WO2021111551A1 - Élément d'électrode, batterie entièrement solide, poudre pour élément d'électrode, procédé de fabrication d'élément d'électrode, et procédé de fabrication de batterie entièrement solide - Google Patents

Élément d'électrode, batterie entièrement solide, poudre pour élément d'électrode, procédé de fabrication d'élément d'électrode, et procédé de fabrication de batterie entièrement solide Download PDF

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Publication number
WO2021111551A1
WO2021111551A1 PCT/JP2019/047454 JP2019047454W WO2021111551A1 WO 2021111551 A1 WO2021111551 A1 WO 2021111551A1 JP 2019047454 W JP2019047454 W JP 2019047454W WO 2021111551 A1 WO2021111551 A1 WO 2021111551A1
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particle size
solid electrolyte
positive electrode
active material
oxide
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PCT/JP2019/047454
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English (en)
Japanese (ja)
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秀文 本林
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株式会社豊島製作所
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Priority to PCT/JP2019/047454 priority Critical patent/WO2021111551A1/fr
Publication of WO2021111551A1 publication Critical patent/WO2021111551A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • 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
    • 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 electrode member, an all-solid-state battery, a powder for an electrode member, a method for manufacturing an electrode member, and a method for manufacturing an all-solid-state battery.
  • all-solid-state batteries as a power source for electric vehicles and small electronic devices is drawing attention.
  • the all-solid-state battery is safer by adopting a solid electrolyte material instead of the liquid electrolyte containing a flammable organic solvent like a conventional lithium-ion battery and making all the constituent parts of the battery solid.
  • Various developments are underway in that a large capacity, high output, and long life can be expected.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2013-149433 describes an example of an all-solid-state battery in which a specific element is solid-solved at the interface between an electrode active material and a solid electrolyte material.
  • Non-Patent Document 1 describes an example of an all-solid-state battery in which a gold layer is introduced at an interface between a solid electrolyte material and an electrode material.
  • Patent Document 1 and Non-Patent Document 1 have taken certain measures from the viewpoint of reducing the resistance of the interface between the solid electrolyte and the positive electrode active material, but the manufacturing method is complicated and the manufacturing method is complicated. The cost required for this is also high, and there is still room for consideration.
  • the present invention is an electrode capable of manufacturing an all-solid-state battery having a low internal resistance that can be driven at room temperature by an inexpensive and simple method without necessarily using a conventionally known high-temperature heat treatment process or vacuum process.
  • a member, an all-solid-state battery, a powder for an electrode member, and a method for manufacturing an electrode member and an all-solid-state battery are provided.
  • the electrode member according to the embodiment of the present invention is arranged on a solid electrolyte layer made of a sintered body of an oxide-based solid electrolyte and a solid electrolyte layer, and has a 10% particle size in a cumulative particle size distribution based on a volume basis.
  • (D 10 ) is 0.01 ⁇ m to 0.5 ⁇ m
  • 50% particle size (D 50 ) is 0.01 ⁇ m to 1.0 ⁇ m
  • the content of particles having a particle size of 0.12 ⁇ m or less is 0.5% by volume.
  • It is an electrode member including a thin-film positive electrode active material layer formed of fine powder made of the above oxide-based positive electrode active material.
  • the positive electrode active material layer not only the positive electrode active material layer is formed only by the fine powder made of the oxide-based positive electrode active material, but also the desired characteristics required for the positive electrode active material layer are exhibited. Therefore, it goes without saying that a material well known to those skilled in the art may be further contained in the fine powder. For example, a mode in which a carbon material powder and / or a metal powder that further promotes electron conductivity is mixed with a fine powder made of an oxide-based positive electrode active material, and a mode in which a solid electrolyte powder is mixed as a lithium ion conductivity aid.
  • the powder solidified body is not limited to the embodiment composed of a single positive electrode active material fine particles, and it is of course possible to form a single layer or a plurality of layers of a powder solidified body composed of different types of fine particles. Is.
  • the electrode member according to the embodiment of the present invention has a solid electrolyte layer of Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 , Li 0.33 La 0.55 TiO 3 , Li 7 La 3 Zr 2 O 12 (lithium site).
  • the positive electrode active material fine powder contains LiCoO 2 (substitution type of Mg etc. to cobalt site) containing either Al or Ga substitution type to Al or Ga and substitution type such as Nb or Ta to zirconium site.
  • LiNi 0.33 Co 0.33 Mn 0.33 O 2 LiNi 0.5 Co 0.3 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.5 Mn 1.5 O 4 , LiNiO 2 , LiFePO 4, etc.
  • Any known positive electrode active material such as a metal pyrophosphate composite oxide such as Li 2 CoP 2 O 7 may be used.
  • the electrode member according to the embodiment of the present invention is arranged on a solid electrolyte layer made of a sintered body of an oxide-based solid electrolyte and a solid electrolyte layer, and is 10% in the cumulative particle size distribution based on the volume.
  • the particle size (D 10 ) is 0.01 ⁇ m to 0.5 ⁇ m
  • the 50% particle size (D 50 ) is 0.01 ⁇ m to 1.0 ⁇ m
  • the content of particles with a particle size of 0.20 ⁇ m or less is 5% by mass or more.
  • It is an electrode member including a thin-film (bulk-like) positive electrode active material layer formed of a fine powder made of LiNi 0.5 Mn 1.5 O 4 of the above.
  • the all-solid-state battery according to the embodiment of the present invention is an all-solid-state battery using the electrode member on one side.
  • the electrode member powder according to the embodiment of the present invention has a 10% particle size (D 10 ) of 0.01 ⁇ m to 0.5 ⁇ m and a 50% particle size (D 50 ) in the cumulative particle size distribution based on the volume.
  • the method for manufacturing an electrode member according to an embodiment of the present invention has a 10% particle size (D 10 ) in a cumulative particle size distribution on a volume basis on a solid electrolyte layer made of a sintered body of an oxide-based solid electrolyte. Is 0.01 ⁇ m to 0.5 ⁇ m, the 50% particle size (D 50 ) is 0.01 ⁇ m to 1.0 ⁇ m, and the content of particles with a particle size of 0.12 ⁇ m or less is 0.5% by volume or more.
  • the thin positive electrode active material layer is formed into a solid electrolyte layer. It is a method of manufacturing an electrode member including forming on the surface.
  • applying a mechanical external force along the surface of the fine powder causes friction between the fine powders or at the interface between the fine powders and the solid electrolyte layer. Including to cause.
  • the method for manufacturing an electrode member according to an embodiment of the present invention includes applying a mechanical external force along the surface of the fine powder to rubbing the surface of the fine powder with a friction member.
  • the method for producing an all-solid-state battery according to the embodiment of the present invention comprises, on one aspect, forming a first metal layer on the positive electrode active material layer formed on the first main surface of the solid electrolyte layer.
  • the electrode member according to the embodiment of the present invention is arranged on a solid electrolyte layer made of a sintered body of an oxide-based solid electrolyte and a solid electrolyte layer, and is 10% in the cumulative particle size distribution based on the volume.
  • the particle size (D 10 ) is 0.01 ⁇ m to 0.5 ⁇ m
  • the 50% particle size (D 50 ) is 0.01 ⁇ m to 1.0 ⁇ m
  • the content of particles having a particle size of 0.12 ⁇ m or less is 0.5.
  • the powder made of an oxide-based solid electrolyte is transferred to Li 7 La 3 Zr 2 O 12 (a substitution type of Al or Ga to lithium site, and zirconium site). (Including Nb or Ta substitution type), Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 , Li 3 BO 3 (Li 3 BO 3 to Li 2 SO 4 , Li 2 CO 3 , Li 4 SiO 4 of the material group (Including amorphous or crystallized glass in which one or more of them are mixed), Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 , Li 0.33 La 0.55 TIO 3 is selected from one or more of the group. To.
  • the powder made of an oxide-based solid electrolyte has a 50% particle size (D 50 ) of 10 ⁇ m or less in the cumulative particle size distribution based on the volume.
  • the electrode member according to the embodiment of the present invention contains 25 to 99% by mass of a powder made of an oxide-based solid electrolyte in the mixture.
  • the battery can be driven at room temperature by an inexpensive and simple method without necessarily using a wet process using a conventionally known binder or an organic solvent, a high-temperature heat treatment process, or a vacuum process.
  • a method for manufacturing an electrode member, an all-solid-state battery, a powder for an electrode member, an electrode member, and an all-solid-state battery that can be manufactured not only in an inert atmosphere but also in an air atmosphere. Can be provided.
  • the electrode member according to the embodiment of the present invention includes a solid electrolyte layer 1 made of a sintered body of an oxide-based solid electrolyte and a positive electrode arranged on the surface of the solid electrolyte layer 1. It includes an active material layer 2.
  • a solid electrolyte layer 1 made of an oxidizing solid electrolyte material can be used.
  • the oxidation-based solid electrolyte material include Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 having a NASICON type crystal structure, Li 0.33 La 0.55 TiO 3 having a perovskite type crystal structure, and Li 7 La 3 Zr 2 O having a garnet type crystal structure. 12 mag is used. Specifically, Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 , Li 0.33 La 0.55 TiO 3 , Li 7 La 3 Zr 2 O 12 (replacement type such as Al or Ga to lithium site, and Nb to zirconium site). Alternatively, any of (including a substitution type such as Ta) is preferably used.
  • LLZ cubic lithium lanthanum zirconium oxide
  • Li 7 La 3 Zr 2 O 12 having a garnet-type crystal structure (substitution type such as Al or Ga to lithium site, and zirconium site
  • substitution type such as Al or Ga to lithium site
  • zirconium site In addition to the high conductivity of lithium ions, the reactivity with metallic lithium is extremely low compared to other oxide-based solid electrolytes, and dendrite formation by lithium ions is avoided.
  • It is particularly preferably used as an oxidation-based solid electrolyte material for the solid electrolyte layer 1 in that it can form a lithium metal layer directly on the surface of a sintered substrate made of an oxide-based solid electrolyte.
  • FIG. 2 A photograph of the fracture surface of the solid electrolyte layer 1 is shown in FIG.
  • the solid electrolyte layer 1 is a sintered body composed of crystal grains having a particle size of approximately 2 to 10 ⁇ m based on electron microscopic observation, and grows into larger crystal grains by binding the crystal grains to each other.
  • the grain boundary interface is unclear.
  • the sintered body of the solid electrolyte layer 1 according to the present embodiment is a dense sintered body and has few pores.
  • the porosity of the solid electrolyte layer 1 is, for example, about 0.1 to 5.0%.
  • the porosity of the solid electrolyte layer 1 can be measured based on, for example, JIS R1634 (1998).
  • the solid electrolyte layer 1 has an ion conductivity of about 5.0E-4 to 2.0E-03 (S / cm). Is shown.
  • the grain boundary resistance of the solid electrolyte layer 1 can be lowered, and the ion conductivity can be improved.
  • an all-solid-state battery that can be driven by a cheaper room temperature process without using a conventional high-temperature process or the like can be obtained.
  • the fine powder used for the positive electrode active material layer 2 include lithium cobalt oxide (LiCoO 2 ), lithium nickel cobalt manganate (LiNi 0.33 Co 0.33 Mn 0.33 O 2 , LiNi 0.5 Co 0.3 Mn 0.2 O 2) .
  • LiNi 0.8 Co 0.1 Mn 0.1 O 2 Lithium nickel manganate (LiNi 0.5 Mn 1.5 O 4 ), Lithium nickel oxide (LiNiO 2 ), Lithium iron phosphate (LiFePO 4 ), Lithium cobalt oxide (Li 2 CoP 2 O) 7 ) etc.
  • the positive electrode active material layer 2 is a fine powder made of an oxide-based positive electrode active material or a powder made of a mixture of an oxide-based positive electrode active material and an oxide-based solid electrolyte powder (hereinafter, also referred to as “positive electrode mixture”).
  • the contained powders are in close contact with each other and solidified, and are composed of a powder solidified body having a thin film shape or a bulk shape.
  • This powder solidified body adheres and solidifies on the surface of a powder containing a fine powder composed of an oxide-based positive electrode active material or a positive electrode mixture by an external mechanical force applied to the powder, and is powdered as if it were a sintered body. It means a layer that is solidified by the binding of grain boundaries and becomes bulky.
  • the production does not necessarily require high temperature conditions (at least 500 ° C. or higher) at the interface with the solid electrolyte layer 1, for example, about room temperature (specifically, about 1 to 30 ° C., more specifically, 15 to 15 to It can be easily produced even under low temperature conditions of 25 ° C.).
  • high temperature conditions at least 500 ° C. or higher
  • room temperature specifically, about 1 to 30 ° C., more specifically, 15 to 15 to It can be easily produced even under low temperature conditions of 25 ° C.
  • the method for forming the positive electrode active material layer (positive electrode mixture layer) 2 made of the solidified powder will be described later.
  • the positive electrode active material layer (positive electrode mixture layer) 2 made of a solidified powder on the solid electrolyte layer 1 it is particularly important to appropriately select the properties of the fine powder as a raw material.
  • the plasticity of the fine powder fine crystal grain superplasticity
  • the mechanical adhesive force including the anchor effect
  • the chemical adhesive force or the diffusion adhesive force. Need to be obtained more appropriately.
  • the higher the ratio of ultrafine powders of less than 100 nm called nanoparticles the more desirable it is, and in particular, the 10% particle size (D 10 ) in the cumulative particle size distribution based on the volume. It is more preferable to use an oxide-based positive electrode active material having a particle size of 0.01 ⁇ m to 0.5 ⁇ m and a 50% particle size (D 50) of 0.01 ⁇ m to 1.0 ⁇ m as a raw material.
  • the 10% particle size (D 10 ) of the fine powder is larger than 0.5 ⁇ m, the fine powders may not adhere well to each other on the solid electrolyte layer 1 and a solidified powder may not be formed.
  • the smaller the average particle size (D 50 ) of the fine powder is, the more preferable it is, and it is 0.15 ⁇ m or less. Is more preferable, and even more preferably 0.12 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the 10% particle size (D 10 ) of the fine powder is not limited to the following, but is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, for example, from the viewpoint of handleability and the like.
  • the 10% particle size (D 10 ) is 0.01 to 0.3 ⁇ m, further 0.01 to 0.2 ⁇ m, and further 0.01 to 0.17 ⁇ m. It is preferable to use the fine powder of.
  • the 10% particle size (D 10 ) is 0.01 to 0.4 ⁇ m, further 0.01 to 0.35 ⁇ m, and further 0.01 to 0. It is preferable to use a fine powder of 3 ⁇ m.
  • a fine powder having a 10% particle size (D 10 ) of 0.01 to 0.5 ⁇ m, more preferably 0.01 to 0.3 ⁇ m can be used. ..
  • the 50% particle size (D 50 ) of the fine powder is larger than 1.0 ⁇ m, the fine powders do not adhere well to each other, and the positive electrode active material layer (positive electrode mixture layer) 2 made of the solidified powder has a required thickness. It may not be possible to form.
  • the lower limit of the particle size of the 50% particle size (D 50 ) of the fine powder is not limited to the following, but can be, for example, 0.01 ⁇ m or more, further 0.05 ⁇ m or more, and the work is easy. From the viewpoint of sex, it is more preferably 0.1 ⁇ m or more.
  • FIG. 3 shows an example of the cumulative particle size distribution of the fine powder suitable as the fine powder used for the positive electrode active material layer (positive electrode mixture layer) 2.
  • the 50% particle size (D 50 ) of the cumulative particle size distribution is in the range of 0.01 to 1.0 ⁇ m, and further in the range of 0.1 ⁇ m to 1.0 ⁇ m. It is particularly preferable to use a certain fine powder from the viewpoint of workability.
  • a fine powder having a ratio (D 50 / D 10 ) of 50% particle size (D 50 ) to 10% particle size (D 10 ) in the cumulative particle size distribution based on the volume is 3 or less, more preferably 2 or less is used. It is preferred, the ratio of 10% particle size and 90% particle diameter (D 90) (D 10) (D 90 / D 10) of 10 or less, more preferably to use a fine powder is 6 or less.
  • the fine powder having such characteristics contains a fine powder having a particle size of about 0.12 ⁇ m or 0.08 ⁇ m or less, which is considered to greatly contribute to the formation of the solidified powder according to the present embodiment, in a predetermined ratio. It is particularly suitable because the solidified powder according to the embodiment can be easily deposited to an appropriate thickness.
  • particles having a particle size of 0.12 ⁇ m or less are contained in the raw material, for example, by 0.5% by volume or more, preferably 0.5% by volume or more. 2% by volume or more, more preferably 5% by volume or more, and particles having a particle size of 0.08 ⁇ m or less are contained in the raw material, for example, 0.1% by volume or more, preferably 0.5% by volume or more, still more preferably 2% by volume. It is preferable to use the fine powder containing the above because the solidified powder can be formed appropriately and easily.
  • the upper limit of the composition ratio of particles having a particle size of 0.12 ⁇ m or less in the raw material is not particularly limited, and the larger the particle size, the more preferable.
  • the particles having a particle size of 0.12 ⁇ m or less are, for example, less than 0.5% by volume.
  • a small amount of the positive electrode active material layer 2 can be formed, it may not be possible to deposit the positive electrode active material layer 2 to a thickness sufficient to function as the positive electrode active material layer of the all-solid-state battery.
  • the content of particles having a particle size of 0.12 ⁇ m or less in the raw material can be preferably 0.5 to 15% by volume, and more preferably 2 to 4% by volume. Is preferable.
  • lithium nickel-cobalt manganate When lithium nickel-cobalt manganate is used as a fine powder, even a material containing 5% by volume or more, preferably 10% by volume or more, and more preferably 15% by volume or more of particles having a particle size of 0.20 ⁇ m or less. Good.
  • the particle size range suitable for forming the solidified powder varies depending on the type of material used for the fine powder, but in the oxide-based positive electrode active material shown above as the material of the positive electrode active material layer (positive electrode mixture layer) 2. Can be said to be suitably usable as long as it is a fine powder containing 0.5% by volume or more of particles having a particle size of 0.12 ⁇ m or less.
  • the content of particles having a predetermined particle size or less is not limited to the above, and the larger the content, the more efficiently the positive electrode active material layer (positive electrode mixture layer) 2 can be formed.
  • the “particle size” refers to a particle size based on a cumulative particle size curve based on the volume of the particle size distribution measured using a laser diffraction / scattering type particle size distribution measuring device.
  • “D 10 ”, “D 50 ” and “D 90 ” indicate 10% particle size, 50% particle size, and 90% particle size, respectively, based on the volume in the cumulative particle size distribution, and are laser diffraction / scattering particle size.
  • the cumulative particle size curve of the particle size distribution measured using the distribution measuring device the particle size when the integrated amount occupies 10%, 50%, and 90%, respectively, on a volume basis is shown.
  • the particle size of the fine powder can be measured using, for example, the laser diffraction / scattering type particle size distribution measuring device "Microtrac MT-3000" manufactured by Microtrac Bell Co., Ltd., and the attached software is used from the measurement results. Then, the cumulative particle size distribution based on the volume can be evaluated.
  • the positive electrode active material fine powders or the positive electrode described later will be used.
  • the active material fine powder and the oxide solid electrolyte powder can be adhered and fixed.
  • the electrode member thus obtained has good adhesiveness between the solid electrolyte layer 1 and the positive electrode active material layer (positive electrode mixture layer) 2 and can form a low resistance interface. Therefore, the electrode member is an all-solid state using the electrode member.
  • the battery can be sufficiently driven at room temperature. A measuring method known to those skilled in the art can be used for the particle size distribution measurement.
  • the electrode member thus obtained is further heat-treated at 100 to 500 ° C. for 10 seconds to 1 hour in an air atmosphere, an inert atmosphere or an oxygen atmosphere to further solidify the electrolyte layer 1 and the positive electrode active material. It may be possible to reduce the resistance of the interface with the layer (positive electrode mixture layer) 2.
  • the above-mentioned fine powder is deposited on the surface of the sintered body of the solid electrolyte layer 1 having minute irregularities, and the solid electrolyte layer is formed.
  • a thin-film positive electrode active material layer 2 is formed by applying a mechanical external force from above 1 toward the inside of the solid electrolyte layer 1. This was sintered by simply applying pressure to the surface of the nanoparticles (particle size 0.1 ⁇ m or less) and the plasticity of the fine powder having a particle size close to the nanoparticles and having a particle size of about 0.1 ⁇ m. This utilizes the phenomenon that fine powders are integrated and bulked as described above.
  • the solid electrolyte layer is released with respect to the release of the enormous surface energy of the fine powder and the solid electrolyte layer 1 having a hardness higher than that of the fine powder.
  • a fine powder having a hardness lower than 1 densification progresses due to the bonding of the positive electrode active material powder to form a solidified powder, and the powder is uniformly and strongly bonded to the solid electrolyte layer due to an adhesive force such as an anchor effect. It is presumed that a thin interface (powder solidified body) having a certain gloss in appearance is formed by forming an interface.
  • a method called a vacuum process such as a conventional sputtering method or PLD (pulse laser deposition method) or an aerosol deposition method is used to inject powder at high speed and use the kinetic energy to form a thin film made of powder material on a substrate.
  • PLD pulse laser deposition method
  • aerosol deposition method is used to inject powder at high speed and use the kinetic energy to form a thin film made of powder material on a substrate.
  • a sintered body of an oxide-based solid electrolyte is used as the solid electrolyte layer 1, and the cumulative amount is accumulated on a volume basis.
  • Particles having a 10% particle size (D 10 ) of 0.01 ⁇ m to 0.5 ⁇ m, a 50% particle size (D 50 ) of 0.01 ⁇ m to 1.0 ⁇ m, and a particle size of 0.12 ⁇ m or less in the particle size distribution are defined as 0.
  • the positive electrode active material layer 2 is arranged with a thin film-like powder solidified body in which fine powders made of an oxide-based positive electrode active material containing 5% by volume or more and further 5% by volume or more are adhered to each other and solidified.
  • the solid electrolyte layer 1 and the positive electrode active material layer 2 can be joined inexpensively and easily at room temperature without using a vacuum process or the like.
  • a metal layer such as gold (Au) is used as the first electrode collecting layer. Is formed.
  • a second negative electrode layer such as metallic lithium (Li) is formed on the second main surface, which is the other surface of the solid electrolyte layer 1 and faces the first main surface, to obtain an all-solid-state battery. ..
  • the internal resistance of the obtained all-solid-state battery is as small as 1000 to 5000 ⁇ ⁇ cm 2 (when the thickness of the solid electrolyte layer is about 0.5 mm to 1 mm), which is a simpler and cheaper method. Therefore, an electrode member capable of driving a battery at room temperature (25 ° C.), an all-solid-state battery, and a method for manufacturing these can be provided.
  • a method for manufacturing an electrode member and an all-solid-state battery according to an embodiment of the present invention will be described.
  • a solid electrolyte layer 1 is prepared, and the 10% particle size (D 10 ) in the cumulative particle size distribution based on the volume is 0.01 ⁇ m to 0.5 ⁇ m on the solid electrolyte layer 1, and the 50% particle size (D 50).
  • the fine powder is deposited over the entire surface on the solid electrolyte layer 1.
  • applying a predetermined pressure to the entire surface of the fine powder can be mentioned.
  • a pressure of about 10 kPa to 500 kPa, preferably 20 kPa to 300 kPa, and further about 50 kPa to 200 kPa from the surface of the fine powder the fine powders are brought into close contact with each other and solidified to form a powder solidified body.
  • a low resistance interface can be formed between the solid electrolyte layer 1 and the solidified powder.
  • a mechanical external force so as to cause friction in the fine powder on the solid electrolyte layer 1.
  • a friction member such as cloth or paper
  • various materials such as paper waste, cloth waste, and resin fiber can be used.
  • the rubbing direction is not particularly limited, and the surface may be rubbed in a specific direction or in multiple directions.
  • the production of the positive electrode active material layer does not necessarily require high-temperature heat treatment, and therefore the interface between the solid electrolyte layer 1 and the positive electrode active material layer 2 In, the reaction and diffusion phenomenon between substances can be suppressed, and the formation of an unintended high resistance layer can be suppressed. As a result, an electrode member having a lower resistance can be manufactured.
  • the electrode member according to another embodiment of the present invention has a 10% particle size (D 10 ) of 0.01 ⁇ m to 0.5 ⁇ m and a 50% particle size (D 50 ) of 0.01 ⁇ m in the cumulative particle size distribution based on the volume.
  • D 10 10% particle size
  • D 50 50% particle size
  • the positive electrode mixture is placed on the solid electrolyte layer 1, and the same predetermined pressure as described above is applied to the entire surface of the positive electrode mixture. Includes forming the material layer 2.
  • Examples of the powder composed of the oxide-based solid electrolyte include Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 (LAGP), Li 3 BO 3 (LBO) (Li 3 BO 3 and Li 2 SO 4 ), in addition to the above-mentioned LLZ. Includes amorphous or crystallized glass of one or more of the materials Li 2 CO 3 and Li 4 SiO 4 ), Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 (LATP), Li 0.33 Materials selected from any one or more of the group consisting of La 0.55 TiO 3 (LLTO) can be used, preferably one or two of these solid electrolyte materials.
  • the particle size of the powder made of the oxide-based solid electrolyte to be added is preferably such that the 50% particle size (D 50 ) in the cumulative particle size distribution based on the volume is 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the optimum composition ratio of the fine powder composed of the oxide-based positive electrode active material in the mixture and the powder composed of the oxide-based solid electrolyte can be adjusted by the combination of materials. It is preferable that the powder composed of the solid electrolyte is contained in an amount of 25 to 99% by volume.
  • LCO lithium cobaltate (LCO) fine powder
  • D 10 particle size
  • D 50 particle size
  • LAGP average particle size of 1.5 ⁇ m
  • the interfacial resistance between the solid electrolyte-positive electrode mixture layer when the mixture is prepared and arranged on the solid electrolyte layer 1 to form the positive electrode active material layer 2 shows a tendency as shown in Table 1.
  • LAGP which is a powder composed of an oxide-based solid electrolyte
  • LAGP is mixed in the mixture by 30 to 50% by mass ratio, and further by mixing 35 to 40%.
  • the interfacial resistance with the solid electrolyte can be made smaller.
  • the interface resistance with the solid electrolyte layer 1 may be further reduced by heat-treating the mixture prior to supporting the mixture on the solid electrolyte layer 1 to form the positive electrode active material layer 2.
  • the solid electrolyte layer 1 and the positive electrode active material layer are obtained by heat-treating a raw material in which LCO: LAGP is mixed at a ratio of 75:25 mass% in an oxygen atmosphere at typically 300 to 400 ° C. for 1 to 10 hours.
  • the interfacial resistance with 2 can be significantly reduced.
  • the optimum heat treatment conditions differ depending on the combination of materials, but at least the heat treatment temperature must be equal to or lower than the temperature at which the mixed materials cause a reaction.
  • the fine powder made of the above-mentioned oxide-based positive electrode active material was used alone. It is the same as the manufacturing method of the case.
  • Example 1- Manufacturing of electrode members
  • Sandpaper manufactured by Sankyo Rikagaku Co., Ltd.
  • Li 7 La 3 Zr 2 O 12 sintered substrate hereinafter referred to as "LLZ substrate”
  • LLZ substrate Li 7 La 3 Zr 2 O 12 sintered substrate
  • the surface of the sintered substrate is fine powder of lithium cobaltate (LCO) (manufactured by Toyoshima Seisakusho Co., Ltd., 10% particle size (D 10 ) 0.097 ⁇ m, 50% particle size (D 50 ) 0.
  • LCO lithium cobaltate
  • the positive electrode active material layer was supported by applying a mechanical external force of 10 kPa to 500 kPa so as to rub it against the LLZ substrate using (manufactured by Nippon Paper Cresia Co., Ltd.). When the supported weight of the positive electrode active material layer formed by the micro balance was measured, it was confirmed that it was 0.25 mg from the difference from the weight of the LLZ substrate measured in advance.
  • the above lithium ion secondary battery was installed in a beaker cell, the Au collecting electrode surface was connected to the anode terminal, the Li negative electrode surface was connected to the cathode terminal, and various electrochemical measurements were performed using a potentiogalvanostat device.
  • a good battery was obtained. The drive was confirmed (Fig. 7).
  • impedance measurement AC impedance measuring device attached to the potential galvanostat device
  • the internal resistance of the all-solid-state battery was about 2 k ⁇ (FIG. 8).
  • the above-mentioned method for producing the electrode member and the production of the all-solid-state battery are performed by changing the material of the solid electrolyte layer and the particle size of the fine powder constituting the positive electrode active material layer to be supported on the solid electrolyte layer as shown in Tables 2 to 4. It was evaluated whether or not the electrode member according to the present embodiment could be produced according to the method.
  • the "content rate" in Tables 2 to 4 is obtained from the measurement results of the cumulative particle size distribution based on the volume using the laser diffraction / scattering type particle size distribution measuring device "Microtrac MT-3000" manufactured by Microtrac Bell Co., Ltd. It was.
  • the 10% particle size (D 10 ) is 0.01 ⁇ m to 0.5 ⁇ m
  • the 50% particle size (D 50 ) is 0.01 ⁇ m to 1.0 ⁇ m
  • the particle size is 0.12 ⁇ m or less.
  • the positive electrode active material layer could be appropriately formed on the solid electrolyte layer.
  • the 10% particle size (D 10 ) and 50% particle size (D 50 ) are outside the appropriate range and do not contain particles with a particle size of 0.12 ⁇ m or less (rightmost column), a positive electrode active material layer should be formed. I could't.
  • the 10% particle size (D 10 ) was 0.01 ⁇ m to 0.5 ⁇ m
  • the 50% particle size (D 50 ) was 0.01 ⁇ m to 1.
  • a fine powder containing 5% by volume or more of particles having a particle size of 0 ⁇ m and a particle size of 0.20 ⁇ m or less was used (left column)
  • the positive electrode active material layer could be appropriately formed.
  • the material (right column) whose properties of the fine powder were out of the appropriate range could not form the positive electrode active material layer.
  • the 10% particle size (D 10 ) is 0.01 ⁇ m to 0.5 ⁇ m
  • the 50% particle size (D 50 ) is 0.01 ⁇ m to 1.0 ⁇ m
  • the particle size is 0.12 ⁇ m or less.
  • the oxide solid electrolyte can be obtained.
  • a solid electrolyte layer could not be formed on the positive electrode active material layer.
  • Example 2- Preparation of positive electrode mixture
  • the same LCO fine powder as in Example 1 and the LAGP solid electrolyte powder prepared by the solid phase synthesis method were mixed so that the LCO: LAGP ratio was 75:25.
  • a mixed powder was obtained by stirring and mixing for 10 minutes using an agate mortar. The obtained mixed powder was heat-treated at 350 ° C. for 3 hours in an air atmosphere to obtain a positive electrode mixture composed of a mixture of LCO and LAGP.
  • LLZ substrate Ga-doped LLZ (hereinafter referred to as "LLZ substrate") having a relative density of 95% or more, a 10 mm square and a thickness of 1 mm is prepared by a solid-phase synthesis method, and one side of this LLZ substrate is sandpaper. Polishing treatment was performed with (# 400). An appropriate amount of the above-mentioned positive electrode mixture was added to the non-woven fabric, and an external pressure of about 10 kPa to 500 kPa was applied to the polished surface of the LLZ substrate to support about 0.3 mg. The LLZ substrate on which this positive electrode mixture was supported was heat-treated at 350 ° C.

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Abstract

L'invention concerne : un élément d'électrode avec lequel il est possible de produire une batterie entièrement solide à l'aide d'un procédé peu coûteux et facile sans nécessairement utiliser un procédé de traitement thermique à haute température déjà connu ou un procédé sous vide, l'élément d'électrode étant également apte à piloter la batterie entièrement solide ainsi produite ; la batterie entièrement solide ; une poudre pour un élément d'électrode ; et des procédés de fabrication de l'élément d'électrode et de la batterie entièrement solide. L'élément d'électrode comprend : une couche d'électrolyte solide composée d'un comprimé fritté d'un électrolyte solide à base d'oxyde ; et une couche de matériau actif d'électrode positive en forme de film mince qui est positionnée sur la couche d'électrolyte solide et est formée d'une poudre fine composée d'un matériau actif d'électrode positive à base d'oxyde pour lequel le diamètre de grain de 10 % (D10) dans la distribution de taille de grain volumétrique cumulative est de 0,01 à 0,5 µm, le diamètre de grain de 50 % (D50) dans ladite distribution de taille de grain cumulative est de 0,01 à 1,0 µm, et la quantité de particules ayant un diamètre de grain inférieur ou égal à 0,12 µm est supérieure ou égale à 0,5 % en volume.
PCT/JP2019/047454 2019-12-04 2019-12-04 Élément d'électrode, batterie entièrement solide, poudre pour élément d'électrode, procédé de fabrication d'élément d'électrode, et procédé de fabrication de batterie entièrement solide WO2021111551A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004213533A (ja) * 2003-01-08 2004-07-29 Seiko Epson Corp 画面受信装置、画面配信装置、画面情報送受信システム、画面受信方法、画面配信方法並びにそのプログラム
JP2009181921A (ja) * 2008-01-31 2009-08-13 Ohara Inc 固体電池
WO2012043566A1 (fr) * 2010-09-28 2012-04-05 トヨタ自動車株式会社 Corps fritté destiné à être utilisé dans une batterie, procédé de fabrication d'un corps fritté destiné à être utilisé dans une batterie, et batterie au lithium entièrement électronique
WO2013140607A1 (fr) * 2012-03-23 2013-09-26 株式会社 東芝 Électrolyte solide, procédé de fabrication d'électrolyte solide, cellule, et bloc-cellule
JP2016001598A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
WO2016175217A1 (fr) * 2015-04-30 2016-11-03 日本電気株式会社 Solution électrolytique pour batteries secondaires, et batterie secondaire
JP2017004824A (ja) * 2015-06-12 2017-01-05 アルプス電気株式会社 二次電池および二次電池の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004213533A (ja) * 2003-01-08 2004-07-29 Seiko Epson Corp 画面受信装置、画面配信装置、画面情報送受信システム、画面受信方法、画面配信方法並びにそのプログラム
JP2009181921A (ja) * 2008-01-31 2009-08-13 Ohara Inc 固体電池
WO2012043566A1 (fr) * 2010-09-28 2012-04-05 トヨタ自動車株式会社 Corps fritté destiné à être utilisé dans une batterie, procédé de fabrication d'un corps fritté destiné à être utilisé dans une batterie, et batterie au lithium entièrement électronique
WO2013140607A1 (fr) * 2012-03-23 2013-09-26 株式会社 東芝 Électrolyte solide, procédé de fabrication d'électrolyte solide, cellule, et bloc-cellule
JP2016001598A (ja) * 2014-05-19 2016-01-07 Tdk株式会社 リチウムイオン二次電池
WO2016175217A1 (fr) * 2015-04-30 2016-11-03 日本電気株式会社 Solution électrolytique pour batteries secondaires, et batterie secondaire
JP2017004824A (ja) * 2015-06-12 2017-01-05 アルプス電気株式会社 二次電池および二次電池の製造方法

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