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WO2015111495A1 - Utilisation d'une cellule entièrement à semi-conducteurs dans diverses applications - Google Patents

Utilisation d'une cellule entièrement à semi-conducteurs dans diverses applications Download PDF

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Publication number
WO2015111495A1
WO2015111495A1 PCT/JP2015/050907 JP2015050907W WO2015111495A1 WO 2015111495 A1 WO2015111495 A1 WO 2015111495A1 JP 2015050907 W JP2015050907 W JP 2015050907W WO 2015111495 A1 WO2015111495 A1 WO 2015111495A1
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positive electrode
active material
electrode active
use according
lithium
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Japanese (ja)
Inventor
和幸 水野
吉田　俊広
鬼頭　賢信
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NGK Insulators Ltd
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NGK Insulators Ltd
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    • 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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

  • the present invention relates to the use of all solid state batteries in various applications.
  • a liquid electrolyte such as an organic solvent using a flammable organic solvent as a diluent solvent has been conventionally used as a medium for moving ions.
  • a battery using such an electrolytic solution may cause problems such as leakage of the electrolytic solution, ignition, and explosion.
  • Patent Document 1 US Pat. No. 8,831,264
  • Patent Document 2 JP 2009-516359 A disclose a positive electrode having a thickness of greater than about 4 ⁇ m and less than about 200 ⁇ m, and a solid electrolyte having a thickness of less than about 10 ⁇ m.
  • the positive electrode disclosed in these documents seems to use a non-oriented positive electrode active material.
  • Patent Document 3 Japanese Patent Laid-Open No. 2012-009193
  • Patent Document 4 Japanese Patent Laid-Open No. 2012-009194
  • Patent Document 5 Japanese Patent No.
  • Patent Document 6 Japanese Patent Laid-Open No. 2011-051800 discloses that the addition of Al in addition to Li, La, and Zr, which are basic elements of LLZ, can improve the density and lithium ion conductivity.
  • Patent Document 7 Japanese Patent Application Laid-Open No. 2011-073962 discloses that lithium ion conductivity can be further improved by adding Nb and / or Ta in addition to Li, La and Zr, which are basic elements of LLZ.
  • Patent Document 8 Japanese Patent Laid-Open No. 2011-073963 includes Li, La, Zr, and Al, and the density can be further improved by setting the molar ratio of Li to La to 2.0 to 2.5. Is disclosed.
  • the inventors of the present invention can obtain battery performance with high capacity and energy density by increasing the thickness of the oriented polycrystal, and It was found that various useful applications that make the most of the characteristics can be provided.
  • the object of the present invention is to provide various useful applications that take full advantage of the characteristics of an all-solid-state battery using an oriented polycrystal as a positive electrode active material, in particular, small size, high energy density, and high safety. It is to provide.
  • Sensors, sensor networks, wireless sensors, wireless sensor networks eg, structural deterioration diagnosis, environmental control / sensing, etc.), ubiquitous networks, remote sensors, agricultural sensors, smart cards, next-generation advanced functions Card, smart card with battery, smart card used for money transaction processing, smart ID card, ID card, IC card, embedded card power supply, credit card, wireless automatic identification device (RFID), RFID sticker, RFID tag, identification Tags, active radio frequency (RF) tag systems for surveillance or punishment applications, identification tags for tracking stored goods or preventing theft of retail goods, computers, laptop computers, portable computers, pocket computers Computers, workstations, supercomputers, computer peripheral hardware, servers, scanners, watches, solar watches, wearable devices (for example, high-
  • FIG. 1 schematically shows an example of an all solid state battery according to the present invention.
  • An all solid state battery 10 shown in FIG. 1 includes a positive electrode layer 14 having a positive electrode active material 12, a solid electrolyte layer 16 made of a lithium ion conductive material, and a negative electrode layer 20 having a negative electrode active material 18.
  • the solid electrolyte layer 16 is sandwiched between the positive electrode layer 14 and the negative electrode layer 20.
  • the positive electrode active material 12 is an oriented polycrystal formed of a plurality of lithium transition metal oxide particles oriented in a certain direction.
  • the all-solid-state battery disclosed in Patent Documents 1 and 2 has a problem that even if the positive electrode layer is formed thick, the increase in capacity and energy density cannot be obtained as expected. . This is considered to be because, in Patent Documents 1 and 2, since the positive electrode active material used for the positive electrode layer is not oriented, it is difficult to efficiently insert and remove lithium ions over the entire thickness of the thick positive electrode layer. . For example, it may happen that lithium existing on the side of the thick positive electrode layer away from the solid electrolyte cannot be sufficiently extracted.
  • the positive electrode active material 12 is an oriented polycrystal composed of a plurality of lithium transition metal oxide particles oriented in a certain direction, even if the positive electrode active material is provided thick, the entire thickness of the positive electrode layer is not affected. In addition, it is easy to remove and insert high-efficiency lithium ions, and the capacity improvement effect brought about by the thick cathode active material can be maximized. For example, lithium existing on the side of the thick positive electrode layer away from the solid electrolyte can be sufficiently extracted. Such an increase in capacity can greatly improve the energy density of the all-solid-state battery. That is, according to the all solid state battery of the present invention, battery performance with high capacity and energy density can be obtained. Therefore, it is possible to realize a highly safe all-solid battery having a high capacity and a high energy density while being relatively thin or small.
  • the all solid state battery has an energy density of 700 Wh / L or more, a thickness of 5 mm or less, and a vertical and horizontal dimension of 100 mm or less, respectively.
  • the all solid state battery has an energy density of 600 Wh / L or more, a thickness of 2 mm or less, and a vertical and horizontal size of 50 mm or less, respectively.
  • the all solid state battery has an energy density of 500 Wh / L or more, a thickness of 1 mm or less, and a length and a width of 50 mm or less, respectively.
  • the all solid state battery has an energy density of 250 Wh / L or more, a thickness of 0.5 mm or less, and a length and a width of 50 mm or less, respectively.
  • the energy density is 100 Wh / L or more
  • the thickness is 0.3 mm or less
  • the length and width are each 50 mm or less.
  • the all-solid-state battery 10 of the present invention capable of realizing a high capacity and a high energy density while being relatively thin or small has been difficult or assumed to be an actual application of the all-solid-state battery until now. It can be advantageously applied in various applications that have not been used.
  • high capacity and high energy density which leads to thinning or miniaturization
  • high safety by not using a flammable electrolyte
  • high weather resistance for example, operating at 80 ° C or higher
  • various advantageous characteristics such as long life (by not using an electrolyte that deteriorates in a high temperature environment) can be realized in the all-solid-state battery of the present invention.
  • a high-voltage battery can be configured by using an all-solid battery having a stack structure in which such unit batteries are stacked.
  • Examples of preferable applications that can make use of these various advantageous characteristics include sensors, sensor networks, wireless sensors, wireless sensor networks (eg, structural deterioration diagnosis, environmental control / sensing, etc.), ubiquitous networks, remote sensors, agricultural sensors.
  • Smart card next-generation high-performance card, smart card with battery, smart card used for money transaction processing, smart ID card, ID card, IC card, embedded card power supply, credit card, wireless automatic identification device (RFID) RFID stickers, RFID tags, identification tags, active radio frequency (RF) tag systems for surveillance or punishment applications, identification tags for tracking stored goods or preventing theft of retail goods, computers, laptop computers, Portable computers, pocket computers, workstations, supercomputers, computer peripheral hardware, servers, scanners, watches, solar watches, wearable devices (for example, high-performance watch-type wearable devices, low-function watch-type wearable devices, eyeglass-type wearable devices) , Wearable computer, mobile phone, portable terminal, portable device, electronic notebook (PDA), pager, pager, blackberry (registered trademark) type terminal, personal digital organizer, personal data assistant device, radio, CD player , Cassette player, media player, MP3 player, multimedia entertainment device, other various entertainment devices, remote control device for TV and stereo system, additional System, GPS system, tire pressure monitoring system, positioning device
  • -Diagnosis of structure deterioration Although it can be performed by a sensor that diagnoses the deterioration of the structure by detecting vibrations, it is required to have high weather resistance and a long life because the structure such as a building is to be diagnosed. .
  • This structure degradation diagnosis is particularly suitable to be performed using a sensor network, in particular a wireless sensor network.
  • -Agricultural sensors Sensors that monitor temperature, humidity, etc. Therefore, high weather resistance and long life are required.
  • -Radiation monitor High weather resistance and large capacity battery performance are required.
  • -Smart card Since a thin battery embedded in the card is required, a high-capacity thin battery is required.
  • the passenger can pass through the ticket gate without any action (acts such as holding the card) by improving the signal strength and the communication distance.
  • a one-time password service can be provided and security can be improved.
  • -Wearable devices Small size and light weight are indispensable, and high-capacity batteries are required for high functionality. Moreover, since it is worn at all times, high safety is required.
  • the positive electrode active material 12 is an oriented polycrystal formed of a plurality of lithium transition metal oxide particles oriented in a certain direction. This certain direction is preferably a lithium ion conduction direction. Typically, the positive electrode active material 12 has a specific crystal plane of each particle oriented in a direction from the positive electrode layer 14 toward the negative electrode layer 20. Configured as a layer.
  • the particles contained in the positive electrode active material 12 are composed of a lithium transition metal oxide.
  • the lithium transition metal oxide preferably has a layered rock salt structure or a spinel structure, and more preferably has a layered rock salt structure.
  • the layered rock salt structure has a property that the oxidation-reduction potential decreases due to occlusion of lithium ions and the oxidation-reduction potential increases due to elimination of lithium ions, and a composition containing a large amount of Ni is particularly preferable.
  • the layered rock salt structure is a crystal structure in which transition metal layers other than lithium and lithium layers are alternately stacked with an oxygen atom layer interposed therebetween, that is, an ion layer and lithium ions of transition metals other than lithium.
  • Crystal structure in which layers are alternately stacked with oxide ions (typically ⁇ -NaFeO 2 type structure: a structure in which transition metal and lithium are regularly arranged in the [111] axis direction of cubic rock salt type structure ).
  • Typical examples of the lithium-transition metal composite oxide having a layered rock salt structure include lithium nickelate, lithium manganate, nickel / lithium manganate, nickel / lithium cobaltate, cobalt / nickel / lithium manganate, and cobalt / manganese. Examples of these materials include Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, and the like.
  • One or more elements such as Sb, Te, Ba, Bi and the like may be further included.
  • the lithium transition metal oxide is Li x M1O 2 or Li x (M1, M2) O 2 (where 0.5 ⁇ x ⁇ 1.10, M1 is selected from the group consisting of Ni, Mn, and Co).
  • M2 is Mg, Al, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, Sb,
  • M1 is Ni and Co
  • M2 is a composition that is at least one selected from the group consisting of Mg, Al, and Zr, more preferably Li x (M1, M2) O 2 , and M1 is Ni and Co.
  • M2 is Al
  • the proportion of Ni in the total amount of M1 and M2 is preferably 0.6 or more in atomic ratio. Any of such compositions can take a layered rock salt structure.
  • a ceramic having a Li x (Ni, Co, Al) O 2 -based composition in which M1 is Ni and Co and M2 is Al may be referred to as NCA ceramics.
  • a lithium transition metal oxide represented by Li x M1O 2 and having a composition in which M1 is Ni, Mn and Co, or M1 is Co is also preferable.
  • the positive electrode active material 12 is an oriented polycrystal composed of a plurality of lithium transition metal oxide particles.
  • the lithium transition metal oxide particles are preferably particles formed in a plate shape having a thickness of about 2 to 100 ⁇ m.
  • the specific crystal plane described above is a (003) plane, and the (003) plane is oriented in a direction from the positive electrode layer 14 toward the negative electrode layer 20.
  • the (101) plane or the (104) plane other than the (003) plane may be oriented along the plate surface of the positive electrode active material 12.
  • Patent Document 3 Japanese Patent Laid-Open No. 2012-009193
  • Patent Document 4 Japanese Patent Laid-Open No. 2012-009194
  • Patent Document 5 Japanese Patent No. 4745463
  • the oriented polycrystalline body constituting the positive electrode active material 12 is suitable for making it thicker than the non-oriented polycrystalline body.
  • the thickness of the oriented polycrystal is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 25 ⁇ m or more.
  • the upper limit of the thickness is not particularly limited, it can be said that it is practically 500 ⁇ m or less, more realistically 200 ⁇ m or less, and practically 100 ⁇ m or less.
  • the positive electrode active material 12 is preferably formed in a sheet shape.
  • a preferred method for producing a positive electrode active material (hereinafter referred to as a positive electrode active material sheet) formed in the form of a sheet will be described later.
  • the positive electrode active material 12 may be constituted by a single positive electrode active material sheet, or a plurality of small pieces obtained by dividing the positive electrode active material sheet may be arranged in layers to constitute the positive electrode active material 12. May be.
  • the lithium ion conductive material constituting the solid electrolyte layer 16 is a garnet-based ceramic material, a nitride-based ceramic material, a perovskite-based ceramic material, a phosphate-based ceramic material, a sulfide-based ceramic material, or a polymer.
  • it is at least one selected from the group consisting of garnet ceramic materials, nitride ceramic materials, perovskite ceramic materials, and phosphate ceramic materials.
  • garnet based ceramic materials include Li—La—Zr—O based materials (specifically, Li 7 La 3 Zr 2 O 12 etc.), Li—La—Ta—O based materials (specifically, Li 7 La 3 Ta 2 O 12 ), and the like.
  • Patent Document 6 Japanese Patent Laid-Open No. 2011-051800
  • Patent Document 7 Japanese Patent Laid-Open No. 2011-073962
  • Patent Document 8 Japanese Patent Laid-Open No. 2011-073963. Publications
  • An example of a nitride ceramic material is Li 3 N.
  • perovskite ceramic materials include Li—La—Zr—O based materials (specifically, LiLa 1-x Ti x O 3 (0.04 ⁇ x ⁇ 0.14), etc.).
  • phosphate ceramic materials include lithium phosphate, nitrogen-substituted lithium phosphate (LiPON), Li—Al—Ti—PO, Li—Al—Ge—PO, and Li—Al—Ti—.
  • Si—P—O specifically, Li 1 + x + y Al x Ti 2 ⁇ x Si y P 3 ⁇ y O 12 (0 ⁇ x ⁇ 0.4, 0 ⁇ y ⁇ 0.6), etc. may be mentioned.
  • a particularly preferable lithium ion conductive material is a garnet-based ceramic material in that a reaction does not occur even when it is in direct contact with negative electrode lithium.
  • an oxide sintered body having a garnet type or a garnet type-like crystal structure containing Li, La, Zr and O is excellent in sinterability and easily densified, and has high ionic conductivity. This is preferable.
  • a garnet-type or garnet-like crystal structure of this type of composition is called an LLZ crystal structure, and is referred to as an X-ray diffraction file No. of CSD (Cambridge Structural Database). It has an XRD pattern similar to 422259 (Li 7 La 3 Zr 2 O 12 ). In addition, No.
  • the constituent elements are different and the Li concentration in the ceramics may be different, so the diffraction angle and the diffraction intensity ratio may be different.
  • the molar ratio Li / La of Li to La is preferably 2.0 or more and 2.5 or less, and the molar ratio Zr / La to La is preferably 0.5 or more and 0.67 or less.
  • This garnet-type or garnet-like crystal structure may further comprise Nb and / or Ta. That is, by replacing a part of Zr of LLZ with one or both of Nb and Ta, the conductivity can be improved as compared with that before the substitution.
  • the substitution amount (molar ratio) of Zr with Nb and / or Ta is preferably set such that the molar ratio of (Nb + Ta) / La is 0.03 or more and 0.20 or less.
  • the garnet-based oxide sintered body preferably further contains Al, and these elements may exist in the crystal lattice or may exist in other than the crystal lattice.
  • the amount of Al added is preferably 0.01 to 1% by mass of the sintered body, and the molar ratio Al / La to La is preferably 0.008 to 0.12.
  • Patent Document 6 Japanese Patent Laid-Open No. 2011-051800
  • Patent Document 7 Japanese Patent Laid-Open No. 2011-073962
  • Patent Document 8 Japanese Patent Laid-Open No. 2011-073963
  • lithium ion conductive material a phosphoric acid-based ceramic material can be cited, and among these, nitrogen-substituted lithium phosphate (LiPON) is preferable.
  • LiPON nitrogen-substituted lithium phosphate
  • the dimensions of the solid electrolyte layer 16 are not particularly limited, but the thickness is preferably 0.0005 mm to 0.5 mm, more preferably 0.001 mm to 0.2 mm, and still more preferably, from the viewpoint of charge / discharge rate characteristics and mechanical strength. Is 0.005 to 0.1 mm.
  • the method for forming the solid electrolyte layer 16 various particle jet coating methods, solid phase methods, solution methods, gas phase methods, and direct bonding methods can be used.
  • the particle jet coating method include an aerosol deposition (AD) method, a gas deposition (GD) method, a powder jet deposition (PJD) method, a cold spray (CS) method, and a thermal spraying method.
  • the aerosol deposition (AD) method is particularly preferable because it can form a film at room temperature, and does not cause a composition shift during the process or formation of a high resistance layer due to a reaction with the positive electrode plate.
  • the solid phase method include a tape lamination method and a printing method.
  • the tape lamination method is preferable because the solid electrolyte layer 16 can be formed thin and the thickness can be easily controlled.
  • the solution method include a hydrothermal synthesis method, a sol-gel method, a precipitation method, a microemulsion method, and a solvent evaporation method.
  • the hydrothermal synthesis method is particularly preferable in that it is easy to obtain crystal grains having high crystallinity at a low temperature.
  • microcrystals synthesized using these methods may be deposited on the positive electrode or may be directly deposited on the positive electrode.
  • the gas phase method examples include laser deposition (PLD) method, sputtering method, evaporation condensation (PVD) method, gas phase reaction method (CVD) method, vacuum deposition method, molecular beam epitaxy (MBE) method and the like.
  • the laser deposition (PLD) method is particularly preferable because there is little composition deviation and a film with relatively high crystallinity can be easily obtained.
  • the direct bonding (direct bonding) method is a method in which the surfaces of the solid electrolyte layer 16 and the positive electrode active material 12 formed in advance are chemically activated and bonded at a low temperature. For activation of the interface, plasma or the like may be used, or chemical modification of a functional group such as a hydroxyl group may be used.
  • Negative electrode active material may be any of various known negative electrode active materials that can be used in an all-solid lithium battery.
  • the negative electrode active material 18 include lithium metal, a lithium alloy, a carbonaceous material, and lithium titanate (LTO).
  • the negative electrode active material 18 is formed by forming a thin film of lithium metal or a metal alloying with lithium on the negative electrode current collector 24 (copper foil or the like) by vacuum deposition, sputtering, CVD, or the like. It can be produced by forming a layer of lithium metal or a metal alloying with lithium.
  • the positive electrode layer 14 preferably includes a positive electrode active material 12 and a positive electrode current collector 22 formed on the end surface of the positive electrode active material 12 opposite to the solid electrolyte layer 16.
  • the negative electrode layer 20 preferably includes a negative electrode active material 18 and a negative electrode current collector 24 formed on the end surface of the negative electrode active material 18 opposite to the solid electrolyte layer 16.
  • materials constituting the positive electrode current collector 22 and the negative electrode current collector 24 include platinum (Pt), platinum (Pt) / palladium (Pd), gold (Au), silver (Ag), aluminum (Al), Examples thereof include copper (Cu) and ITO (indium-tin oxide film).
  • Container The container 26 is not particularly limited as long as it can accommodate a unit battery or a stack in which a plurality of unit batteries are stacked in series or in parallel.
  • the container 26 can adopt a relatively simple container form.
  • a chip form for mounting on an electronic circuit or a laminate cell form for example, a multilayer product of aluminum (Al) / polypropylene (PP) for thin and wide space applications can be employed.
  • raw material particles particles obtained by appropriately mixing particles of compounds such as Li, Co, Ni, and Mn so that the composition after synthesis is a positive electrode active material LiMO 2 having a layered rock salt structure. Used. Alternatively, raw material particles having a composition of LiMO 2 (synthesized particles) can be used.
  • LiMO 2 is obtained by further reacting the fired molded body with the lithium compound after the firing process of the molded body.
  • a lithium compound may be added in an excess of 0.5 to 30 mol%.
  • 0.001 to 30 wt% of a low melting point oxide such as bismuth oxide or a low melting point glass such as borosilicate glass may be added.
  • the raw material particles are formed into a sheet-like self-supporting compact. That is, the “self-supporting molded body” typically can maintain the shape of a sheet-shaped molded body by itself. In addition, even if it alone can not keep the shape of the sheet-like molded body, it may be attached to any substrate or formed into a film and peeled off from this substrate before or after firing, Included in “self-supported compact”.
  • a doctor blade method using a slurry containing raw material particles can be used.
  • a drum dryer may be used for forming a formed body, in which a slurry containing a raw material is applied onto a heated drum and the dried material is scraped off with a scraper.
  • a disk drier can be used for forming the formed body, in which a slurry is applied to a heated disk surface, dried and scraped with a scraper.
  • the hollow granulated body obtained by setting the conditions of a spray dryer suitably can also be regarded as the sheet-like molded object with a curvature, it can be used suitably as a molded object.
  • an extrusion molding method using a clay containing raw material particles can also be used as a molding method of the molded body.
  • the slurry is applied to a flexible plate (for example, an organic polymer plate such as a PET film), and the applied slurry is dried and solidified to form a molded product, and the molded product and the plate are peeled off. By doing so, you may produce the molded object before baking of a plate-like polycrystalline particle.
  • a flexible plate for example, an organic polymer plate such as a PET film
  • inorganic particles may be dispersed in a suitable dispersion medium, and a binder, a plasticizer, or the like may be added as appropriate.
  • the slurry is preferably prepared so as to have a viscosity of 500 to 4000 cP, and is preferably degassed under reduced pressure.
  • the molded body obtained in the molding process is placed on a setter and fired, for example, in a molded state (a sheet state).
  • the firing step may be one in which a sheet-like formed body is appropriately cut and crushed and placed in a sheath and fired.
  • the raw material particles are mixed particles before synthesis, synthesis, further sintering and grain growth occur in this firing step.
  • a molded object is a sheet form
  • the grain growth of the thickness direction is restricted. For this reason, after the grains have grown until the number of crystal grains becomes one in the thickness direction of the compact, grain growth proceeds only in the in-plane direction of the compact. At this time, a specific crystal plane which is stable in terms of energy spreads on the sheet surface (plate surface). Therefore, a film-like sheet (self-supporting film) oriented such that a specific crystal plane is parallel to the sheet surface (plate surface) is obtained.
  • the (101) plane and (104) plane which are crystal planes in which lithium ions can enter and exit satisfactorily, can be oriented so as to be exposed on the sheet surface (plate surface).
  • the (h00) plane which becomes the (104) plane when reacted with a lithium compound to form LiMO 2 , It can be oriented so as to be exposed on the sheet surface (plate surface).
  • the firing temperature is preferably 800 ° C to 1350 ° C.
  • the firing time is preferably between 1 and 50 hours. If it is shorter than 1 hour, the degree of orientation becomes low. On the other hand, if it is longer than 50 hours, energy consumption becomes too large.
  • the firing atmosphere is appropriately set so that decomposition does not proceed during firing.
  • the volatilization of lithium proceeds, it is preferable to arrange lithium carbonate or the like in the same sheath to create a lithium atmosphere.
  • firing is preferably performed in an atmosphere having a high oxygen partial pressure.
  • a positive electrode active material film oriented so as to be exposed to the surface is obtained.
  • lithium is introduced by sprinkling the orientation sheet lithium nitrate so that the molar ratio Li / M of Li and M is 1 or more and heat-treating.
  • the heat treatment temperature is preferably 600 ° C. to 800 ° C. At a temperature lower than 600 ° C., the reaction does not proceed sufficiently. At a temperature higher than 800 ° C., the orientation deteriorates.
  • a positive electrode active material sheet using LiCoO 2 particles can be produced, for example, as follows. First, a green sheet containing Co 3 O 4 and Bi 2 O 3 is formed. This green sheet is fired at a temperature in the range of 900 to 1300 ° C. for a predetermined time, so that it is an independent thin film sheet made up of a large number of plate-like Co 3 O 4 particles oriented (h00) in the particle plate surface direction. (Self-supporting film) is formed.
  • “(h00) orientation” indicates that the (h00) plane is oriented so as to be parallel to the plate surface.
  • the “independent” sheet refers to a sheet that can be handled as a single unit independently of other supports after firing. That is, the “independent” sheet does not include a sheet that is fixed to another support (substrate or the like) by firing and integrated with the support (unseparable or difficult to separate).
  • the amount of material existing in the thickness direction is extremely small compared to the particle plate surface direction, that is, the in-plane direction (direction perpendicular to the thickness direction). Few.
  • the grain growth direction is limited to the in-plane two-dimensional direction. This reliably promotes grain growth in the surface direction. In particular, even if the thickness of the green sheet is relatively thick, such as about 100 ⁇ m or more, the grain growth in the plane direction is more surely promoted by promoting the grain growth as much as possible. At this time, only particles having a crystal plane having the lowest surface energy in the plane of the green sheet selectively grow in a flat shape (plate shape) in the in-plane direction.
  • plate-like crystal grains made of CoO having a large aspect ratio and a specific crystal plane (here, (h00) plane) oriented in the grain plate plane direction are obtained by sheet firing. Furthermore, it is oxidized from CoO to Co 3 O 4 in the process of lowering the temperature. In this case, Co 3 O 4 plate-like crystal grains in which a specific crystal plane (here, (h00) plane) is oriented in the grain plate plane direction are obtained by taking over the orientation orientation of CoO. During the oxidation from CoO to Co 3 O 4 , the degree of orientation tends to decrease.
  • a thin film (self-supporting film) is formed in which the number of crystal grains in the thickness direction is substantially one.
  • the meaning of “substantially one crystal grain in the thickness direction” does not exclude that a part (for example, end portions) of crystal grains adjacent in the plane direction overlap each other in the thickness direction.
  • This self-supporting film can be a dense ceramic sheet in which a large number of thin plate-like particles as described above are bonded without gaps.
  • Lithium is introduced into the Co 3 O 4 particles by mixing the (h00) -oriented Co 3 O 4 ceramic sheet obtained by the above process and Li 2 CO 3 and heating the mixture for a predetermined time.
  • a sheet for the film-like positive electrode active material 12 having the (003) plane oriented in the direction from the positive electrode layer 14 to the negative electrode layer 20 and the (104) plane oriented along the plate surface is obtained.
  • the “independent” sheet refers to a sheet that can be handled by itself independently from another support after firing. That is, the “independent” sheet does not include a sheet that is fixed to another support (substrate or the like) by firing and integrated with the support (unseparable or difficult to separate).
  • the amount of the material existing in the thickness direction is very small compared to the plate surface direction, that is, the in-plane direction (direction orthogonal to the thickness direction).
  • the grain growth direction is limited to the in-plane two-dimensional direction. This reliably promotes grain growth in the surface direction.
  • the grain growth in the plane direction is more surely promoted by promoting the grain growth as much as possible. That is, the grain growth in the plane direction of the grains parallel to the plate surface direction, that is, the in-plane direction (direction orthogonal to the thickness direction) is promoted preferentially.
  • a large number of thin plate-like particles oriented so that a specific crystal plane is parallel to the plate surface of the particles are formed at the grain boundary portion.
  • a free-standing film bonded in the plane direction can be obtained. That is, a self-supporting film is formed so that the number of crystal grains in the thickness direction is substantially one.
  • the meaning of “substantially one crystal grain in the thickness direction” does not exclude that a part (for example, end portions) of crystal grains adjacent in the plane direction overlap each other in the thickness direction.
  • This self-supporting film can be a dense ceramic sheet in which a large number of thin plate-like particles as described above are bonded without gaps.
  • the (h00) -oriented (Ni, Co, Al) O ceramic sheet obtained by the above-described process and lithium nitrate (LiNO 3 ) are mixed and heated for a predetermined time, thereby (Ni, Co, Al). ) Lithium is introduced into the O particles. Thereby, the Li (Ni 0.75 Co 0 for the film-like positive electrode active material 12 in which the (003) plane is oriented in the direction from the positive electrode layer 14 to the negative electrode layer 20 and the (104) plane is oriented along the plate surface. .2 Al 0.05 ) O 2 sheet is obtained.
  • a raw material containing a Li component, a La component and a Zr component is fired to obtain a primary fired powder for ceramic synthesis containing Li, La, Zr and oxygen.
  • the primary fired powder obtained in the first firing step is fired to synthesize a ceramic having a garnet-type or garnet-like crystal structure containing Li, La, Zr, and oxygen.
  • Li component, La component and Zr component These various components are not particularly limited, and various metal salts such as metal oxides, metal hydroxides, and metal carbonates containing the respective metal components can be appropriately selected and used.
  • Li 2 CO 3 or LiOH can be used as the Li component
  • La (OH) 3 or La 2 O 3 can be used as the La component
  • ZrO 2 can be used as the Zr component.
  • oxygen is usually included as an element constituting a part of a compound containing these constituent metal elements.
  • the raw material for obtaining the ceramic material can contain a Li component, a La component, and a Zr component to such an extent that an LLZ crystal structure can be obtained from each Li component, La component, Zr component, and the like by a solid phase reaction or the like.
  • the Li component, La component and Zr component can be used in a composition close to 7: 3: 2 or a composition ratio.
  • the Li component includes an amount increased by about 10% from the molar ratio equivalent amount based on the stoichiometry of Li in LLZ, and the La component and the Zr component are each in an LLZ molar ratio. It can contain so that it may become the quantity equivalent to.
  • the molar ratio of Li: La: Zr is 7.7: 3: 2.
  • the molar ratio is about 3.85: about 3: about 2 when Li 2 CO 3 : La (OH) 3 : ZrO 2 , and Li 2 CO 3 :
  • the molar ratio is about 3.85: about 1.5: about 2
  • LiOH: La (OH) 3 : ZrO 2 is about 7.7: about 3: about 2.
  • LiOH: La 2 O 3 : ZrO 2 it is about 7.7: about 1.5: about 2.
  • a known raw material powder preparation method in the synthesis of ceramic powder can be appropriately employed.
  • the mixture can be mixed uniformly by putting it into a reiki machine or a suitable ball mill.
  • the first firing step is a step of obtaining a primary fired powder for facilitating the thermal decomposition of at least the Li component and the La component to easily form the LLZ crystal structure in the second firing step.
  • the primary fired powder may already have an LLZ crystal structure.
  • the firing temperature is preferably 850 ° C. or higher and 1150 ° C. or lower.
  • the first baking step may include a step of heating at a lower heating temperature and a step of heating at a higher heating temperature within the above temperature range. By providing such a heating step, a more uniform ceramic powder can be obtained, and a high-quality sintered body can be obtained by the second firing step.
  • the heat treatment step constituting the first firing step is preferably performed by a heat treatment step of 850 ° C. or more and 950 ° C. or less and a heat treatment step of 1075 ° C. or more and 1150 ° C. or less. More preferably, a heat treatment step of 875 ° C. to 925 ° C.
  • the first baking step the total heating time at the maximum temperature set as the heating temperature as a whole is preferably about 10 hours to 15 hours. In the case where the first baking step is composed of two heat treatment steps, it is preferable that the heating time at the maximum temperature is about 5 to 6 hours.
  • the first firing step can be shortened by changing one or more components of the starting material.
  • an LLZ component containing Li, La and Zr is heated at a maximum temperature in a heat treatment step of 850 ° C. or more and 950 ° C. or less.
  • the heating time can be 10 hours or less. This is because LiOH used as a starting material forms a liquid phase at a low temperature, and thus easily reacts with other components at a lower temperature.
  • a 2nd baking process can be made into the process of heating the primary baking powder obtained at the 1st baking process at the temperature of 950 degreeC or more and 1250 degrees C or less.
  • the primary firing powder obtained in the first firing step is fired, and finally a ceramic having an LLZ crystal structure that is a composite oxide can be obtained.
  • an LLZ component including Li, La, and Zr is heat-treated at a temperature of 1125 ° C. or higher and 1250 ° C. or lower.
  • Li 2 CO 3 is used as the Li raw material, it is preferable to perform heat treatment at 1125 ° C. or higher and 1250 ° C. or lower.
  • the temperature of the second firing step can be lowered by changing one or more components of the starting material.
  • an LLZ constituent component including Li, La, and Zr can be heat-treated at a temperature of 950 ° C. or higher and lower than 1125 ° C. This is because LiOH used as a starting material forms a liquid phase at a low temperature, and thus easily reacts with other components at a lower temperature.
  • the heating time at the heating temperature in the second firing step is preferably about 18 hours or more and 50 hours or less. When the time is shorter than 18 hours, the formation of the LLZ ceramics is not sufficient.
  • the primary fired powder is pressure-molded using a well-known press technique to give a desired three-dimensional shape (for example, a shape and size that can be used as a solid electrolyte of an all-solid battery)
  • a desired three-dimensional shape for example, a shape and size that can be used as a solid electrolyte of an all-solid battery
  • the molded body containing the primary fired powder is fired and sintered in the second firing step, it is preferable to carry out the process so that the molded body is buried in the same powder. By doing so, the loss of Li can be suppressed and the change in composition before and after the second firing step can be suppressed.
  • the molded body of the raw material powder is usually buried in the raw material powder in a state where the raw material powder is spread and placed. By carrying out like this, reaction with a setter can be suppressed.
  • the curvature at the time of baking of a sintered compact can be prevented by pressing a molded object with a setter from the upper and lower sides of a filling powder as needed.
  • the primary fired powder compact can be sintered without being embedded in the same powder. This is because the loss of Li is relatively suppressed and the reaction with the setter can be suppressed by lowering the temperature of the second baking step.
  • the solid electrolyte layer 16 having an LLZ crystal structure can be obtained.
  • the solid electrolyte layer having a crystal structure and containing aluminum is obtained by carrying out either or both of the first firing step and the second firing step in the presence of an aluminum (Al) -containing compound. You may make it manufacture.
  • Example 1 An all solid state battery 10 having the configuration shown in FIG. 1 was produced.
  • the positive electrode active material 12 has a layered rock salt structure and the composition is Li (Ni 1/3 Co 1/3 Mn 1/3 ) O 2 (hereinafter referred to as NCM), and the (003) plane is from the positive electrode layer 14.
  • NCM Li (Ni 1/3 Co 1/3 Mn 1/3 ) O 2
  • a positive electrode active material sheet oriented in the direction toward the negative electrode layer 20 was produced. The thickness of the positive electrode active material sheet was 30 ⁇ m.
  • a solid electrolyte layer 16 was formed on the sheet-like positive electrode active material 12.
  • the lithium ion conductive material constituting the solid electrolyte layer 16 a ceramic material having a garnet crystal structure made of Li 7 La 3 Zr 2 O 12 (hereinafter referred to as LLZ-Al) to which Al is added was used.
  • the thickness of the solid electrolyte layer 16 was 10 ⁇ m.
  • the negative electrode active material 18 was made of lithium metal and had a thickness of 10 ⁇ m.
  • the positive electrode current collector 22 was composed of an aluminum foil having a thickness of 10 ⁇ m, and the negative electrode current collector 24 was composed of a copper foil having a thickness of 10 ⁇ m.
  • a laminate composed of these components was obtained as a unit cell.
  • This unit battery was laminated with a multilayer product of aluminum (Al) / polypropylene (PP).
  • the size (vertical x horizontal) of the all-solid battery thus obtained as viewed from above was 20 mm x 30 mm, and the thickness of the all-solid battery was 0.24 mm.
  • Example 2 The unit batteries obtained in Example 1 were stacked in parallel to produce a battery with a capacity of 100 mAh.
  • the energy density was determined in the same manner as in Example 1, it was 650 Wh / L.
  • Example 3 The unit batteries obtained in Example 1 were stacked in parallel to produce a battery with a capacity of 300 mAh. When the energy density was determined in the same manner as in Example 1, it was 750 Wh / L.
  • Example 4 A lithium ion conductive material constituting the solid electrolyte layer 16 was LiPON, and the thickness of the solid electrolyte layer 16 was 5 ⁇ m. This unit cell was laminated and covered in the same manner as in Example 1. The size (vertical x horizontal) of the all-solid battery thus obtained as viewed from above was 20 mm x 30 mm, and the thickness of the all-solid battery was 0.24 mm. When the volume energy density of the obtained all solid state battery was determined in the same manner as in Example 1, the capacity was 20 mAh and the energy density was 542 Wh / L.
  • Example 5 The unit batteries obtained in Example 4 were stacked in parallel to produce a battery with a capacity of 100 mAh.
  • the energy density was determined in the same manner as in Example 4, it was 650 Wh / L.
  • Example 6 The unit cells obtained in Example 4 were stacked in parallel to produce a battery with a capacity of 300 mAh. When the energy density was determined in the same manner as in Example 1, it was 750 Wh / L.
  • Table 1 The size and performance of the battery shown in Table 1 are extremely suitable for various applications envisioned by the present invention. For reference, the size and performance of the battery that Applicants believe is desired in some applications is shown in Table 2 below. It turns out that the all-solid-state battery of this invention is very promising for the various uses mentioned above including the use shown by Table 2. Although Table 2 includes applications with extremely high capacity such as electric vehicles, such high capacity can be realized by stacking unit cells in parallel.

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Abstract

　L'invention porte sur une diversité d'applications utiles qui réalisent la plupart des caractéristiques d'une cellule entièrement à semi-conducteurs dans laquelle un corps polycristallin orienté est utilisé en tant que matériau actif d'électrode positive ; les caractéristiques, en particulier, étant des avantages tels qu'une petite taille, une densité énergétique élevée, et un degré de sécurité élevé. Une utilisation d'une cellule entièrement à semi-conducteurs convient à au moins une application sélectionnée parmi les suivantes : des capteurs, des cartes intelligentes, une identification radiofréquence (RFID), des dispositifs vestimentaires, des terminaux portables, des systèmes de suivi, des dispositifs de surveillance de rayonnement, des sources d'alimentation à collecte d'énergie, des applications médicales, des perceuses sans câble et d'autres outils-machine électriques, et des blindages 3G et analogues. La cellule comporte : une couche d'électrode positive ayant un matériau actif d'électrode positive, le matériau actif d'électrode positive étant un corps polycristallin orienté comprenant une pluralité de particules d'oxyde de métal de transition au lithium orientées dans une direction fixe ; une couche d'électrolyte solide comprenant un matériau conducteur d'ions de lithium ; et une couche d'électrode négative ayant un matériau actif d'électrode négative.
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WO2018179580A1 (fr) * 2017-03-28 2018-10-04 株式会社村田製作所 Batterie entièrement solide, dispositif électronique, carte électronique, dispositif portable et véhicule électrique
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KR102171623B1 (ko) 2018-10-15 2020-10-29 주식회사 지2터치 최소의 터치 센서 제어 신호를 갖는 터치 스크린, 표시 장치 및 터치 스크린의 터치 스캔 방법
KR102575988B1 (ko) 2021-04-22 2023-09-08 주식회사 지2터치 인터럽트 방식을 이용하여 저 소비 전력을 구현한 터치 스크린 및 이를 이용한 센싱 방법

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WO2018179580A1 (fr) * 2017-03-28 2018-10-04 株式会社村田製作所 Batterie entièrement solide, dispositif électronique, carte électronique, dispositif portable et véhicule électrique
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US11959166B2 (en) 2018-08-14 2024-04-16 Massachusetts Institute Of Technology Methods of fabricating thin films comprising lithium-containing materials

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