WO2022118928A1 - 全固体電池のシステム - Google Patents

全固体電池のシステム Download PDF

Info

Publication number
WO2022118928A1
WO2022118928A1 PCT/JP2021/044315 JP2021044315W WO2022118928A1 WO 2022118928 A1 WO2022118928 A1 WO 2022118928A1 JP 2021044315 W JP2021044315 W JP 2021044315W WO 2022118928 A1 WO2022118928 A1 WO 2022118928A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
solid
positive electrode
solid electrolyte
state battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/044315
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
関谷智仁
片山祐也
土江宏典
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Maxell Ltd
Original Assignee
Maxell Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Maxell Ltd filed Critical Maxell Ltd
Priority to CN202180081328.9A priority Critical patent/CN116547832A/zh
Priority to US18/265,019 priority patent/US20240105926A1/en
Priority to EP21900678.0A priority patent/EP4258378A4/en
Priority to JP2022566984A priority patent/JPWO2022118928A1/ja
Publication of WO2022118928A1 publication Critical patent/WO2022118928A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/46—Accumulators structurally combined with charging apparatus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • 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

  • the present invention relates to an all-solid-state battery system having excellent discharge capacity characteristics after storage.
  • lithium-containing composite oxides are used as the positive electrode active material, graphite or the like is used as the negative electrode active material, and organic solvents are used as non-aqueous electrolytes.
  • An organic electrolytic solution containing a lithium salt is used.
  • lithium-ion secondary batteries With the further development of equipment to which lithium-ion secondary batteries are applied, there is a demand for longer life, higher capacity, and higher energy density of lithium-ion secondary batteries, as well as longer life and higher life. The reliability of lithium-ion secondary batteries with higher capacity and higher energy density is also highly required.
  • the organic electrolytic solution used in the lithium ion secondary battery contains an organic solvent which is a flammable substance, the organic electrolytic solution abnormally generates heat when an abnormal situation such as a short circuit occurs in the battery. there is a possibility. Further, with the recent increase in energy density of lithium ion secondary batteries and the increasing tendency of the amount of organic solvent in organic electrolytic solutions, the reliability of lithium ion secondary batteries is further required.
  • an all-solid-state lithium secondary battery (all-solid-state battery) that does not use an organic solvent is drawing attention.
  • the all-solid-state battery uses a molded body of a solid electrolyte that does not use an organic solvent instead of the conventional organic solvent-based electrolyte, and has high safety without the risk of abnormal heat generation of the solid electrolyte.
  • all-solid-state batteries are not only highly safe, but also highly reliable, highly environmentally resistant, and have a long life, so they are maintenance-free and can continue to contribute to the development of society as well as safety and security. It is expected as a battery.
  • SDGs Sustainable Development Goals
  • Goal 12 to ensure sustainable production and consumption
  • Goal 3 for all ages
  • Goal 7 ensure access to cheap, reliable and sustainable modern energy for all
  • Goal 11 (inclusive) It can contribute to the achievement of a safe, resilient and sustainable city and human settlement).
  • Patent Document 1 describes a specific range of the capacity ratio of the negative electrode capacity to the positive electrode capacity in an all-solid-state battery having a positive electrode layer, a negative electrode layer, and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer. It is disclosed that an all-solid-state battery having a good initial discharge capacity is provided by controlling the battery.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an all-solid-state battery system having excellent discharge capacity characteristics after storage.
  • the all-solid-state battery system of the present invention includes an all-solid-state battery and a charging device, and the all-solid-state battery includes a positive electrode, a negative electrode, and a solid electrolyte layer interposed between the positive electrode and the negative electrode.
  • the negative electrode contains a negative electrode active material and a solid electrolyte, the negative electrode active material contains a lithium titanium oxide, and the negative electrode discharge utilization rate X calculated from the following formula is 134 mAh / g or less. And.
  • Negative electrode discharge utilization rate X Battery capacity Q (mAh) ⁇ Mass of negative electrode active material in the negative electrode (g)
  • the battery capacity Q is the discharge capacity when the battery is charged at a constant current of 0.2 C to the upper limit voltage, then charged at a constant voltage until 0.002 C, and then discharged at 0.002 C to 1 V (the discharge capacity Q).
  • mAh Battery capacity Q (mAh) ⁇ Mass of negative electrode active material in the negative electrode
  • FIG. 1 is a cross-sectional view schematically showing an example of an all-solid-state battery used in the all-solid-state battery system of the present invention.
  • the all-solid-state battery used in the all-solid-state battery system of the present invention has a negative electrode containing a negative electrode active material and a solid electrolyte, a positive electrode, and a solid electrolyte layer interposed between the negative electrode and the positive electrode. ..
  • lithium titanium oxide is used as the negative electrode active material.
  • the negative electrode potential changes almost flat during charging, but the negative electrode potential drops sharply from there as charging progresses.
  • lithium ions further move from the positive electrode to the negative electrode, but the acceptance of lithium ions in the lithium titanium oxide itself becomes close to a saturated state, and as a result, the resistance of the lithium titanium oxide increases.
  • the resistance of the battery itself increases when it is stored at high temperature. If the design is such that the lithium titanium oxide is charged to a region where the resistance is high, the lithium ion acceptability on the negative electrode side at the time of charging is lowered, and the charging capacity is lowered due to the increase in resistance due to high temperature storage. As a result, the recovery capacity after high temperature storage is reduced.
  • the negative electrode discharge utilization rate X of the all-solid-state battery is adjusted to 134 mAh / g or less, and when lithium titanium oxide is used as the negative electrode active material, it is controlled so that the battery is not charged until the potential drops at the end of charging. Therefore, the present inventors have found that it is possible to suppress the increase in resistance of the lithium titanium oxide.
  • the negative electrode discharge utilization rate X in the all-solid-state battery system of the present invention can be expressed by the following equation.
  • Negative electrode discharge utilization rate X Battery capacity Q (mAh) ⁇ Mass of negative electrode active material in the negative electrode (g)
  • the battery capacity Q is the discharge capacity when the battery is charged at a constant current of 0.2 C to the upper limit voltage, then charged at a constant voltage until 0.002 C, and then discharged at 0.002 C to 1 V (the discharge capacity Q).
  • mAh Battery capacity Q (mAh) ⁇ Mass of negative electrode active material in the negative electrode
  • the negative electrode discharge utilization rate is determined by the battery capacity and the amount of negative electrode active material, it can be controlled by adjusting each.
  • the negative electrode discharge utilization rate is controlled by adjusting the amount of positive electrode active material and / or the amount of negative electrode active material in the battery, adjusting the type of positive electrode active material, adjusting the upper limit voltage of battery charging, and the like. be able to.
  • the negative electrode of the all-solid-state battery in the present invention contains a negative electrode active material and a solid electrolyte, and contains lithium titanium oxide as the negative electrode active material.
  • the negative electrode may contain a conductive auxiliary agent or the like, if necessary.
  • the negative electrode can be manufactured, for example, by mixing these without using a solvent to prepare a negative electrode mixture and molding the mixture into pellets or the like. Further, the molded body of the negative electrode mixture obtained as described above may be bonded to the current collector to form a negative electrode.
  • the negative electrode mixture and the solvent are mixed to prepare a negative electrode mixture-containing composition, which is applied onto a substrate such as a current collector or a solid electrolyte layer facing the negative electrode, dried, and then pressed. By performing the treatment, a molded body of the negative electrode mixture may be formed.
  • Examples of the negative electrode include a negative electrode composed of only the molded body and a negative electrode having a structure in which the molded body and a current collector are integrated.
  • lithium titanium oxide examples include those represented by the following general composition formula (1).
  • M 1 is at least one element selected from the group consisting of Na, Mg, K, Ca, Sr and Ba
  • M 2 is Al, V, Cr and Fe. It is at least one element selected from the group consisting of Co, Ni, Zn, Ym, Zr, Nb, Mo, Ta and W, and has 0 ⁇ s ⁇ 1/3 and 0 ⁇ t ⁇ 5/3.
  • a part of the Li site may be substituted with the element M 1 .
  • s representing the ratio of the element M 1 is preferably less than 1/3.
  • Li does not have to be substituted with the element M 1 , so s representing the ratio of the element M 1 may be 0.
  • the element M 2 is a component for enhancing the electron conductivity of the lithium titanium oxide, and t representing the ratio of the element M 2 is 0.
  • ⁇ t ⁇ 5/3
  • a negative electrode active material other than the lithium titanium oxide used in lithium ion secondary batteries and the like can also be used together with the lithium titanium oxide.
  • the proportion of the negative electrode active material other than the lithium titanium oxide in the total amount of the negative electrode active material is preferably 30% by mass or less.
  • the content of the negative electrode active material in the negative electrode mixture is preferably 40% by mass or more, preferably 45% by mass or more, and more preferably 45% by mass or more, from the viewpoint of enhancing the output characteristics of the all-solid-state battery and further increasing the capacity. It is 60% by mass or less, preferably 55% by mass or less.
  • a sulfide-based solid electrolyte as the solid electrolyte of the negative electrode.
  • the sulfide-based solid electrolyte has particularly excellent ionic conductivity among the solid electrolytes that can be used for all-solid-state batteries, and by using this not only for the negative electrode but also for the positive electrode and the solid electrolyte layer, the output characteristics of the battery can be obtained. Is improved.
  • the solid electrolyte of the negative electrode it is particularly preferable to use a sulfide-based solid electrolyte represented by the general composition formula (2).
  • the solid electrolyte represented by the general composition formula (2) is called an argylodite-type sulfide-based solid electrolyte, and is particularly excellent in ionic conductivity among the solid electrolytes that can be used for all-solid-state batteries. It can contribute to the improvement of the output characteristics of. Further, by using this not only for the negative electrode but also for the positive electrode and the solid electrolyte layer, the output characteristics of the battery are further improved.
  • sulfide-based solid electrolyte Although only a sulfide-based solid electrolyte may be used for the negative electrode, other solid electrolytes can be used together with the sulfide-based solid electrolyte. Examples of the solid electrolyte that can be used in combination with the sulfide-based solid electrolyte include hydride-based solid electrolytes and oxide-based solid electrolytes.
  • Examples of the hydride-based solid electrolyte include a solid solution of LiBH 4 , LiBH 4 and the following alkali metal compound (for example, one having a molar ratio of LiBH 4 to the alkali metal compound of 1: 1 to 20: 1). Can be mentioned.
  • Examples of the alkali metal compound in the solid solution include lithium halide (LiI, LiBr, LiF, LiCl, etc.), rubidium halide (RbI, RbBr, RbF, RbCl, etc.), and cesium halide (CsI, CsBr, CsF, CsCl, etc.).
  • oxide-based solid electrolyte examples include Li 7 La 3 Zr 2 O 12 , LiTi (PO 4 ) 3 , LiGe (PO 4 ) 3 , and LiLaTIO 3 .
  • the proportion of the solid electrolyte other than the sulfide-based solid electrolyte in the total amount of the solid electrolyte used in the negative electrode mixture is preferably 30% by mass or less.
  • the content of the solid electrolyte in the negative electrode mixture is 50 parts by mass or more when the content of the negative electrode active material is 100 parts by mass from the viewpoint of further enhancing the output characteristics of the all-solid-state battery and further increasing the capacity. It is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, preferably 130 parts by mass or less, and more preferably 120 parts by mass or less. , 110 parts by mass or less is more preferable.
  • a carbon material such as carbon black or graphene can be used as the conductive auxiliary agent for the negative electrode.
  • graphene when graphene is used as a conductive auxiliary agent, side reactions between the solid electrolyte and graphene are unlikely to occur, and the recovery capacity retention rate at high temperature storage is high.
  • the average particle size of graphene is preferably 4 ⁇ m or more, more preferably 6 ⁇ m or more, and 15 ⁇ m or less so as not to inhibit ionic conduction, in order to enhance the electron conductivity of the negative electrode mixture. It is preferably 12 ⁇ m or less, and more preferably 12 ⁇ m or less.
  • the average particle size of graphene referred to in the present specification is a volume reference when the integrated volume is obtained from particles having a small particle size by using a particle size distribution measuring device (such as a microtrack particle size distribution measuring device "HRA9320" manufactured by Nikkiso Co., Ltd.). It means the value of 50% diameter (D 50 ) in the integrated fraction of.
  • the BET specific surface area of graphene is preferably 20 m 2 / g or more, more preferably 22 m 2 / g or more, and more preferably 22 m 2 / g or more, in order to enhance the electron conductivity of the molded product of the negative electrode mixture. It is preferably 35 m 2 / g or less, and more preferably 32 m 2 / g or less in order to facilitate dispersion in the medium.
  • the BET specific surface area of graphene is a value obtained by the BET method according to the Japanese Industrial Standards (JIS) K6217.
  • JIS Japanese Industrial Standards
  • a specific surface area measuring device by a nitrogen adsorption method (“Macsorb HM model” manufactured by Moontech) It can be measured using 1201 ").
  • the thickness of graphene is preferably 5 nm or more in order to enhance the electron conductivity of the negative electrode mixture, and is preferably 100 nm or less in order to enhance the filling property of the positive electrode mixture during pressurization. It is more preferably 50 nm or less.
  • the content of the conductive auxiliary agent in the negative electrode mixture is 10 parts by mass when the content of the negative electrode active material is 100 parts by mass from the viewpoint of further enhancing the output characteristics of the all-solid-state battery and further increasing the capacity.
  • the above is preferable, 12 parts by mass or more is more preferable, 15 parts by mass or more is further preferable, 30 parts by mass or less is preferable, and 25 parts by mass or less is more preferable. It is preferably 22 parts by mass or less, and more preferably 22 parts by mass or less.
  • the negative electrode mixture may or may not contain a resin binder.
  • the resin binder include fluororesins such as polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the negative electrode mixture does not contain a resin binder, or if it does, the content thereof is 0.5% by mass or less.
  • the content of the resin binder in the negative electrode mixture is more preferably 0.3% by mass or less, and further preferably 0% by mass (that is, the resin binder is not contained).
  • a current collector When a current collector is used for the negative electrode, copper or nickel foil, punching metal, net, expanded metal, foamed metal; carbon sheet; etc. can be used as the current collector.
  • the molded body of the negative electrode mixture is, for example, a negative electrode mixture prepared by mixing a negative electrode active material, a solid electrolyte and a conductive auxiliary agent, and a binder added as needed, and the like is compressed by pressure molding or the like.
  • a negative electrode mixture prepared by mixing a negative electrode active material, a solid electrolyte and a conductive auxiliary agent, and a binder added as needed, and the like is compressed by pressure molding or the like.
  • a negative electrode having a current collector it can be manufactured by bonding the molded body of the negative electrode mixture formed by the above method by crimping it to the current collector.
  • the thickness of the molded body of the negative electrode mixture is from the viewpoint of increasing the capacity of the battery. , 200 ⁇ m or more is preferable.
  • the output characteristics of the battery are generally easily improved by thinning the positive electrode and the negative electrode, but according to the present invention, the output characteristics can be improved even when the molded body of the negative electrode mixture is as thick as 200 ⁇ m or more. It is possible.
  • the thickness of the molded product of the negative electrode mixture is usually 3000 ⁇ m or less.
  • the positive electrode of an all-solid-state battery has a molded body of a positive electrode mixture containing a positive electrode active material, a solid electrolyte, a conductive auxiliary agent, and the like.
  • a positive electrode having a structure in which and is integrated with each other.
  • the positive electrode active material is particularly limited as long as it is a positive electrode active material used in a conventionally known lithium ion secondary battery, that is, an active material capable of storing and releasing Li ions such as a lithium-containing composite oxide. do not have.
  • Specific examples of the positive electrode active material include LiM x Mn 2-x O 4 (where M is Li, B, Mg, Ca, Sr, Ba, Ti, V, Cr, Fe, Co, Ni, Cu, Al). , Sn, Sb, In, Nb, Mo, W, Y, Ru and Rh, which is at least one element selected from the group and is represented by 0.01 ⁇ x ⁇ 0.5).
  • Manganese composite oxide Li x Ni (1-yz) Mn y M z O (2-k) F l
  • M is Co, Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn. , Zr, Mo, Sn, Ca, Sr and W, at least one element selected from the group consisting of 0.8 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0. .5, layered compound represented by k + l ⁇ 1, ⁇ 0.1 ⁇ k ⁇ 0.2, 0 ⁇ l ⁇ 0.1), LiCo 1-x M x O 2 (where M is Al, Mg.
  • LiNi 1-x M x O 2 (where M is Al, Mg, Ti, Zr, Fe, Co, Cu, Zn, Ga, Ge, Nb, Mo, Sn, Sb.
  • LiM 1-x N x PO 4 (where M is Fe), a lithium nickel composite oxide represented by 0 ⁇ x ⁇ 0.5), which is at least one element selected from the group consisting of and Ba.
  • Mn and Co at least one element selected from the group consisting of Al, Mg, Ti, Zr, Ni, Cu, Zn, Ga, Ge, Nb, Mo, Sn, Sb and Ba. It is at least one element selected from the group, and examples thereof include an olivine type composite oxide represented by 0 ⁇ x ⁇ 0.5), and only one of these may be used, and two kinds may be used. The above may be used together.
  • lithium cobalt oxide Since lithium cobalt oxide has a high true density and a high working potential, the energy density per volume can be increased by using it as a positive electrode active material. Further, the content of the positive electrode active material in the positive electrode mixture is set to a specific amount, and a well-balanced all-solid-state battery having a high capacity and a high output can be obtained.
  • the average particle size of the positive electrode active material is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, preferably 10 ⁇ m or less, and more preferably 8 ⁇ m or less.
  • the positive electrode active material may be primary particles or secondary particles in which the primary particles are aggregated. When a positive electrode active material having an average particle size in the above range is used, many interfaces with the solid electrolyte can be obtained, so that the load characteristics of the battery are further improved.
  • the average particle size of the positive electrode active material referred to in the present specification is a case where the integrated volume is obtained from particles having a small particle size distribution using a particle size distribution measuring device (such as a microtrack particle size distribution measuring device "HRA9320" manufactured by Nikkiso Co., Ltd.). It means the value of 50% diameter (d 50 ) in the integrated fraction based on the volume of.
  • a particle size distribution measuring device such as a microtrack particle size distribution measuring device "HRA9320" manufactured by Nikkiso Co., Ltd.
  • the content of the positive electrode active material in the positive electrode mixture is preferably 50% by mass or more and preferably 80% by mass or less. Within this range, an all-solid-state battery with a good balance between discharge capacity and expansion / contraction can be obtained.
  • the content of the positive electrode active material in the positive electrode mixture is more preferably 60% by mass or more, and more preferably 70% by mass or less.
  • the positive electrode active material has a reaction suppressing layer on its surface for suppressing the reaction with the solid electrolyte.
  • the reaction suppressing layer may be made of a material having ionic conductivity and capable of suppressing the reaction between the positive electrode active material and the solid electrolyte.
  • the material that can form the reaction suppression layer for example, an oxide containing Li and at least one element selected from the group consisting of Nb, P, B, Si, Ge, Ti and Zr, more specifically. Examples include Nb-containing oxides such as LiNbO 3 , Li 3 PO 4 , Li 3 BO 3 , Li 4 SiO 4 , Li 4 GeO 4 , LiTIO 3 , LiZrO 3 and the like.
  • the reaction suppression layer may contain only one of these oxides, or may contain two or more of these oxides, and a plurality of these oxides may be a composite compound. May be formed.
  • these oxides it is preferable to use an Nb-containing oxide, and it is more preferable to use LiNbO 3 .
  • the reaction suppressing layer is preferably present on the surface in an amount of 0.1 to 1.0 part by mass with respect to 100 parts by mass of the positive electrode active material. Within this range, the reaction between the positive electrode active material and the solid electrolyte can be satisfactorily suppressed, and deterioration of the load characteristics can be prevented.
  • Examples of the method for forming the reaction suppressing layer on the surface of the positive electrode active material include a sol-gel method, a mechanofusion method, a CVD method, and a PVD method.
  • the solid electrolyte of the positive electrode one or more of the same solid electrolytes as those exemplified above can be used as the solid electrolyte that can be used for the negative electrode.
  • the output characteristics of the battery can be improved by using the algyrodite-type sulfide-based solid electrolyte represented by the above-mentioned general composition formula (2).
  • sulfide-based solid electrolyte Although only a sulfide-based solid electrolyte may be used for the positive electrode, other solid electrolytes can be used together with the sulfide-based solid electrolyte.
  • the solid electrolyte that can be used in combination with the sulfide-based solid electrolyte include the same hydride-based solid electrolyte and oxide-based solid electrolyte as those exemplified above as those that can be used for the negative electrode.
  • the proportion of the solid electrolyte other than the sulfide-based solid electrolyte in the total amount of the solid electrolyte used in the positive electrode mixture is preferably 30% by mass or less.
  • the content of the solid electrolyte in the positive electrode mixture is 15% by mass or more in the molded body of the positive electrode mixture for the positive electrode for the all-solid-state battery from the viewpoint of further enhancing the output characteristics of the all-solid-state battery and further increasing the capacity. It is preferably 20% by mass or more, more preferably 25% by mass or more, more preferably 45% by mass or less, still more preferably 40% by mass or less. It is more preferably 35% by mass or less.
  • a carbon material such as carbon black can be used as the conductive auxiliary agent for the positive electrode.
  • fibrous carbon and granular carbon together as a conductive auxiliary agent, a good conductive network can be formed in the molded body of the positive electrode mixture, thereby increasing the capacity of the battery as the molded body of the positive electrode mixture. It is also possible to secure excellent load characteristics while trying.
  • the fibrous carbon used has a fiber length to fiber diameter (fiber diameter) ratio of 20 or more. Is preferable.
  • the fiber length of the fibrous carbon is more preferably 3 to 600 ⁇ m, and the fiber diameter is further preferably 1 to 300 nm.
  • the fiber length and fiber diameter of the fibrous carbon referred to in the present specification 50 fibers whose contours can be confirmed in an image of carbon observed at a magnification of 30,000 using a scanning electron microscope (SEM) were selected and selected. It is a value obtained by measuring the fiber length and the fiber diameter of the fiber by the two-point method and calculating the average value (number average) of all the fibers.
  • Specific examples of the fibrous carbon include vapor-grown carbon fibers, carbon nanofibers, and carbon nanotubes. As the fibrous carbon, only one of the above-exemplified ones may be used, or two or more of them may be used in combination.
  • the granular carbon is in the state of primary particles, and the ratio of the longest diameter to the shortest diameter is 1 to 1. It is preferably the one of 3.
  • the average particle size of the granular carbon is preferably 10 nm to 1000 nm.
  • the particle size of the primary particles of granular carbon referred to in the present specification is a value obtained as follows. Using a scanning electron microscope (SEM), 50 particles whose contours can be confirmed are selected in an image in which carbon is observed at a magnification of 30,000, and the longest diameter and the shortest diameter are measured for the selected particles by a two-point method.
  • the longest diameter of the granular carbon is the average value (number average) of all the longest diameters measured, and the shortest diameter is the average value (number average) of all the shortest diameters measured.
  • the average particle size of the granular carbon is the longest diameter (the average value of all the longest diameters) obtained as described above.
  • granular carbon examples include highly crystalline carbon materials such as graphite (natural graphite and artificial graphite) and graphene (single-layer graphene and multi-layer graphene); and low-crystalline carbon materials such as carbon black; ..
  • fibrous carbon and granular carbon are used in combination as a conductive auxiliary agent for a positive electrode for an all-solid-state battery, it is preferable to use a granular carbon containing a hydrophilic portion in a proportion of 10% by mass or more.
  • a granular carbon containing a hydrophilic portion in a proportion of 10% by mass or more, it becomes easier to lower the porosity of the molded product of the positive electrode mixture and increase the density.
  • the granular carbon forms a composite with the fibrous carbon, but by using the granular carbon containing a hydrophilic portion in a proportion of 10% by mass or more, the fibrous carbon is used. It also facilitates complex formation with.
  • Fibrous carbon tends to aggregate, and even if it is mixed with a positive electrode active material during preparation of a positive electrode mixture, it often exists in an aggregated state without being crushed.
  • a positive electrode mixture since the aggregated fibrous carbon is bulky, it becomes difficult to form a molded body of the positive electrode mixture having few voids and a high density. Therefore, it is preferable to use the fibrous carbon as a composite complex with granular carbon.
  • the fibrous carbon forms a composite with the granular carbon, the granular carbon adhering to the surface of the fibrous carbon suppresses the aggregation of the fibrous carbon. This facilitates the formation of a molded body of the positive electrode mixture having a low porosity and a high density, for example.
  • the composite of fibrous carbon and granular carbon can be obtained, for example, by dry-mixing fibrous carbon and granular carbon.
  • the ratio of the fibrous carbon to the granular carbon is granular with respect to 100 parts by mass of the fibrous carbon from the viewpoint of better suppressing the aggregation of the fibrous carbon.
  • the amount of carbon is preferably 10 parts by mass or more, and more preferably 30 parts by mass or more.
  • the ratio of the fibrous carbon to the granular carbon is determined.
  • the amount of granular carbon is preferably 100 parts by mass or less, and more preferably 70 parts by mass or less with respect to 100 parts by mass of fibrous carbon.
  • the total amount of the conductive auxiliary agent is preferably 1 to 10% by mass in the molded body of the positive electrode mixture of the positive electrode for the all-solid-state battery.
  • the positive electrode mixture may or may not contain a resin binder.
  • the resin binder include fluororesins such as polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the positive electrode mixture does not contain a resin binder, or when it is contained, the content thereof is preferably 0.5% by mass or less.
  • the content of the resin binder in the positive electrode mixture is more preferably 0.3% by mass or less, and further preferably 0% by mass (that is, the resin binder is not contained).
  • a metal foil such as aluminum or stainless steel, punching metal, net, expanded metal, foamed metal; carbon sheet; etc. can be used as the current collector.
  • the molded body of the positive electrode mixture is prepared by mixing, for example, a positive electrode active material, a solid electrolyte and a conductive auxiliary agent, and a binder added as needed, and the positive electrode mixture is compressed by pressure molding or the like. It can be formed by.
  • a positive electrode having a current collector it can be manufactured by bonding the molded body of the positive electrode mixture formed by the above method by crimping it to the current collector.
  • the thickness of the molded body of the positive electrode mixture (in the case of a positive electrode having a current collector, the thickness of the molded body of the positive electrode mixture per one side of the current collector; the same applies hereinafter) is from the viewpoint of increasing the capacity of the battery. , 200 ⁇ m or more is preferable.
  • the thickness of the molded product of the positive electrode mixture is usually 2000 ⁇ m or less.
  • Solid electrolyte layer It is preferable to use a sulfide-based solid electrolyte as the solid electrolyte in the solid electrolyte layer of the all-solid-state battery.
  • the sulfide-based solid electrolyte is particularly excellent in ionic conductivity among the solid electrolytes that can be used for all-solid-state batteries. As described above, by using this not only for the solid electrolyte layer but also for the positive electrode and the negative electrode, The output characteristics of the battery are improved.
  • the sulfide-based solid electrolyte it is more preferable to use the same solid electrolyte that can be used for the negative electrode as exemplified above. Only the sulfide-based solid electrolyte may be used for the solid electrolyte layer, but other solid electrolytes can be used together with the sulfide-based solid electrolyte. Examples of the solid electrolyte that can be used in combination with the sulfide-based solid electrolyte include the same hydride-based solid electrolyte and oxide-based solid electrolyte as those exemplified above as those that can be used for the negative electrode.
  • the proportion of the solid electrolyte other than the sulfide-based solid electrolyte in the total amount of the solid electrolyte used for the solid electrolyte layer is preferably 30% by mass or less.
  • a composition for forming a solid electrolyte layer prepared by dispersing the solid electrolyte in a solvent is applied onto a base material, a positive electrode, and a negative electrode, dried, and if necessary, pressure molding such as press treatment is performed. It can be formed by doing.
  • a solvent that does not easily deteriorate the solid electrolyte as the solvent used in the composition for forming the solid electrolyte layer.
  • sulfide-based solid electrolytes and hydride-based solid electrolytes cause a chemical reaction with a very small amount of water, and are therefore represented by hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, decalin, toluene, and xylene.
  • hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, decalin, toluene, and xylene.
  • a non-polar aproton solvent it is more preferable to use a super dehydrating solvent having a water content of 0.001% by mass (10 ppm) or less.
  • fluorine-based solvents such as “Bertrel (registered trademark)” manufactured by Mitsui Dupont Fluorochemical, “Zeorolla (registered trademark)” manufactured by Zeon Corporation, and “Novec (registered trademark)” manufactured by Sumitomo 3M, as well as , Dichloromethane, diethyl ether and other non-aqueous organic solvents can also be used.
  • the thickness of the solid electrolyte layer is preferably 15 to 300 ⁇ m.
  • the positive electrode and the negative electrode can be used in a battery in the form of a laminated electrode body laminated via a solid electrolyte layer or a wound electrode body wound around the laminated electrode body.
  • FIG. 1 shows a cross-sectional view schematically showing an example of the all-solid-state battery of the present invention.
  • the all-solid-state battery 1 shown in FIG. 1 has a positive electrode 10, a negative electrode 20, and a positive electrode 10 and a negative electrode in an exterior body formed of an outer can 40, a sealing can 50, and a resin gasket 60 interposed between them.
  • a solid electrolyte layer 30 interposed between the 20 and 20 is enclosed.
  • the sealing can 50 is fitted to the opening of the outer can 40 via the gasket 60, and the opening end of the outer can 40 is tightened inward, whereby the gasket 60 comes into contact with the sealing can 50.
  • the opening of the outer can 40 is sealed and the inside of the battery has a sealed structure.
  • Stainless steel can be used for the outer can and the sealing can.
  • polypropylene, nylon, etc. can be used as the material of the gasket, and if heat resistance is required in relation to the use of the battery, tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), etc. can be used.
  • a glass hermetic seal can be used for the sealing.
  • the form of the all-solid-state battery is as shown in FIG. 1, which has an exterior body composed of an exterior can, a sealing can, and a gasket, that is, a form generally referred to as a coin-shaped battery or a button-shaped battery.
  • an exterior body composed of an exterior can, a sealing can, and a gasket, that is, a form generally referred to as a coin-shaped battery or a button-shaped battery.
  • a gasket that is, a form generally referred to as a coin-shaped battery or a button-shaped battery.
  • an exterior body made of a resin film or a metal-resin laminated film, or a metal bottomed tubular (cylindrical or square tubular) exterior can and its opening are sealed. It may have an exterior body having a sealing structure for stopping.
  • the all-solid-state battery of the present invention can be applied to the same applications as the conventionally known secondary batteries, but has excellent heat resistance because it has a solid electrolyte instead of an organic electrolyte, and has a high temperature. It can be preferably used for applications that are exposed to.
  • the all-solid-state battery system of the present invention includes the all-solid-state battery of the present invention and a charging device, and the upper limit of the voltage applied to the all-solid-state battery by the charging device is determined, and the battery capacity is determined.
  • the battery capacity in the present invention refers to the discharge capacity when a constant current is charged to the upper limit voltage of charging at 0.2 C, a constant voltage is charged until 0.002 C, and then the battery is discharged to 1 V at 0.002 C. ..
  • the all-solid-state battery system of the present invention preferably charges up to a voltage of 2.8 V.
  • the all-solid-state battery used in such a system can exhibit good output characteristics.
  • the charging device according to the all-solid-state battery system of the present invention it is preferable that the all-solid-state battery can be charged under the condition that the final voltage is 2.8 V or less, and the charge device for all-solid-state batteries known conventionally is used.
  • a charging device for example, a charging device capable of performing constant voltage charging after constant current charging, a charging device capable of performing pulse charging, and the like can be used.
  • a charging / discharging device (a device for charging and discharging a battery) having a discharging function may be used.
  • the all-solid-state battery system of the present invention can be applied to the same applications as the conventionally known secondary battery and secondary battery system, but because it has a solid electrolyte instead of the organic electrolyte. It has excellent heat resistance and can be preferably used in applications that are exposed to high temperatures.
  • Example 1 ⁇ Manufacturing of conductive aid> Carbon nanotubes [“VGCF (trade name)” manufactured by Showa Denko Co., Ltd .: fibrous carbon having a fiber length to fiber diameter ratio of 30 or more] and granular carbon having an average primary particle diameter of 200 nm are used in a planetary ball mill. Was dry-mixed for 60 minutes at a mass ratio of 2: 1 to obtain a composite of fibrous carbon and granular carbon.
  • VGCF trade name
  • ⁇ Preparation of positive electrode mixture LiCo 0.98 Al 0.01 Mg 0.01 O 2 (positive electrode active material) having an average particle size of 5 ⁇ m and a layer made of LiNbO 3 on the surface, and a sulfide solid electrolyte (Li 5.4 PS 4.4 Cl) having an algyrodite type structure with an average particle size of 3 ⁇ m. 0.8 Br 0.8 ) and a composite (conductive aid) of the fibrous carbon and granular carbon were mixed at a mass ratio of 65: 31: 4 to prepare a positive electrode mixture.
  • the amount of the layer composed of LiNbO 3 on the surface of LiCo 0.98 Al 0.01 Mg 0.01 O 2 was 0.5 parts by mass with respect to 100 parts by mass of LiCo 0.98 Al 0.01 Mg 0.01 O 2 : 100 parts by mass.
  • the negative electrode mixture 100 mg is added onto the molded sulfide solid electrolyte to form a laminate of three layers, and then a pressure of 1000 MPa (10 ton ⁇ f / cm 2 ) is used using a press machine.
  • a laminated electrode body composed of a positive electrode / a solid electrolyte layer / a negative electrode was produced by pressure molding.
  • the laminated electrode body of the positive electrode / solid electrolyte layer / negative electrode is placed on the inner bottom surface of the sealed can made of steel so that the negative electrode is on the base material side, and further punched to the same size as described above.
  • Aluminum "Celmet (trade name)", thickness: 1 mm, pore ratio: 97%] is placed on the positive electrode of the laminated electrode body, and then stainless steel.
  • a flat all-solid-state battery was produced by covering it with a steel outer can and crimping the open end of the outer can inward to seal it. This flat all-solid-state battery was combined with a charging / discharging device to form an all-solid-state battery system having a charge upper limit voltage of 2.6 V.
  • Example 2 A laminated electrode body was produced in the same manner as in Example 1 except that the amount of the mixture was changed to the positive electrode mixture: 75 mg and the negative electrode mixture: 98 mg.
  • a flat all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used. Using this flat all-solid-state battery, an all-solid-state battery system was constructed in the same manner as in Example 1.
  • Example 3 A laminated electrode body was produced in the same manner as in Example 1 except that the amount of the mixture was changed to the positive electrode mixture: 63 mg and the negative electrode mixture: 107 mg.
  • a flat all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used. This flat all-solid-state battery was combined with a charging / discharging device to construct an all-solid-state battery system having a charge upper limit voltage of 2.8V.
  • Example 4 A positive electrode mixture was prepared in the same manner as in Example 1 except that the positive electrode active material was changed to LiNi 0.33 Co 0.33 Mn 0.33 O 2 having an average particle size of 5 ⁇ m and a layer composed of LiNbO 3 on the surface.
  • a laminated electrode body was produced in the same manner as in Example 1 except that 69 mg of this positive electrode mixture was used.
  • a flat all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used. Using this flat all-solid-state battery, an all-solid-state battery system was constructed in the same manner as in Example 1.
  • Example 5 A positive electrode mixture was prepared in the same manner as in Example 1 except that the positive electrode active material was changed to LiNi 0.5 Co 0.2 Mn 0.3 O 2 having an average particle size of 5 ⁇ m and a layer composed of LiNbO 3 on the surface. Using 67 mg of this positive electrode mixture, a laminated electrode body was produced in the same manner as in Example 1 except that the amount of the negative electrode mixture in Example 1 was changed to 102 mg. A flat all-solid-state battery was produced in the same manner as in Example 1 except that this electrode laminate was used. Using this flat all-solid-state battery, an all-solid-state battery system was constructed in the same manner as in Example 1.
  • Example 6 A positive electrode mixture was prepared in the same manner as in Example 1 except that the positive electrode active material was changed to LiNi 0.8 Co 0.15 Al 0.05 O 2 having an average particle size of 5 ⁇ m and a layer composed of LiNbO 3 on the surface. Using this positive electrode mixture 59 mg, a laminated electrode body was produced in the same manner as in Example 1 except that the amount of the negative electrode mixture in Example 1 was changed to 109 mg. A flat all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used. Using this flat all-solid-state battery, an all-solid-state battery system was constructed in the same manner as in Example 1.
  • Example 7 Using the same positive electrode active material, sulfide solid electrolyte, and conductive auxiliary agent as in Example 1, a positive electrode mixture was prepared in the same manner as in Example 1 except that the mixing ratio was changed to 70:27: 3 by mass ratio. .. Using this positive electrode mixture 71 mg, a laminated electrode body was produced in the same manner as in Example 1 except that the amount of the negative electrode mixture in Example 1 was changed to 102 mg. A flat all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used. Using this flat all-solid-state battery, an all-solid-state battery system was constructed in the same manner as in Example 1.
  • Example 8 A laminated electrode body was produced in the same manner as in Example 1 except that the amount of the mixture was changed to the positive electrode mixture: 67 mg and the negative electrode mixture: 88 mg, and the pressure molding conditions were set to 5 ton ⁇ f / cm 2 .
  • a flat all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used. Using this flat all-solid-state battery, an all-solid-state battery system was constructed in the same manner as in Example 1.
  • Example 9 A laminated electrode body was produced in the same manner as in Example 1 except that the amount of the mixture was changed to the positive electrode mixture: 61 mg and the negative electrode mixture: 108 mg.
  • a flat all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used. This flat all-solid-state battery was combined with a charging / discharging device to construct an all-solid-state battery system having a charge upper limit voltage of 2.9V.
  • Example 1 A laminated electrode body was produced in the same manner as in Example 1 except that the amount of the mixture was changed to the positive electrode mixture: 76 mg and the negative electrode mixture: 98 mg.
  • a flat all-solid-state battery was produced in the same manner as in Example 1 except that this laminated electrode body was used. Using this flat all-solid-state battery, an all-solid-state battery system was constructed in the same manner as in Example 1.
  • the negative electrode discharge utilization rate and the recovery capacity maintenance rate were measured by the following methods.
  • each of the all-solid-state battery systems of Examples and Comparative Examples is constantly charged with a current value of 0.2 C until the voltage reaches the charging upper limit voltage of each all-solid-state battery system, and then the current value is 0. It was charged at a constant voltage until it reached .002C, and then discharged at a current value of 0.002C until the voltage reached 1V.
  • the discharge capacity at that time was defined as the battery capacity Q.
  • the all-solid-state battery is discharged at a current value of 0.002C until the voltage reaches 1V, and then constant current charging and constant voltage charging are performed under the same conditions as when the initial capacity is measured, and the current value is 0.002C.
  • the battery was discharged until the voltage reached 1 V, and the discharge capacity after storage was measured.
  • the value obtained by dividing the discharge capacity after storage by the initial capacity was expressed as a percentage to obtain the recovery capacity maintenance rate, and the output characteristics were evaluated.
  • Table 1 shows the results of each evaluation.
  • the present application can be implemented in a form other than the above as long as it does not deviate from the purpose.
  • the embodiments disclosed in the present application are examples, and the present invention is not limited thereto.
  • the scope of the present application shall be construed in preference to the description of the appended claims over the description of the specification described above, and all changes within the scope of the claims shall be included in the scope of the claims. It is something that can be done.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
PCT/JP2021/044315 2020-12-03 2021-12-02 全固体電池のシステム Ceased WO2022118928A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202180081328.9A CN116547832A (zh) 2020-12-03 2021-12-02 全固体电池的系统
US18/265,019 US20240105926A1 (en) 2020-12-03 2021-12-02 All-solid-state battery system
EP21900678.0A EP4258378A4 (en) 2020-12-03 2021-12-02 ALL-SOLID-STATE BATTERY SYSTEM
JP2022566984A JPWO2022118928A1 (https=) 2020-12-03 2021-12-02

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020201014 2020-12-03
JP2020-201014 2020-12-03

Publications (1)

Publication Number Publication Date
WO2022118928A1 true WO2022118928A1 (ja) 2022-06-09

Family

ID=81853348

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/044315 Ceased WO2022118928A1 (ja) 2020-12-03 2021-12-02 全固体電池のシステム

Country Status (5)

Country Link
US (1) US20240105926A1 (https=)
EP (1) EP4258378A4 (https=)
JP (1) JPWO2022118928A1 (https=)
CN (1) CN116547832A (https=)
WO (1) WO2022118928A1 (https=)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117236068A (zh) * 2023-10-25 2023-12-15 四川新能源汽车创新中心有限公司 全固态电池极片的设计方法
WO2024144375A1 (ko) * 2022-12-27 2024-07-04 주식회사 엘지에너지솔루션 전고체 전지용 양극 및 이를 포함하는 전고체 전지
CN119230961A (zh) * 2024-09-29 2024-12-31 广州鹏辉能源科技股份有限公司 一种固态锂电池及其制备方法和涉电设备

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121282404B (zh) * 2025-12-09 2026-02-27 内蒙古工业大学 一种用于全固态电池富锂锰基电极材料的活化方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001185141A (ja) * 1999-12-22 2001-07-06 Kyocera Corp リチウム電池
JP2012074352A (ja) * 2010-09-01 2012-04-12 Idemitsu Kosan Co Ltd 電極材料及びそれを用いたリチウムイオン電池
JP2017152146A (ja) * 2016-02-23 2017-08-31 凸版印刷株式会社 全固体二次電池、全固体二次電池の製造方法、全固体二次電池用の積層体グリーンシート、全固体二次電池用の集電箔付き積層体グリーンシート及び全固体二次電池用の連続積層体グリーンシート
JP2020004685A (ja) 2018-07-02 2020-01-09 トヨタ自動車株式会社 全固体電池
JP2021034328A (ja) * 2019-08-29 2021-03-01 マクセルホールディングス株式会社 全固体電池および全固体電池のシステム
JP2021034326A (ja) * 2019-08-29 2021-03-01 マクセルホールディングス株式会社 全固体電池
JP2021163553A (ja) * 2020-03-31 2021-10-11 マクセルホールディングス株式会社 全固体電池

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5141805B1 (ja) * 2011-08-02 2013-02-13 トヨタ自動車株式会社 固体二次電池、および電池システム
JP2013222530A (ja) * 2012-04-13 2013-10-28 Idemitsu Kosan Co Ltd 全固体電池及び全固体電池の充放電方法
JP6409794B2 (ja) * 2016-02-18 2018-10-24 トヨタ自動車株式会社 正極合剤の製造方法、正極の製造方法、及び全固体リチウムイオン二次電池の製造方法
US11205798B2 (en) * 2018-07-30 2021-12-21 GM Global Technology Operations LLC Capacitor-assisted solid-state battery
EP3832775B1 (en) * 2018-09-26 2023-11-29 Maxell, Ltd. Flat solid-state battery and method for manufacturing same
US11522215B2 (en) * 2019-03-22 2022-12-06 Toyota Jidosha Kabushiki Kaisha All-solid-state battery production method and all-solid-state battery

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001185141A (ja) * 1999-12-22 2001-07-06 Kyocera Corp リチウム電池
JP2012074352A (ja) * 2010-09-01 2012-04-12 Idemitsu Kosan Co Ltd 電極材料及びそれを用いたリチウムイオン電池
JP2017152146A (ja) * 2016-02-23 2017-08-31 凸版印刷株式会社 全固体二次電池、全固体二次電池の製造方法、全固体二次電池用の積層体グリーンシート、全固体二次電池用の集電箔付き積層体グリーンシート及び全固体二次電池用の連続積層体グリーンシート
JP2020004685A (ja) 2018-07-02 2020-01-09 トヨタ自動車株式会社 全固体電池
JP2021034328A (ja) * 2019-08-29 2021-03-01 マクセルホールディングス株式会社 全固体電池および全固体電池のシステム
JP2021034326A (ja) * 2019-08-29 2021-03-01 マクセルホールディングス株式会社 全固体電池
JP2021163553A (ja) * 2020-03-31 2021-10-11 マクセルホールディングス株式会社 全固体電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4258378A4

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024144375A1 (ko) * 2022-12-27 2024-07-04 주식회사 엘지에너지솔루션 전고체 전지용 양극 및 이를 포함하는 전고체 전지
CN117236068A (zh) * 2023-10-25 2023-12-15 四川新能源汽车创新中心有限公司 全固态电池极片的设计方法
CN117236068B (zh) * 2023-10-25 2024-04-16 四川新能源汽车创新中心有限公司 全固态电池极片的设计方法
CN119230961A (zh) * 2024-09-29 2024-12-31 广州鹏辉能源科技股份有限公司 一种固态锂电池及其制备方法和涉电设备

Also Published As

Publication number Publication date
EP4258378A4 (en) 2024-10-30
CN116547832A (zh) 2023-08-04
JPWO2022118928A1 (https=) 2022-06-09
US20240105926A1 (en) 2024-03-28
EP4258378A1 (en) 2023-10-11

Similar Documents

Publication Publication Date Title
JP6963866B2 (ja) 全固体電池用負極および全固体電池
WO2022118928A1 (ja) 全固体電池のシステム
JPWO2022118928A5 (https=)
JP2020161364A (ja) 全固体リチウム二次電池およびその製造方法
US20230216043A1 (en) Negative electrode for all-solid-state secondary battery, method for manufacturing the same, and all-solid-state secondary battery
JP2021034328A (ja) 全固体電池および全固体電池のシステム
JP2021144906A (ja) 全固体電池用正極および全固体電池
JP7401359B2 (ja) 全固体電池用電極および全固体電池
JP2021034325A (ja) 固体電解質シートおよび全固体リチウム二次電池
CN112602212B (zh) 非水电解质二次电池
JP7284666B2 (ja) 全固体電池
JP2022152275A (ja) 全固体電池用電極および全固体電池
JP7033697B2 (ja) 全固体電池用電極および全固体電池
US20240387947A1 (en) All-solid-state battery
JP7657576B2 (ja) 全固体電池用正極および全固体電池
JP7453037B2 (ja) 全固体電池
WO2022138886A1 (ja) 全固体電池用電極および全固体電池
CN116490992A (zh) 全固体二次电池用负极及全固体二次电池
JPWO2022138886A5 (https=)
JP2021039860A (ja) 全固体電池用負極および全固体電池
JP7328166B2 (ja) 全固体二次電池
JP7797395B2 (ja) 全固体二次電池用負極および全固体二次電池
US20250140908A1 (en) All-solid-state battery
JP2021144915A (ja) 全固体二次電池用正極および全固体二次電池
JP2021012835A (ja) 全固体電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21900678

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022566984

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 18265019

Country of ref document: US

Ref document number: 202180081328.9

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021900678

Country of ref document: EP

Effective date: 20230703