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WO2025146872A1 - Électrolyte solide, et membrane d'électrolyte solide et batterie rechargeable tout solide le comprenant - Google Patents

Électrolyte solide, et membrane d'électrolyte solide et batterie rechargeable tout solide le comprenant Download PDF

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Publication number
WO2025146872A1
WO2025146872A1 PCT/KR2024/004365 KR2024004365W WO2025146872A1 WO 2025146872 A1 WO2025146872 A1 WO 2025146872A1 KR 2024004365 W KR2024004365 W KR 2024004365W WO 2025146872 A1 WO2025146872 A1 WO 2025146872A1
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Prior art keywords
solid electrolyte
lithium
solid
particles
active material
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English (en)
Korean (ko)
Inventor
성시현
김영수
김국한
오정은
박진환
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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
    • 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

  • It relates to a solid electrolyte, a solid electrolyte membrane containing the same, and an all-solid-state secondary battery.
  • All-solid-state secondary batteries are batteries in which all materials are solid, so there is no risk of explosion due to electrolyte leakage, and they are safe. In addition, they have the advantage of making it easy to manufacture thin batteries, and since the thickness of the negative electrode can be reduced, high-speed charge/discharge performance can be improved, and high-voltage operation and high-energy density can be realized.
  • a sulfide-based solid electrolyte with high ionic conductivity is mainly used.
  • an argyrodite-type sulfide-based solid electrolyte can exhibit high ionic conductivity close to the ionic conductivity of a general liquid electrolyte, which is in the range of 10 -4 to 10 -2 S/cm, at room temperature, and has the advantage of having soft mechanical properties, which can form a close bond between solid electrolytes and a close bond between the solid electrolyte and the positive active material.
  • an all-solid-state secondary battery using an argyrodite-type sulfide-based solid electrolyte can exhibit improved rate characteristics, Coulombic efficiency, and cycle life characteristics.
  • argyrodite-type sulfide-based solid electrolytes are very vulnerable to moisture and air, and when exposed to air during the manufacturing and distribution processes or during battery operation, they react with H2O , CO2 , O2 , etc. to generate by-products such as hydrogen sulfide, and there is a problem that their performance deteriorates, such as surface damage or rapid decrease in ionic conductivity.
  • a solid electrolyte which comprises argyrodite-type sulfide-based solid electrolyte particles, and a lithium salt positioned on the surface of the particles, wherein the lithium salt has F and P-O functional groups.
  • a solid electrolyte membrane comprising the solid electrolyte is provided.
  • an all-solid-state secondary battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer positioned between the positive electrode and the negative electrode, wherein at least one of the positive electrode, the negative electrode, and the solid electrolyte layer comprises the solid electrolyte.
  • a solid electrolyte comprises an argyrodite-type sulfide, and has excellent atmospheric stability and level stability, effectively suppressing the continuous decrease in ionic conductivity over time of atmospheric exposure and providing a relatively stable resistance value so that lithium ions can move smoothly.
  • a solid electrolyte membrane and an all-solid-state secondary battery using the same can implement excellent electrochemical characteristics such as excellent life characteristics.
  • Figures 1 and 2 are cross-sectional views schematically illustrating an all-solid-state secondary battery according to one embodiment.
  • Figure 3 is a graph showing the change in weight of a symmetrical cell according to exposure time after leaving the solid electrolyte membranes of Example 1, Comparative Example 1, and Comparative Example 2 in a dry room.
  • Figure 4 is a graph showing the change in the ionic conductivity retention rate according to the exposure time after the solid electrolyte membranes of Example 1, Comparative Example 1, and Comparative Example 2 were left in a dry room.
  • the term “layer” here includes not only a shape formed on the entire surface when observed in a plan view, but also a shape formed on a portion of the surface.
  • the average particle size can be measured by a method well known to those skilled in the art, for example, by measuring with a particle size analyzer, or by measuring with a transmission electron microscope image or a scanning electron microscope image.
  • the average particle size can be obtained by measuring using a dynamic light scattering method, performing data analysis to count the number of particles for each particle size range, and calculating from the counted number.
  • the average particle size can mean the diameter (D50) of particles having a cumulative volume of 50% by volume in a particle size distribution.
  • the average particle size can be obtained by randomly measuring the sizes (diameter or length of the major axis) of about 20 particles in a scanning electron microscope image to obtain a particle size distribution, and taking the diameter (D50) of particles having a cumulative volume of 50% by volume in the particle size distribution as the average particle size.
  • Metal is interpreted as a concept that includes common metals, transition metals, and metalloids (semi-metals).
  • a solid electrolyte which comprises argyrodite-type sulfide-based solid electrolyte particles, and a lithium salt positioned on the surface of the particles, wherein the lithium salt has F and P-O functional groups.
  • the P-O functional group has a high affinity for the argyrodite-type sulfide-based solid electrolyte particles and thus can be stably attached to the surface of the particles, and further, the F functional group has strong hydrophobicity and thus can effectively prevent moisture from coming into contact with the particles.
  • This lithium salt can be evenly attached to the surface of the argyrodite-type sulfide-based solid electrolyte particles and effectively suppress deterioration due to moisture.
  • solid electrolytes can control chemical side reactions and maintain high ionic conductivity characteristics even in a dry room process exposure environment.
  • the solid electrolyte can effectively suppress weight loss that occurs when exposed to a dry room or the atmosphere. Since the lithium salt protects the surface of the argyrodite-type sulfide-based solid electrolyte particles, side reactions and irreversibility on the particle surface due to exposure to the atmosphere can be suppressed, and the content of by-products generated by the side reactions can be reduced, thereby improving the ionic conductivity maintenance characteristics and enhancing the performance of the all-solid-state secondary battery.
  • the above lithium salt may include, but is not limited to, LiPOF 4 , LiPO 2 F 2 , Li 2 PO 3 F, or combinations thereof.
  • the PO functional group may be, for example, a PO 2 functional group.
  • the PO 2 functional group has high affinity for the argyrodite-type sulfide-based solid electrolyte particles, and therefore, a lithium salt containing the PO 2 functional group can be stably attached to the surface of the particles and also be evenly distributed on the surface of the particles.
  • the lithium salt may be included in an amount of 1 mol% to 30 mol% based on 100 mol% of the azirodite-type sulfide-based solid electrolyte particles and the lithium salt, for example, 2 mol% to 25 mol%, 3 mol% to 20 mol%, 4 mol% to 18 mol%, or 5 mol% to 15 mol%.
  • the lithium salt is included in the above range, the surface of the azirodite-type sulfide-based solid electrolyte particles is sufficiently protected, thereby ensuring moisture stability and improving lithium ion conductivity.
  • the above lithium salt may be partially present on the surface of the argyrodite-type sulfide-based solid electrolyte particles, may be coated in an island form, or may be present in a continuous film form.
  • the solid electrolyte may include argyrodite-type sulfide-based solid electrolyte particles and a coating layer positioned on the surface of the particles, wherein the coating layer may include a lithium salt containing F and PO functional groups.
  • argyrodite-type sulfide-based solid electrolyte particles include argyrodite-type sulfide, and may include, for example, a compound represented by the chemical formula 11 below.
  • M 1 is Mg, Ca, Cu, Ag, or a combination thereof, 0 ⁇ b ⁇ 0.5, M 2 is Na, K, or a combination thereof, 0 ⁇ c ⁇ 0.5, M 3 is Sn, Zn, Si, Sb, Ge, or a combination thereof, 0 ⁇ d ⁇ 4, 0 ⁇ e ⁇ 1, M 4 is N, O, SO n , or a combination thereof, 1.5 ⁇ n ⁇ 5, 3 ⁇ f ⁇ 12, 0 ⁇ g ⁇ 2, and X is F, Cl, Br, I, or a combination thereof, and 0 ⁇ h ⁇ 2.
  • SO n may be, for example, S 4 O 6 , S 3 O 6 , S 2 O 3 , S 2 O 4 , S 2 O 5 , S 2 O 6 , S 2 O 7 , S 2 O 8 , SO 4 , or SO 5 , and for example, it may be SO 4 .
  • the argyrodite-type sulfide-based solid electrolyte particles include Li 3 PS 4 , Li 7 P 3 S 11 , Li 7 PS 6 , Li 6 PS 5 Cl, Li 6 PS 5 Br, Li 5.8 PS 4.8 Cl 1.2 , Li 6.2 PS 5.2 Br 0.8 , Li 5.75 PS 4.75 Cl 1.25 , (Li 5.69 Cu 0.06 )PS 4.75 Cl 1.25 , (Li 5.72 Cu 0.03 )PS 4.75 Cl 1.25 , (Li 5.69 Cu 0.06 )P(S 4.70 (SO 4 ) 0.05 )Cl 1.25 , (Li 5.69 Cu 0.06 )P(S 4.60 (SO 4 ) 0.15 )Cl 1.25 , (Li 5.72 Cu 0.03 )P(S 4.725 (SO 4 ) 0.025 )Cl 1.25 , (Li 5.72 Na 0.03 )P(S 4.725 (SO 4 ) 0.025 )Cl 1.25 , Li 5.72 Na 0.03
  • the sulfide-based solid electrolyte including such argyrodite-type sulfides has a high ionic conductivity close to the ionic conductivity of a typical liquid electrolyte at room temperature, which is in the range of 10 -4 to 10 -2 S/cm, and can form a close bond between a cathode active material and a solid electrolyte without causing a decrease in ionic conductivity, and further can form a close interface between an electrode layer and a solid electrolyte layer.
  • An all-solid-state secondary battery including the same can have improved battery performances, such as rate characteristics, Coulombic efficiency, and cycle life characteristics.
  • the argyrodite-type sulfide-based solid electrolyte can be manufactured by, for example, mixing lithium sulfide and phosphorus sulfide, and optionally lithium halide. After mixing these, a heat treatment may be performed. The heat treatment may include, for example, two or more heat treatment steps.
  • manufacturing the argyrodite-type sulfide-based solid electrolyte may include, for example, a first heat treatment of mixing raw materials and calcining at 120° C. to 350° C., and a second heat treatment of mixing the resultant of the first heat treatment again and calcining at 350° C. to 800° C.
  • the average particle size ( D50 ) of the above-described argyrodite-type sulfide-based solid electrolyte particles may be 5.0 ⁇ m or less, and may be, for example, 0.1 ⁇ m to 5.0 ⁇ m, 0.5 ⁇ m to 5.0 ⁇ m, 0.5 ⁇ m to 4.0 ⁇ m, 0.5 ⁇ m to 3.0 ⁇ m, 0.5 ⁇ m to 2.0 ⁇ m, or 0.5 ⁇ m to 1.0 ⁇ m.
  • the solid electrolyte particles may be small particles having a size of 0.1 ⁇ m to 1.5 ⁇ m, large particles having a size of 2.0 ⁇ m to 5.0 ⁇ m, or a mixture thereof.
  • the average particle size of the solid electrolyte particles may be measured by an electron microscope image, and for example, a particle size distribution may be obtained by measuring the sizes (diameter or major axis length) of about 20 particles in a scanning electron microscope image, and D50 may be calculated therefrom.
  • the above solid electrolyte can be manufactured by mixing argyrodite-type sulfide-based solid electrolyte particles and a lithium salt having F and P-O functional groups.
  • the lithium salt may be mixed in an amount of 1 mol% to 30 mol% with respect to the total of 100 mol% of the azirodite-type sulfide-based solid electrolyte particles and the lithium salt, for example, 2 mol% to 25 mol%, 3 mol% to 20 mol%, 4 mol% to 18 mol%, or 5 mol% to 15 mol%.
  • the mixing may be performed at a temperature range of, for example, 5°C to 50°C, or 10°C to 40°C, or at room temperature, and may be performed for 30 seconds to 1 hour, 30 seconds to 30 minutes, 30 seconds to 20 minutes, or 30 seconds to 10 minutes.
  • the method for manufacturing the above solid electrolyte may be a kind of solid-state or dry coating method.
  • a solid electrolyte membrane including the above-described solid electrolyte is provided.
  • the solid electrolyte membrane according to one embodiment can realize high ionic conductivity by including the above-described solid electrolyte, has high stability against moisture, and can realize high ionic conductivity maintenance even when exposed for a long time, and has low side reactions of the solid electrolyte due to moisture, so that battery safety and life characteristics can be improved.
  • the above solid electrolyte membrane may include argyrodite-type sulfide-based solid electrolyte particles and a lithium salt containing F and PO functional groups, and the lithium salt may be uniformly dispersed in the solid electrolyte membrane.
  • the above solid electrolyte membrane can be manufactured by a conventional solvent-casting method, and in this case, it is possible to manufacture a solid electrolyte membrane with a low ion conductivity reduction rate.
  • the above solid electrolyte membrane may further include, in addition to the above-described solid electrolyte, another oxide-based solid electrolyte such as a halide-based solid electrolyte, and optionally, may further include a binder.
  • Oxide-based solid electrolytes include, for example, Li 1+x Ti 2-x Al(PO 4 ) 3 (LTAP)(0 ⁇ x ⁇ 4), Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), BaTiO 3 , Pb(Zr,Ti)O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT)(0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), PB(Mg 3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT), HfO 2 , SrTiO 3 , SnO 2 , CeO 2 , Na 2 O, MgO, NiO, CaO, BaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiO 2 , lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti
  • a halide-based solid electrolyte contains a halogen element as a main component, and may mean that the ratio of the halide element to all elements constituting the solid electrolyte is 50 mol% or more, 70 mol% or more, 90 mol% or more, or 100 mol%.
  • the halide-based solid electrolyte may be one that does not contain a sulfur element.
  • the halide-based solid electrolyte may be represented by, for example, Li a M 1 X 6 (M is Al, As, B, Bi, Ca, Cd, Co, Cr, Fe, Ga, Hf, In, Mg, Mn, Ni, Sb, Sc, Sn, Ta, Ti, Y, Zn, Zr, or a combination thereof, and X is F, Cl, Br, I, or a combination thereof, and 2 ⁇ a ⁇ 3).
  • M Al, As, B, Bi, Ca, Cd, Co, Cr, Fe, Ga, Hf, In, Mg, Mn, Ni, Sb, Sc, Sn, Ta, Ti, Y, Zn, Zr, or a combination thereof
  • X is F, Cl, Br, I, or a combination thereof, and 2 ⁇ a ⁇ 3).
  • the above halide-based solid electrolyte may include , but is not limited to, Li 2 ZrCl 6 , Li 2.7 Y 0.7 Zr 0.3 Cl 6 , Li 2.5 Y 0.5 Zr 0.5 Cl 6 , Li 2.5 In 0.5 Zr 0.5 Cl 6 , Li 2 In 0.5 Zr 0.5 Cl 6 , Li 3 YBr 6 , Li 3 YCl 6 , Li 3 YBr 2 Cl 4 , Li 3 YbCl 6 , Li 2.6 Hf 0.4 Yb 0.6 Cl 6 , or a combination thereof.
  • the binder may include, for example, nitrile-butadiene rubber, hydrogenated nitrile-butadiene rubber, styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, fluoroelastomer, polydimethylsiloxane, polyethylene oxide, polyvinylpyrrolidone, polyvinylpyridine, chlorosulfonated polyethylene, polyvinyl alcohol, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polyethylene, polypropylene, ethylene propylene copolymer, ethylene propylene diene copolymer, polyamideimide, polyimide, poly(meth)acrylate,
  • the binder content relative to 100 wt% of the solid electrolyte membrane may be about 0.1 wt% to 5 wt%, or 0.5 wt% to 3 wt%.
  • the negative electrode current collector may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.
  • the precipitation-type negative electrode (400') may include, for example, a current collector (401), a lithium metal layer (404) positioned on the current collector, and a negative electrode coating layer (405) positioned on the metal layer.
  • the lithium metal layer (404) refers to a layer in which lithium metal or the like is precipitated during the charging process of the battery, and may be referred to as a metal layer, a lithium layer, a lithium deposition layer, or a negative electrode active material layer.
  • the metal may be a lithium-philic metal, and may include, for example, gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, zinc, or a combination thereof, and may be composed of one kind of these or may be composed of several kinds of alloys.
  • the average particle diameter (D50) thereof may be about 4 ⁇ m or less, for example, 10 nm to 4 ⁇ m.
  • the carbon material can be, for example, crystalline carbon, amorphous carbon, or a combination thereof.
  • the crystalline carbon can be, for example, natural graphite, artificial graphite, mesophase carbon microbeads, or a combination thereof.
  • the amorphous carbon can be, for example, carbon black, activated carbon, acetylene black, Denka black, Ketjen black, or a combination thereof.
  • the thickness of the above cathode coating layer (405) may be, for example, 100 nm to 20 ⁇ m, or 500 nm to 10 ⁇ m, or 1 ⁇ m to 5 ⁇ m.
  • the thickness of the lithium metal layer (404) may be 1 ⁇ m to 500 ⁇ m, 1 ⁇ m to 200 ⁇ m, 1 ⁇ m to 100 ⁇ m, or 1 ⁇ m to 50 ⁇ m. If the thickness of the lithium metal layer (404) is too thin, it may be difficult to perform the role of a lithium storage, and if it is too thick, the battery volume may increase and the performance may deteriorate.
  • the cathode coating layer (405) can play a role in protecting the lithium metal layer (404) and suppressing the precipitation growth of lithium deadlight. Accordingly, short-circuiting and capacity reduction of the all-solid-state battery can be suppressed, and the life characteristics can be improved.
  • the current collector comprises a cathode active material layer positioned on the current collector, wherein the cathode active material layer comprises a cathode active material and a solid electrolyte, and may optionally comprise a binder and/or a conductive material.
  • the cathode active material layer may comprise the above-described solid electrolyte.
  • the above positive electrode active material can be applied without limitation as long as it is generally used in all-solid-state secondary batteries.
  • the above positive electrode active material may be a compound capable of reversible intercalation and deintercalation of lithium, and may include a compound represented by any one of the following chemical formulas.
  • Li a FePO 4 (0.90 ⁇ a ⁇ 1.8).
  • A is selected from the group consisting of Ni, Co, Mn, and combinations thereof;
  • X is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements, and combinations thereof;
  • D is selected from the group consisting of O, F, S, P, and combinations thereof;
  • E is selected from the group consisting of Co, Mn, and combinations thereof;
  • T is selected from the group consisting of F, S, P, and combinations thereof;
  • G is selected from the group consisting of Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, and combinations thereof;
  • Q is selected from the group consisting of Ti, Mo, Mn, and combinations thereof;
  • Z is selected from the group consisting of Cr, V, Fe, Sc, Y, and combinations thereof;
  • J is selected from the group consisting of V, Cr, Mn, Co, Ni, Cu, and combinations thereof.
  • M 3 is at least one element selected from the group consisting of Al, B, Ba, Ca, Ce, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Se, Si, Sn, Sr, Ti, V, W, Y, Zn, and Zr
  • X is at least one element selected from the group consisting of F, P, and S.
  • M 4 is at least one element selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, Mg, Mn, Mo, Ni, Se, Si, Sn, Sr, Ti, V, W, Y, Zn, and Zr
  • X is at least one element selected from the group consisting of F, P, and S.
  • the average particle diameter (D50) of the positive electrode active material may be from 1 ⁇ m to 25 ⁇ m, for example, from 3 ⁇ m to 25 ⁇ m, from 1 ⁇ m to 20 ⁇ m, from 1 ⁇ m to 18 ⁇ m, from 3 ⁇ m to 15 ⁇ m, or from 5 ⁇ m to 15 ⁇ m.
  • the positive electrode active material may include small particles having an average particle diameter (D50) of from 1 ⁇ m to 9 ⁇ m and large particles having an average particle diameter (D50) of from 10 ⁇ m to 25 ⁇ m.
  • the positive electrode active material having such a particle diameter range can be harmoniously mixed with other components in the positive electrode active material layer and can implement high capacity and high energy density.
  • the average particle size may be obtained by selecting about 20 random particles from a scanning electron microscope image of the positive electrode active material, measuring their particle sizes (diameter, major axis, or major axis length), obtaining a particle size distribution, and then taking the diameter (D50) of the particles having a cumulative volume of 50% by volume from the particle size distribution as the average particle size.
  • the above positive electrode active material may be in the form of a secondary particle formed by agglomeration of a plurality of primary particles, or may be in the form of a single particle.
  • the above positive electrode active material may be in a spherical or nearly spherical shape, or may be in a polyhedral or irregular shape.
  • the positive electrode active material may include a buffer layer on the particle surface.
  • the buffer layer may be expressed as a coating layer, a protective layer, etc., and may play a role in lowering the interfacial resistance between the positive electrode active material and the sulfide-based solid electrolyte particles.
  • the buffer layer may include a lithium-metal-oxide, wherein the metal may be one or more elements selected from the group consisting of Al, B, Ca, Ce, Cr, Fe, Mg, Mo, Nb, Si, Sn, Sr, Ta, V, W, and Zr.
  • the lithium-metal-oxide is excellent in lowering the interfacial resistance between the positive electrode active material and the solid electrolyte particles while improving the performance of the positive electrode active material by facilitating the movement of lithium ions and electron conduction.
  • the positive electrode active material may be included in an amount of 55 wt% to 99 wt% with respect to 100 wt% of the positive electrode active material layer, for example, 65 wt% to 95 wt%, or 75 wt% to 91 wt%.
  • the above binder serves to attach the positive electrode active material particles well to each other and also to attach the positive electrode active material well to the current collector, and representative examples thereof include, but are not limited to, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc.
  • the above-described positive electrode active material layer may further include a conductive material.
  • the conductive material is used to provide conductivity to the electrode, and any material that does not cause a chemical change in the battery to be formed and is electronically conductive may be used.
  • Examples of such conductive materials include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanofibers, and carbon nanotubes; metal-based materials containing copper, nickel, aluminum, silver, and the like in the form of metal powder or metal fibers; conductive polymers such as polyphenylene derivatives; or conductive materials including mixtures thereof.
  • the content of the conductive material in the positive electrode active material layer may be 0 wt% to 3 wt%, 0.01 wt% to 2 wt%, or 0.1 wt% to 1 wt% with respect to 100 wt% of the positive electrode active material layer.
  • the positive electrode active material may be included in an amount of 65 wt% to 99 wt% and the solid electrolyte in an amount of 1 wt% to 35 wt%, based on the total weight of the positive electrode active material and the solid electrolyte, for example, the positive electrode active material may be included in an amount of 80 wt% to 90 wt% and the solid electrolyte in an amount of 10 wt% to 20 wt%.
  • the solid electrolyte is included in the positive electrode in such an amount, the efficiency and life characteristics of the all-solid-state battery can be improved without reducing the capacity.
  • Aluminum foil may be used as the above positive electrode collector, but is not limited thereto.
  • the shape of the above-mentioned all-solid-state secondary battery is not particularly limited, and may be, for example, coin-shaped, button-shaped, sheet-shaped, stacked, cylindrical, flat, etc.
  • the above-mentioned all-solid-state secondary battery can be applied to large-sized batteries used in electric vehicles, etc.
  • the above-mentioned all-solid-state secondary battery can be used in hybrid vehicles, such as plug-in hybrid electric vehicles (PHEVs).
  • PHEVs plug-in hybrid electric vehicles
  • it can be used in fields that require a large amount of power storage, and for example, it can be used in electric bicycles or power tools.
  • the above-mentioned all-solid-state secondary battery can be used in various fields, such as portable electronic devices.
  • the solid electrolyte was added to an isobutyryl isobutyrate (IBIB) solvent containing an acrylic binder and mixed to prepare a slurry.
  • the slurry contains 98 wt% of the solid electrolyte and 2 wt% of the binder.
  • the slurry was applied onto a release PET film using a blade coater and dried to prepare a solid electrolyte membrane having a thickness of about 100 to 150 ⁇ m.
  • a cathode composition was prepared by mixing 85 wt% of LiNi 0.8 Co 0.15 Mn 0.05 O 2 cathode active material coated with Li 2 O-ZrO 2 , 13.5 wt% of lithium argyrodite-type solid electrolyte Li 6 PS 5 Cl, 1.0 wt% of polyvinylidene fluoride binder, and 0.5 wt% of carbon nanotube conductive material.
  • the prepared cathode composition was coated on a cathode current collector using a bar coater, and dried and rolled to prepare a cathode.
  • An Ag/C composite was prepared by mixing carbon black having a primary particle size ( D50 ) of about 30 nm and silver (Ag) having an average particle size ( D50 ) of about 60 nm in a weight ratio of 3:1, and 0.25 g of the composite was added to 2 g of an NMP solution containing 7 wt% of polyvinylidene fluoride binder and mixed to prepare a negative electrode coating layer composition. This was applied to a nickel foil current collector using a bar coater and vacuum-dried to prepare a deposition-type negative electrode in which a negative electrode coating layer was formed on the current collector.
  • a unit cell was manufactured by laminating a positive electrode, a solid electrolyte membrane, and a negative electrode in that order, and then placing this in a laminate film and subjecting it to warm isostatic pressing (WIP) at 80°C and 500 MPa for 30 minutes to manufacture an all-solid-state secondary battery.
  • WIP warm isostatic pressing
  • a solid electrolyte was prepared in substantially the same manner as in Example 1, except that 10 molar parts of LiI were used instead of LiPO 2 F 2 , and then a solid electrolyte membrane and an all-solid-state secondary battery were prepared.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un électrolyte solide, et une membrane d'électrolyte solide et une batterie rechargeable tout solide qui le comprennent, l'électrolyte solide comprenant des particules d'électrolyte solide à base de sulfure de type argyrodite et un sel de lithium situé sur les surfaces des particules, le sel de lithium ayant des groupes fonctionnels F et P-O.
PCT/KR2024/004365 2024-01-04 2024-04-03 Électrolyte solide, et membrane d'électrolyte solide et batterie rechargeable tout solide le comprenant Pending WO2025146872A1 (fr)

Applications Claiming Priority (2)

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KR1020240001649A KR20250106993A (ko) 2024-01-04 2024-01-04 고체 전해질과 이를 포함하는 고체 전해질 막 및 전고체 이차 전지
KR10-2024-0001649 2024-01-04

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WO2025146872A1 true WO2025146872A1 (fr) 2025-07-10

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160128670A (ko) * 2015-04-29 2016-11-08 현대자동차주식회사 고체 전해질 및 이를 포함하는 전고체 전지
KR20210110698A (ko) * 2019-01-31 2021-09-08 다이킨 고교 가부시키가이샤 구조체, 복합체, 전지 및 복합체의 제조 방법
WO2023286614A1 (fr) * 2021-07-16 2023-01-19 パナソニックＩｐマネジメント株式会社 Matériau d'électrode positive et batterie
KR20230145831A (ko) * 2022-04-11 2023-10-18 삼성에스디아이 주식회사 전고체 전지용 양극과 이의 제조 방법 및 이를 포함하는 전고체 전지
KR20230163736A (ko) * 2022-05-24 2023-12-01 포항공과대학교 산학협력단 액체-고체 복합 전해질, 이의 제조방법 및 이의 용도

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160128670A (ko) * 2015-04-29 2016-11-08 현대자동차주식회사 고체 전해질 및 이를 포함하는 전고체 전지
KR20210110698A (ko) * 2019-01-31 2021-09-08 다이킨 고교 가부시키가이샤 구조체, 복합체, 전지 및 복합체의 제조 방법
WO2023286614A1 (fr) * 2021-07-16 2023-01-19 パナソニックＩｐマネジメント株式会社 Matériau d'électrode positive et batterie
KR20230145831A (ko) * 2022-04-11 2023-10-18 삼성에스디아이 주식회사 전고체 전지용 양극과 이의 제조 방법 및 이를 포함하는 전고체 전지
KR20230163736A (ko) * 2022-05-24 2023-12-01 포항공과대학교 산학협력단 액체-고체 복합 전해질, 이의 제조방법 및 이의 용도

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