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WO2018135061A1 - Matériau actif d'électrode positive, électrode positive, batterie, bloc-batterie, dispositif électronique, véhicule électrique, dispositif de stockage électrique, et système d'alimentation électrique - Google Patents

Matériau actif d'électrode positive, électrode positive, batterie, bloc-batterie, dispositif électronique, véhicule électrique, dispositif de stockage électrique, et système d'alimentation électrique Download PDF

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Publication number
WO2018135061A1
WO2018135061A1 PCT/JP2017/038625 JP2017038625W WO2018135061A1 WO 2018135061 A1 WO2018135061 A1 WO 2018135061A1 JP 2017038625 W JP2017038625 W JP 2017038625W WO 2018135061 A1 WO2018135061 A1 WO 2018135061A1
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Prior art keywords
positive electrode
battery
active material
electrode active
power
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English (en)
Japanese (ja)
Inventor
宮崎　武志
雄大 稲葉
真之介 服部
敏幸 国清
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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
    • 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
    • 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

Definitions

  • This technology relates to a positive electrode active material, a positive electrode, a battery, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system.
  • lithium cobaltate (LiCoO 2 ) used as a positive electrode active material for lithium ion secondary batteries is operated as an electrode active material while all the lithium contained in an uncharged state is electrochemically desorbed
  • the initial charge capacity can be as high as 270 mAh / g, but the reliability of the charge capacity maintenance rate with the progress of the charge / discharge cycle is significantly reduced due to the significant decrease in charge / discharge efficiency. There is.
  • the first is the development of a new positive electrode material with higher capacity and higher energy density than the positive electrode active material that has been used in the past.
  • the capacity and capacity of the battery can be increased. This is intended to increase energy density.
  • examples thereof include a lithium-rich material such as Li 1 + X Ni a Mn b Co c O 2 , or a polyanion material containing a large amount of lithium such as Li 2 FeSiO 4 .
  • These materials are expected to exhibit a large charge / discharge capacity exceeding 300 mAh / g, and thus are considered promising as a technology for dramatically increasing the capacity and energy density of the battery.
  • the second is to determine the practical limit for the positive electrode active material that has been used in the past, and to expand the practical range until just before the limit, thereby increasing the capacity and energy density of the battery. For example, in recent years, development of increasing charge / discharge capacity by removing and inserting more lithium by raising the upper limit of the potential of lithium cobalt oxide LiCoO 2 has been underway.
  • the charging potential is raised to the high potential side within a range that does not hinder the characteristics of the positive electrode active material that has already been put into practical use, and materials other than the positive electrode active material (for example, electrolyte solution) Etc.) to ensure resistance to the potential.
  • An object of the present technology is to provide a positive electrode active material, a positive electrode, a battery, a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system that can suppress a decrease in initial charge / discharge efficiency.
  • the positive electrode active material of the present technology includes a lithium transition metal composite oxide having a layered rock salt structure, and in an X-ray absorption fine structure spectrum measured in an uncharged state, An X-ray absorption edge giving an intensity of 0.5 exists within a range where the energy is 1302 eV or more and 1312 eV or less.
  • An X-ray absorption edge giving an intensity of 0.5 exists within a range where the energy is 1302 eV or more and 1312 eV or less.
  • the peaks having the absorption edge the peak in the lowest energy side except for the pre-edge peak.
  • the high energy side spectral intensity minimum point is 1312.5 eV or more.
  • the positive electrode, the battery, the battery pack, the electronic device, the electric vehicle, the power storage device, and the power system of the present technology include the above-described positive electrode active material.
  • the present technology it is possible to suppress a decrease in the initial charge / discharge efficiency of the battery.
  • the effects described here are not necessarily limited, and may be any of the effects described in the present disclosure or effects different from those.
  • FIG. 4 is a cross-sectional view of a wound electrode body taken along line IV-IV in FIG. 3. It is a block diagram which shows an example of a structure of the electronic device as an application example. It is the schematic which shows an example of a structure of the electrical storage system in the vehicle as an application example.
  • Embodiments of the present technology will be described in the following order. 1 1st Embodiment (example of positive electrode active material) 2 Second Embodiment (Example of Cylindrical Battery) 3 Third Embodiment (Example of Laminated Film Type Battery) 4 Application 1 (battery pack and electronic equipment) 5 Application Example 2 (Power Storage System in Vehicle) 6 Application 3 (electric storage system in a house)
  • the positive electrode active material according to the first embodiment of the present technology includes a lithium transition metal composite oxide having a layered rock salt type structure.
  • XANES X-ray absorption near edge structure
  • an intensity of 0.5 is given within a range where the X-ray energy is 1302 eV or more and 1312 eV or less.
  • the high energy side spectral intensity minimum point (hereinafter simply referred to as “high energy side spectral intensity minimum point”) at the lowest energy peak excluding the pre-edge peak is 1312.5 eV or more.
  • This positive electrode active material is, for example, for a lithium ion secondary battery.
  • a sample lithium transition metal composite compound
  • X-ray energy about 1303 eV
  • the intensity and the intensity of the MgK ⁇ fluorescent X-ray generated from the sample are measured.
  • the position of the absorption edge and the intensity of the spectrum reflect the electronic state of the Mg unbound vacant orbit, and therefore reflect the redox state or the local structure around Mg.
  • This facility is, for example, the synchrotron radiation research facility beam line BL-11A of the Institute for Materials Structure Science, High Energy Accelerator Research Organization, or the synchrotron radiation research facility beam line BL10 of the Ritsumeikan University SR Center.
  • the MgK ⁇ fluorescent X-ray may be measured together with the MgK ⁇ fluorescent X-ray.
  • a KTiPO 4 (001) double crystal spectrometer is used as the spectrometer, and a silicon drift detector (SDD) is used as the fluorescent X-ray detector. Note that instead of the intensity of fluorescent X-rays, the intensity of X-rays transmitted through the sample or the intensity of current flowing through the sample may be measured.
  • the XAFS spectrum (raw spectrum) is obtained by plotting the value obtained by dividing the intensity of fluorescent X-rays by the intensity of irradiated X-rays against the X-ray energy to be irradiated.
  • a standard sample commercially available MgO polycrystalline powder
  • the positive electrode active material is capable of occluding and releasing lithium (Li), and includes a lithium transition metal composite oxide having a layered rock salt type structure including Co (cobalt) and Mg (magnesium). . A part of Li and a part of Co in the lithium transition metal composite oxide are substituted with Mg.
  • Lithium transition metal composite oxides can be made of aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn) as required.
  • Molybdenum (Mo), tin (Sn), tungsten (W), zirconium (Zr), yttrium (Y), niobium (Nb), calcium (Ca), strontium (Sr), bismuth (Bi), sodium (Na) ), Potassium (K), silicon (Si), phosphorus (P), manganese (Mn), and nickel (Ni) may further be included.
  • the lithium transition metal composite oxide may be one in which a part of Li and part of Co in LiCoO 2 are substituted with Mg, or a lithium transition having an average composition represented by the following formula (1)
  • a part of Li and part of Co in the metal composite oxide may be substituted with Mg.
  • M is Al, B, Ti, V, Cr, Fe, Cu, Zn, Mo, Sn, W, Zr, Y, Nb, Ca, Sr, Bi, Na, K, Si. , P, Mn, and Ni
  • x is 0 ⁇ x ⁇ 1.0
  • y 0 ⁇ y ⁇ 0.50
  • z is ⁇ 0.10 ⁇ z ⁇ 0.20.
  • typical sites occupied by Mg in the LiCoO 2 structure are a Co site and a Li site.
  • there is a function that Mg assumes when it occupies a Co site and a function that Mg assumes when it occupies a Li site. Therefore, the optimum characteristics are shown as a whole.
  • the high energy side spectral intensity minimum point in the above XANES spectrum has a correlation with the amount of Mg occupying the Co site and Li site, and as the Mg occupying the Li site increases, It came to show that it shows the tendency to shift. More specifically, if the high energy side spectral intensity minimum point is 1312.5 eV or more, the amount of Mg that occupies the Co site and Li site becomes an appropriate amount. It came to discover that the fall of discharge efficiency could be suppressed.
  • the positive electrode active material is a lithium ion used in a region where the positive electrode potential (vsLi / Li + ) in a fully charged state is preferably 4.30 V or higher, more preferably 4.35 V or higher, and even more preferably 4.40 V or higher.
  • the positive electrode active material is for a lithium ion secondary battery used in a region where the positive electrode potential (vsLi / Li + ) in a fully charged state is less than 4.30 V (for example, 4.2 V or 4.25 V). Also good.
  • the upper limit of the positive electrode potential (vsLi / Li + ) in the fully charged state of the lithium ion secondary battery using the positive electrode active material is not particularly limited, but is preferably 6.00 V or less, more preferably 4 .60V or less, and even more preferably 4.50V or less.
  • the high energy side spectral intensity minimum point is 1312.5 eV or more, and therefore Mg occupies an appropriate amount of both the Co site and the Li site. Both the function carried by Mg and the function carried by Mg when occupying the Li site are exhibited. In a battery equipped with such a positive electrode active material, it is possible to suppress a decrease in initial charge / discharge efficiency due to the addition of Mg.
  • the positive electrode active material according to the first embodiment has a feature that the shape of the MgANXANES peak is constant, more specifically, the high energy side spectral intensity minimum point is 1312.5 eV or more. It can suppress the fall of the first time charge / discharge efficiency by Mg addition. Furthermore, when the charge potential is raised for the purpose of increasing the energy density, the effect of suppressing the first-time charge / discharge efficiency is significantly manifested.
  • the initial charge / discharge efficiency can be improved as described above. Therefore, the increase in the discharge capacity when the charge potential is raised is large, which is suitable for raising the charge potential. High energy density is achieved.
  • the high energy side spectral intensity minimum point is less than 1312.5 eV, the initial charge / discharge efficiency is lowered, so that the increase in the discharge capacity when the charge potential is raised is small, and the charge potential is increased corresponding to the increase. Realization of energy density is difficult.
  • This secondary battery is, for example, a so-called lithium ion secondary battery in which the capacity of the negative electrode is represented by a capacity component due to insertion and extraction of lithium (Li) as an electrode reactant.
  • This secondary battery is called a so-called cylindrical type, and a pair of strip-like positive electrode 21 and strip-like negative electrode 22 are laminated and wound inside a substantially hollow cylindrical battery can 11 via a separator 23.
  • a wound electrode body 20 is provided.
  • the battery can 11 is made of iron (Fe) plated with nickel (Ni), and has one end closed and the other end open.
  • an electrolytic solution as a liquid electrolyte is injected and impregnated in the positive electrode 21, the negative electrode 22, and the separator 23.
  • a pair of insulating plates 12 and 13 are respectively disposed perpendicular to the winding peripheral surface so as to sandwich the wound electrode body 20.
  • a battery lid 14 At the open end of the battery can 11, a battery lid 14, a safety valve mechanism 15 provided inside the battery lid 14, and a thermal resistance element (Positive16Temperature ⁇ Coefficient; PTC element) 16 are provided via a sealing gasket 17. It is attached by caulking. Thereby, the inside of the battery can 11 is sealed.
  • the battery lid 14 is made of, for example, the same material as the battery can 11.
  • the safety valve mechanism 15 is electrically connected to the battery lid 14, and when the internal pressure of the battery exceeds a certain level due to an internal short circuit or external heating, the disk plate 15A is reversed and wound with the battery lid 14.
  • the electrical connection with the rotary electrode body 20 is cut off.
  • the sealing gasket 17 is made of, for example, an insulating material, and the surface is coated with asphalt.
  • a center pin 24 is inserted in the center of the wound electrode body 20.
  • a positive electrode lead 25 made of aluminum (Al) or the like is connected to the positive electrode 21 of the wound electrode body 20, and a negative electrode lead 26 made of nickel or the like is connected to the negative electrode 22.
  • the positive electrode lead 25 is electrically connected to the battery lid 14 by being welded to the safety valve mechanism 15, and the negative electrode lead 26 is welded to and electrically connected to the battery can 11.
  • the positive electrode 21 has, for example, a structure in which a positive electrode active material layer 21B is provided on both surfaces of a positive electrode current collector 21A. Although not shown, the positive electrode active material layer 21B may be provided only on one surface of the positive electrode current collector 21A.
  • the positive electrode current collector 21A is made of, for example, a metal foil such as an aluminum foil, a nickel foil, or a stainless steel foil.
  • the positive electrode active material layer 21B includes the positive electrode active material according to the first embodiment.
  • the positive electrode active material layer 21B may further include a positive electrode active material other than the positive electrode active material according to the first embodiment.
  • the positive electrode active material layer 21B may further contain an additive as necessary. As the additive, for example, at least one of a conductive agent and a binder can be used.
  • binder examples include resin materials such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC), and resins thereof. At least one selected from copolymers mainly composed of materials is used.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PAN polyacrylonitrile
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • Examples of the conductive agent include carbon materials such as graphite, carbon fiber, carbon black, ketjen black, and carbon nanotube. One of these may be used alone, or two or more may be mixed. May be used. In addition to the carbon material, a metal material or a conductive polymer material may be used as long as it is a conductive material.
  • the negative electrode 22 has, for example, a structure in which a negative electrode active material layer 22B is provided on both surfaces of a negative electrode current collector 22A. Although not shown, the negative electrode active material layer 22B may be provided only on one surface of the negative electrode current collector 22A.
  • the negative electrode current collector 22A is made of, for example, a metal foil such as a copper foil, a nickel foil, or a stainless steel foil.
  • the negative electrode active material layer 22B contains one or more negative electrode active materials capable of inserting and extracting lithium.
  • the negative electrode active material layer 22B may further contain additives such as a binder and a conductive agent as necessary.
  • the electrochemical equivalent of the negative electrode 22 or the negative electrode active material is larger than the electrochemical equivalent of the positive electrode 21, and theoretically, lithium metal is not deposited on the negative electrode 22 during charging. It is preferable that
  • Examples of the negative electrode active material include carbon materials such as non-graphitizable carbon, graphitizable carbon, graphite, pyrolytic carbons, cokes, glassy carbons, organic polymer compound fired bodies, carbon fibers, and activated carbon. Is mentioned.
  • examples of coke include pitch coke, needle coke, and petroleum coke.
  • An organic polymer compound fired body refers to a carbonized material obtained by firing a polymer material such as phenol resin or furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon.
  • These carbon materials are preferable because the change in crystal structure that occurs during charge and discharge is very small, a high charge and discharge capacity can be obtained, and good cycle characteristics can be obtained.
  • graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density.
  • non-graphitizable carbon is preferable because excellent cycle characteristics can be obtained.
  • those having a low charge / discharge potential, specifically, those having a charge / discharge potential close to that of lithium metal are preferable because a high energy density of the battery can be easily realized.
  • a material containing at least one of a metal element and a metalloid element as a constituent element for example, an alloy, a compound, or a mixture
  • a high energy density can be obtained by using such a material.
  • the use with a carbon material is more preferable because a high energy density can be obtained and excellent cycle characteristics can be obtained.
  • the alloy includes an alloy including one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements.
  • the nonmetallic element may be included.
  • Examples of such a negative electrode active material include a metal element or a metalloid element capable of forming an alloy with lithium.
  • a metal element or a metalloid element capable of forming an alloy with lithium.
  • magnesium, boron, aluminum, titanium, gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin, lead (Pb), bismuth (Bi), cadmium (Cd), Silver (Ag), zinc, hafnium (Hf), zirconium, yttrium (Y), palladium (Pd), or platinum (Pt) can be used. These may be crystalline or amorphous.
  • the negative electrode active material preferably contains a group 4B metal element or metalloid element in the short-period periodic table as a constituent element, and more preferably contains at least one of silicon and tin as a constituent element. This is because silicon and tin have a large ability to occlude and release lithium, and a high energy density can be obtained.
  • Examples of such a negative electrode active material include a simple substance, an alloy or a compound of silicon, a simple substance, an alloy or a compound of tin, or a material having one or more phases thereof at least in part.
  • Examples of the silicon alloy include, as the second constituent element other than silicon, tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony (Sb), and chromium.
  • the thing containing at least 1 sort (s) of a group is mentioned.
  • As an alloy of tin for example, as a second constituent element other than tin, among the group consisting of silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium The thing containing at least 1 sort (s) of these is mentioned.
  • tin compound or the silicon compound examples include those containing oxygen or carbon, and may contain the second constituent element described above in addition to tin or silicon.
  • the Sn-based negative electrode active material cobalt, tin, and carbon are included as constituent elements, the carbon content is 9.9 mass% or more and 29.7 mass% or less, and tin and cobalt A SnCoC-containing material in which the proportion of cobalt with respect to the total is 30% by mass to 70% by mass is preferable. This is because a high energy density can be obtained in such a composition range, and excellent cycle characteristics can be obtained.
  • This SnCoC-containing material may further contain other constituent elements as necessary.
  • other constituent elements for example, silicon, iron, nickel, chromium, indium, niobium, germanium, titanium, molybdenum, aluminum, phosphorus (P), gallium, or bismuth are preferable, and two or more kinds may be included. This is because the capacity or cycle characteristics can be further improved.
  • This SnCoC-containing material has a phase containing tin, cobalt, and carbon, and this phase preferably has a low crystallinity or an amorphous structure.
  • this SnCoC-containing material it is preferable that at least a part of carbon that is a constituent element is bonded to a metal element or a metalloid element that is another constituent element.
  • the decrease in cycle characteristics is thought to be due to the aggregation or crystallization of tin or the like, but this is because such aggregation or crystallization can be suppressed by combining carbon with other elements. .
  • XPS X-ray photoelectron spectroscopy
  • the peak of the carbon 1s orbital (C1s) appears at 284.5 eV in an energy calibrated apparatus so that the peak of the gold atom 4f orbital (Au4f) is obtained at 84.0 eV if it is graphite. .
  • Au4f gold atom 4f orbital
  • it will appear at 284.8 eV.
  • the charge density of the carbon element increases, for example, when carbon is bonded to a metal element or a metalloid element, the C1s peak appears in a region lower than 284.5 eV.
  • the peak of the synthetic wave of C1s obtained for the SnCoC-containing material appears in a region lower than 284.5 eV
  • at least a part of the carbon contained in the SnCoC-containing material is a metal element or a half of other constituent elements. Combined with metal elements.
  • the C1s peak is used to correct the energy axis of the spectrum.
  • the C1s peak of the surface-contaminated carbon is set to 284.8 eV, which is used as an energy standard.
  • the waveform of the C1s peak is obtained as a shape including the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. Therefore, by analyzing using, for example, commercially available software, the surface contamination The carbon peak and the carbon peak in the SnCoC-containing material are separated. In the waveform analysis, the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).
  • Examples of other negative electrode active materials include metal oxides or polymer compounds that can occlude and release lithium.
  • Examples of the metal oxide include lithium titanium oxide containing titanium and lithium, such as lithium titanate (Li 4 Ti 5 O 12 ), iron oxide, ruthenium oxide, or molybdenum oxide.
  • Examples of the polymer compound include polyacetylene, polyaniline, and polypyrrole.
  • binder examples include at least one selected from resin materials such as polyvinylidene fluoride, polytetrafluoroethylene, polyacrylonitrile, styrene butadiene rubber and carboxymethyl cellulose, and copolymers mainly composed of these resin materials. Is used.
  • resin materials such as polyvinylidene fluoride, polytetrafluoroethylene, polyacrylonitrile, styrene butadiene rubber and carboxymethyl cellulose, and copolymers mainly composed of these resin materials. Is used.
  • the conductive agent the same carbon material as that of the positive electrode active material layer 21B can be used.
  • the separator 23 separates the positive electrode 21 and the negative electrode 22 and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes.
  • the separator 23 is made of, for example, a porous film made of a resin such as polytetrafluoroethylene, polypropylene, or polyethylene, and may have a structure in which two or more kinds of these porous films are laminated.
  • a porous film made of polyolefin is preferable because it is excellent in the effect of preventing short circuit and can improve the safety of the battery due to the shutdown effect.
  • polyethylene is preferable as a material constituting the separator 23 because it can obtain a shutdown effect within a range of 100 ° C.
  • the porous film may have a structure of three or more layers in which a polypropylene layer, a polyethylene layer, and a polypropylene layer are sequentially laminated.
  • the separator 23 may have a configuration including a base material and a surface layer provided on one or both surfaces of the base material.
  • the surface layer includes inorganic particles having electrical insulating properties and a resin material that binds the inorganic particles to the surface of the base material and binds the inorganic particles to each other.
  • This resin material may have, for example, a three-dimensional network structure in which the fibers are fibrillated and the fibrils are continuously connected to each other.
  • the inorganic particles can be maintained in a dispersed state without being connected to each other by being supported on the resin material having the three-dimensional network structure.
  • the resin material may be bound to the surface of the base material or the inorganic particles without being fibrillated. In this case, higher binding properties can be obtained.
  • the base material is a porous layer having porosity. More specifically, the base material is a porous film composed of an insulating film having a large ion permeability and a predetermined mechanical strength, and the electrolytic solution is held in the pores of the base material. It is preferable that the base material has a predetermined mechanical strength as a main part of the separator, while having a high resistance to an electrolytic solution, a low reactivity, and a property of being difficult to expand.
  • a polyolefin resin such as polypropylene or polyethylene, an acrylic resin, a styrene resin, a polyester resin, or a nylon resin.
  • polyethylenes such as low density polyethylene, high density polyethylene, linear polyethylene, or their low molecular weight wax, or polyolefin resins such as polypropylene are suitable because they have an appropriate melting temperature and are easily available.
  • a material including a porous film made of a polyolefin resin is excellent in separability between the positive electrode 21 and the negative electrode 22 and can further reduce a decrease in internal short circuit.
  • a non-woven fabric may be used as the base material.
  • fibers constituting the nonwoven fabric aramid fibers, glass fibers, polyolefin fibers, polyethylene terephthalate (PET) fibers, nylon fibers, or the like can be used. Moreover, it is good also as a nonwoven fabric by mixing these 2 or more types of fibers.
  • the inorganic particles contain at least one of metal oxide, metal nitride, metal carbide, metal sulfide and the like.
  • the metal oxide include aluminum oxide (alumina, Al 2 O 3 ), boehmite (hydrated aluminum oxide), magnesium oxide (magnesia, MgO), titanium oxide (titania, TiO 2 ), zirconium oxide (zirconia, ZrO 2). ), Silicon oxide (silica, SiO 2 ), yttrium oxide (yttria, Y 2 O 3 ) or the like can be suitably used.
  • silicon nitride Si 3 N 4
  • aluminum nitride AlN
  • boron nitride BN
  • titanium nitride TiN
  • metal carbide silicon carbide (SiC) or boron carbide (B4C)
  • metal sulfide barium sulfate (BaSO 4 ) or the like can be preferably used.
  • zeolite M 2 / n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O, M represents a metal element, x ⁇ 2, y ⁇ 0 ) porous aluminosilicates such as layered silicates, titanates Minerals such as barium (BaTiO 3 ) or strontium titanate (SrTiO 3 ) may be used.
  • alumina titania (particularly those having a rutile structure), silica or magnesia, and more preferably alumina.
  • the inorganic particles have oxidation resistance and heat resistance, and the surface layer on the side facing the positive electrode containing the inorganic particles has strong resistance to an oxidizing environment in the vicinity of the positive electrode during charging.
  • the shape of the inorganic particles is not particularly limited, and any of a spherical shape, a plate shape, a fiber shape, a cubic shape, a random shape, and the like can be used.
  • Resin materials constituting the surface layer include fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, fluorine-containing rubbers such as vinylidene fluoride-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene copolymer, styrene -Butadiene copolymer or hydride thereof, acrylonitrile-butadiene copolymer or hydride thereof, acrylonitrile-butadiene-styrene copolymer or hydride thereof, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester Copolymer, acrylonitrile-acrylic ester copolymer, rubber such as ethylene propylene rubber, polyvinyl alcohol, polyvinyl acetate, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carbo Cellulose derivatives such as
  • resin materials may be used alone or in combination of two or more.
  • fluorine resins such as polyvinylidene fluoride are preferable from the viewpoint of oxidation resistance and flexibility, and aramid or polyamideimide is preferably included from the viewpoint of heat resistance.
  • the particle size of the inorganic particles is preferably in the range of 1 nm to 10 ⁇ m. If it is smaller than 1 nm, it is difficult to obtain, and even if it can be obtained, it is not worth the cost. On the other hand, if it is larger than 10 ⁇ m, the distance between the electrodes becomes large, and a sufficient amount of active material cannot be obtained in a limited space, resulting in a low battery capacity.
  • a slurry composed of a matrix resin, a solvent and an inorganic substance is applied on a base material (porous membrane), and is passed through a poor solvent of the matrix resin and a solvate bath of the above solvent.
  • a method of separating and then drying can be used.
  • the inorganic particles described above may be contained in a porous film as a base material. Further, the surface layer may not be composed of inorganic particles and may be composed only of a resin material.
  • the separator 23 is impregnated with an electrolytic solution that is a liquid electrolyte.
  • the electrolytic solution contains a solvent and an electrolyte salt dissolved in the solvent.
  • the electrolytic solution may contain a known additive in order to improve battery characteristics.
  • cyclic carbonates such as ethylene carbonate or propylene carbonate can be used, and it is preferable to use one of ethylene carbonate and propylene carbonate, particularly a mixture of both. This is because the cycle characteristics can be improved.
  • the solvent in addition to these cyclic carbonates, it is preferable to use a mixture of chain carbonates such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate or methylpropyl carbonate. This is because high ionic conductivity can be obtained.
  • the solvent preferably further contains 2,4-difluoroanisole or vinylene carbonate. This is because 2,4-difluoroanisole can improve discharge capacity, and vinylene carbonate can improve cycle characteristics. Therefore, it is preferable to use a mixture of these because the discharge capacity and cycle characteristics can be improved.
  • examples of the solvent include butylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3- Dioxolane, methyl acetate, methyl propionate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropironitrile, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, N, N-dimethyl Examples include imidazolidinone, nitromethane, nitroethane, sulfolane, dimethyl sulfoxide, and trimethyl phosphate.
  • a compound obtained by substituting at least a part of hydrogen in these non-aqueous solvents with fluorine may be preferable because the reversibility of the electrode reaction may be improved depending on the type of electrode to be combined.
  • lithium salt As electrolyte salt, lithium salt is mentioned, for example, 1 type may be used independently, and 2 or more types may be mixed and used for it.
  • Lithium salts include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB (C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , LiAlCl 4 , LiSiF 6 , LiCl, difluoro [oxolato-O, O ′] lithium borate, lithium bisoxalate borate, or LiBr.
  • LiPF 6 is preferable because it can obtain high ion conductivity and can improve cycle characteristics.
  • the positive electrode potential (vsLi / Li + ) in the fully charged state is preferably 4.30 V or more, more preferably 4.35 V or more, and even more preferably 4.40 V or more.
  • the positive electrode potential (vsLi / Li + ) in the fully charged state may be less than 4.30 V (for example, 4.2 V or 4.25 V).
  • the upper limit value of the positive electrode potential (vsLi / Li + ) in the fully charged state is not particularly limited, but is preferably 6.00 V or less, more preferably 4.60 V or less, and even more preferably 4.50 V or less. is there.
  • a positive electrode material according to the first embodiment, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and this positive electrode mixture is mixed with N-methyl-2-pyrrolidone (NMP) or the like.
  • NMP N-methyl-2-pyrrolidone
  • a paste-like positive electrode mixture slurry is prepared by dispersing in a solvent.
  • this positive electrode mixture slurry is applied to the positive electrode current collector 21 ⁇ / b> A, the solvent is dried, and the positive electrode active material layer 21 ⁇ / b> B is formed by compression molding with a roll press or the like, thereby forming the positive electrode 21.
  • a negative electrode active material and a binder are mixed to prepare a negative electrode mixture, and this negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a paste-like negative electrode mixture slurry Is made.
  • the negative electrode mixture slurry is applied to the negative electrode current collector 22A, the solvent is dried, and the negative electrode active material layer 22B is formed by compression molding using a roll press or the like, and the negative electrode 22 is manufactured.
  • the positive electrode lead 25 is attached to the positive electrode current collector 21A by welding or the like, and the negative electrode lead 26 is attached to the negative electrode current collector 22A by welding or the like.
  • the positive electrode 21 and the negative electrode 22 are wound through the separator 23.
  • the front end of the positive electrode lead 25 is welded to the safety valve mechanism 15, and the front end of the negative electrode lead 26 is welded to the battery can 11, and the wound positive electrode 21 and negative electrode 22 are connected with the pair of insulating plates 12 and 13. It is housed inside the sandwiched battery can 11.
  • the electrolytic solution is injected into the battery can 11 and impregnated in the separator 23.
  • the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are fixed to the opening end of the battery can 11 by caulking through a sealing gasket 17. Thereby, the secondary battery shown in FIG. 2 is obtained.
  • the positive electrode active material layer 21B contains the positive electrode active material according to the first embodiment, it is possible to suppress a decrease in the initial charge / discharge efficiency. Thereby, the effective discharge capacity of the positive electrode 21 can be increased and the energy density can be improved. In particular, when the positive electrode potential (vsLi / Li + ) in the fully charged state is 4.30 V or more, the above effect is remarkably exhibited.
  • FIG. 3 is an exploded perspective view illustrating a configuration example of the secondary battery according to the third embodiment of the present technology.
  • This secondary battery is a so-called flat type or square type, in which a wound electrode body 30 to which a positive electrode lead 31 and a negative electrode lead 32 are attached is accommodated in a film-shaped exterior member 40. It is possible to reduce the size, weight and thickness.
  • the positive electrode lead 31 and the negative electrode lead 32 are each led out from the inside of the exterior member 40 to the outside, for example, in the same direction.
  • the positive electrode lead 31 and the negative electrode lead 32 are made of, for example, a metal material such as aluminum, copper, nickel, or stainless steel, and each have a thin plate shape or a mesh shape.
  • the exterior member 40 is made of, for example, a rectangular aluminum laminated film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order.
  • the exterior member 40 is disposed, for example, so that the polyethylene film side and the wound electrode body 30 face each other, and the outer edge portions are in close contact with each other by fusion or an adhesive.
  • An adhesive film 41 is inserted between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32 to prevent intrusion of outside air.
  • the adhesion film 41 is made of a material having adhesion to the positive electrode lead 31 and the negative electrode lead 32, for example, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, or modified polypropylene.
  • the exterior member 40 may be configured by a laminated film having another structure, a polymer film such as polypropylene, or a metal film instead of the above-described aluminum laminated film.
  • a laminate film in which an aluminum film is used as a core and a polymer film is laminated on one or both sides thereof may be used.
  • FIG. 4 is a cross-sectional view taken along the line IV-IV of the wound electrode body 30 shown in FIG.
  • the wound electrode body 30 is obtained by stacking and winding a positive electrode 33 and a negative electrode 34 via a separator 35 and an electrolyte layer 36, and the outermost periphery is protected by a protective tape 37.
  • the positive electrode 33 has a structure in which a positive electrode active material layer 33B is provided on one or both surfaces of a positive electrode current collector 33A.
  • the negative electrode 34 has a structure in which a negative electrode active material layer 34B is provided on one surface or both surfaces of a negative electrode current collector 34A, and the negative electrode active material layer 34B and the positive electrode active material layer 33B are arranged to face each other. Yes.
  • the configurations of the positive electrode current collector 33A, the positive electrode active material layer 33B, the negative electrode current collector 34A, the negative electrode active material layer 34B, and the separator 35 are respectively the positive electrode current collector 21A, the positive electrode active material layer 21B, and the negative electrode in the second embodiment. This is the same as the current collector 22A, the negative electrode active material layer 22B, and the separator 23.
  • the electrolyte layer 36 includes an electrolytic solution and a polymer compound serving as a holding body that holds the electrolytic solution, and has a so-called gel shape.
  • the gel electrolyte layer 36 is preferable because high ion conductivity can be obtained and battery leakage can be prevented.
  • the electrolytic solution is an electrolytic solution according to the second embodiment.
  • the polymer compound include polyacrylonitrile, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, and polysiloxane.
  • polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene or polyethylene oxide is preferable from the viewpoint of electrochemical stability.
  • the inorganic substance similar to the inorganic substance described in the description of the resin layer of the separator 23 in the second embodiment may be included in the gel electrolyte layer 36. This is because the heat resistance can be further improved. Further, an electrolytic solution may be used instead of the electrolyte layer 36.
  • a precursor solution containing a solvent, an electrolyte salt, a polymer compound, and a mixed solvent is applied to each of the positive electrode 33 and the negative electrode 34, and the mixed solvent is volatilized to form the electrolyte layer 36.
  • the positive electrode lead 31 is attached to the end portion of the positive electrode current collector 33A by welding
  • the negative electrode lead 32 is attached to the end portion of the negative electrode current collector 34A by welding.
  • the positive electrode 33 and the negative electrode 34 on which the electrolyte layer 36 is formed are laminated via a separator 35 to form a laminated body, and then the laminated body is wound in the longitudinal direction, and a protective tape 37 is attached to the outermost peripheral portion.
  • the wound electrode body 30 is formed by bonding.
  • the wound electrode body 30 is sandwiched between the exterior members 40, and the outer edges of the exterior members 40 are sealed and sealed by thermal fusion or the like.
  • the adhesion film 41 is inserted between the positive electrode lead 31 and the negative electrode lead 32 and the exterior member 40. Thereby, the secondary battery shown in FIGS. 4 and 4 is obtained.
  • this secondary battery may be manufactured as follows. First, the positive electrode 33 and the negative electrode 34 are produced as described above, and the positive electrode lead 31 and the negative electrode lead 32 are attached to the positive electrode 33 and the negative electrode 34. Next, the positive electrode 33 and the negative electrode 34 are laminated and wound via the separator 35, and a protective tape 37 is adhered to the outermost peripheral portion to form a wound body. Next, the wound body is sandwiched between the exterior members 40, and the outer peripheral edge except for one side is heat-sealed to form a bag shape, which is then stored inside the exterior member 40.
  • an electrolyte composition including a solvent, an electrolyte salt, a monomer that is a raw material of the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary is prepared, and the exterior member Inject into 40.
  • the opening of the exterior member 40 is heat-sealed in a vacuum atmosphere and sealed.
  • the gelled electrolyte layer 36 is formed by applying heat to polymerize the monomer to obtain a polymer compound.
  • the secondary battery shown in FIG. 4 is obtained.
  • the electronic device 400 includes an electronic circuit 401 of the electronic device body and a battery pack 300.
  • the battery pack 300 is electrically connected to the electronic circuit 401 via the positive terminal 331a and the negative terminal 331b.
  • the electronic device 400 has a configuration in which the battery pack 300 is detachable by a user.
  • the configuration of the electronic device 400 is not limited to this, and the battery pack 300 is built in the electronic device 400 so that the user cannot remove the battery pack 300 from the electronic device 400. May be.
  • the positive terminal 331a and the negative terminal 331b of the battery pack 300 are connected to the positive terminal and the negative terminal of a charger (not shown), respectively.
  • the positive terminal 331a and the negative terminal 331b of the battery pack 300 are connected to the positive terminal and the negative terminal of the electronic circuit 401, respectively.
  • the electronic device 400 for example, a notebook personal computer, a tablet computer, a mobile phone (for example, a smartphone), a portable information terminal (Personal Digital Assistant: PDA), a display device (LCD, EL display, electronic paper, etc.), imaging Devices (eg digital still cameras, digital video cameras, etc.), audio equipment (eg portable audio players), game machines, cordless phones, e-books, electronic dictionaries, radio, headphones, navigation systems, memory cards, pacemakers, hearing aids, Electric tools, electric shavers, refrigerators, air conditioners, TVs, stereos, water heaters, microwave ovens, dishwashers, washing machines, dryers, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights, etc. It is, but not such limited thereto.
  • the electronic circuit 401 includes, for example, a CPU, a peripheral logic unit, an interface unit, a storage unit, and the like, and controls the entire electronic device 400.
  • the battery pack 300 includes an assembled battery 301 and a charge / discharge circuit 302.
  • the assembled battery 301 is configured by connecting a plurality of secondary batteries 301a in series and / or in parallel.
  • the plurality of secondary batteries 301a are connected, for example, in n parallel m series (n and m are positive integers).
  • FIG. 5 shows an example in which six secondary batteries 301a are connected in two parallel three series (2P3S).
  • the battery according to the second or third embodiment is used as the secondary battery 301a.
  • the battery pack 300 includes the assembled battery 301 including a plurality of secondary batteries 301 a
  • the battery pack 300 includes a single secondary battery 301 a instead of the assembled battery 301. It may be adopted.
  • the charging / discharging circuit 302 is a control unit that controls charging / discharging of the assembled battery 301. Specifically, during charging, the charging / discharging circuit 302 controls charging of the assembled battery 301. On the other hand, at the time of discharging (that is, when the electronic device 400 is used), the charging / discharging circuit 302 controls the discharging of the electronic device 400.
  • FIG. 6 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 car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once 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 power driving force conversion device 7203, and the regenerative power generated by the power driving force conversion device 7203 by this rotational force is applied to the battery 7208. Accumulated.
  • the battery 7208 is connected to an external power source of the hybrid vehicle, so that the battery 7208 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.
  • a series hybrid vehicle that runs on a motor using electric power generated by a generator driven by an engine or electric power stored once in a battery has been described as an example.
  • the present disclosure is also effective for a parallel hybrid vehicle that uses both the engine and motor outputs as the drive source, 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.
  • 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. At the same time, 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 battery unit 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.
  • the 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 Asynchronous Receiver-Transmitter), Bluetooth (registered trademark), ZigBee, Wi-Fi.
  • a communication interface such as UART (Universal Asynchronous Receiver-Transmitter), Bluetooth (registered trademark), ZigBee, Wi-Fi.
  • the Bluetooth method 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 the name of 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, various sensors 9011, the server 9013 and the information network 9012, for example, a function of adjusting 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.
  • LiOH.H 2 O containing 95 mol% of Li and Co 3 O 4 (Co-containing raw material (1)) containing 95 mol% of Co were sampled, and appropriate amounts of pure water were put in a mortar.
  • the mixture was wet-mixed and baked in an air atmosphere at 900 ° C. for 10 hours.
  • Lithium phosphate (LiPF 6 ) was dissolved to a concentration of 1 mol / kg to prepare a non-aqueous electrolyte.
  • a 2016-size coin-type battery was prepared using the above electrode as a working electrode, a Li metal as a counter electrode, a polyethylene microporous film as a separator, and the non-aqueous electrolyte as an electrolyte.
  • a coin-type battery was fabricated in the same manner as in Example 1 except that the Mg-added LiCoO 2 obtained as described above was used as an electrode active material.
  • a coin-type battery was fabricated in the same manner as in Example 1 except that the Mg-added LiCoO 2 obtained as described above was used as an electrode active material.
  • Mg XANES spectrum For the Mg-added LiCoO 2 (uncharged state) of Examples 1 to 3 and Comparative Examples 1 to 4, MgK-edge XANES spectra were measured by the fluorescence method. A KTiPO 4 (001) double crystal spectrometer was used as the spectrometer. The high energy side spectral intensity minimum point in the lowest energy side peak excluding the pre-edge peak of the MgK-edge XANES spectrum obtained for the Mg-added LiCoO 2 of Examples 1 to 3 and Comparative Examples 1 to 4 It was shown in 3.
  • the high energy side spectral intensity minimum point was a value of less than 1312.5 eV, but in all of Mg-added LiCoO 2 of Examples 1 to 3, the high energy side The spectral intensity minimum point was 1312.5 eV or more.
  • the initial charge / discharge efficiency (%) (discharge capacity / charge capacity) ⁇ 100) was calculated using the obtained charge capacity and discharge capacity.
  • the above initial charge / discharge efficiency is calculated for each of the three batteries of Examples 1 to 3 and Comparative Examples 1 to 4, and the initial charge / discharge efficiencies of the three batteries are averaged (arithmetic average). Asked. The results are shown in Table 3.
  • Table 1 shows the synthesis conditions of Mg-added LiCoO 2 in Examples 1 to 3 and Comparative Example 4. 1) The raw material mixing ratio indicates the atomic molar ratio of Li: Co: Mg contained in the mixed state before firing.
  • Table 2 shows the synthesis conditions of Mg-added LiCoO 2 in Comparative Examples 1 to 3. 2)
  • the solid solution amount (mol%) of Mg indicates a value relative to Co.
  • the raw material mixing ratio indicates the atomic molar ratio of Li: Co: Mg contained in the mixed state before firing.
  • Table 3 shows the evaluation results of the high energy side spectral intensity minimum points of Mg-added LiCoO 2 of Examples 1 to 3 and Comparative Examples 1 to 4, and the initial charge / discharge efficiency of the coin-type battery.
  • the initial charge / discharge efficiency is shown as an average value of the initial charge / discharge efficiencies of the three batteries.
  • FIG. 8 shows Mg XANES spectra of Example 1 and Comparative Example 3.
  • the position shown by the arrow in FIG. 8 is the position of the high energy side spectral intensity minimum point.
  • the high energy side spectral intensity minimum point is 1312.5 eV or higher, whereas in Comparative Example 3 in which the initial charge / discharge characteristic is reduced, high energy is obtained.
  • the side spectral intensity minimum point is less than 1312.5 eV.
  • FIG. 9 shows the results obtained by theoretical calculation of the XANES spectrum when Mg occupies the Co site and Li site in LiCoO 2 . From FIG. 9, the high energy side spectral intensity minimum point has a correlation with the amount of Mg occupying the Co site and Li site, and the high energy side spectral intensity minimum point when Mg occupies the Li site is , Mg becomes higher than the high energy side spectral intensity minimum point when the Co site is occupied.
  • Example 1 showing good initial charge / discharge characteristics
  • the amount of Mg occupying the Li site is larger than that in Comparative Example 3 in which the initial charge / discharge characteristics are reduced, and thus high energy is obtained. It is considered that the side spectral intensity minimum point is shifted to the high energy side.
  • the present technology can be applied to a secondary battery such as a square type or a coin type, and the present technology can be applied to a flexible battery mounted on a wearable terminal such as a smart watch, a head-mounted display, or iGlass (registered trademark). It is also possible to apply technology.
  • the present technology is applied to the wound type and stack type secondary batteries.
  • the structure of the battery is not limited to this, for example, The present technology can also be applied to a secondary battery having a structure in which a positive electrode and a negative electrode are folded.
  • the present technology is applied to a lithium ion secondary battery and a lithium ion polymer secondary battery have been described.
  • the types of batteries to which the present technology can be applied are limited thereto. Yes.
  • the present technology may be applied to a bulk type all solid state battery.
  • the configuration in which the electrode includes the current collector and the active material layer has been described as an example.
  • the configuration of the electrode is not limited thereto.
  • the electrode may be composed of only the active material layer.
  • the present technology can also employ the following configurations.
  • (1) Including a lithium transition metal composite oxide having a layered rock salt type structure, In the X-ray absorption fine structure spectrum measured in an uncharged state, an X-ray absorption edge giving an intensity of 0.5 exists within the range where the X-ray energy is 1302 eV or more and 1312 eV or less, and the peak has the absorption edge.
  • the positive electrode active material whose high energy side spectrum intensity minimum point in the peak of the lowest energy side except a pre-edge peak among groups is 1312.5 eV or more.
  • (2) The positive electrode active material according to (1), wherein the lithium transition metal composite oxide includes cobalt and magnesium.
  • the positive electrode active material according to (2) wherein a part of the lithium and a part of the cobalt are substituted with magnesium.
  • the lithium transition metal composite oxide is the positive electrode active material according to (1), in which a part of Li and part of Co in LiCoO 2 are substituted with Mg.
  • the lithium transition metal composite oxide is obtained by replacing part of Li and part of Co in the lithium transition metal composite oxide represented by the following formula (1) with Mg: Positive electrode active material.
  • Li x Co 1-y M y O 2-z ⁇ (1) (In the formula (1), M is Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn, Mo, Sn, W, Zr, Y, Nb, Ca, Sr, Bi, Na, K.
  • a battery pack comprising: (12) The battery according to (9) or (10) is provided, An electronic device that receives power from the battery.
  • the battery according to (9) or (10) is provided, A power storage device that supplies electric power to an electronic device connected to the battery.
  • a power information control device that transmits and receives signals to and from other devices via a network, The power storage device according to (14), wherein charge / discharge control of the battery is performed based on information received by the power information control device.
  • the battery according to (9) or (10) is provided, An electric power system that receives supply of electric power from the battery.

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Abstract

La présente invention concerne un matériau actif d'électrode positive contenant un oxyde composite de métal de transition de lithium ayant une structure de sel gemme en couches. Dans le spectre de structure fine d'absorption de rayons x mesuré sur le matériau actif d'électrode positive dans l'état non chargé, un bord d'absorption de rayons x produisant une intensité de 0,5 est présent dans la plage d'énergie de rayons x de 1302-1312 eV ; et, à l'exclusion des pics de pré-bord, à l'intérieur d'un groupe de pics ayant ce bord d'absorption, le point d'intensité spectrale minimale sur le côté à haute énergie dans le pic sur le côté à énergie la plus basse est à 1312,5 eV ou plus.
PCT/JP2017/038625 2017-01-23 2017-10-26 Matériau actif d'électrode positive, électrode positive, batterie, bloc-batterie, dispositif électronique, véhicule électrique, dispositif de stockage électrique, et système d'alimentation électrique Ceased WO2018135061A1 (fr)

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