WO2020116324A1 - Batterie au lithium-ion entièrement solide, et mélange d'électrode négative - Google Patents

Batterie au lithium-ion entièrement solide, et mélange d'électrode négative Download PDF

Info

Publication number
WO2020116324A1
WO2020116324A1 PCT/JP2019/046657 JP2019046657W WO2020116324A1 WO 2020116324 A1 WO2020116324 A1 WO 2020116324A1 JP 2019046657 W JP2019046657 W JP 2019046657W WO 2020116324 A1 WO2020116324 A1 WO 2020116324A1
Authority
WO
WIPO (PCT)
Prior art keywords
less
solid
negative electrode
mass
solid electrolyte
Prior art date
Application number
PCT/JP2019/046657
Other languages
English (en)
Japanese (ja)
Inventor
千明 外輪
Original Assignee
昭和電工株式会社
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 昭和電工株式会社 filed Critical 昭和電工株式会社
Publication of WO2020116324A1 publication Critical patent/WO2020116324A1/fr

Links

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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 lithium-ion battery.
  • -Lithium-ion batteries have high voltage and high energy density, and are widely used.
  • studies on all-solid-state lithium-ion batteries using a solid electrolyte that does not leak and does not leak instead of the organic electrolyte have been actively studied. ..
  • an all-solid-state lithium-ion battery that uses an inorganic ceramics-based lithium-ion conductor as a solid electrolyte has been studied for a long time.
  • Patent Documents 1 to 4 metal-based materials such as In, Al, Si, and Sn, ceramic-based materials such as Li 4 Ti 5 O 12 , graphite, mesocarbon microbeads (MCMB), highly oriented graphite (HOPG). It is disclosed that a carbon-based material such as hard carbon or soft carbon, or a material having a particle surface coated with a carbon layer can be used as the negative electrode active material.
  • JP, 2011-181260, A JP 2013-16423 A (US Pat. No. 9,172,113, US Pat. No. 9,845,597) JP, 2013-41749, A JP-A-2015-191864 (US Patent Publication No. 2017/0237115)
  • Patent Document 4 discloses that two or more kinds of materials are mixed and used as a negative electrode active material, but the optimum particle size of the solid electrolyte to be used, the physical properties of the materials, and the like have not been examined.
  • An all-solid-state lithium-ion battery including a negative electrode mixture layer, a positive electrode mixture layer, and a solid electrolyte layer, wherein the negative electrode mixture layer contains 35.0% by mass or more and 80.0% by mass or less of a negative electrode active material,
  • the solid electrolyte contains 19.0% by mass or more and 64.0% by mass or less, the conductive aid contains 0.1% by mass or more and less than 5.0% by mass, and the negative electrode active material has a graphite crystal plane spacing d002 of 0.3354 nm or more 0 0.3370 nm or less, and the non-aggregated graphite particles having a 50% diameter D50 in the volume-based cumulative particle size distribution of 0.1 ⁇ m or more and less than 10.0 ⁇ m are included, and the solid electrolyte is an oxide-based solid electrolyte and a sulfide-based solid electrolyte.
  • An all-solid-state lithium-ion battery which is at least one kind selected from solid electrolytes and has D50 of 0.10 ⁇ m or more and 3.00 ⁇ m or less.
  • the all-solid-state lithium ion battery according to 1 or 2 wherein the graphite particles have a circularity of 0.50 or more and 0.94 or less.
  • the all-solid-state lithium-ion battery according to any one of 1 to 6 above, wherein the R value (R ID/IG) is 0.01 or more and 0.40 or less.
  • the ratio (I(110)/I(004)) of the peak intensity of the (110) plane to the peak intensity of the (004) plane measured by powder X-ray diffraction measurement of the graphite particles is 0.01 or more 0 8.
  • a negative electrode mixture containing a negative electrode active material and a solid electrolyte wherein the negative electrode mixture contains 35.0% by mass or more and 80.0% by mass or less of the negative electrode active material and 19.0% by mass or more and 64% by mass of the solid electrolyte. 0.0% by mass or less, 0.1% by mass or more and less than 5.0% by mass of a conductive auxiliary agent, the negative electrode active material has a graphite crystal plane spacing d002 of 0.3354 nm or more and 0.3370 nm or less, and a volume-based cumulative grain.
  • the solid electrolyte includes graphite particles having a non-aggregated structure having a 50% diameter D50 in a diameter distribution of 0.1 ⁇ m or more and less than 10.0 ⁇ m, and the solid electrolyte is at least one selected from an oxide solid electrolyte and a sulfide solid electrolyte.
  • D50 is particles having a particle size of 0.10 ⁇ m or more and 3.00 ⁇ m or less, a negative electrode mixture.
  • an all-solid-state lithium-ion battery having excellent contact between the solid electrolyte and the negative electrode active material, excellent rate characteristics, cycle characteristics, and Coulomb efficiency.
  • the all-solid-state lithium-ion battery of the present invention includes at least a negative electrode mixture layer, a solid electrolyte layer, and a positive electrode mixture layer.
  • the negative electrode mixture layer contains at least a negative electrode active material, a solid electrolyte, and a conductive additive.
  • the solid electrolyte layer contains at least a solid electrolyte, and the solid electrolyte is at least one selected from oxide solid electrolytes and sulfide solid electrolytes.
  • the positive electrode mixture layer contains at least a positive electrode active material.
  • the negative electrode material mixture layer includes a negative electrode active material of 35.0% by mass or more and 80.0% by mass or less, a solid electrolyte of 19.0% by mass or more and 64.0% by mass or less, and a conductive additive. 0.1 mass% or more and less than 5.0 mass%.
  • the negative electrode active material is preferably contained in an amount of 40.0% by mass or more, more preferably 45.0% by mass or more.
  • the content of the negative electrode active material is preferably 75.0% by mass or less, and more preferably 70.0% by mass or less.
  • the solid electrolyte content is preferably 24.0 mass% or more, more preferably 29.0 mass% or more.
  • the solid electrolyte content is preferably 59.0 mass% or less, more preferably 54.0 mass% or less.
  • the conductive additive is preferably contained in an amount of 0.5% by mass or more, more preferably 1.0% by mass or more.
  • the conductive additive is preferably contained in an amount of 4.5% by mass or less, more preferably 4.0% by mass or less.
  • the content of the conductive additive is 0.1% by mass or more, the conductivity in the mixture layer is improved, and thus the rate characteristic is improved.
  • the content of the conductive additive is less than 5.0% by mass, the ionic conductivity in the mixture layer is good and the rate characteristics are improved.
  • the negative electrode active material according to one embodiment of the present invention is graphite particles having a non-aggregated structure.
  • the non-aggregated structure has a solid structure inside, and is less likely to cause intra-particle peeling even when repeated expansion and contraction due to charge and discharge, and has excellent cycle characteristics. Further, artificial graphite particles having a non-aggregated structure are preferable.
  • the non-aggregated structure means a state where the primary particles are not converted into secondary particles.
  • the 50% particle size (D50) in the volume-based cumulative particle size distribution of the graphite particles according to an embodiment of the present invention is 0.1 ⁇ m or more. This is because when it is 0.1 ⁇ m or more, the solid electrolyte is likely to be uniformly dispersed in the gaps between the graphite particles, the resistance is lowered, and the rate characteristic is improved. From the same viewpoint, it is preferably 2.0 ⁇ m or more, more preferably 4.0 ⁇ m or more. D50 is less than 10.0 ⁇ m. When it is less than 10.0 ⁇ m, good contact with the solid electrolyte particles is obtained, the resistance is lowered, and the rate characteristic is improved. From the same viewpoint, it is preferably 9.0 ⁇ m or less, more preferably 8.0 ⁇ m or less.
  • the graphite particles used in the present invention have a graphite crystal plane spacing d002 of 0.3354 nm or more determined by a powder X-ray diffraction method.
  • 0.3354 nm is the theoretical lower limit of graphite.
  • d002 is 0.3370 nm or less. This is because if the thickness is 0.3370 nm or less, graphitization is sufficiently advanced and the discharge capacity is increased. From the same viewpoint, 0.3368 nm or less is preferable, and 0.3366 nm or less is more preferable.
  • the graphite crystal plane spacing d002 can be measured by a powder X-ray diffraction (XRD) method by the Gakushin method (2004 version) (Inayoshi Noda, Michio Inagaki, Japan Society for the Promotion of Science, 117th Committee Material, 117). -71-A-1 (1963), Michio Inagaki et al., Japan Society for the Promotion of Science, 117th Committee materials, 117-121-C-5 (1972), Michio Inagaki, "Carbon", 1963, No. 36, 25. -34; Iwashita et al., Carbon vol. 42 (2004), pp. 701-714).
  • XRD powder X-ray diffraction
  • the circularity of the graphite particles according to one embodiment of the present invention is preferably 0.50 or more. When it is 0.50 or more, the packing property of particles is improved and the electrode density can be increased. From the same viewpoint, 0.60 or more is preferable, and 0.70 or more is further preferable.
  • the circularity is preferably 0.94 or less. When it is 0.94 or less, there is a tendency that the number of particles including solid electrolyte particles is increased and the electron conductivity is improved. From the same viewpoint, 0.93 or less is preferable, and 0.92 or less is more preferable.
  • Graphite includes hexagonal graphite and rhombohedral graphite.
  • Hexagonal graphite has a so-called AB type laminated structure in which layers each having a hexagonal net plane structure of carbon are moved in parallel by (2/3, 1/3) and stacked.
  • a layer having a hexagonal net plane structure of carbon is first translated by (2/3, 1/3) and then translated by (1/3, 2/3) to be stacked, that is, so-called. It has an ABC type laminated structure.
  • Hexagonal graphite exhibits a diffraction peak (hexagonal 100 diffraction line and hexagonal 101 diffraction line) in a diffraction angle range of 41.7 degrees to 42.7 degrees and a range of 43.7 degrees to 44.7 degrees, and has a rhombohedral shape.
  • diffraction peaks (rhombohedral 101 diffraction line and rhombohedral 012 diffraction line) appear in the diffraction angle range of 42.7 degrees to 43.7 degrees and in the range of 45.5 degrees to 46.5 degrees.
  • the rhombohedral crystal structure is formed by lattice distortion generated when pulverizing hexagonal graphite.
  • the graphite particles used in the present invention preferably do not contain rhombohedral crystals. Graphite that does not contain rhombohedral crystals has very little lattice distortion, and therefore tends to have excellent charge-discharge cycle characteristics.
  • the BET specific surface area of the graphite particles according to one embodiment of the present invention is preferably 1.0 m 2 /g or more. When it is 1.0 m 2 /g or more, the contact area with the solid electrolyte particles becomes large and the rate characteristics are improved. From the same viewpoint, 1.5 m 2 /g or more is more preferable, and 2.0 m 2 /g or more is most preferable.
  • the upper limit is preferably 9.0 m 2 /g or less. When it is 9.0 m 2 /g or less, side reactions are suppressed, and the initial Coulombic efficiency becomes high. More preferably 8.0 m 2 / g or less from the same viewpoint, the following are most preferred 7.0 m 2 / g.
  • the graphite particles according to one embodiment of the present invention are preferably coated with low crystalline carbon.
  • the initial Coulombic efficiency is improved by repairing defects on the surface of graphite, and the effect of facilitating insertion and desorption of lithium ions, which is a characteristic of low crystalline carbon, is also obtained, and rate characteristics are improved.
  • the low crystalline carbon is amorphous carbon.
  • a method of coating the surface of the graphite particles with low crystalline carbon a method of adhering an organic compound to the surface of the graphite particles and firing it in an inert gas atmosphere at a temperature range of 900 to 1500° C. can be mentioned.
  • the organic compound it is preferable to use petroleum pitch, coal pitch, phenol resin, polyvinyl alcohol resin, furan resin, cellulose resin, polystyrene resin, polyimide resin and epoxy resin, and more preferably petroleum pitch or coal pitch. ..
  • the addition amount is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the graphite particles. If the amount is 0.01 parts by mass or more, the initial Coulomb efficiency tends to be excellent.
  • 0.10 parts by mass or more is more preferable, and 0.50 parts by mass or more is most preferable.
  • the addition amount is preferably 5.00 parts by mass or less. When it is 5.00 parts by mass or less, mixing with the solid electrolyte tends to be excellent. From the same viewpoint, it is more preferably 4.00 parts by mass or less, and most preferably 2.00 parts by mass or less.
  • an organic compound is mixed with a solvent to be in a liquid state and mixed and kneaded with the graphite particles, and then the solvent is volatilized, and the graphite particles are coated with a low crystalline carbon layer by performing a baking treatment. It can.
  • a method in which the organic compound and the graphite particles are simply mixed with each other and the mixture is heat-treated may be used.
  • the surface of the graphite particles When the surface of the graphite particles is coated with low crystalline carbon, it has the merit that lithium ions from various directions can be quickly accepted and released. Therefore, by combining a structure with high crystallinity inside the graphite particles and a structure with low crystallinity on the surface of the graphite particles, a battery with excellent rate characteristics and high capacity can be obtained.
  • the R value (ID/IG) which is the intensity ratio of the peak intensity (ID) near 1350 cm ⁇ 1 and the peak intensity (IG) near 1580 cm ⁇ 1 obtained by Raman spectroscopy for the graphite particles.
  • the crystallinity can be determined. The larger the R value, the lower the crystallinity of the surface. If the crystallinity of the surface of the graphite particles is low, the electric resistance on the surface tends to be low, and the low temperature charge/discharge characteristics tend to be good. Therefore, the R value of the graphite particles according to one embodiment of the present invention is preferably 0.01 or more. 0.03 or more is more preferable, and 0.05 or more is further preferable.
  • the R value of the graphite particles is preferably 0.40 or less, more preferably 0.35 or less, and further preferably 0.30 or less.
  • the graphite particles according to one embodiment of the present invention relatively soft graphite particles are used. This is because when the graphite particles are a soft material, the area that is deformed during compression molding and comes into contact with the solid electrolyte is increased, and the rate characteristics are improved.
  • the ratio I(110)/I(004) of the intensity of the (004) plane diffraction peak and the intensity of the (110) plane diffraction peak measured by the powder X-ray diffraction method indicates the ease of deformation of the particles. Yes, when it is low, the particles are easily deformed, and when it is high, it is difficult to deform.
  • the I(110)/I(004) of the graphite particles according to one embodiment of the present invention is preferably 0.01 or more, more preferably 0.02 or more. When it is 0.01 or more, high rate characteristics can be obtained because excessive orientation is suppressed. I(110)/I(004) is preferably 0.70 or less. When it is 0.70 or less, it is likely to be deformed during compression molding, and the area in contact with the solid electrolyte is increased, so that the rate characteristic is improved. From the same viewpoint, 0.10 or less is more preferable, and 0.05 or less is most preferable. [Solid electrolyte]
  • the solid electrolyte according to one embodiment of the present invention uses at least one selected from an oxide solid electrolyte and a sulfide solid electrolyte.
  • oxide-based solid electrolyte examples include garnet-type complex oxide, perovskite-type complex oxide, LISICON-type complex oxide, NASICON-type complex oxide, Li-alumina-type complex oxide, LIPON, and oxide glass.
  • oxide-based solid electrolytes it is preferable to select an oxide-based solid electrolyte that can be stably used even if the negative electrode potential is low.
  • La 0.51 Li 0.34 TiO 2.94 Li 1.3 Al 10.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , 50Li 4 SiO 4 .50Li 3 BO 3 , Li 2.9 PO 3.3 N 0.46 , Li 3.6 Si. 0.6 P 0.4 O 4, Li 1.07 Al 0.69 Ti 1.46 (PO 4) 3, Li 1.5 Al 10.5 Ge 1.5 (PO 4) 3 is preferred.
  • sulfide-based solid electrolyte examples include sulfide glass, sulfide glass ceramic, and Thio-LISICON type sulfide.
  • sulfide-based solid electrolytes it is preferable to select a sulfide-based solid electrolyte that can be stably used even if the negative electrode potential is low.
  • Li 10 GeP 2 S 12 Li 3.25 Ge 0.25 P 0.75 S 4 , 30Li 2 S.26B 2 S 3 .44LiI, 63Li 2 S.36SiS 2 .1Li 3 PO 4 , 57Li 2 S.38SiS 2 .5Li 4 SiO 4 , 70Li 2 S ⁇ 30P 2 S 5 , 50Li 2 S ⁇ 50GeS 2 , Li 7 P 3 S 11 , Li 3.25 P 0.95 S 4 , Li 3 PS 4 , Li 2 S ⁇ P 2 S 3 ⁇ P 2 S 5 is preferred.
  • the battery performance of an all-solid-state lithium-ion battery is further improved.
  • the above solid electrolytes may be used alone or in combination of two or more. It is more preferable to use a sulfide-based solid electrolyte for the solid electrolyte according to one embodiment of the present invention.
  • the D50 of the solid electrolyte according to one embodiment of the present invention is 0.10 ⁇ m or more. This is because when the thickness is 0.10 ⁇ m or more, the solid electrolyte has excellent crystallinity and good ionic conductivity. From the same viewpoint, 0.20 ⁇ m or more is preferable, and 0.30 ⁇ m or more is further preferable. D50 is 3.00 ⁇ m or less. When the thickness is 3.00 ⁇ m or less, the contact with the negative electrode active material is good and the ionic conductivity is excellent. From the same viewpoint, it is preferably 1.00 ⁇ m or less, more preferably 0.50 ⁇ m or less.
  • the D50 of the solid electrolyte according to one embodiment of the present invention is preferably 1/10 or less of the D50 of the graphite particles. This is because when the size of the solid electrolyte particles is set to be equal to or smaller than the size of the graphite particles, the solid electrolyte is easily dispersed in the gaps between the graphite particles and the ionic conductivity is excellent. From the same viewpoint, 1/12 or less is more preferable, and 1/15 or less is most preferable.
  • the conduction aid it is preferable to use a particulate carbonaceous conduction aid or a fibrous carbonaceous conduction aid.
  • the particulate carbonaceous conductive aids include Denka Black (registered trademark) (manufactured by Denki Kagaku Kogyo KK), Ketjen Black (registered trademark) (manufactured by Lion Corporation), graphite fine powder SFG series (manufactured by Timcal), Particulate carbon such as graphene can be used.
  • VGCF vapor-phase carbon fiber
  • VGCF registered trademark
  • VGCF registered trademark-H
  • Vapor grown carbon fiber manufactured by Showa Denko KK is most preferable because it has excellent cycle characteristics.
  • the solid electrolyte layer is not particularly limited as long as it is a layer containing a solid electrolyte, and can be appropriately selected according to the purpose.
  • the solid electrolyte is preferably the same as that used for the negative electrode mixture layer.
  • the positive electrode mixture layer is not particularly limited as long as it is a layer containing a positive electrode active material, and can be appropriately selected according to the purpose.
  • the positive electrode mixture layer preferably contains a solid electrolyte. It is further preferable that the solid electrolyte is the same as that used for the negative electrode mixture layer.
  • a known positive electrode active material can be adopted as the positive electrode active material.
  • rock salt type layered active materials such as LiCoO 2 , LiMnO 2 , LiNiO 2 , LiVO 2 , LiNi 1/3 Mn 1/3 Co 1/3 O 2 , spinel type active materials such as LiMn 2 O 4 , LiFePO 4 ,
  • An olivine-type active material such as LiMnPO 4 , LiNiPO 4 , LiCuPO 4 or a sulfide active material such as Li 2 S can be used.
  • the 50% particle size (D50) in the volume-based cumulative particle size distribution of the positive electrode active material is preferably 1 ⁇ m or more and 30 ⁇ m or less, more preferably 3 ⁇ m or more and 10 ⁇ m or less.
  • the particle size of the positive electrode active material is preferably 10 times or more that of the solid electrolyte contained in the solid electrolyte layer.
  • a known binder may be used to maintain the shapes of the negative electrode and the positive electrode.
  • polyvinylidene fluoride, polyurethane, polysiloxane, polytetrafluoroethylene, polybutadiene, etc. can be used.
  • the means for producing the solid electrolyte particles is not particularly limited, but it can be obtained by performing mechanical milling treatment using, for example, a mortar, a planetary mill, a ball mill, a vibration mill, Mechanofusion (registered trademark) or the like.
  • the method for producing the solid electrolyte layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of compression-molding the solid electrolyte particles.
  • the method for producing the positive electrode is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a positive electrode active material, a solid electrolyte, and a conductive additive are mixed in a mortar for 10 minutes, and a planetary ball mill is used.
  • a cylindrical positive electrode mixture layer can be obtained by homogenizing by milling at 100 rpm for 1 hour and press-molding at 400 MPa with a uniaxial press molding machine using a polyethylene die having an inner diameter of 10 mm ⁇ and a SUS punch. ..
  • a positive electrode can be obtained by bringing the positive electrode current collector into close contact therewith.
  • Electrode collector Aluminum foil or SUS foil can be used for the positive electrode current collector, and carbon-coated or oxide-coated foil can also be used.
  • the method of coating is not particularly limited.
  • the carbon contained in the carbon coat layer is not particularly limited, and acetylene black, Ketjen Black (registered trademark), carbon nanotube, graphene, vapor grown carbon fiber, artificial graphite fine powder, or the like can be used. Both rolled foil and electrolytic foil can be used for the current collector.
  • the method for producing the negative electrode is not particularly limited and may be appropriately selected depending on the intended purpose, for example, a negative electrode active material, a solid electrolyte, and a conductive additive are mixed in a mortar in a glove box in an argon gas atmosphere, Further, the mixture was homogenized by milling at 100 rpm for 1 hour using a planetary ball mill, and press-molded at 400 MPa with a uniaxial press molding machine using a polyethylene die having an inner diameter of 10 mm ⁇ and a SUS punch to obtain a cylindrical negative electrode mixture. An agent layer can be obtained. The negative electrode can be obtained by bringing the negative electrode current collector into close contact therewith.
  • Nickel foil can be used for the negative electrode current collector, and carbon foil or oxide coated nickel foil can also be used.
  • the method of coating is not particularly limited.
  • the carbon contained in the carbon coat layer is not particularly limited, and acetylene black, Ketjen Black (registered trademark), carbon nanotube, graphene, vapor grown carbon fiber, artificial graphite fine powder, or the like can be used. Both rolled foil and electrolytic foil can be used for the current collector.
  • the method for manufacturing the all-solid-state battery is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the negative electrode mixture layer, the solid electrolyte layer, the positive electrode mixture layer may be provided with a current collector.
  • Graphite particles B 100 parts by mass of graphite particles A and 2 parts by mass of coal-based pitch were mixed and kneaded for 30 minutes while applying heat at 200°C. Then, a firing furnace treatment was performed at 1000° C. for 1 hour in a nitrogen gas stream, and finally, a graphite particle B coated with amorphous carbon was obtained by passing through a sieve having an opening of 45 ⁇ m.
  • Graphite particles D 100 parts by mass of graphite particles C and 2 parts by mass of coal-based pitch were mixed and kneaded for 30 minutes while applying heat at 200°C. Then, a firing furnace treatment was performed at 1000° C. for 1 hour under a nitrogen gas stream, and finally, a graphite particle D covered with amorphous carbon was obtained by passing through a sieve having an opening of 45 ⁇ m.
  • Graphite particles F 100 parts by mass of graphite particles E and 2 parts by mass of coal-based pitch were mixed and kneaded for 30 minutes while applying heat at 200°C. After that, a firing treatment was performed at 1000° C. for 1 hour in a nitrogen gas stream, and finally, a graphite particle F was obtained by passing through a sieve having an opening of 45 ⁇ m.
  • Rhombohedral diffraction peak A sample plate made of sample glass (sample plate window 18 ⁇ 20 mm, depth 0.2 mm) was filled and measured under the following conditions.
  • XRD device SmartLab manufactured by Rigaku
  • X-ray type Cu-K ⁇ ray K ⁇ ray removal method: Ni filter X-ray output: 45 kV, 200 mA Measuring range: 5.0 to 100.0 deg.
  • Scan speed 2.0 deg. /Min.
  • the obtained waveform it was confirmed whether or not there were peaks on the (100) plane and the (101) plane of the rhombohedral crystal structure.
  • (100) plane 42.7 to 43.7 deg. (101) plane: 45.5 to 46.5 deg.
  • this peak did not exist, it was determined that rhombohedral crystals did not exist.
  • Circularity Circularity measuring device Flow-type particle image analyzer FPIA-3000 (manufactured by Sysmex Corporation) The circularity is obtained by dividing the circumference of a circle having the same area as the observed area of a particle image by the circumference of the particle image, and the closer to 1 the closer to a perfect circle.
  • the circularity can be expressed by the following equation, where S is the area of the particle image and L is the perimeter.
  • Circularity (4 ⁇ S) 1/2 /L
  • the graphite particles were purified by passing through a filter with an opening of 106 ⁇ m, 0.1 g of the sample was added to 20 ml of ion-exchanged water, and 0.1-0.5% by mass of a surfactant was added to uniformly disperse the sample.
  • a sample solution for measurement was prepared. The dispersion was performed by using an ultrasonic cleaner UT-105S (manufactured by Sharp Manufacturing System Co.) for 5 minutes. The obtained sample solution for measurement was put into an apparatus, and the median of circularity was calculated from the number-based frequency distribution of circularity analyzed for 10,000 particles in the LPF mode.
  • BET specific surface area measuring device NOVA2200e manufactured by Quantachrome 3 g of the sample was placed in a sample cell (9 mm ⁇ 135 mm), dried at 300° C. under vacuum condition for 1 hour, and then measured. N 2 was used as the gas for measuring the BET specific surface area.
  • Raman spectroscopic analysis Raman spectroscopy: NRS-5100 manufactured by JASCO Corporation Measurement was performed under the conditions of an excitation wavelength of 532.36 nm, an entrance slit width of 200 ⁇ m, an exposure time of 15 seconds, an integration number of 2 times, and a diffraction grating of 600 lines/mm, and a peak intensity (ID) in the range of 1300 to 1400 cm ⁇ 1.
  • the intensity ratio of the intensity (IG) of the peak in the range of 1580 to 1620 cm ⁇ 1 was taken as the R value (ID/IG).
  • press molding was performed by a uniaxial press molding machine to obtain a solid electrolyte layer having a thickness of 960 ⁇ m used for a battery evaluation test.
  • the discharge capacity when discharged at 2.5 mA (0.1 C) was taken as 100%, and the ratio of the discharge capacity when discharged at 75 mA (3.0 C) to this was taken as the rate characteristic (%).
  • the initial discharge capacity measured at 25° C. was taken as 100%, and the discharge capacity after 500 cycles was taken as the cycle characteristic (%).
  • the constant current charge of 5.0mA (0.2C) is performed until the charge reaches 4.2V, and then the constant voltage is reduced to 0.05C at the constant voltage of 4.2V. Charged.
  • the discharge was performed by constant current discharge of 25 mA (1.0 C) until the voltage reached 2.75V.
  • Examples 1-10, Comparative Examples 1-9 An electrode and a battery were prepared in the types and amounts shown in Table 1 for the graphite particles, the solid electrolyte, and the conductive additive used for the negative electrode mixture layer, and their respective properties were evaluated. The results are shown in Table 2. The production of the positive electrode and the solid electrolyte layer is as described above.

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)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne une batterie au lithium-ion entièrement solide contenant une couche de mélange d'électrode négative, une couche de mélange d'électrode positive et une couche d'électrolyte solide. Cette batterie au lithium-ion entièrement solide est caractéristique en ce que ladite couche de mélange d'électrode négative contient 35,0% en masse ou plus à 80,0% en masse ou moins d'une matière active d'électrode négative, 19,0% en masse ou plus à 64,0% en masse ou moins d'un électrolyte solide, et 0,1% en masse à moins de 5,0% en masse d'un agent auxiliaire de conduction. Ladite matière active d'électrode négative contient des particules de graphite de structure non agglomérée qui présentent une distance interréticulaire de cristaux de graphite (d002) supérieure ou égale à ０,３３５４ｎｍ et inférieure ou égale à ０,３３７０ｎｍ, et un diamètre à 50% (D50) dans une distribution de diamètre de particule cumulé en volume supérieur ou égal à ０,１μｍ et inférieur à １０,０μｍ. Ledit électrolyte solide consiste en au moins un électrolyte solide choisi parmi un électrolyte solide à base d'oxyde et un électrolyte solide à base de sulfure, et consiste en des particules de diamètre à 50% (D50) supérieur ou égal à ０,１０μｍ et inférieur ou égal à ３,００μｍ. Plus précisément, l'invention permet de fournir une batterie au lithium-ion entièrement solide qui présente un contact satisfaisant entre l'électrolyte solide et la matière active d'électrode négative, et qui se révèle excellente en termes de caractéristiques de régime, de caractéristiques de cycle et d'efficacité coulombienne.
PCT/JP2019/046657 2018-12-05 2019-11-28 Batterie au lithium-ion entièrement solide, et mélange d'électrode négative WO2020116324A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-228375 2018-12-05
JP2018228375A JP2022029465A (ja) 2018-12-05 2018-12-05 全固体リチウムイオン電池

Publications (1)

Publication Number Publication Date
WO2020116324A1 true WO2020116324A1 (fr) 2020-06-11

Family

ID=70975153

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/046657 WO2020116324A1 (fr) 2018-12-05 2019-11-28 Batterie au lithium-ion entièrement solide, et mélange d'électrode négative

Country Status (2)

Country Link
JP (1) JP2022029465A (fr)
WO (1) WO2020116324A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021045987A1 (fr) * 2019-09-05 2021-03-11 TeraWatt Technology Inc. Systèmes et procédés de fabrication de batteries à semi-conducteurs et anodes de batterie à semi-conducteurs associées
CN115117434A (zh) * 2022-07-22 2022-09-27 欣旺达电子股份有限公司 复合材料及其制备方法、固态电池以及用电设备

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012243645A (ja) * 2011-05-20 2012-12-10 Sumitomo Electric Ind Ltd 電極、および全固体型非水電解質電池
WO2015152215A1 (fr) * 2014-03-31 2015-10-08 株式会社クレハ Procédé de fabrication d'électrode négative pour batterie tout solide, et électrode négative pour batterie tout solide
WO2015152214A1 (fr) * 2014-03-31 2015-10-08 株式会社クレハ Électrode négative pour batterie entièrement solide et batterie entièrement solide comprenant celle-ci
WO2018123967A1 (fr) * 2016-12-26 2018-07-05 昭和電工株式会社 Batterie au lithium-ion tout solide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012243645A (ja) * 2011-05-20 2012-12-10 Sumitomo Electric Ind Ltd 電極、および全固体型非水電解質電池
WO2015152215A1 (fr) * 2014-03-31 2015-10-08 株式会社クレハ Procédé de fabrication d'électrode négative pour batterie tout solide, et électrode négative pour batterie tout solide
WO2015152214A1 (fr) * 2014-03-31 2015-10-08 株式会社クレハ Électrode négative pour batterie entièrement solide et batterie entièrement solide comprenant celle-ci
WO2018123967A1 (fr) * 2016-12-26 2018-07-05 昭和電工株式会社 Batterie au lithium-ion tout solide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021045987A1 (fr) * 2019-09-05 2021-03-11 TeraWatt Technology Inc. Systèmes et procédés de fabrication de batteries à semi-conducteurs et anodes de batterie à semi-conducteurs associées
CN115117434A (zh) * 2022-07-22 2022-09-27 欣旺达电子股份有限公司 复合材料及其制备方法、固态电池以及用电设备

Also Published As

Publication number Publication date
JP2022029465A (ja) 2022-02-18

Similar Documents

Publication Publication Date Title
JP6404530B1 (ja) 全固体リチウムイオン電池
KR101887952B1 (ko) 리튬 이온 2차 전지용 음극 재료
JP6572551B2 (ja) リチウムイオン２次電池用負極活物質およびその製造方法
EP2602851B1 (fr) Méthode de procédé d'un matériau actif d'anode au graphite pour batterie rechargeable au lithium
US20220246924A1 (en) Silicon-oxygen particle for electrode material, preparation method therefor and use thereof
US20190334173A1 (en) Composite graphite particles, method for producing same, and use thereof
JP2016110969A (ja) リチウムイオン２次電池用負極活物質およびその製造方法
CN114597326B (zh) 一种负极活性材料及含有该负极活性材料的负极片和电池
JPWO2019131861A1 (ja) リチウムイオン二次電池用負極材
JP2018170246A (ja) リチウム二次電池用複合活物質およびその製造方法
WO2019031543A1 (fr) Matériau actif d'électrode négative destiné à une batterie secondaire et batterie secondaire comprenant ce dernier
JP2011060467A (ja) リチウムイオン二次電池用負極材料およびその製造方法
JP2007294374A (ja) 非水電解液二次電池用負極材、該負極材を用いた非水電解液二次電池用負極および非水電解液二次電池
WO2020129879A1 (fr) Mélange d'électrode négative de batterie au lithium-ion tout solide et batterie au lithium-ion tout solide
WO2020116324A1 (fr) Batterie au lithium-ion entièrement solide, et mélange d'électrode négative
WO2020110942A1 (fr) Électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion
JP2016115418A (ja) ケイ素黒鉛複合粒子の使用方法、非水系二次電池用黒鉛負極の放電容量改良材、混合粒子、電極および非水電解質二次電池
JP7009049B2 (ja) リチウムイオン二次電池負極用炭素材料、その中間体、その製造方法、及びそれを用いた負極又は電池
JP2015219989A (ja) リチウムイオン２次電池用負極活物質およびその製造方法
WO2020110943A1 (fr) Électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion
US20240282965A1 (en) Graphite negative electrode material, preparation method therefor and use thereof
JP2018055999A (ja) リチウムイオン二次電池の負極活物質用低結晶性炭素材料及びその製造方法並びにそれを用いたリチウムイオン二次電池用負極及びリチウムイオン二次電池
WO2020116323A1 (fr) Batterie au lithium-ion entièrement solide, et mélange d'électrode négative
WO2024134778A1 (fr) Carbone dur et procédé de production associé
JP2021144818A (ja) 全固体リチウムイオン電池

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: 19892232

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19892232

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP