WO2022186211A1 - 電池及び電池の製造方法 - Google Patents
電池及び電池の製造方法 Download PDFInfo
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- WO2022186211A1 WO2022186211A1 PCT/JP2022/008644 JP2022008644W WO2022186211A1 WO 2022186211 A1 WO2022186211 A1 WO 2022186211A1 JP 2022008644 W JP2022008644 W JP 2022008644W WO 2022186211 A1 WO2022186211 A1 WO 2022186211A1
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- Prior art keywords
- solid electrolyte
- positive electrode
- negative electrode
- battery
- active material
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Classifications
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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- 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
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- 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 a battery and a method of manufacturing a battery.
- This application claims priority based on Japanese Patent Application No. 2021-031357 filed in Japan on March 1, 2021, the content of which is incorporated herein.
- a sintering method and a powder molding method are examples of methods for manufacturing an all-solid-state battery.
- a negative electrode, a solid electrolyte layer, and a positive electrode are laminated and then sintered to form an all-solid battery.
- the powder molding method after laminating a negative electrode, a solid electrolyte layer, and a positive electrode, pressure is applied to form an all-solid battery.
- Materials that can be used for the solid electrolyte layer vary depending on the manufacturing method.
- Known solid electrolytes include oxide-based solid electrolytes, sulfide-based solid electrolytes, complex hydride-based solid electrolytes (such as LiBH4 ), and the like.
- Patent Document 1 discloses a solid electrolyte secondary battery having a positive electrode, a negative electrode, and a solid electrolyte composed of a compound represented by the general formula Li 3-2X M X In 1-Y M' Y L 6-Z L' Z. disclosed.
- M and M' are metal elements
- L and L' are halogen elements.
- X, Y and Z independently satisfy 0 ⁇ X ⁇ 1.5, 0 ⁇ Y ⁇ 1 and 0 ⁇ Z ⁇ 6.
- the positive electrode also includes a positive electrode layer containing a positive electrode active material containing Li element and a positive electrode current collector.
- the negative electrode also includes a negative electrode layer containing a negative electrode active material and a negative electrode current collector.
- Patent Document 2 discloses a solid electrolyte material represented by the following compositional formula (1). Li 6-3Z Y Z X 6 Formula (1) Here, 0 ⁇ Z ⁇ 2 is satisfied, and X is Cl or Br. Further, Patent Document 2 describes a battery in which at least one of a negative electrode and a positive electrode contains the solid electrolyte material.
- Patent Literature 3 describes an all-solid battery including an electrode active material layer having a first solid electrolyte material and a second solid electrolyte material.
- the first solid electrolyte material is a single-phase electron-ion mixed conductor, and is a material having an active material and an anion component in contact with the active material and different from the anion component of the active material.
- the second solid electrolyte material is an ionic conductor that is in contact with the first solid electrolyte material, has the same anion component as the first solid electrolyte material, and does not have electronic conductivity.
- the first solid electrolyte material is Li2ZrS3 .
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a battery with high charge/discharge efficiency and a method for manufacturing the same.
- a battery according to a first aspect includes a battery element comprising a positive electrode, a negative electrode, and a solid electrolyte layer between the positive electrode and the negative electrode, wherein the positive electrode, the negative electrode, and the solid electrolyte layer At least one of and includes a solid electrolyte represented by the following formula (1).
- E is at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf, and lanthanides
- G is Na, K, Rb, Cs, Mg, Ca
- Bi is an element
- D is at least one selected from the group consisting of CO 3 , SO 4 , BO 3 , PO 4 , NO 3 , SiO 3 , OH and O 2
- X is F, Cl, Br
- the water content in the accommodation space may be 600 ppmv or less.
- the method for manufacturing a battery according to the above aspect includes an element manufacturing step of sandwiching a solid electrolyte layer between a positive electrode and a negative electrode and pressure-molding them to manufacture a battery element; and at least one of the positive electrode, the negative electrode, and the solid electrolyte layer contains the solid electrolyte represented by the above formula (1), and the dew point in the accommodating step is -20. °C lower than -90 °C or higher.
- the battery according to the above aspect is excellent in charge/discharge efficiency.
- FIG. 1 is a perspective view of an all-solid-state battery according to an embodiment
- FIG. 1 is a cross-sectional view of an all-solid-state battery according to an embodiment
- FIG. 1 is a perspective view of an all-solid-state battery 100 according to this embodiment.
- An all-solid-state battery 100 shown in FIG. 1 includes a battery element 10 and an exterior body 20 .
- the battery element 10 is housed in the housing space K inside the exterior body 20 .
- FIG. 1 shows the state immediately before the battery element 10 is accommodated in the exterior body 20 .
- the battery element 10 has external terminals 12 and 14 electrically connected to the outside.
- the exterior body 20 has, for example, a metal foil 22 and resin layers 24 laminated on both sides of the metal foil 22 (see FIG. 2).
- the exterior body 20 is a metal laminate film in which a metal foil 22 is coated from both sides with polymer films (resin layers 24).
- the metal foil 22 is, for example, aluminum foil.
- the resin layer 24 is, for example, a polymer film such as polypropylene.
- the resin layer 24 may be the same or different on the inside and outside.
- a polymer with a high melting point such as polyethylene terephthalate (PET), polyamide (PA), etc.
- PE polyethylene
- PP polypropylene
- PVC polyvinyl chloride
- FEP fluoroethylene propylene resin
- CTFE trifluoroethylene chloride resin
- PVF vinylidene fluoride resin
- PFA perfluorinated alkoxy resin
- Materials having high heat resistance, oxidation resistance, reduction resistance, corrosion resistance, and weather resistance can be used. From the viewpoint of further improving heat resistance, oxidation resistance, reduction resistance, corrosion resistance, and weather resistance, a resin layer obtained by molding two or more kinds of resins into a matrix or a resin layer having a multilayer structure of two or more layers is used. You can use it.
- FIG. 2 is a cross-sectional view of the all-solid-state battery 100 according to this embodiment.
- the all-solid-state battery 100 includes a positive electrode 11 (positive electrode current collector 11A, positive electrode active material layer 11B), a negative electrode 13 (negative electrode current collector 13A, negative electrode active material layer 13B), a solid electrolyte layer 15, external terminals 12, 14, and an accommodation space K.
- the solid electrolyte layer 15 is, for example, between the positive electrode active material layer 11B and the negative electrode active material layer 13B.
- Battery element 10 has cathode current collector 11A/positive electrode active material layer 11B/solid electrolyte layer 15/negative electrode active material layer 13B/negative electrode active material layer 13A.
- the all-solid-state battery 100 is charged or discharged by giving and receiving electrons through the positive electrode current collector 11A and the negative electrode current collector 13A and by giving and receiving lithium ions through the solid electrolyte layer 15 .
- the all-solid-state battery 100 may be a laminated body in which the positive electrode 11, the negative electrode 13 and the solid electrolyte layer 15 are laminated, or a wound body.
- the all-solid-state battery 100 is used, for example, as a laminate battery, a prismatic battery, a cylindrical battery, a coin-shaped battery, a button-shaped battery, and the like.
- the amount of water in the housing space K between the battery element 10 and the exterior body 20 is preferably less than 1100 ppmv, for example, from the viewpoint of suppressing the generation of halogenated gas due to the reaction between the solid electrolyte and water. Suppression of halogenated gas suppresses deterioration of current collection function due to corrosion of metal parts (current collectors, conductive aids, storage containers, etc.) of the battery element 10, and can reduce locally uneven electrochemical reactions. Therefore, the charge/discharge efficiency of the all-solid-state battery 100 is improved.
- the amount of water contained in the housing space K can be measured by, for example, a capacitance moisture meter, Karl Fischer method, FTIR, GC/MS, tunable semiconductor laser light absorption spectroscopy, cavity ring-down spectroscopy, and atmospheric pressure ionization mass spectrometry. , and the like.
- the water content in the housing space K between the battery element 10 and the exterior body 20 is, for example, 600 ppmv or less. This is preferable from the viewpoint of suppressing the generation of halogenated gas due to the reaction between the solid electrolyte and moisture. Suppression of halogenated gas suppresses deterioration of the current collection function due to corrosion of the metal parts (current collector, conductive aid, storage container, etc.) of the battery element 10, and can suppress locally uneven electrochemical reactions. Therefore, the charge/discharge efficiency of the all-solid-state battery 100 is further improved.
- Solid electrolyte layer 15 contains a solid electrolyte.
- the solid electrolyte layer 15 contains, for example, a solid electrolyte represented by the following formula (1). Li 3+ ae E 1-b G b D c X de (1)
- E is a trivalent element.
- E is, for example, at least one element selected from the group consisting of Al, Sc, Y, Zr, Hf, and lanthanides.
- Lanthanides are La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
- E preferably contains Sc or Zr, particularly preferably Zr.
- E contains Sc or Zr, the ionic conductivity of the solid electrolyte increases.
- G is an element that is contained as necessary.
- G is Na, K, Rb, Cs, Mg, Ca, Sr, Ba, B, Si, Al, Ti, Cu, Sc, Y, Zr, Nb, Ag, In, Sn, Sb, Hf, Ta, W , Au, and Bi.
- the amount of lithium ions, which are carrier ions increases or decreases, the ionic conductivity increases, and the potential window on the reduction side widens.
- G in formula (1) may be a monovalent element selected from Na, K, Rb, Cs, and Ag among the above.
- G is a monovalent element, the resulting solid electrolyte has high ionic conductivity and a wide potential window on the reduction side.
- G is particularly preferably Na and/or Cs.
- G in formula (1) may be a divalent element selected from Mg, Ca, Ba, Sr, Cu, and Sn among the above.
- G is a divalent element, carrier ions increase, resulting in a solid electrolyte with high ionic conductivity and a wide potential window on the reduction side.
- G is particularly preferably Mg and/or Ca.
- G in formula (1) may be trivalent selected from Al, Y, In, Au, and Bi among the above.
- G is a trivalent element, the number of carrier ions increases, resulting in a solid electrolyte with high ionic conductivity.
- G is preferably any one selected from the group consisting of In, Au, and Bi.
- G in formula (1) may be Zr, Hf, or Sn, which are tetravalent elements among the above.
- G is a tetravalent element
- the solid electrolyte has high ionic conductivity.
- G particularly preferably contains Hf and/or Zr.
- G in formula (1) may be a pentavalent element selected from Nb, Sb, and Ta among the above.
- G is a pentavalent element, holes are formed to facilitate movement of carrier ions, resulting in a solid electrolyte with high ionic conductivity.
- G particularly preferably contains Sb and/or Ta.
- G in formula (1) may be W, which is a hexavalent element among the above.
- the solid electrolyte has high ionic conductivity.
- D in formula (1) is included as necessary.
- D is at least one selected from the group consisting of CO3 , SO4 , BO3 , PO4, NO3 , SiO3, OH and O2 .
- the potential window on the reduction side of the solid electrolyte becomes wide.
- D is preferably at least one selected from the group consisting of SO 4 , CO 3 , PO 4 and O 2 , particularly preferably SO 4 .
- SO 4 the stronger the covalent bond between D and E, the stronger the ionic bond between E and X. Therefore, it is presumed that the E in the compound is difficult to be reduced and the compound has a wide potential window on the reduction side.
- X in formula (1) is an essential element.
- X is at least one selected from the group consisting of F, Cl, Br and I;
- X has a large ionic radius per valence.
- Including X in the solid electrolyte increases the conductivity of lithium ions in the solid electrolyte.
- X preferably contains Cl.
- X preferably contains F in order to improve the balance between oxidation resistance and reduction resistance of the solid electrolyte.
- X preferably contains I in order to increase the resistance to reduction of the solid electrolyte.
- a is the above numerical value determined according to the valence of G.
- b is 0 or more and less than 0.5.
- the solid electrolyte represented by formula (1) contains E as an essential element, but may not contain G. If b is 0.1 or more, the effect obtained by including G in the solid electrolyte can be sufficiently obtained. Moreover, when b is less than 0.5, it is possible to suppress a decrease in the ionic conductivity of the solid electrolyte due to an excessive G content. b is preferably 0.45 or less.
- c is 0 or more and 5 or less. Therefore, D does not have to be contained in the solid electrolyte.
- c is preferably 0.1 or more.
- c is 0.1 or more, the effect of widening the potential window on the reduction side of the solid electrolyte due to the inclusion of D can be sufficiently obtained. If the content of D is too large, there is a concern that the ionic conductivity of the solid electrolyte will decrease due to the narrow space in which carrier ions move. The following are preferable.
- d is greater than 0 and less than or equal to 7.1.
- d is 7.1 or less, the binding force to carrier ions due to the excessive content of X can be suppressed, and a decrease in the ionic conductivity of the solid electrolyte can be suppressed, which is preferable.
- e is 0 or more and 2 or less. Also, 0 ⁇ de.
- formula (1) satisfies 0 ⁇ e ⁇ 2 and 0 ⁇ de, the Li content and X content contained in the compound represented by formula (1) are appropriate, and the ionic conductivity of the solid electrolyte is increase.
- the solid electrolyte represented by Formula (1) preferably has Zr as E and Cl as X.
- the compound represented by Formula (1) is preferably Li 2 ZrCl 6 , Li 2 ZrSO 4 Cl 4 , or Li 2 ZrOCl 4 as a solid electrolyte having a good balance between ionic conductivity and potential window. .
- Solid electrolyte layer 15 may contain other substances in addition to the solid electrolyte represented by formula (1).
- the ionic conductivity of the solid electrolyte layer 15 increases. Although the details of the reason are unknown, it is considered as follows.
- the above other substances have the function of helping the ionic connection between the particles of the solid electrolyte represented by formula (1). It is presumed that this reduces the grain boundary resistance between particles of the solid electrolyte represented by the formula (1) and increases the ionic conductivity of the solid electrolyte layer 15 as a whole.
- the content of other substances in the solid electrolyte layer 15 is, for example, 0.1% by mass or more and 1.0% by mass or less.
- the content of other substances is 0.1% by mass or more, the effect of reducing the grain boundary resistance between grains becomes remarkable. Further, when the content of other substances is 1.0% by mass or less, the solid electrolyte layer 15 becomes hard, and an interface that assists ionic connection between particles does not become difficult to form satisfactorily between particles. .
- the solid electrolyte layer 15 may contain a binder.
- the solid electrolyte layer 15 is made of, for example, fluorine-based resins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), imide-based resins such as cellulose, styrene-butadiene rubber, ethylene-propylene rubber, polyimide resin, and polyamide-imide resin. It may also contain a resin, an ion conductive polymer, and the like.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- imide-based resins such as cellulose, styrene-butadiene rubber, ethylene-propylene rubber, polyimide resin, and polyamide-imide resin. It may also contain a resin, an ion conductive polymer, and the like.
- Ion-conductive polymers are, for example, monomers of polymer compounds (polyether polymer compounds such as polyethylene oxide and polypropylene oxide, polyphosphazenes, etc.) and lithium salts such as LiClO 4 , LiBF 4 , LiPF 6 and LiTFSI. Alternatively, it is a compound obtained by combining an alkali metal salt mainly composed of lithium.
- the content of the binder is preferably 0.1% by volume or more and 30% by volume or less of the entire solid electrolyte layer 15 .
- the binder helps maintain good bonding between the solid electrolytes of the solid electrolyte layer 15, prevents cracks between the solid electrolytes, and suppresses a decrease in ionic conductivity and an increase in grain boundary resistance. .
- the positive electrode 11 has, for example, a positive electrode current collector 11A and a positive electrode active material layer 11B containing a positive electrode active material.
- the positive electrode current collector 11A preferably has high conductivity.
- metals such as silver, palladium, gold, platinum, aluminum, copper, nickel, titanium, stainless steel, alloys thereof, or conductive resins can be used.
- the positive electrode current collector 11A may be in the form of powder, foil, punched, or expanded. From the viewpoint of not lowering the current collecting function of the positive electrode current collector, it is preferable to dehydrate the material by heat vacuum drying or the like in a glove box in which argon gas is circulated, and then store the material in a glass bottle, an aluminum laminate bag, or the like.
- the dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 90° C. or higher.
- (Positive electrode active material layer) Mixing of the positive electrode material mixture used for the positive electrode active material layer 11B is preferably performed using an agate mortar, a pot mill, a blender, a hybrid mixer, or the like, for example, in a glove box in which argon gas is circulated.
- the dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 90° C. or higher from the viewpoint of good pressure molding.
- the oxygen concentration in the glove box is, for example, 1 ppm or less.
- the positive electrode active material layer 1B is formed on one side or both sides of the positive electrode current collector 1A.
- the positive electrode active material layer 1B contains a positive electrode active material.
- the positive electrode active material layer 1B may contain, for example, the solid electrolyte represented by the above formula (1).
- the positive electrode active material layer 1B may also contain a conductive aid and a binder.
- the positive electrode active material contained in the positive electrode active material layer 11B includes, for example, lithium-containing transition metal oxides, transition metal fluorides, polyanions, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, and transition metal oxynitrides. is.
- the positive electrode active material is not particularly limited as a positive electrode active material as long as it can reversibly progress lithium ion release and absorption, and lithium ion desorption and insertion, and is used in known lithium ion secondary batteries. can be used.
- the positive electrode active material used for the positive electrode active material layer 11B is dehydrated by heat vacuum drying or the like in a glove box in which argon gas is circulated from the viewpoint of good pressure molding, and is stored in a glass bottle, an aluminum laminate bag, or the like. good.
- the dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 90° C. or higher.
- a positive electrode active material that does not contain lithium can be used by starting the battery from discharging.
- positive electrode active materials include lithium-free metal oxides ( MnO2 , V2O5 , etc.), lithium-free metal sulfides (MoS2, etc.), lithium - free fluorides ( FeF3 , VF3 , etc.). ) and the like.
- the negative electrode 13 has, for example, a negative electrode current collector 13A and a negative electrode active material layer 13B containing a negative electrode active material.
- the negative electrode current collector 13A preferably has high conductivity. For example, it is preferable to use metals such as silver, palladium, gold, platinum, aluminum, copper, nickel, stainless steel, iron, alloys thereof, or conductive resins.
- the negative electrode current collector 13A may be in the form of powder, foil, punched, or expanded. From the viewpoint of not lowering the current collecting function of the negative electrode current collector, it is preferable to dehydrate the material by heat vacuum drying or the like in a glove box in which argon gas is circulated, and then store the material in a glass bottle, an aluminum laminate bag, or the like. The dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 90° C. or higher.
- Negative electrode active material layer Mixing of the negative electrode mixture used for the negative electrode active material layer 13B is preferably performed, for example, in a glove box in which argon gas is circulated, using an agate mortar, a pot mill, a blender, a hybrid mixer, or the like.
- the dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 90° C. or higher from the viewpoint of good pressure molding.
- the oxygen concentration in the glove box is, for example, 1 ppm or less.
- the negative electrode active material layer 13B is formed on one side or both sides of the negative electrode current collector 13A.
- the negative electrode active material layer 13B contains a negative electrode active material.
- the negative electrode active material layer 13B may contain, for example, the solid electrolyte represented by the above formula (1). Further, the negative electrode active material layer 13B may contain a conductive aid and a binder.
- the negative electrode active material contained in the negative electrode active material layer 13B may be any compound that can occlude and release mobile ions, and negative electrode active materials used in known lithium ion secondary batteries can be used.
- the negative electrode active material include carbon materials such as simple alkali metals, alkali metal alloys, graphite (natural graphite, artificial graphite), carbon nanotubes, non-graphitizable carbon, easily graphitizable carbon, low-temperature fired carbon, aluminum, silicon, Metals that can combine with metals such as alkali metals such as tin, germanium and their alloys, SiO x (0 ⁇ x ⁇ 2), oxides such as iron oxide, titanium oxide, tin dioxide, lithium titanate (Li 4 Ti 5 O 12 ) and other lithium metal oxides.
- the negative electrode active material used for the negative electrode active material layer 13B is dehydrated by heat vacuum drying or the like in a glove box in which argon gas is circulated, and stored in a glass bottle, an aluminum laminate bag, or the like, from the viewpoint of good pressure molding. good.
- the dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 90° C. or higher.
- the conductive aid is not particularly limited as long as it improves the electron conductivity of the positive electrode active material layer 11B and the negative electrode active material layer 13B, and known conductive aids can be used.
- Conductive agents include, for example, carbon-based materials such as graphite, carbon black, graphene, and carbon nanotubes, metals such as gold, platinum, silver, palladium, aluminum, copper, nickel, stainless steel, iron, and conductive oxides such as ITO. or mixtures thereof.
- the conductive aid may be in the form of powder or fiber.
- the material it is preferable to dehydrate the material by heat vacuum drying or the like in a glove box in which argon gas is circulated, and store the material in a glass bottle or an aluminum laminate bag.
- the dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 90° C. or higher.
- the binders are the positive electrode current collector 11A and the positive electrode active material layer 11B, the negative electrode current collector 13A and the negative electrode active material layer 13B, the positive electrode active material layer 11B, the negative electrode active material layer 13B and the solid electrolyte layer 15, and the positive electrode active material.
- Various materials forming the layer 11B and various materials forming the negative electrode active material layer 13B are joined.
- the binder is preferably used within a range that does not impair the functions of the positive electrode active material layer 11B and the negative electrode active material layer 13B.
- Any binding material may be used as long as the above bonding is possible, and examples thereof include fluororesins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- the binder for example, cellulose, styrene/butadiene rubber, ethylene/propylene rubber, polyimide resin, polyamideimide resin, or the like may be used.
- a conductive polymer having electronic conductivity or an ion-conductive polymer having ionic conductivity may be used as the binder.
- Examples of conductive polymers having electronic conductivity include polyacetylene. In this case, it is not necessary to add a conductive additive because the binder also exhibits the function of the conductive additive particles.
- the ion conductive polymer having ion conductivity for example, one that conducts lithium ions can be used, and polymer compounds (polyether polymer compounds such as polyethylene oxide and polypropylene oxide, polyphosphazene etc.) with a lithium salt such as LiClO 4 , LiBF 4 , LiPF 6 , LiTFSI, LiFSI, or an alkali metal salt mainly composed of lithium.
- Polymerization initiators used for compositing include, for example, photopolymerization initiators or thermal polymerization initiators compatible with the above monomers. Properties required for the binder include oxidation/reduction resistance and good adhesiveness.
- the content of the binder in the positive electrode active material layer 11B is not particularly limited, it is preferably 0.5 to 30% by volume of the positive electrode active material layer from the viewpoint of lowering the resistance of the positive electrode active material layer 11B. 0% by volume is preferable from the viewpoint of improving the energy density.
- the content of the binder in the negative electrode active material layer 13B is not particularly limited, it is preferably 0.5 to 30% by volume of the negative electrode active material layer from the viewpoint of lowering the resistance of the negative electrode active material layer 13B. 0% by volume is preferable from the viewpoint of improving the energy density.
- At least one of the positive electrode active material layer 11B, the negative electrode active material layer 13B, and the solid electrolyte layer 15 contains a non-aqueous electrolyte, an ionic liquid, or a gel electrolyte for the purpose of improving rate characteristics, which are one of battery characteristics. may be
- a method for producing the solid electrolyte represented by Formula (1) will be described.
- a solid electrolyte is obtained by mixing and reacting raw material powders at a predetermined molar ratio so as to obtain a desired composition. Any reaction method can be used, and mechanochemical milling, sintering, melting, liquid phase, solid phase, and the like can be used.
- a solid electrolyte can be produced, for example, by a mechanochemical milling method.
- a planetary ball mill device is prepared.
- a planetary ball mill is a device that puts media (hard balls for grinding or promoting mechanochemical reactions) and materials into a special container, rotates and revolves, and grinds the materials or causes mechanochemical reactions between materials. be.
- a predetermined amount of zirconia balls are prepared in a zirconia container in a glove box in which argon gas is circulated.
- the dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 90° C. or higher.
- the oxygen concentration in the glove box is, for example, 1 ppm or less.
- predetermined raw materials are prepared in a zirconia container at a predetermined molar ratio so as to obtain the desired composition, and the container is sealed with a zirconia lid.
- the raw material may be powder or liquid.
- titanium chloride (TiCl 4 ) and tin chloride (SnCl 4 ) are liquid at room temperature.
- a mechanochemical reaction occurs.
- a powdery solid electrolyte composed of a compound having a desired composition can be obtained.
- the all-solid-state battery according to this embodiment can be manufactured, for example, by a method including an element manufacturing step of manufacturing the battery element 10 and a housing step of housing the battery element 10 in the exterior body 20 .
- the battery element 10 according to this embodiment is manufactured using, for example, a powder molding method.
- the powder compacting method is carried out in an environment where the dew point is lower than -20°C and higher than -90°C.
- the powder forming method is preferably carried out in an environment with a dew point of -30°C or lower and -85°C or higher.
- the powder forming method is performed by adjusting the dew point in the glove box, for example.
- a resin holder having a through hole in the center, a lower punch, and an upper punch are prepared.
- a metal holder made of die steel may be used instead of the resin holder in order to improve moldability.
- the diameter of the through hole of the resin holder is, for example, 10 mm, and the diameters of the lower and upper punches are, for example, 9.99 mm.
- a lower punch is inserted from below the through-hole of the resin holder, and a solid electrolyte in powder form is introduced from the opening side of the resin holder.
- an upper punch is inserted onto the charged powdery solid electrolyte, placed on a pressing machine, and pressed.
- the press pressure is, for example, 373 MPa.
- the powdered solid electrolyte is pressed by an upper punch and a lower punch in a resin holder to form the solid electrolyte layer 15 .
- the upper punch is once removed, and the material for the positive electrode active material layer is put on the upper punch side of the solid electrolyte layer 15 . After that, the upper punch is inserted again and pressed.
- the press pressure is, for example, 373 MPa.
- the material of the positive electrode active material layer becomes the positive electrode active material layer 11B by pressing.
- the lower punch is temporarily removed, and the material for the negative electrode active material layer is put on the lower punch side of the solid electrolyte layer 15 .
- the sample is turned upside down, and the material for the negative electrode active material layer is put on the solid electrolyte layer 15 so as to face the positive electrode active material layer 11B.
- the lower punch is inserted again and pressed.
- the press pressure is, for example, 373 MPa.
- the material of the negative electrode active material layer becomes the negative electrode active material layer 13B by pressing.
- the upper punch is once removed, and the positive electrode current collector 11A and the upper punch are inserted in this order onto the positive electrode active material layer 11B.
- the lower punch is once removed, and the negative electrode current collector 13A and the lower punch are inserted in this order onto the negative electrode active material layer 13B.
- the positive electrode current collector 11A and the negative electrode current collector 13A are, for example, aluminum foil or copper foil with a diameter of 10 mm.
- the battery element 10 is a stainless steel disk and a bakelite disk having screw holes at four locations as required, and is composed of stainless steel disk/bakelite disk/upper punch/battery element 10/lower punch/bakelite. It is also possible to load the discs in the order of stainless disc/stainless disc and tighten the four screws. This is preferable from the viewpoint of further improving the bonding between the upper punch and the positive electrode current collector 11A, the positive electrode current collector 11A and the positive electrode active material 11B, the lower punch and the negative electrode current collector 13A, and the negative electrode current collector 13A and the negative electrode active material 13B. . Battery element 10 may be a similar mechanism with a shape-retaining function.
- the accommodation step is performed, for example, in a glove box in which argon gas is circulated.
- the dew point in the glove box should be lower than -20°C and higher than -90°C.
- the dew point in the glove box is preferably ⁇ 30° C. or lower and ⁇ 85° C. or higher.
- the oxygen concentration in the glove box is, for example, 1 ppm or less.
- Screws are inserted into the screw holes provided on the sides of the upper punch and the lower punch, respectively, and inserted into the exterior body to which the external terminals 12 and 14 are attached. , 14 are connected with lead wires or the like. After that, it is housed in the exterior body 20, and the opening of the exterior body 20 is heat-sealed to be sealed. The exterior body 20 improves the weather resistance of the all-solid-state battery 100 .
- the method for manufacturing the battery element 10 described above has been described by taking the powder molding method as an example, it may be manufactured by a sheet molding method containing a resin.
- the sheet molding method is also made in the glove box.
- the sheet molding method is also carried out in an environment where the dew point is lower than -20°C and higher than -90°C.
- the sheet molding method is preferably carried out in an environment with a dew point of -30°C or lower and -85°C or higher.
- the sheet molding method is performed by adjusting the dew point in the glove box, for example.
- a solid electrolyte paste containing a powdery solid electrolyte is prepared.
- the solid electrolyte layer 15 is fabricated by applying the prepared solid electrolyte paste to a PET film, a fluororesin film, or the like, drying, preforming, and peeling.
- the positive electrode 11 is manufactured by applying a positive electrode active material paste containing a positive electrode active material onto the positive electrode current collector 11A, drying it, and temporarily molding it to form a positive electrode active material layer 11B.
- the negative electrode 13 is manufactured by applying a paste containing a negative electrode active material onto the negative electrode current collector 13A, drying it, and temporarily molding it to form the negative electrode active material layer 13B.
- the positive electrode 11, the negative electrode 13, and the solid electrolyte layer 15 can be punched into the required size and shape.
- the solid electrolyte layer 15 is sandwiched between the positive electrode 11 and the negative electrode 13 so that the positive electrode active material layer 11B and the negative electrode active material layer 13B face each other, and the whole is pressed and bonded.
- the battery element 10 of the present embodiment is obtained.
- the all-solid-state battery 100 according to the present embodiment is manufactured in an environment in which the moisture content is adjusted.
- the deterioration of the current collection function due to corrosion of the current collector, conductive aid, storage container, etc.) is suppressed, and the locally uneven electrochemical reaction can be suppressed, so the charge and discharge efficiency of the all-solid-state battery 100 is improved.
- Example 1 Synthesis of solid electrolyte-
- a solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 50 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh. As a result, Li 2 ZrSO 4 Cl 4 powder was obtained as a solid electrolyte.
- the positive electrode mixture was weighed and mixed in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm, in which argon gas was circulated.
- Lithium cobaltate (LiCoO 2 ):Li 2 ZrSO 4 Cl 4 :carbon black 77:18:5 parts by weight, and mixed for 5 minutes in an agate mortar to obtain a positive electrode mixture.
- a battery element consisting of a positive electrode current collector/positive electrode mixture layer/electrolyte layer/negative electrode mixture layer/negative electrode current collector was produced by a powder molding method. .
- the battery element was fabricated in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- a resin holder having a through hole in the center, a lower punch made of SKD11 material, and an upper punch were prepared. A lower punch was inserted from below the through-hole of the resin holder, and 110 mg of solid electrolyte was charged from the opening side of the resin holder. The upper punch was then inserted over the solid electrolyte.
- This first unit was placed on a press and pressed at a pressure of 373 MPa to form a solid electrolyte layer. The first unit was removed from the press and the upper punch removed.
- the upper punch was once removed, and the positive electrode current collector (aluminum foil, diameter 10 mm, thickness 20 um) and the upper punch were sequentially inserted on the positive electrode active material layer.
- the lower punch was once removed, and the negative electrode current collector (copper foil, diameter 10 mm, thickness 10 um) and the lower punch were inserted on the negative electrode active material layer in this order. In this way, a battery element composed of positive electrode current collector/positive electrode active material layer/solid electrolyte layer/negative electrode active material layer/negative electrode current collector was produced.
- the obtained battery element was housed in an outer package.
- the battery elements were housed in a glove box having a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- a stainless steel disk and a bakelite disk with a diameter of 50 mm and a thickness of 5 mm having four screw holes were prepared, and battery elements were set as follows.
- the stainless disc/bakelite disc/upper punch/battery element/lower punch/bakelite disc/stainless disc were stacked in this order, and screws were tightened at four locations to produce a fourth unit. Screws for connecting external terminals were inserted into the screw holes on the sides of the upper and lower punches.
- An A4 size aluminum laminate bag was prepared as an outer package to enclose the 4th unit.
- An aluminum foil (width 4 mm, length 40 mm, thickness 100 ⁇ m) wrapped with maleic anhydride-grafted polypropylene (PP) and nickel foil (width 4 mm, length 40 mm in thickness and 100 ⁇ m in thickness) were thermally bonded with a space therebetween so as not to cause a short circuit.
- the positive electrode current collector and the negative electrode current collector were taken out, the surface was observed using an optical microscope (50x objective lens), and the unused positive electrode current collector or negative electrode current collector The areas of the portions with different contrasts were obtained.
- the moisture content in the storage space K was measured using a capacitance transmitter (Easidew Online, +ED Transmitter-99J, manufactured by Michelle) in a glove box with a dew point of -90°C, an oxygen concentration of 1 ppm, and a temperature of 25°C with circulating argon gas. measured within.
- a capacitance transmitter Essidew Online, +ED Transmitter-99J, manufactured by Michelle
- the charge/discharge test was performed in a constant temperature bath at 25°C. Charging was performed at 0.05C and constant current and constant voltage up to 2.8V. Charging was terminated until the current became 1/40C. A constant current discharge was performed at 0.05C to 1.3V. Then, the initial charge/discharge efficiency was calculated from the following formula (2).
- Example 1 The results of Example 1 are summarized in Table 1 below.
- Example 2-8 Comparative Examples 1-2
- Examples 2 to 8 and Comparative Examples 1 to 2 were the same as in Example 1, except that the battery elements were housed in a glove box with a dew point of -20 to -85°C and an oxygen concentration of 1 ppm in which argon gas was circulated.
- the discoloration of the positive electrode current collector and the negative electrode current collector was observed, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
- Examples 2-8 The results of Comparative Examples 1-2 are summarized in Table 1 below.
- Example 9 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- LiCl and ZrCl 4 as raw material powders were weighed so that the molar ratio was 2:1.
- the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 50 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh. Li 2 ZrCl 6 was thus obtained as a solid electrolyte.
- Example 9 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the color change observation of the positive electrode current collector and the negative electrode current collector, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Example 9 are summarized in Table 1 below.
- Example 10-16 Comparative Examples 3-4
- Examples 10 to 16 and Comparative Examples 3 to 4 were the same as Example 9, except that the battery elements were housed in a glove box with a dew point of -20 to -85°C and an oxygen concentration of 1 ppm in which argon gas was circulated.
- the discoloration of the positive electrode current collector and the negative electrode current collector was observed, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
- Table 1 The results of Examples 10-16 and Comparative Examples 3-4 are summarized in Table 1 below.
- Example 17 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- Li 2 O and ZrCl 4 as raw material powders were weighed so as to have a molar ratio of 1:1.
- the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 50 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh. Li 2 ZrOCl 4 was thus obtained as a solid electrolyte.
- Example 17 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the color change observation of the positive electrode current collector and the negative electrode current collector, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Example 17 are summarized in Table 2 below.
- Example 18-24, Comparative Examples 5-6) Examples 18 to 24 and Comparative Examples 5 to 6 were the same as in Example 17, except that the battery elements were housed in a glove box with a dew point of -20 to -85°C and an oxygen concentration of 1 ppm in which argon gas was circulated. In the same manner as in (2), the discoloration of the positive electrode current collector and the negative electrode current collector was observed, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
- Table 2 The results of Examples 18-24 and Comparative Examples 5-6 are summarized in Table 2 below.
- Example 25 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- raw material powders Li 2 SO 4 and ZrCl 4 were weighed so that the molar ratio was 0.9:1.
- the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 50 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh. As a result, Li 1.8 Zr(SO 4 ) 0.9 Cl 4 was obtained as a solid electrolyte.
- Example 25 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the color change observation of the positive electrode current collector and the negative electrode current collector, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Example 25 are summarized in Table 2 below.
- Example 26-32, Comparative Examples 7-8 Examples 26 to 32 and Comparative Examples 7 to 8 were similar to Example 25, except that the battery elements were housed in a glove box with a dew point of -20 to -85°C and an oxygen concentration of 1 ppm in which argon gas was circulated. In the same manner as in (2), the discoloration of the positive electrode current collector and the negative electrode current collector was observed, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
- Table 2 The results of Examples 26-32 and Comparative Examples 7-8 are summarized in Table 2 below.
- Example 33 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- raw material powders Li 2 SO 4 and ZrCl 4 were weighed so that the molar ratio was 1.1:1.
- the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 50 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh.
- Li 2.2 Zr(SO 4 ) 1.1 Cl 4 was obtained as a solid electrolyte.
- Example 33 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the color change observation of the positive electrode current collector and the negative electrode current collector, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Example 33 are summarized in Table 3 below.
- Example 34-40 Comparative Examples 9-10
- Example 34 to 40 and Comparative Examples 9 to 10 were similar to Example 33, except that the battery elements were housed in a glove box with a dew point of -20 to -85°C and an oxygen concentration of 1 ppm in which argon gas was circulated.
- the discoloration of the positive electrode current collector and the negative electrode current collector was observed, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
- Table 3 The results of Examples 34-40 and Comparative Examples 9-10 are summarized in Table 3 below.
- Example 41 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- raw material powders Li 2 SO 4 and ZrCl 4 were weighed so that the molar ratio was 1.5:1.
- the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 50 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh. As a result, Li 3 Zr(SO 4 ) 1.5 Cl 4 was obtained as a solid electrolyte.
- Example 41 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the color change observation of the positive electrode current collector and the negative electrode current collector, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Example 41 are summarized in Table 3 below.
- Examples 42-48, Comparative Examples 11-12 were the same as Example 41, except that the battery elements were housed in a glove box with a dew point of -20 to -85°C and an oxygen concentration of 1 ppm in which argon gas was circulated.
- the discoloration of the positive electrode current collector and the negative electrode current collector was observed, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
- the results of Examples 42-48 and Comparative Examples 11-12 are summarized in Table 3 below.
- Example 49 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- raw material powders Li 3 PO 4 and ZrCl 4 were weighed in a molar ratio of 0.33:1.
- the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 50 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh.
- LiZr(PO 4 ) 0.33 Cl 4 was obtained as a solid electrolyte.
- Example 49 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the color change observation of the positive electrode current collector and the negative electrode current collector, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Example 49 are summarized in Table 4 below.
- Examples 50 to 56 and Comparative Examples 13 to 14 were the same as Example 49, except that the battery elements were housed in a glove box with a dew point of -20 to -85°C and an oxygen concentration of 1 ppm in which argon gas was circulated.
- the discoloration of the positive electrode current collector and the negative electrode current collector was observed, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
- the results of Examples 50-56 and Comparative Examples 13-14 are summarized in Table 4 below.
- Example 57 the solid electrolyte was synthesized in a glove box with a dew point of ⁇ 85° C. and an oxygen concentration of 1 ppm in which argon gas was circulated.
- raw material powders Li 3 PO 4 and YCl 3 were weighed so that the molar ratio was 0.33:1.
- the weighed raw material powder was placed in a Zr container together with Zr balls having a diameter of 5 mm, and mechanochemical milling was performed using a planetary ball mill. The treatment was carried out by mixing for 50 hours at a rotation speed of 500 rpm and then sieving through a 200 ⁇ m mesh. LiY(PO 4 ) 0.33 Cl 3 was thus obtained as a solid electrolyte.
- Example 57 differs from Example 1 in that the composition of the solid electrolyte was changed. Other conditions were the same as in Example 1, and the color change observation of the positive electrode current collector and the negative electrode current collector, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured. The results of Example 57 are summarized in Table 4 below.
- Examples 58-64, Comparative Examples 15-16 were similar to Example 49, except that the battery elements were housed in a glove box with a dew point of -20 to -85°C and an oxygen concentration of 1 ppm in which argon gas was circulated. In the same manner as in (2), the discoloration of the positive electrode current collector and the negative electrode current collector was observed, the water content in the housing space K, and the initial charge/discharge efficiency of the all-solid-state battery were measured.
- the results of Examples 58-64 and Comparative Examples 15-16 are summarized in Table 4 below.
- the water content in the housing space K is less than 1100 ppmv, the discoloration of the positive electrode current collector and the negative electrode current collector is suppressed, and the all-solid-state batteries according to Comparative Examples 1 to 16 Both charge and discharge efficiencies were better than those of batteries.
- the water content in the housing space K exceeded 1100 ppmv, discoloration of the positive electrode current collector and the negative electrode current collector could not be suppressed, and the charge and discharge efficiency was reduced. was also poor.
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Abstract
Description
本願は、2021年3月1日に、日本に出願された特願2021-031357号に基づき優先権を主張し、その内容をここに援用する。
Li6-3ZYZX6 式(1)
ここで、0<Z<2、を満たし、Xは、ClまたはBrである。
また、特許文献2には、負極と正極のうちの少なくとも1つは、前記固体電解質材料を含む電池が記載されている。
Li3+a-eE1-bGbDcXd-e (1)
式(1)中において、EはAl、Sc、Y、Zr、Hf、ランタノイドからなる群から選択される少なくとも1種の元素であり、Gは、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、B、Si、Al、Ti、Cu、Sc、Y、Zr、Nb、Ag、In、Sn、Sb、Hf、Ta、W、Au、Biからなる群から選択される少なくとも1種の元素であり、DはCO3、SO4、BO3、PO4、NO3、SiO3、OH、O2からなる群から選択される少なくとも1種であり、XはF、Cl、Br、Iからなる群から選択される少なくとも1種の元素であり、n=(Eの価数)-(Gの価数)としたときa=nbであり、0≦b<0.5、0≦c≦5、0<d≦7.1、0≦e≦2、0<d-eである。また第1の態様にかかる電池は前記電池要素を覆う外装体をさらに備え、前記電池要素と前記外装体との間の収容空間における水分量は、1100ppmv未満である。
固体電解質層15は、固体電解質を含む。固体電解質層15は、例えば、下記式(1)で表される固体電解質を含む。
Li3+a-eE1-bGbDcXd-e (1)
図2に示すように、正極11は、例えば、正極集電体11Aと、正極活物質を含む正極活物質層11Bとを有する。
正極集電体11Aは、導電率が高いことが好ましい。例えば、銀、パラジウム、金、プラチナ、アルミニウム、銅、ニッケル、チタン、ステンレス等の金属およびそれらの合金、または導電性樹脂を用いることができる。正極集電体11Aは、粉体、箔、パンチング、エクスパンドの各形態であっても良い。正極集電体の集電機能を低下させない観点からアルゴンガスを循環させたグローブボックス内で、加熱真空乾燥などにより脱水しガラス瓶やアルミニウムラミネート袋などを用いて保管すると良い。グローブボックス内の露点は、-30℃以下-90℃以上とすることが好ましい。
正極活物質層11Bに用いる正極合剤の混合は、例えばアルゴンガスを循環させたグローブボックス内で、メノウ乳鉢やポットミル、ブレンダー、ハイブリッドミキサーなどを用いて行うことが好ましい。加圧成型を良好に行う観点からグローブボックス内の露点は、-30℃以下-90℃以上とすることが好ましい。グローブボックス内の酸素濃度は、例えば、1ppm以下とする。
正極活物質層11Bに含まれる正極活物質は、例えば、リチウム含有遷移金属酸化物、遷移金属フッ化物、ポリアニオン、遷移金属硫化物、遷移金属オキシフッ化物、遷移金属オキシ硫化物、遷移金属オキシ窒化物である。
正極活物質層11Bに用いる正極活物質は、加圧成型を良好に行う観点からアルゴンガスを循環させたグローブボックス内で、加熱真空乾燥などにより脱水しガラス瓶やアルミニウムラミネート袋などを用いて保管すると良い。グローブボックス内の露点は、-30℃以下-90℃以上とすることが好ましい。
図2に示すように、負極13は、例えば、負極集電体13Aと、負極活物質を含む負極活物質層13Bとを有する。
負極集電体13Aは、導電率が高いことが好ましい。例えば、銀、パラジウム、金、プラチナ、アルミニウム、銅、ニッケル、ステンレス、鉄等の金属およびそれらの合金、または、導電性樹脂を用いることが好ましい。負極集電体13Aは、粉体、箔、パンチング、エクスパンドの各形態であっても良い。また負極集電体の集電機能を低下させない観点からアルゴンガスを循環させたグローブボックス内で、加熱真空乾燥などにより脱水しガラス瓶やアルミニウムラミネート袋などを用いて保管すると良い。グローブボックス内の露点は、-30℃以下-90℃以上とすることが好ましい。
負極活物質層13Bに用いる負極合剤の混合は、例えばアルゴンガスを循環させたグローブボックス内で、メノウ乳鉢やポットミル、ブレンダー、ハイブリッドミキサーなどを用いて行うことが好ましい。加圧成型を良好に行う観点からグローブボックス内の露点は、-30℃以下-90℃以上とすることが好ましい。グローブボックス内の酸素濃度は、例えば、1ppm以下とする。
負極活物質層13Bに含まれる負極活物質は、可動イオンを吸蔵・放出可能な化合物であればよく、公知のリチウムイオン二次電池に用いられる負極活物質を使用できる。負極活物質は、例えば、アルカリ金属単体、アルカリ金属合金、黒鉛(天然黒鉛、人造黒鉛)、カーボンナノチューブ、難黒鉛化炭素、易黒鉛化炭素、低温度焼成炭素等の炭素材料、アルミニウム、シリコン、スズ、ゲルマニウムおよびその合金等のアルカリ金属等の金属と化合することのできる金属、SiOx(0<x<2)、酸化鉄、酸化チタン、二酸化スズ等の酸化物、チタン酸リチウム(Li4Ti5O12)等のリチウム金属酸化物である。負極活物質層13Bに用いる負極活物質は、加圧成型を良好に行う観点からアルゴンガスを循環させたグローブボックス内で、加熱真空乾燥などにより脱水しガラス瓶やアルミニウムラミネート袋などを用いて保管すると良い。グローブボックス内の露点は、-30℃以下-90℃以上とすることが好ましい。
導電助剤は、正極活物質層11B、負極活物質層13Bの電子伝導性を良好にするものであれば特に限定されず、公知の導電助剤を使用できる。導電助剤は、例えば、黒鉛、カーボンブラック、グラフェン、カーボンナノチューブ等の炭素系材料や、金、白金、銀、パラジウム、アルミニウム、銅、ニッケル、ステンレス、鉄等の金属、ITOなどの伝導性酸化物、またはこれらの混合物が挙げられる。導電助剤は、粉体、繊維の各形態であっても良い。また導電助剤の集電機能を低下させない観点からアルゴンガスを循環させたグローブボックス内で、加熱真空乾燥などにより脱水しガラス瓶やアルミニウムラミネート袋などを用いて保管すると良い。グローブボックス内の露点は、-30℃以下-90℃以上とすることが好ましい。
結着材は、正極集電体11Aと正極活物質層11B、負極集電体13Aと負極活物質層13B、正極活物質層11B、および負極活物質層13Bと固体電解質層15、正極活物質層11Bを構成する各種材料、負極活物質層13Bを構成する各種材料を接合する。
式(1)で表される固体電解質の製造方法について説明する。固体電解質は、目的とする組成となるように所定のモル比で原料粉末を混合、反応させることで得られる。反応させる方法は問わないが、メカノケミカルミリング法、焼結法、溶融法、液相法、固相法などを用いることができる。
次いで、本実施形態にかかる全固体電池の製造方法について説明する。本実施形態にかかる全固体電池は、例えば、電池要素10を作製する素子作製工程と、電池要素10を外装体20内に収容する収容工程と、を有する方法によって作製することができる。本実施形態にかかる電池要素10は、例えば、粉末成型法を用いて作製される。粉末成形法は、露点が-20℃より低く-90℃以上の環境で行う。粉末形成法は、露点が-30℃以下-85℃以上の環境で行うことが好ましい。粉末形成法は、例えば、グローブボックス内の露点を調整して行う。
まず、中央に貫通穴を有する樹脂ホルダーと、下パンチと、上パンチとを用意する。成型性をよくするために樹脂ホルダーの代わりにダイス鋼製の金属ホルダーを用いてもよい。樹脂ホルダーの貫通穴の直径は例えば10mmとし、下パンチ及び上パンチの直径は例えば9.99mmとする。樹脂ホルダーの貫通穴の下から下パンチを挿入し、樹脂ホルダーの開口側から、粉末状の固体電解質を投入する。次いで投入した粉末状の固体電解質の上に上パンチを挿入し、プレス機に載置し、プレスする。プレスの圧力は、例えば、373MPaとする。粉末状の固体電解質は、樹脂ホルダー内で上パンチと下パンチとでプレスされることで、固体電解質層15となる。
収容工程は、例えばアルゴンガスを循環させたグローブボックス内で行う。グローブボックス内の露点は、-20℃より低く-90℃以上とする。グローブボックス内の露点は、-30℃以下-85℃以上であることが好ましい。グローブボックス内の酸素濃度は、例えば、1ppm以下とする。
‐固体電解質の合成‐
アルゴンガスを循環している露点-85℃、酸素濃度1ppmのグローブボックス内で固体電解質の合成を行った。まず原料粉として、Li2SO4、ZrCl4とをモル比で1:1となるように秤量した。次いで、秤量した原料粉をZr容器内に直径5mmのZrボールとともに入れ、遊星型ボールミルを用いてメカノケミカルミリング処理を行った。処理は、回転数500rpmの条件で、50時間混合し、その後200μmメッシュの篩にかけた。これにより固体電解質としてLi2ZrSO4Cl4の粉末を得た。
ついで、アルゴンガスを循環している露点-85℃、酸素濃度1ppmのグローブボックス内で正極合剤の秤量および混合を行った。コバルト酸リチウム(LiCoO2):Li2ZrSO4Cl4:カーボンブラック=77:18:5重量部になるように秤量し、めのう乳鉢で5分間混合して、正極合剤を得た。
次に、アルゴンガスを循環している露点-85℃、酸素濃度1ppmのグローブボックス内で負極合剤の秤量および混合を行った。チタン酸リチウム(Li4Ti5O12):Li2ZrSO4Cl4:カーボンブラック=72:22:6重量部になるように秤量し、めのう乳鉢で5分間混合して、負極合剤を得た。
上記の固体電解質、正極合剤、負極合剤を用いて、粉末成型法により、正極集電体/正極合剤層/電解質層/負極合剤層/負極集電体からなる電池要素を作製した。電池要素の作製は、アルゴンガスを循環させた露点-85℃、酸素濃度1ppmのグローブボックス内で行った。
まず、中央に貫通穴を有する樹脂ホルダーと、SKD11材製の下パンチと、上パンチとを用意した。
樹脂ホルダーの貫通穴の下から下パンチを挿入し、樹脂ホルダーの開口側から固体電解質を110mg投入した。次いで固体電解質の上に上パンチを挿入した。この第1ユニットをプレス機に載置し、圧力373MPaでプレスし固体電解質層を成形した。第1ユニットをプレス機から取り出し、上パンチを取り外した。
次に、得られた電池要素を外装体に収容した。電池要素の収容は、アルゴンガスを循環している露点-85℃、酸素濃度1ppmのグローブボックス内のグローブボックス内で行った。
実施例2~8、比較例1~2は、電池要素の収容をアルゴンガスが循環している露点-20~-85℃、酸素濃度1ppmのグローブボックス内で行った以外は実施例1と同様にと同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例2~8比較例1~2の結果は、以下の表1にまとめた。
実施例9は、アルゴンガスを循環している露点-85℃、酸素濃度1ppmのグローブボックス内で固体電解質の合成を行った。まず原料粉としてLiClとZrCl4とを、モル比で2:1となるように秤量した。次いで、秤量した原料粉をZr容器内に直径5mmのZrボールとともに入れ、遊星型ボールミルを用いてメカノケミカルミリング処理を行った。処理は、回転数500rpmの条件で、50時間混合し、その後200μmメッシュの篩にかけた。これにより固体電解質としてLi2ZrCl6を得た。
固体電解質の組成を変更した点が実施例1と異なる。その他の条件は、実施例1と同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例9の結果は、以下の表1にまとめた。
実施例10~16、比較例3~4は、電池要素の収容をアルゴンガスが循環している露点-20~-85℃、酸素濃度1ppmのグローブボックス内で行った以外は実施例9と同様にと同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例10~16比較例3~4の結果は、以下の表1にまとめた。
固体電解質の組成を変更した点が実施例1と異なる。その他の条件は、実施例1と同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例17の結果は、以下の表2にまとめた。
実施例18~24、比較例5~6は、電池要素の収容をアルゴンガスが循環している露点-20~-85℃、酸素濃度1ppmのグローブボックス内で行った以外は実施例17と同様にと同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例18~24、比較例5~6の結果は、以下の表2にまとめた。
固体電解質の組成を変更した点が実施例1と異なる。その他の条件は、実施例1と同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例25の結果は、以下の表2にまとめた。
実施例26~32、比較例7~8は、電池要素の収容をアルゴンガスが循環している露点-20~-85℃、酸素濃度1ppmのグローブボックス内で行った以外は実施例25と同様にと同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例26~32、比較例7~8の結果は、以下の表2にまとめた。
固体電解質の組成を変更した点が実施例1と異なる。その他の条件は、実施例1と同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例33の結果は、以下の表3にまとめた。
実施例34~40、比較例9~10は、電池要素の収容をアルゴンガスが循環している露点-20~-85℃、酸素濃度1ppmのグローブボックス内で行った以外は実施例33と同様にと同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例34~40、比較例9~10の結果は、以下の表3にまとめた。
固体電解質の組成を変更した点が実施例1と異なる。その他の条件は、実施例1と同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例41の結果は、以下の表3にまとめた。
実施例42~48、比較例11~12は、電池要素の収容をアルゴンガスが循環している露点-20~-85℃、酸素濃度1ppmのグローブボックス内で行った以外は実施例41と同様にと同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例42~48、比較例11~12の結果は、以下の表3にまとめた。
固体電解質の組成を変更した点が実施例1と異なる。その他の条件は、実施例1と同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例49の結果は、以下の表4にまとめた。
実施例50~56、比較例13~14は、電池要素の収容をアルゴンガスが循環している露点-20~-85℃、酸素濃度1ppmのグローブボックス内で行った以外は実施例49と同様にと同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例50~56、比較例13~14の結果は、以下の表4にまとめた。
固体電解質の組成を変更した点が実施例1と異なる。その他の条件は、実施例1と同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例57の結果は、以下の表4にまとめた。
実施例58~64、比較例15~16は、電池要素の収容をアルゴンガスが循環している露点-20~-85℃、酸素濃度1ppmのグローブボックス内で行った以外は実施例49と同様にと同様にして、正極集電体、負極集電体の変色観察、収容空間Kの水分量、全固体電池の初回充放電効率のそれぞれを測定した。実施例58~64、比較例15~16の結果は、以下の表4にまとめた。
比較例1~16に係る全固体電池は、収容空間K内の水分含有量が1100ppmvを超えており、正極集電体、負極集電体の変色が抑制できておらず、充放電効率がいずれも不良であった。
11A 正極集電体
11B 正極活物質層
12 外部端子
13 負極
13A 負極集電体
13B 負極活物質層
14 外部端子
15 固体電解質層
10 電池要素
20 外装体
K 収容空間
100 全固体電池
Claims (3)
- 正極と、負極と、前記正極と前記負極との間にある固体電解質層と、を備える電池要素を含み、
前記正極、前記負極、前記固体電解質層とのうち少なくとも一つは、以下の式(1)で表される固体電解質を含み、
Li3+a-eE1-bGbDcXd-e (1)
式(1)中において、
EはAl、Sc、Y、Zr、Hf、ランタノイドからなる群から選択される少なくとも1種の元素であり、
Gは、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、B、Si、Al、Ti、Cu、Sc、Y、Zr、Nb、Ag、In、Sn、Sb、Hf、Ta、W、Au、Biからなる群から選択される少なくとも1種の元素であり、
DはCO3、SO4、BO3、PO4、NO3、SiO3、OH、O2からなる群から選択される少なくとも1種であり、
XはF、Cl、Br、Iからなる群から選択される少なくとも1種の元素であり、
n=(Eの価数)-(Gの価数)としたとき、a=nb、0≦b<0.5、0≦c≦5、0<d≦7.1、0≦e≦2、0<d-eであり、
前記電池要素を覆う外装体をさらに備え、前記電池要素と前記外装体との間の収容空間における水分量は、1100ppmv未満である電池。 - 前記収容空間における水分量は、600ppmv以下である、請求項1に記載の電池。
- 正極と負極との間に固体電解質層を挟み、これらを加圧成形し電池要素を作製する素子作製工程と、前記電池要素を外装体内に収容する収容工程と、を有し、
前記正極、前記負極、前記固体電解質層とのうち少なくとも一つは、以下の式(1)で表される固体電解質を含み、
Li3+a-eE1-bGbDcXd-e (1)
式(1)中において、
EはAl、Sc、Y、Zr、Hf、ランタノイドからなる群から選択される少なくとも1種の元素であり、
Gは、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、B、Si、Al、Ti、Cu、Sc、Y、Zr、Nb、Ag、In、Sn、Sb、Hf、Ta、W、Au、Biからなる群から選択される少なくとも1種の元素であり、
DはCO3、SO4、BO3、PO4、NO3、SiO3、OH、O2からなる群から選択される少なくとも1種であり、
XはF、Cl、Br、Iからなる群から選択される少なくとも1種の元素であり、
n=(Eの価数)-(Gの価数)としたとき、a=nb、0≦b<0.5、0≦c≦5、0<d≦7.1、0≦e≦2、0<d-eであり、
前記収容工程における露点を-20℃より低く-90℃以上とする、電池の製造方法。
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JP2024103031A (ja) * | 2023-01-20 | 2024-08-01 | Tdk株式会社 | Naイオン電導性化合物、固体電解質及び固体電解質電池 |
KR20240122221A (ko) * | 2023-02-03 | 2024-08-12 | 주식회사 엘지에너지솔루션 | 파우치 필름 적층체 및 이차 전지 |
WO2024180579A1 (ja) * | 2023-02-27 | 2024-09-06 | 日産自動車株式会社 | 全固体電池 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008235256A (ja) * | 2007-02-21 | 2008-10-02 | Riken Technos Corp | ラミネート外装材を用いたリチウム二次電池 |
WO2019003846A1 (ja) * | 2017-06-28 | 2019-01-03 | 日本電気硝子株式会社 | 全固体ナトリウムイオン二次電池 |
WO2019135315A1 (ja) * | 2018-01-05 | 2019-07-11 | パナソニックIpマネジメント株式会社 | 固体電解質材料、および、電池 |
WO2020050269A1 (ja) * | 2018-09-04 | 2020-03-12 | 三井金属鉱業株式会社 | 硫化物系化合物粒子、固体電解質及びリチウム二次電池 |
WO2020136952A1 (ja) * | 2018-12-26 | 2020-07-02 | パナソニックIpマネジメント株式会社 | ハロゲン化物の製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10223043A (ja) * | 1997-02-05 | 1998-08-21 | Shin Etsu Chem Co Ltd | 複合固体電解質およびこれを用いて作製される薄型固体電池 |
JP5108205B2 (ja) | 2005-02-28 | 2012-12-26 | 国立大学法人静岡大学 | 全固体型リチウム二次電池 |
JP5660079B2 (ja) | 2012-06-11 | 2015-01-28 | トヨタ自動車株式会社 | 全固体電池および全固体電池の製造方法 |
CN114937812A (zh) | 2016-08-04 | 2022-08-23 | 松下知识产权经营株式会社 | 固体电解质材料和电池 |
US11404726B2 (en) * | 2017-06-09 | 2022-08-02 | Nippon Electric Glass Co., Ltd. | All-solid-state sodium ion secondary battery |
JP7417924B2 (ja) * | 2018-01-05 | 2024-01-19 | パナソニックIpマネジメント株式会社 | 固体電解質材料、および、電池 |
JP2021031357A (ja) | 2019-08-28 | 2021-03-01 | 三星ダイヤモンド工業株式会社 | 分断方法および分断装置 |
-
2021
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2022
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008235256A (ja) * | 2007-02-21 | 2008-10-02 | Riken Technos Corp | ラミネート外装材を用いたリチウム二次電池 |
WO2019003846A1 (ja) * | 2017-06-28 | 2019-01-03 | 日本電気硝子株式会社 | 全固体ナトリウムイオン二次電池 |
WO2019135315A1 (ja) * | 2018-01-05 | 2019-07-11 | パナソニックIpマネジメント株式会社 | 固体電解質材料、および、電池 |
WO2020050269A1 (ja) * | 2018-09-04 | 2020-03-12 | 三井金属鉱業株式会社 | 硫化物系化合物粒子、固体電解質及びリチウム二次電池 |
WO2020136952A1 (ja) * | 2018-12-26 | 2020-07-02 | パナソニックIpマネジメント株式会社 | ハロゲン化物の製造方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024171935A1 (ja) * | 2023-02-13 | 2024-08-22 | Tdk株式会社 | 固体電解質及び固体電解質電池 |
WO2024195744A1 (ja) * | 2023-03-17 | 2024-09-26 | Tdk株式会社 | 固体電解質電池 |
WO2024204182A1 (ja) * | 2023-03-31 | 2024-10-03 | Tdk株式会社 | 電極及び全固体電池 |
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