression bonded at 100 ° C. for 10 minutes. Note that the number of stacks was adjusted so that the average thickness of the battery finally obtained would be the value shown in Table 3, unlike the stack shown in FIG. Next, the laminate was heated at 300 ° C. for 10 hours to remove the acrylic binder, and then sintered at 400 ° C. for 30 minutes. Thereby, an all-solid-state battery was obtained.
  • the first side surface of the all solid state battery in which the positive electrode layer and the positive electrode current collecting layer are exposed the second side of the all solid state battery in which the negative electrode layer and the negative electrode current collecting layer are exposed.
  • the side surfaces were sequentially attached to the conductive paste.
  • the all solid state battery was sintered at 400 ° C. for 1 hour to form a positive electrode and a negative electrode terminal on the first and second side surfaces of the all solid state battery, respectively. As a result, the intended all solid state battery was obtained.
  • Example 16 to 21 First, a solid electrolyte green sheet, a positive electrode green sheet, and a negative electrode green sheet were obtained in the same manner as in Example 6 except that the green sheet was punched into a rectangular shape together with the release film. Next, an all solid state battery was obtained in the same manner as in Examples 9 to 14 except that these green sheets were used.
  • Mass ratio of positive electrode active material in positive electrode layer, mass ratio of negative electrode active material in negative electrode The mass ratio of the positive electrode active material in the positive electrode layer and the mass ratio of the negative electrode active material in the negative electrode were determined by the calculation method described in the first embodiment.
  • volume occupation ratio of the positive electrode active material in the positive electrode layer and the volume occupation ratio of the negative electrode active material in the negative electrode layer were obtained by the calculation method described in the first embodiment.
  • the average thickness of the battery, the positive electrode layer, and the negative electrode layer was determined by the calculation method described in the first embodiment. Moreover, the average thickness of the positive electrode current collecting layer, the negative electrode current collecting layer, and the insulating layer was determined in the same manner as the method for calculating the average thickness of the battery, the positive electrode layer, and the negative electrode layer.
  • the ratio of the total thickness of the positive electrode layer and the negative electrode layer to the average thickness of the battery was determined by the calculation method described in the first embodiment.
  • the ratio of the total volume of the positive electrode layer and the negative electrode layer to the battery volume was determined by the calculation method described in the first embodiment.
  • the ionic conductivity of the solid electrolyte layers of Examples 1 to 8 was determined as follows. First, solid electrolyte green sheets were prepared in the same manner as in Examples 1-8. Next, the produced solid electrolyte green sheet was heated at 300 ° C. for 10 hours to remove the acrylic binder and then sintered at 400 ° C. for 30 minutes to obtain a solid electrolyte layer as a measurement sample. Next, the ionic conductivity of the solid electrolyte layer was determined by the ionic conductivity measurement method described in the first embodiment. As a result, the ionic conductivity was 2 ⁇ 10 ⁇ 7 S / cm.
  • volume energy density For the all solid state batteries of Examples 1 to 8 and Comparative Examples 1 to 3 obtained as described above, the volume energy density was determined as follows. First, a gold-plated battery evaluation jig was electrically joined to the SUS plate and the negative electrode layer for the produced battery. Next, charging / discharging was performed under the following charging / discharging conditions, and the discharge capacity (Ah) was measured. Next, after obtaining the discharge energy amount (Wh) from the discharge capacity (Ah) and the average discharge voltage (V) of the battery, the volume energy density (Wh / L) is obtained by dividing this by the volume (L) of the battery. Asked.
  • Charging conditions environmental temperature 23 ° C., CCCV (Constant Current / Constant Voltage), charging voltage 4.2 V, charging current 0.1 C, 0.01 C cut Discharge conditions: ambient temperature 23 ° C., CC (Constant Current), discharge current 0.1 C, final voltage 2.0 V
  • the volume energy density was determined as follows. First, current leads were connected to the positive electrode and negative electrode terminal of the produced battery. Next, charging / discharging was performed under the same charging / discharging conditions as in Examples 1 to 8 and Comparative Examples 1 to 3, and the volume energy density (Wh / L) was obtained.
  • Tables 1 and 2 show the configurations and evaluation results of all solid state batteries of Examples 1 to 8 and Comparative Examples 1 to 3.
  • Tables 3 and 4 show the configurations and evaluation results of all solid state batteries of Examples 9 to 15.
  • Tables 5 and 6 show the configurations and evaluation results of the all solid state batteries of Examples 16 to 21.
  • electrode thickness ratio means “a ratio of the sum of the average thicknesses of the positive electrode layer and the negative electrode layer to the average thickness of the battery”.
  • Electrorode occupation volume means “a ratio of the sum of the volume of the positive electrode layer and the negative electrode layer to the battery volume”.
  • the battery volume is 5 cc or less.
  • a high volume energy density of 400 Wh / L or more can be obtained.
  • the battery volume is 5 cc or less. Only a low volumetric energy density of less than 400 Wh / L is obtained.
  • FIG. 8 is a graph showing the relationship between battery volume and volumetric energy density.
  • FIG. 8 shows the evaluation results of commercially available small lithium ion secondary batteries in addition to the evaluation results of the batteries of Examples 9 to 15 and 16 to 21. From FIG. 8, it can be seen that in the battery having the volume occupancy of 40 vol% or more, the effect of improving the volume energy density of the battery is particularly remarkable when the battery volume is 5 cc or less.
  • the all-solid-state battery described above can be mounted on a printed circuit board 1202 together with a charging circuit or the like, as shown in FIG.
  • an electronic circuit such as an all-solid battery 1203 and a charging circuit can be mounted on the printed circuit board 1202 by a reflow process.
  • a battery module 1201 in which an electronic circuit such as an all-solid battery 1203 and a charging circuit is mounted on a printed circuit board 1202 is referred to as a battery module 1201.
  • the battery module 1201 has a card type configuration as necessary, and can be configured as a portable card type mobile battery.
  • An all solid state battery 1203 is formed on the printed circuit board 1202.
  • a charge control IC (Integrated Circuit) 1204, a battery protection IC 1205, and a battery remaining amount monitoring IC 1206 are formed using the printed circuit board 1202 in common.
  • the battery protection IC 1205 controls the charging / discharging operation so that the charging voltage does not become excessive at the time of charging / discharging, an overcurrent flows due to a load short circuit, and no overdischarging occurs.
  • a USB (Universal Serial Bus) interface 1207 is attached to the printed circuit board 1202.
  • the all-solid-state battery 1203 is charged by the power supplied through the USB interface 1207.
  • the charging operation is controlled by the charging control IC 1204.
  • predetermined power for example, a voltage of 4.2 V
  • the remaining battery level of the all-solid battery 1203 is monitored by the remaining battery level monitoring IC 1206 so that a display (not shown) indicating the remaining battery level can be seen from the outside.
  • the USB interface 1207 may be used for load connection.
  • a specific example of the load 1209 described above is as follows. 1. Wearable devices (sports watches, watches, hearing aids, etc.) 2. IoT terminals (sensor network terminals, etc.) 3. Amusement devices (portable game terminals, game controllers) 4). IC board embedded battery (real-time clock IC) 5). Energy harvesting equipment (storage elements for power generation elements such as solar power generation, thermoelectric power generation, vibration power generation)
  • Universal credit card as an application
  • a card called a universal credit card in which functions such as a plurality of credit cards and point cards are integrated into one card has been put into practical use.
  • information such as the number and expiration date of various credit cards and point cards can be taken into this card, so if you put one card in your wallet, you can use it whenever you want. You can select and use the correct card.
  • FIG. 10 shows an example of the configuration of the universal credit card 1301. It has a card type shape and contains an IC chip and an all-solid battery according to the present technology. Further, a display 1302 that consumes less power and an operation unit such as direction keys 1303a and 1303b are provided. Further, a charging terminal 1304 is provided on the surface of the universal credit card 1301.
  • the user can specify a credit card or the like loaded in advance on the universal credit card 1301 by operating the direction keys 1303a and 1303b while looking at the display 1302.
  • a credit card or the like loaded in advance on the universal credit card 1301 by operating the direction keys 1303a and 1303b while looking at the display 1302.
  • information indicating each credit card is displayed on the display 1302, and the user can designate a desired credit card by operating the direction keys 1303a and 1303b. After that, it can be used like a conventional credit card.
  • the all-solid-state battery according to the present technology can be applied to any electronic card other than the universal credit card 1301.
  • a wireless terminal in a wireless sensor network is referred to as a sensor node, and includes one or more wireless chips, a microprocessor, a power supply (battery), and the like.
  • Specific examples of sensor networks are used to monitor energy saving management, health management, industrial measurement, traffic conditions, agriculture, and the like.
  • As the type of sensor voltage, temperature, gas, illuminance, and the like are used.
  • a power monitor node In the case of energy saving management, a power monitor node, a temperature / humidity node, an illuminance node, a CO 2 node, a human sensor node, a remote control node, a router (relay machine), and the like are used as sensor nodes. These sensor nodes are provided so as to constitute a wireless network in homes, office buildings, factories, stores, amusement facilities, and the like.
  • Data such as temperature, humidity, illuminance, CO 2 concentration, and electric energy is displayed so that the energy saving status of the environment can be seen. Furthermore, on / off control of lighting, air-conditioning facilities, ventilation facilities, etc. is performed according to commands from the control station.
  • ZigBee (registered trademark) can be used as one of the wireless interfaces of the sensor network.
  • This wireless interface is one of the short-range wireless communication standards, and has a feature that it is inexpensive and consumes less power, instead of having a short transferable distance and a low transfer speed. Therefore, it is suitable for mounting on a battery-driven device.
  • the basic part of this communication standard is standardized as IEEE 802.15.4.
  • the ZigBee (Registered Trademark) Alliance has formulated specifications for communication protocols between devices above the logical layer.
  • FIG. 11 shows an example of the configuration of the wireless sensor node 1401.
  • a detection signal of the sensor 1402 is supplied to an AD conversion circuit 1404 of a microprocessor (MPU) 1403.
  • MPU microprocessor
  • the various sensors described above can be used as the sensor 1402.
  • a memory 1406 is provided in association with the microprocessor 1403.
  • the output of the battery 1407 is supplied to the power supply control unit 1408, and the power supply of the wireless sensor node 1401 is managed.
  • the battery 1407 the above-described all-solid battery, card-type battery pack, or the like can be used.
  • the charge / discharge device according to the present technology is applied when an all-solid battery is used.
  • the program is installed in the microprocessor 1403.
  • the microprocessor 1403 processes the detection result data of the sensor 1402 output from the AD conversion circuit 1404 according to the program.
  • a wireless communication unit 1409 is connected to the communication control unit 1405 of the microprocessor 1403, and detection result data is transmitted from the wireless communication unit 1409 to a network terminal (not shown) using, for example, ZigBee (registered trademark). Connected to the network via a network terminal.
  • a predetermined number of wireless sensor nodes can be connected to one network terminal.
  • the network type may be a tree type, a mesh type, a linear type, or the like.
  • a wearable terminal is a wristband type electronic device.
  • the wristband type activity meter is also called a smart band, and it is possible to obtain data on human activities such as the number of steps, distance traveled, calories burned, sleep amount, heart rate, etc. just by wrapping around the wrist. It can be done.
  • the acquired data can also be managed with a smartphone.
  • a mail transmission / reception function can be provided. For example, a mail notification function that notifies a user of an incoming mail by an LED (Light Emitting Diode) lamp and / or vibration is used.
  • LED Light Emitting Diode
  • FIG. 12 and 13 show an example of a wristband type activity meter that measures, for example, a pulse.
  • FIG. 12 shows an example of the external configuration of the wristband type activity meter 1501.
  • FIG. 13 shows a configuration example of the main body 1502 of the wristband type activity meter 1501.
  • the wristband type activity meter 1501 is a wristband type measuring device that measures, for example, a pulse of a subject by an optical method. As shown in FIG. 12, the wristband type activity meter 1501 includes a main body 1502 and a band 1503, and the band 1503 is attached to the arm (wrist) 1504 of the subject like a wristwatch. And the main-body part 1502 irradiates the measurement light of a predetermined wavelength to the part containing the pulse of a test subject's arm 1504, and measures a test subject's pulse based on the intensity
  • the main body 1502 is configured to include a substrate 1521, an LED 1522, a light receiving IC (Integrated Circuit) 1523, a light shield 1524, an operation unit 1525, an arithmetic processing unit 1526, a display unit 1527, and a wireless device 1528.
  • the LED 1522, the light receiving IC 1523, and the light shield 1524 are provided over the substrate 1521.
  • the LED 1522 irradiates a portion including the pulse of the arm 1504 of the subject under measurement light of a predetermined wavelength under the control of the light receiving IC 1523.
  • the light receiving IC 1523 receives light that has returned after the measurement light is applied to the arm 1504.
  • the light receiving IC 1523 generates a digital measurement signal indicating the intensity of the returned light, and supplies the generated measurement signal to the arithmetic processing unit 1526.
  • the light shield 1524 is provided between the LED 1522 and the light receiving IC 1523 on the substrate 1521.
  • the light shield 1524 prevents measurement light from the LED 1522 from directly entering the light receiving IC 1523.
  • the operation unit 1525 is composed of various operation members such as buttons and switches, and is provided on the surface of the main body 1502 or the like.
  • the operation unit 1525 is used to operate the wristband type activity meter 1501 and supplies a signal indicating the operation content to the arithmetic processing unit 1526.
  • the arithmetic processing unit 1526 performs arithmetic processing for measuring the pulse of the subject based on the measurement signal supplied from the light receiving IC 1523.
  • the arithmetic processing unit 1526 supplies the pulse measurement result to the display unit 1527 and the wireless device 1528.
  • the display unit 1527 is configured by a display device such as an LCD (Liquid Crystal Display), and is provided on the surface of the main body unit 1502.
  • the display unit 1527 displays the measurement result of the subject's pulse and the like.
  • the wireless device 1528 transmits the measurement result of the subject's pulse to an external device by wireless communication of a predetermined method. For example, as illustrated in FIG. 13, the wireless device 1528 transmits the measurement result of the subject's pulse to the smartphone 1505 and causes the screen 1506 of the smartphone 1505 to display the measurement result. Furthermore, the measurement result data is managed by the smartphone 1505, and the measurement result can be browsed by the smartphone 1505 or stored in a server on the network. Note that any method can be adopted as a communication method of the wireless device 1528.
  • the light receiving IC 1523 can also be used when measuring a pulse in a part other than the subject's arm 1504 (eg, finger, earlobe, etc.).
  • the wristband type active mass meter 1501 described above can accurately measure the pulse wave and pulse of the subject by removing the influence of body movement by the signal processing in the light receiving IC 1523. For example, even if the subject performs intense exercise such as running, the pulse wave and pulse of the subject can be accurately measured. In addition, for example, even when the subject wears the wristband type activity meter 1501 for a long time and performs measurement, the influence of the subject's body movement can be removed and the pulse wave and the pulse can be accurately measured. .
  • the power consumption of the wristband type activity meter 1501 can be reduced by reducing the amount of calculation. As a result, for example, it is possible to perform measurement by wearing the wristband type activity meter 1501 on the subject for a long time without performing charging or battery replacement.
  • the wristband type activity meter 1501 includes an electronic circuit of the main body and a battery pack.
  • the battery pack is detachable by the user.
  • the electronic circuit is a circuit included in the main body 1502 described above. The present technology can be applied when using an all-solid battery as a battery.
  • FIG. 14 and 15 show another example of the wristband type electronic device.
  • FIG. 14 shows an example of the external configuration of the wristband type electronic device 1601.
  • FIG. 15 shows a configuration block diagram of a wristband type electronic device 1601 (hereinafter simply referred to as “electronic device 1601”).
  • the electronic device 1601 is, for example, a watch-type so-called wearable device that is detachable from the human body.
  • the electronic device 1601 includes, for example, a band portion 1611 attached to the arm, a display device 1612 that displays numbers, characters, symbols, and the like, and operation buttons 1613.
  • the band portion 1611 is formed with a plurality of hole portions 1611a and protrusions 1611b formed on the inner peripheral surface (the surface that comes into contact with the arm when the electronic device 1601 is attached).
  • the electronic device 1601 In the use state, the electronic device 1601 is bent so that the band portion 1611 has a substantially circular shape as shown in FIG. 14, and the protrusion 1611b is inserted into the hole portion 1611a and attached to the arm. By adjusting the position of the hole 1611a into which the protrusion 1611b is inserted, the diameter can be adjusted corresponding to the thickness of the arm.
  • the protrusion 1611b is removed from the hole 1611a, and the band 1611 is stored in a substantially flat state.
  • the sensor according to the embodiment of the present technology is provided over the entire band portion 1611.
  • FIG. 15 is a block diagram illustrating a configuration example of the electronic device 1601.
  • the electronic device 1601 includes a sensor 1620 including a controller IC 1615 as a drive control unit and a host device 1616 in addition to the display device 1612 described above.
  • the sensor 1620 may include a controller IC 1615.
  • the sensor 1620 can detect both pressing and bending.
  • the sensor 1620 detects a change in capacitance according to the pressing, and outputs an output signal corresponding to the change to the controller IC 1615. Further, the sensor 1620 detects a change in resistance value (resistance change) according to bending, and outputs an output signal corresponding to the change to the controller IC 1615.
  • the host device 1616 executes various processes based on information supplied from the controller IC 1615. For example, processing such as displaying character information and image information on the display device 1612, moving the cursor displayed on the display device 1612, scrolling the screen, and the like is executed.
  • the display device 1612 is a flexible display device, for example, and displays a video (screen) based on a video signal or a control signal supplied from the host device 1616.
  • Examples of the display device 1612 include a liquid crystal display, an electroluminescence (EL) display, and electronic paper, but are not limited thereto.
  • the electronic device 1601 includes a main body electronic circuit and a battery pack.
  • the battery pack is detachable by the user.
  • the present technology can be applied to a case where an all-solid battery is used as the battery.
  • Smart watch as an application Hereinafter, application examples in which the present technology is applied to a smart watch will be described.
  • This smart watch has the same or similar appearance as the design of an existing wristwatch, and is worn on the user's arm in the same way as a wristwatch.
  • the information displayed on the display is used for telephone and e-mail. It has a function of notifying the user of various messages such as incoming calls.
  • smart watches having functions such as an electronic money function and an activity meter have been proposed.
  • a display is incorporated on the surface of the main body portion of the electronic device, and various information is displayed on the display.
  • the smart watch can also cooperate with functions, contents, and the like of the communication terminal by performing short-range wireless communication such as Bluetooth (registered trademark) with a communication terminal (smart phone or the like).
  • a plurality of segments connected in a band, a plurality of electronic components arranged in the plurality of segments, and a plurality of electronic components in the plurality of segments are connected to each other in at least one segment.
  • a device including a flexible circuit board arranged in a meandering shape has been proposed. By having such a meandering shape, the flexible circuit board is not stressed even when the band is bent, and the circuit is prevented from being cut.
  • a portion corresponding to a band of a normal wristwatch is a main body, and the band (belt) alone is formed as an electronic device. That is, a conventional watch can be used as it is for the watch body that displays the time with a hand or the like.
  • a band-type electronic device attached to the watch body incorporates a communication function and a notification function.
  • the smart watch of this application example can perform notifications such as e-mails and incoming calls, log recording of user action history, telephone calls, and the like.
  • the smart watch has a function as a non-contact IC card, and can perform settlement, authentication, and the like in a non-contact manner.
  • the smart watch of this application example has built-in circuit components that perform communication processing and notification processing in a metal band.
  • the band is configured by connecting a plurality of segments, and a circuit board, a vibration motor, a battery, and an acceleration sensor are accommodated in each segment.
  • Components such as circuit boards, vibration motors, batteries, and acceleration sensors of each segment are connected by a flexible printed circuit board (hereinafter referred to as “FPC”).
  • FPC flexible printed circuit board
  • the FPC meanders.
  • the meandering shape may be any shape such as an S shape, a V shape, a U shape, a Z shape, a curved shape, a semicircular shape, a polygonal line shape, and the like. By doing so, even if a metal band is bent, the meandering shape of the FPC only extends and the FPC does not break. Furthermore, the entrance / exit of the FPC in the segment part is pressed with rubber packing (relatively soft resin). The mating portion keeps the waterproofness of each segment by allowing the FPC to move freely without pressing the doorway. By introducing this “pairing part”, it is possible to prevent the FPC from being cut while ensuring the waterproofness of the main body. In the case where an electronic component is completed with only one component (segment), this “pairing portion” can be omitted.
  • an antenna for Bluetooth registered trademark
  • an antenna for NFC Near Field Communication
  • an insulator is sandwiched between the adjacent parts.
  • a component with a built-in antenna uses the entire surface (approximately six surfaces) of the component as an antenna, but the antenna characteristics deteriorate when it comes into contact with the user's skin, so the surface that contacts the user's skin is not used as an antenna.
  • a material other than metal may be used.
  • an insulating layer may be sandwiched between a metal part that touches the user's skin and a part that functions as an antenna.
  • a component with a built-in antenna may be provided with a slit and used as a slit antenna.
  • a part for arranging the antenna for Bluetooth (registered trademark) and a part for arranging the antenna for NFC may be different parts.
  • Bluetooth registered trademark
  • wireless communication uses the 2.4 GHz band
  • wireless communication is performed between a smart watch and a smartphone without any obstacles
  • pairing is possible up to about 10 m on average. It was.
  • the antenna problem can be solved by introducing a technique using the metal casing itself as an antenna.
  • FIG. 16 shows the overall configuration of the smart watch.
  • the band-type electronic device 2000 is a metal band attached to the watch main body 3000 and is attached to the user's arm.
  • the watch body 3000 includes a dial 3100 for displaying time.
  • the watch body 3000 may display the time electronically on a liquid crystal display or the like instead of the dial 3100.
  • the band-type electronic device 2000 has a configuration in which a plurality of segments 2110 to 2230 are connected.
  • the segment 2110 is attached to one band attachment hole of the watch body 3000, and the segment 2230 is attached to the other band attachment hole of the watch body 3000.
  • each of the segments 2110 to 2230 is made of metal.
  • 16 and 17 show a state in which the watch body 3000 and the segment 2230 are separated in order to explain the configuration of the band-type electronic device 2000, but the segment 2230 is attached to the watch body 3000 in actual use. It is done.
  • the band-type electronic device 2000 can be worn on the user's arm in the same manner as a normal wristwatch.
  • the connection location of each segment 2110 to 2230 can be moved. Since the connection part of the segment is movable, the band-type electronic device 2000 can be fitted to the user's arm.
  • a buckle portion 2300 is disposed between the segment 2170 and the segment 2160.
  • the buckle portion 2300 extends long when unlocked and shortens when locked.
  • Each segment 2110 to 2230 has a plurality of sizes. For example, the segment 2170 connected to the buckle portion 2300 is the largest size.
  • FIG. 18 shows a part of the internal configuration of the band-type electronic apparatus 2000.
  • the inside of three segments 2170, 2180, 2190, 2200, and 2210 is shown.
  • a flexible circuit board 2400 is arranged inside five continuous segments 2170 to 2210.
  • Various electronic components are arranged in the segment 2170, batteries 2411 and 2421 are arranged in the segments 2190 and 2210, and these components are electrically connected by the flexible circuit board 2400.
  • a segment 2180 between the segment 2170 and the segment 2190 has a relatively small size, and the flexible circuit board 2400 in a meandering state is disposed.
  • the flexible circuit board 2400 is disposed in a state of being sandwiched between waterproofing members.
  • the inside of the segments 2170 to 2210 has a waterproof structure. The waterproof structure of the segments 2170 to 2210 will be described later.
  • FIG. 19 is a block diagram illustrating a circuit configuration of the band-type electronic apparatus 2000.
  • the circuit inside the band-type electronic device 2000 has a configuration independent of the watch main body 3000.
  • the watch main body 3000 includes a movement unit 3200 that rotates hands arranged on the dial 3100.
  • a battery 3300 is connected to the movement unit 3200.
  • the movement unit 3200 and the battery 3300 are built in the casing of the watch main body 3000.
  • a data processing unit 4101 In the segment 2170, a data processing unit 4101, a wireless communication unit 4102, an NFC communication unit 4104, and a GPS unit 4106 are arranged.
  • Antennas 4103, 4105, and 4107 are connected to the wireless communication unit 4102, the NFC communication unit 4104, and the GPS unit 4106, respectively.
  • Each antenna 4103, 4105, 4107 is arranged in the vicinity of a slit 2173 described later of the segment 2170.
  • the wireless communication unit 4102 performs short-range wireless communication with other terminals based on, for example, Bluetooth (registered trademark) standards.
  • the NFC communication unit 4104 performs wireless communication with an adjacent reader / writer according to the NFC standard.
  • the GPS unit 4106 is a positioning unit that receives radio waves from a satellite of a system called GPS (Global Positioning System) and measures the current position. Data obtained by the wireless communication unit 4102, the NFC communication unit 4104, and the GPS unit 4106 is supplied to the data processing unit 4101.
  • GPS Global Positioning System
  • a display 4108 In the segment 2170, a display 4108, a vibrator 4109, a motion sensor 4110, and an audio processing unit 4111 are arranged.
  • the display 4108 and the vibrator 4109 function as a notification unit that notifies the wearer of the band-type electronic device 2000.
  • the display 4108 includes a plurality of light emitting diodes, and notifies the user by lighting or blinking of the light emitting diodes.
  • the plurality of light emitting diodes are disposed, for example, in a slit 2173 described later of the segment 2170, and notification of incoming calls or reception of e-mails is made by lighting or blinking.
  • the display 4108 may be a type that displays characters, numbers, and the like.
  • Vibrator 4109 is a member that vibrates segment 2170.
  • the band-type electronic device 2000 notifies the incoming call or the reception of an e-mail by the vibration of the segment 2170 by the vibrator 4109.
  • the motion sensor 4110 detects the movement of the user wearing the band-type electronic device 2000.
  • an acceleration sensor As the motion sensor 4110, an acceleration sensor, a gyro sensor, an electronic compass, an atmospheric pressure sensor, or the like is used.
  • the segment 2170 may incorporate a sensor other than the motion sensor 4110.
  • a biosensor that detects the pulse of the user wearing the band-type electronic device 2000 may be incorporated.
  • a microphone 4112 and a speaker 4113 are connected to the audio processing unit 4111, and the audio processing unit 4111 performs a call process with the other party connected by wireless communication in the wireless communication unit 4102.
  • the voice processing unit 4111 can also perform processing for voice input operation.
  • a battery 2411 is built in, and in the segment 2210, a battery 2421 is built.
  • the batteries 2411 and 2421 are configured by, for example, all solid state batteries, and supply driving power to the circuits in the segment 2170.
  • the circuit in the segment 2170 and the batteries 2411 and 2421 are connected by a flexible circuit board 2400 (FIG. 18).
  • the segment 2170 includes terminals for charging the batteries 2411 and 2421.
  • electronic components other than the batteries 2411 and 2421 may be arranged in the segments 2190 and 2210.
  • the segments 2190 and 2210 may include a circuit that controls charging and discharging of the batteries 2411 and 2421.
  • FIG. 18 shows a configuration of segments 2170 to 2210 in which electronic components and the like are arranged, and a buckle portion 2300 connected to the segment 2170.
  • the segments 2170 to 2210 are shown with a lid member (not shown) opened.
  • the casing constituting each of the segments 2170 to 2210 is formed of a metal such as stainless steel.
  • FIG. 18 shows a state where the first member 2310 and the second member 2320 of the buckle portion 2300 are opened.
  • the buckle portion 2300 is disposed at a position overlapping the back surface of the segment 2170 (upper side in FIG. 18) when the first member 2310 and the second member 2320 are closed.
  • the segment 2170 has a larger size than the other segments, and each electronic component shown in FIG. 19 is accommodated.
  • an internal housing 2500 made of a transparent resin (or translucent resin) is disposed, and a flexible circuit board 2400 and the like are disposed in the internal housing 2500.
  • One connecting portion 2171 of the segment 2170 is connected to the connecting portion 2330 of the buckle portion 2300.
  • the other connecting portion 2172 of the segment 2170 is connected to the connecting portion 2183 of the segment 2180.
  • a connecting portion 2184 of the segment 2180 is connected to the segment 2190.
  • a segment 2200 is connected next to the segment 2190, and a segment 2210 is connected next to the segment 2200.
  • two segments are connected using a connection pin (not shown).
  • a slit 2173 is formed on the surface of the segment 2170.
  • a plurality of light emitting diodes constituting the display 4108 is disposed in the inner casing 2500 made of a transparent or translucent resin in the vicinity of the slit 2173. Therefore, the user can confirm light emission or blinking of the light emitting diode through the slit 2173 of the segment 2170. By such light emission and blinking of the light emitting diodes, various states such as incoming calls and reception of e-mails are notified.
  • the antennas 4103, 4105, and 4107 are arranged in the internal housing 2500 close to the slit 2173. Therefore, the antennas 4103, 4105, and 4107 can maintain a good communication state with the outside of the metal segment 2170.
  • the first portion 2401 of the flexible circuit board 2400 is disposed in the internal housing 2500 of the segment 2170.
  • the first portion 2401 of the flexible circuit board 2400 is connected to the rigid board 2440 through the connection member 2431.
  • Various electronic components 2441, 2442, 2443,... Are connected to the rigid board 2440.
  • the electronic components 2441, 2442, 2443,... Correspond to the processing units 4101 to 4113 shown in FIG.
  • Segment 2190 and segment 2210 are sized to accommodate batteries 2411 and 2421. Segment 2180 and segment 2200 are smaller in size than segments 2190 and 2210.
  • the second portion 2402 of the flexible circuit board 2400 is disposed in a meandering state on the segment 2180.
  • a battery 2411 is connected to the third portion 2403 of the flexible circuit board 2400.
  • the fourth portion 2404 of the flexible circuit board 2400 is disposed in a meandering state on the segment 2200.
  • a battery 2421 is connected to the fifth portion 2405 of the flexible circuit board 2400. Details of the meandering state of the flexible circuit board 2400 will be described with reference to FIG.
  • FIG. 20 is a cross-sectional view showing a state in which the flexible circuit board 2400 is disposed inside the segments 2170 to 2190.
  • the flexible circuit board 2400 is continuously arranged in each of the segments 2170 to 2190.
  • the flexible circuit board 2400 passes through the inside of the connecting portion 2171 of the segment 2170 and the connecting portion 2183 of the segment 2180.
  • a waterproof member 2174 is disposed inside the connecting portion 2171 at a location where the flexible circuit board 2400 passes, and water intrusion into the segment 2170 is prevented.
  • a waterproof member 2175 is also disposed in the internal housing 2500 of the segment 2170.
  • waterproof members 2181 and 2182 are arranged inside the segment 2180, and water intrusion into the segment 2180 is prevented.
  • Each waterproof member 2174, 2175, 2181, 2182 is formed of a relatively soft resin, for example, and the gap between the inside of the segment 2180 and the flexible circuit board 2400 is closed.
  • the flexible circuit board 2400 is arranged in a meandering state. That is, a curved meandering portion 2400X is formed on the flexible circuit board 2400 inside the segment 2180.
  • the meandering portion 2400X of the flexible circuit board 2400 functions to prevent damage to the flexible circuit board 2400. For example, even when the connecting portion between the segment 2180 and the segment 2170 is bent greatly, the meandering portion 2400X of the flexible circuit board 2400 extends linearly and the flexible circuit board 2400 is not pulled. Therefore, the trouble that the circuit pattern in the flexible circuit board 2400 breaks does not occur.
  • the meandering portion 2400X shown in FIG. 20 is an example, and other shapes may be used. That is, the meandering portion 2400X can have various meandering shapes such as an S shape, a V shape, a U shape, a Z shape, a curved shape, a semicircular shape, and a polygonal line shape.
  • the present technology can be applied when an all solid state battery is used as the battery 2411 described above.
  • FIG. 21 shows a state where the battery 2411 is arranged in the segment 2190.
  • the configuration in which the battery 2421 is arranged in the segment 2210 is the same.
  • a battery 2411 is arranged at a battery arrangement location 2191 inside the segment 2190.
  • the adhesive sheet 2703 is arranged between the battery arrangement location 2191 and the battery 2411.
  • the third portion 2403 of the flexible circuit board 2400 is bonded to the surface of the battery 2411 (upper side in FIG. 21) with an adhesive sheet 2701.
  • the adhesive sheet 2701 By adhesion using the adhesive sheet 2701, the electrodes 2411A and 2411B on the surface of the battery 2411 are connected to the circuit pattern in the flexible circuit board 2400.
  • the surface of the battery 2411 is bonded to a lid (not shown) of the segment 2190 via the adhesive sheet 2702.
  • the adhesive sheet 2701 is configured to block the periphery of the surface of the battery 2411. Therefore, the adhesive sheet 2701 functions as a waterproof member for the battery 2411 in the segment 2190.
  • the battery may be disposed in another segment of the band type electronic device 2000.
  • the above-mentioned smart watch can perform notifications such as incoming e-mails and telephone calls, log recording of user activity history, telephone calls, and the like.
  • the smart watch has a function as a non-contact type IC card and can perform settlement and authentication using the non-contact type IC card.
  • the smart watch of this example can use the same watch body as that of a conventional watch, it can be a wristwatch with excellent design.
  • the plurality of segments have a waterproof structure, and the flexible circuit board is meanderingly arranged, so that the circuit pattern does not cut.
  • the antenna in the metal segment 2170 is arranged in the vicinity of the slit of the segment 2170, transmission and reception can be performed satisfactorily.
  • Glasses type terminal as an application example
  • a head-mounted display glass-type terminal represented by a kind of head-mounted display (HMD)
  • the glasses-type terminal described below can display information such as text, symbols, and images superimposed on the scenery in front of you. That is, a light-weight and thin image display device display module dedicated to a transmissive glasses-type terminal is mounted.
  • This image display device comprises an optical engine and a hologram light guide plate.
  • the optical engine emits image light such as an image and text using a micro display lens. This image light is incident on the hologram light guide plate.
  • the hologram light guide plate has hologram optical elements incorporated at both ends of the transparent plate, and the image light from the optical engine is propagated through a very thin transparent plate having a thickness of 1 mm to the eyes of the observer. deliver.
  • a lens having a transmittance of, for example, 85% and a thickness of 3 mm (including protective plates before and after the light guide plate) is realized. With such a glasses-type terminal, it is possible to see the results of players and teams in real time while watching sports, and to display a tourist guide at a destination.
  • the image display unit has a glasses-type configuration as shown in FIG. That is, as with normal glasses, the frame 5003 for holding the right image display unit 5001 and the left image display unit 5002 is provided in front of the eyes.
  • the frame 5003 includes a front portion 5004 disposed in front of the observer, and two temple portions 5005 and 5006 that are rotatably attached to both ends of the front portion 5004 via hinges.
  • the frame 5003 is made of the same material as that of normal glasses, such as metal, alloy, plastic, or a combination thereof.
  • a headphone unit may be provided.
  • the right image display unit 5001 and the left image display unit 5002 are arranged so as to be positioned in front of the user's right eye and in front of the left eye, respectively.
  • Temple units 5005 and 5006 hold a right image display unit 5001 and a left image display unit 5002 on the user's head.
  • a right display driving unit 5007 is disposed inside the temple unit 5005 at a connection portion between the front unit 5004 and the temple unit 5005.
  • a left display driving unit 5008 is arranged inside the temple unit 5006 at a connection portion between the front unit 5004 and the temple unit 5006.
  • a frame, an acceleration sensor, a gyroscope, an electronic compass, a microphone / speaker, and the like are mounted on the frame 5003.
  • the present technology can be applied when using an all-solid battery as a battery.
  • an image pickup apparatus is attached, and still images / moving images can be taken.
  • a controller connected to the glasses unit via, for example, a wireless or wired interface is provided.
  • the controller is provided with a touch sensor, various buttons, a speaker, a microphone, and the like.
  • it has a linkage function with a smartphone. For example, it is possible to provide information according to the user's situation by utilizing the GPS function of a smartphone.
  • the image display device the right image display unit 5001 or the left image display unit 5002 will be mainly described.
  • FIG. 23 shows a conceptual diagram of a first example of an image display device (right image display unit 5001 or left image display unit 5002) of a glasses-type terminal.
  • the image display device in the eyeglass-type terminal of the first example includes the first configuration of the image generation device and the first configuration of the optical device.
  • the image display device 5100 receives the light emitted from the image generation device 5110 configured from the image generation device having the first configuration and the image generation device 5110, is guided, and is emitted toward the pupil 5041 of the observer.
  • the optical device 5120 is attached to the image generation device 5110.
  • the optical device 5120 includes the optical device having the first configuration, and the light incident from the image generation device 5110 propagates through the interior by total reflection, and then is emitted toward the observer's pupil 5041.
  • the first light deflecting unit 5130 that deflects the light incident on the light guide plate 5121 and the light guide plate 5121 are propagated by total reflection so that the light incident on the light guide plate 5121 is totally reflected inside the light guide plate 5121.
  • second deflection means 5140 is provided that deflects the light propagated through the light guide plate 5121 by total reflection over a plurality of times.
  • the first deflecting unit 5130 and the second deflecting unit 5140 are disposed inside the light guide plate 5121.
  • the first deflecting unit 5130 reflects the light incident on the light guide plate 5121
  • the second deflecting unit 5140 transmits the light propagating through the light guide plate 5121 by total reflection, and transmits and reflects the light.
  • the first deflecting unit 5130 functions as a reflecting mirror
  • the second deflecting unit 5140 functions as a semi-transmissive mirror.
  • the first deflecting means 5130 provided inside the light guide plate 5121 is made of aluminum, and is composed of a light reflecting film (a kind of mirror) that reflects light incident on the light guide plate 5121. .
  • the second deflecting means 5140 provided inside the light guide plate 5121 is composed of a multilayer laminated structure in which a large number of dielectric laminated films are laminated.
  • the dielectric laminated film is composed of, for example, a TiO 2 film as a high dielectric constant material and an SiO 2 film as a low dielectric constant material.
  • a six-layer dielectric laminated film is shown, but the present invention is not limited to this.
  • a thin piece made of the same material as that constituting the light guide plate 5121 is sandwiched between the dielectric laminated film and the dielectric laminated film.
  • the parallel light incident on the light guide plate 5121 is reflected (or diffracted) so that the parallel light incident on the light guide plate 5121 is totally reflected inside the light guide plate 5121.
  • the parallel light propagated through the light guide plate 5121 by total reflection is reflected (or diffracted) a plurality of times and is emitted from the light guide plate 5121 in the state of parallel light.
  • the first deflecting unit 5130 cuts out a portion 5124 of the light guide plate 5121 where the first deflecting unit 5130 is provided, thereby providing the light guide plate 5121 with an inclined surface on which the first deflecting unit 5130 is to be formed, and vacuuming the light reflecting film on the inclined surface. After vapor deposition, the cut-out portion 5124 of the light guide plate 5121 may be bonded to the first deflecting means 5130.
  • the second deflecting unit 5140 is formed by laminating a large number of the same material (for example, glass) as the material constituting the light guide plate 5121 and a dielectric laminated film (for example, it can be formed by a vacuum deposition method).
  • a multilayer laminated structure is manufactured, and a portion 5125 provided with the second deflecting means 5140 of the light guide plate 5121 is cut out to form a slope, and the multilayer laminated structure is bonded to the slope and polished to adjust the outer shape. That's fine. In this way, an optical device 5120 in which the first deflection unit 5130 and the second deflection unit 5140 are provided inside the light guide plate 5121 can be obtained.
  • the light guide plate 5121 made of optical glass or plastic material has two parallel surfaces (a first surface 5122 and a second surface 5123) extending in parallel with the axis of the light guide plate 5121.
  • the first surface 5122 and the second surface 5123 are opposed to each other. Then, parallel light enters from the first surface 5122 corresponding to the light incident surface, propagates through the interior by total reflection, and then exits from the first surface 5122 corresponding to the light exit surface.
  • the image generation device 5110 includes the first configuration image generation device, the image formation device 5111 having a plurality of pixels arranged in a two-dimensional matrix, and the pixels of the image formation device 5111.
  • a collimating optical system 5112 for emitting light as parallel light is provided.
  • the image forming apparatus 5111 includes a reflective spatial light modulator 5150 and a light source 5153 including a light emitting diode that emits white light. More specifically, the reflective spatial light modulator 5150 reflects a part of light from a liquid crystal display (LCD) 5151 composed of LCOS (Liquid Crystal On On Silicon) as a light valve and a light source 5153.
  • the polarizing beam splitter 5152 is guided to the liquid crystal display device 5151, and part of the light reflected by the liquid crystal display device 5151 is transmitted to the collimating optical system 5112.
  • the LCD is not limited to the LCOS type.
  • the liquid crystal display device 5151 includes a plurality of (for example, 320 ⁇ 240) pixels arranged in a two-dimensional matrix.
  • the polarization beam splitter 5152 has a known configuration and structure. Non-polarized light emitted from the light source 5153 collides with the polarization beam splitter 5152. In the polarization beam splitter 5152, the P-polarized component passes and is emitted out of the system. On the other hand, the S-polarized component is reflected by the polarization beam splitter 5152, enters the liquid crystal display device 5151, is reflected inside the liquid crystal display device 5151, and is emitted from the liquid crystal display device 5151.
  • the light emitted from the liquid crystal display device 5151 contains a lot of P-polarized light components, and the light emitted from the pixel displaying “black” is S-polarized light. Contains many ingredients. Therefore, among the light emitted from the liquid crystal display device 5151 and colliding with the polarization beam splitter 5152, the P-polarized component passes through the polarization beam splitter 5152 and is guided to the collimating optical system 5112.
  • the liquid crystal display device 5151 includes, for example, a plurality of (for example, 320 ⁇ 240) pixels (the number of liquid crystal cells is three times the number of pixels) arranged in a two-dimensional matrix.
  • the collimating optical system 112 is composed of, for example, a convex lens, and in order to generate parallel light, the image forming apparatus 5111 (more specifically, the liquid crystal display device 5151) is located at the focal position (position) in the collimating optical system 5112. Is arranged.
  • One pixel is composed of a red light emitting subpixel that emits red, a green light emitting subpixel that emits green, and a blue light emitting subpixel that emits blue.
  • the image display device is incident and guided by the light emitted from the image generation device and the image generation device, toward the observer's pupil. It is comprised from the optical device (light guide means) radiate
  • the optical device can be configured to be attached to the image generation device, for example.
  • the second example is a modification of the first example.
  • a conceptual diagram of an image display device 5200 in the glasses-type terminal of the second example is shown in FIG.
  • the image generation device 5210 is composed of an image generation device having a second configuration. Specifically, the light source 5251, the collimating optical system 5252 that converts the light emitted from the light source 5251 into parallel light, the scanning unit 5253 that scans the parallel light emitted from the collimating optical system 5252, and the scanning unit 5253 are scanned.
  • the relay optical system 5254 relays and emits the parallel light. Note that the image generation device 5210 is covered with a cover 5213.
  • the light source 5251 includes a red light emitting element 5251R that emits red light, a green light emitting element 5251G that emits green light, and a blue light emitting element 5251B that emits blue light.
  • Each light emitting element is formed of a semiconductor laser element.
  • the light of the three primary colors emitted from the light source 5251 passes through the cross prism 5255, color synthesis is performed, the optical path is unified, and enters the collimating optical system 5252 having a positive optical power as a whole, It is emitted as parallel light.
  • the parallel light is reflected by the total reflection mirror 5256, the micro mirror is rotatable in a two-dimensional direction, and scanning that is made of MEMS (Micro Electro Mechanical Systems) capable of two-dimensionally scanning the incident parallel light.
  • the means 5253 performs horizontal scanning and vertical scanning to form a kind of two-dimensional image and generate virtual pixels.
  • light from the virtual pixel passes through a relay optical system 5254 configured by a well-known relay optical system, and a light beam converted into parallel light enters the optical device 5120.
  • the optical device 5120 in which the light beam converted into parallel light by the relay optical system 5254 is incident, guided, and emitted has the same configuration and structure as the optical device described in the first example. Is omitted. Further, as described above, the glasses-type terminal of the second example has substantially the same configuration and structure as the glasses-type terminal of the first example, except that the image generation device 5210 is different. Is omitted.
  • the third example is also a modification of the first example.
  • a conceptual diagram of an image display device 5300 in the glasses-type terminal of the third example is shown in FIG. 25A.
  • FIG. 25B shows a schematic cross-sectional view showing a part of the reflection type volume hologram diffraction grating in an enlarged manner.
  • the image generation device 5110 has the same configuration as that of the first example.
  • the optical device (light guide unit) 5320 has the same basic configuration as the optical device 5120 of the first example, except that the configuration and structure of the first deflection unit and the second deflection unit are different.
  • the light incident from the image generating device 5110 propagates through the interior by total reflection, and then is emitted toward the pupil 5041 of the observer, the light guide plate
  • the first deflection means 5330 for deflecting the light incident on the light guide plate 5321 and the light propagated through the light guide plate 5321 by total reflection so that the light incident on the light guide plate 5321 is totally reflected inside the light guide plate 5321.
  • second deflecting means 5340 is provided that deflects light propagated through the light guide plate 5321 by total reflection over a plurality of times.
  • the optical device 5320 is composed of the optical device having the second configuration. That is, the first deflection unit and the second deflection unit are disposed on the surface of the light guide plate 5321 (specifically, the second surface 5323 of the light guide plate 5321).
  • the first deflecting unit diffracts the light incident on the light guide plate 5321
  • the second deflecting unit diffracts the light propagated through the light guide plate 5321 by total reflection over a plurality of times.
  • the first deflecting unit and the second deflecting unit include a diffraction grating element, specifically a reflective diffraction grating element, and more specifically a reflective volume hologram diffraction grating.
  • first deflecting means composed of the reflective volume hologram diffraction grating is referred to as a “first diffraction grating member 5330” for convenience
  • second deflecting means composed of the reflective volume hologram diffraction grating is referred to as “first diffraction means for convenience.
  • Each diffraction grating layer made of a photopolymer material is formed with interference fringes corresponding to one type of wavelength band (or wavelength), and is produced by a conventional method.
  • a structure in which a diffraction grating layer that diffracts and reflects red light, a diffraction grating layer that diffracts and reflects green light, and a diffraction grating layer that diffracts and reflects blue light is stacked.
  • the diffraction grating member 5330 and the second diffraction grating member 5340 are included.
  • the pitch of the interference fringes formed in the diffraction grating layer (diffractive optical element) is constant, the interference fringes are linear, and are parallel to the Z-axis direction.
  • the axial direction of the first diffraction grating member 5330 and the second diffraction grating member 5340 is defined as the Y-axis direction, and the normal direction is defined as the X-axis direction.
  • the first diffraction grating member 5330 and the second diffraction grating member 5340 are shown as one layer.
  • FIG. 25B shows an enlarged schematic partial sectional view of the reflective volume hologram diffraction grating.
  • the reflection type volume hologram diffraction grating interference fringes having an inclination angle ⁇ are formed.
  • the inclination angle ⁇ refers to an angle formed between the surface of the reflective volume hologram diffraction grating and the interference fringes.
  • the interference fringes are formed from the inside to the surface of the reflection type volume hologram diffraction grating.
  • the interference fringes satisfy the Bragg condition.
  • the Bragg condition refers to a condition that satisfies the following formula (A).
  • Equation (A) m is a positive integer, ⁇ is the wavelength, d is the pitch of the grating plane (the interval in the normal direction of the virtual plane including the interference fringes), and ⁇ is the complementary angle of the angle incident on the interference fringes To do.
  • ⁇ the relationship among ⁇ , the tilt angle ⁇ , and the incident angle ⁇ is as shown in Expression (B).
  • the first diffraction grating member 5330 is disposed (adhered) to the second surface 5323 of the light guide plate 5321, and the parallel light incident on the light guide plate 5321 from the first surface 5322 is reflected on the light guide plate 5321.
  • the parallel light incident on the light guide plate 5321 is diffracted and reflected so as to be totally reflected inside.
  • the second diffraction grating member 5340 is disposed (adhered) to the second surface 5323 of the light guide plate 5321, and a plurality of the parallel lights propagated through the light guide plate 5321 by total reflection. Diffracted and reflected once, and is emitted from the first surface 5322 as parallel light from the light guide plate 5321.
  • the total number of reflections until reaching the second diffraction grating member 5340 differs depending on the angle of view. More specifically, out of the parallel light incident on the light guide plate 5321, the number of reflections of parallel light incident at an angle in a direction approaching the second diffraction grating member 5340 has an angle in a direction away from the second diffraction grating member 5340. This is less than the number of reflections of parallel light incident on the light guide plate 5321.
  • the shape of the interference fringes formed inside the second diffraction grating member 5340 and the shape of the interference fringes formed inside the first diffraction grating member 5330 are on a virtual plane perpendicular to the axis of the light guide plate 5321. There is a symmetrical relationship.
  • the light guide plate 5321 in the fourth example described later also basically has the same configuration and structure as the light guide plate 5321 described above.
  • the glasses-type terminal of the third example has substantially the same configuration and structure as the glasses-type terminal of the first example, except that the optical device 5320 is different. .
  • the fourth example is a modification of the third example.
  • the conceptual diagram of the image display apparatus in the glasses-type terminal of the fourth example is shown in FIG.
  • the light source 5251, the collimating optical system 5252, the scanning unit 5253, the relay optical system 5254, and the like in the image display device 5400 of the fourth example have the same configuration and structure as the second example.
  • the optical device 5320 in the fourth example has the same configuration and structure as the optical device 5320 in the third example. Since the glasses-type terminal of the fourth example has substantially the same configuration and structure as the glasses-type terminal of the first example except for the above differences, detailed description thereof will be omitted.
  • FIG. 27 schematically illustrates an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present disclosure is applied.
  • a series hybrid system is a vehicle that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power that is temporarily stored in a battery.
  • the hybrid vehicle 7200 includes an engine 7201, a generator 7202, a power driving force conversion device 7203, a driving wheel 7204a, a driving wheel 7204b, a wheel 7205a, a wheel 7205b, a battery 7208, a vehicle control device 7209, various sensors 7210, and a charging port 7211. Is installed.
  • the above-described power storage device of the present disclosure is applied to the battery 7208.
  • Hybrid vehicle 7200 travels using power driving force conversion device 7203 as a power source.
  • An example of the power driving force conversion device 7203 is a motor.
  • the electric power / driving force conversion device 7203 is operated by the electric power of the battery 7208, and the rotational force of the electric power / driving force conversion device 7203 is transmitted to the driving wheels 7204a and 7204b.
  • the power driving force conversion device 7203 can be applied to either an AC motor or a DC motor by using DC-AC (DC-AC) or reverse conversion (AC-DC conversion) where necessary.
  • Various sensors 7210 control the engine speed through the vehicle control device 7209 and control the opening of a throttle valve (throttle opening) (not shown).
  • Various sensors 7210 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.
  • the rotational force of the engine 7201 is transmitted to the generator 7202, and the electric power generated by the generator 7202 by the rotational force can be stored in the battery 7208.
  • the resistance force at the time of deceleration is applied as a rotational force to the electric power driving force conversion device 7203, and the regenerative electric power generated by the electric power driving force conversion device 7203 by this rotational force is supplied to the battery 7208. Accumulated.
  • the battery 7208 is connected to a power source outside the hybrid vehicle, so that it can receive power from the external power source using the charging port 211 as an input port and store the received power.
  • an information processing apparatus that performs information processing related to vehicle control based on information related to the secondary battery may be provided.
  • an information processing apparatus for example, there is an information processing apparatus that displays a remaining battery level based on information on the remaining battery level.
  • the series hybrid vehicle that runs on the motor using the electric power generated by the generator driven by the engine or the electric power stored once in the battery has been described as an example.
  • the present disclosure is also effective for a parallel hybrid vehicle that uses both engine and motor outputs as drive sources, and switches between the three modes of running with the engine alone, running with the motor alone, and engine and motor running as appropriate. Applicable.
  • the present disclosure can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.
  • the technology according to the present disclosure can be suitably applied to the battery 7208 among the configurations described above. Specifically, by using an all-solid-state battery as the battery 7208 and applying the technology according to the present technology as the charge / discharge device, it is possible to prevent the battery from being deteriorated.
  • Storage system in a house as an application example An example in which the present disclosure is applied to a residential power storage system will be described with reference to FIG.
  • a power storage system 9100 for a house 9001 power is stored from a centralized power system 9002 such as a thermal power generation 9002a, a nuclear power generation 9002b, and a hydropower generation 9002c through a power network 9009, an information network 9012, a smart meter 9007, a power hub 9008, and the like. Supplied to the device 9003.
  • power is supplied to the power storage device 9003 from an independent power source such as the home power generation device 9004.
  • the electric power supplied to the power storage device 9003 is stored. Electric power used in the house 9001 is supplied using the power storage device 9003.
  • the same power storage system can be used not only for the house 9001 but also for buildings.
  • the house 9001 is provided with a power generation device 9004, a power consumption device 9005, a power storage device 9003, a control device 9010 that controls each device, a smart meter 9007, and a sensor 9011 that acquires various types of information.
  • Each device is connected by a power network 9009 and an information network 9012.
  • a solar cell, a fuel cell, or the like is used, and the generated power is supplied to the power consumption device 9005 and / or the power storage device 9003.
  • the power consuming apparatus 9005 is a refrigerator 9005a, an air conditioner 9005b, a television receiver 9005c, a bath 9005d, or the like.
  • the electric power consumption device 9005 includes an electric vehicle 9006.
  • the electric vehicle 9006 is an electric vehicle 9006a, a hybrid car 9006b, and an electric motorcycle 9006c.
  • the all-solid battery of the present disclosure described above is applied to the power storage device 9003.
  • the power storage device 9003 is composed of a secondary battery or a capacitor.
  • a lithium ion battery is used.
  • the lithium ion battery may be a stationary type or used in the electric vehicle 9006.
  • the smart meter 9007 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company.
  • the power network 9009 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.
  • Various sensors 9011 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by the various sensors 9011 is transmitted to the control device 9010. Based on the information from the sensor 9011, the weather condition, the condition of the person, and the like can be grasped, and the power consumption device 9005 can be automatically controlled to minimize the energy consumption. Furthermore, the control device 9010 can transmit information on the house 9001 to an external power company or the like via the Internet.
  • the power hub 9008 performs processing such as branching of power lines and DC / AC conversion.
  • Communication methods of the information network 9012 connected to the control device 9010 include a method using a communication interface such as UART (Universal synchronous receiver-transmitter: Asynchronous serial communication transceiver circuit), Bluetooth (registered trademark), ZigBee, Wi-Fi.
  • a communication interface such as UART (Universal synchronous receiver-transmitter: Asynchronous serial communication transceiver circuit), Bluetooth (registered trademark), ZigBee, Wi-Fi.
  • the Bluetooth (registered trademark) system is applied to multimedia communication and can perform one-to-many connection communication.
  • ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Electronics) (802.15.4).
  • IEEE 802.15.4 is a name for a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.
  • the control device 9010 is connected to an external server 9013.
  • the server 9013 may be managed by any one of the house 9001, the electric power company, and the service provider.
  • Information transmitted / received by the server 9013 is, for example, information on power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device (for example, a television receiver) in the home, or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, for example, a television receiver, a mobile phone, a PDA (Personal Digital Assistant) or the like.
  • a control device 9010 that controls each unit is configured by a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 9003 in this example.
  • the control device 9010 is connected to the power storage device 9003, the home power generation device 9004, the power consumption device 9005, the various sensors 9011, the server 9013, and the information network 9012.
  • the control device 9010 functions to adjust the amount of commercial power used and the amount of power generation. have. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.
  • electric power can be stored not only in the centralized power system 9002 such as the thermal power 9002a, the nuclear power 9002b, and the hydropower 9002c but also in the power storage device 9003 in the power generation device 9004 (solar power generation, wind power generation). it can. Therefore, even if the generated power of the home power generation apparatus 9004 fluctuates, it is possible to perform control such that the amount of power to be sent to the outside is constant or discharge is performed as necessary.
  • the power obtained by solar power generation is stored in the power storage device 9003, and midnight power with a low charge is stored in the power storage device 9003 at night, and the power stored by the power storage device 9003 is discharged during a high daytime charge. You can also use it.
  • control device 9010 is stored in the power storage device 9003.
  • control device 9010 may be stored in the smart meter 9007, or may be configured independently.
  • the power storage system 9100 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.
  • the technology according to the present technology can be preferably applied to the power storage device 9003.
  • the present technology supplies DC power, it is necessary to convert DC power into AC power for supply to household AC devices.
  • the present technology can also employ the following configurations.
  • Solid battery (2) The all-solid-state battery according to (1), wherein an energy density of the all-solid-state battery is 400 Wh / L or more. (3) The all-solid-state battery according to (1) or (2), wherein the volume of the all-solid-state battery is 5 cc or less.
  • the ratio of the sum total of the volume of the said positive electrode layer and the said negative electrode layer with respect to the volume of the said all-solid-state battery is an all-solid-state battery in any one of (1) to (3) which is 50 vol% or more.
  • the ratio of the sum total of the average thickness of the said positive electrode layer and the said negative electrode layer with respect to the average thickness of the said all-solid-state battery is 60% or more, The all-solid-state battery in any one of (4).
  • All of the oxide glass and the oxide glass ceramics include at least one of germanium oxide, silicon oxide, boron oxide, and phosphorus oxide and lithium oxide (1) to (6).
  • Solid battery. (8) The all-solid-state battery according to any one of (1) to (7), wherein the at least one kind is sintered.
  • the all-solid-state battery in any one of (1) to (8) whose sintering temperature of the said oxide glass and the said oxide glass ceramic is 550 degrees C or less.
  • the positive electrode layer includes a lithium-containing compound.
  • An electronic card, a wearable device, an IoT terminal, an amusement device, an IC board embedded battery, or an energy harvesting device that receives power from the all solid state battery according to any one of (1) to (16).
  • An electric vehicle comprising: a control device that performs information processing related to vehicle control based on information related to the all solid state battery.
  • An electric power system that receives supply of electric power from the all solid state battery according to any one of (1) to (16).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Cette batterie tout solide possède une couche d'électrode positive, une couche d'électrode négative et un électrolyte solide. Au moins une couche parmi la couche d'électrode positive et la couche d'électrode négative contient une couche de matériau actif ainsi qu'un verre d'oxyde et/ou une céramique de verre d'oxyde, la proportion volumétrique du matériau actif étant d'au moins 40 %.
PCT/JP2017/035527 2016-11-17 2017-09-29 Batterie tout solide, dispositif électronique, carte électronique, dispositif vestimentaire et véhicule électrique Ceased WO2018092434A1 (fr)

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JP2016-224028 2016-11-17

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CN113013557A (zh) * 2019-12-20 2021-06-22 位速科技股份有限公司 蓄电装置及蓄电装置组结构
CN113544891A (zh) * 2019-03-08 2021-10-22 Tdk株式会社 全固体二次电池
US20220328868A1 (en) * 2019-12-19 2022-10-13 Murata Manufacturing Co., Ltd. Solid-state battery
WO2023210188A1 (fr) * 2022-04-26 2023-11-02 太陽誘電株式会社 Batterie tout solide et son procédé de fabrication
US12046752B2 (en) 2021-06-21 2024-07-23 Samsung Electronics Co., Ltd. Composite positive electrode active material, method of preparing the same, positive electrode including the same, and secondary battery including the same
US12244013B2 (en) 2021-07-19 2025-03-04 Samsung Electronics Co., Ltd. Composite cathode active material, method of preparing the same, cathode including the same, and secondary battery including the composite cathode active material

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JP2011165410A (ja) * 2010-02-05 2011-08-25 Ohara Inc 全固体リチウムイオン二次電池及びその製造方法
WO2014020654A1 (fr) * 2012-07-30 2014-02-06 株式会社 日立製作所 Batterie secondaire à ion entièrement solide
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CN113544891A (zh) * 2019-03-08 2021-10-22 Tdk株式会社 全固体二次电池
CN113544891B (zh) * 2019-03-08 2023-11-28 Tdk株式会社 全固体二次电池
US20220328868A1 (en) * 2019-12-19 2022-10-13 Murata Manufacturing Co., Ltd. Solid-state battery
CN113013557A (zh) * 2019-12-20 2021-06-22 位速科技股份有限公司 蓄电装置及蓄电装置组结构
US12046752B2 (en) 2021-06-21 2024-07-23 Samsung Electronics Co., Ltd. Composite positive electrode active material, method of preparing the same, positive electrode including the same, and secondary battery including the same
US12244013B2 (en) 2021-07-19 2025-03-04 Samsung Electronics Co., Ltd. Composite cathode active material, method of preparing the same, cathode including the same, and secondary battery including the composite cathode active material
WO2023210188A1 (fr) * 2022-04-26 2023-11-02 太陽誘電株式会社 Batterie tout solide et son procédé de fabrication

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