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WO2025063415A1 - Batterie rechargeable entièrement solide - Google Patents

Batterie rechargeable entièrement solide Download PDF

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Publication number
WO2025063415A1
WO2025063415A1 PCT/KR2024/004363 KR2024004363W WO2025063415A1 WO 2025063415 A1 WO2025063415 A1 WO 2025063415A1 KR 2024004363 W KR2024004363 W KR 2024004363W WO 2025063415 A1 WO2025063415 A1 WO 2025063415A1
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Prior art keywords
solid electrolyte
solid
secondary battery
state secondary
carbon
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English (en)
Korean (ko)
Inventor
이재준
이은경
김재민
이건욱
이시은
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • 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

  • Lithium secondary batteries which have high energy density and are easy to carry, are mainly used as power sources for mobile information terminals such as mobile phones, laptops, and smart phones. Recently, research is actively being conducted to use lithium secondary batteries with high energy density as power sources for driving hybrid or electric vehicles or as power storage power sources.
  • An all-solid-state secondary battery that uses a solid electrolyte instead of the electrolyte has been proposed.
  • An all-solid-state secondary battery is a battery in which all materials are solid, so there is no risk of explosion due to electrolyte leakage, and it has the advantage of being easy to manufacture a thin battery, and since the thickness of the negative electrode can be reduced, the high-speed charge/discharge performance is improved, and high-voltage operation and high energy density can be realized.
  • an all-solid-state secondary battery comprising a cathode, an anode, and a solid electrolyte layer positioned between the cathode and the anode, wherein the solid electrolyte layer includes a region including solid electrolyte particles and an electron conductive material on a side in contact with the cathode.
  • the contact area between the negative electrode and the solid electrolyte layer is maximized and the contact uniformity is high, so that the interfacial resistance is reduced, and the contact between the negative electrode and the solid electrolyte layer is maintained even when the electrode volume changes during charge and discharge, and the formation of lithium dendrites is suppressed, so that the electrochemical characteristics such as the initial charge and discharge efficiency are improved.
  • Figures 1 and 2 are cross-sectional views schematically showing an all-solid-state secondary battery according to one embodiment.
  • the term “layer” here includes not only the shape formed on the entire surface when observed in a plan view, but also the 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. Alternatively, 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. Unless otherwise defined, the average particle size may mean the diameter (D50) of particles having a cumulative volume of 50% by volume in a particle size distribution.
  • the average particle size may 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).
  • an all-solid-state secondary battery comprising a cathode, an anode, and a solid electrolyte layer positioned between the cathode and the anode, wherein the solid electrolyte layer is characterized by including a region including solid electrolyte particles and an electron conductive material on a side in contact with the cathode.
  • FIG. 1 is a cross-sectional view of an all-solid-state secondary battery according to an embodiment.
  • an all-solid-state secondary battery (100') may have a structure in which an electrode assembly in which an anode (400) including an anode current collector (401) and an anode active material layer (403), a solid electrolyte layer (300), and a cathode (200) including an anode active material layer (203) and a cathode current collector (201) are laminated is housed in a battery case.
  • the all-solid-state secondary battery (100') may further include an elastic layer (500) on the outer side of at least one of the cathode (200) and the anode (400).
  • FIG. 1 illustrates one electrode assembly including an anode (400), a solid electrolyte layer (300), and a cathode (200), an all-solid-state secondary battery may be manufactured by laminating two or more electrode assemblies.
  • the above solid electrolyte layer includes solid electrolyte particles.
  • the solid electrolyte layer according to one embodiment includes a region including solid electrolyte particles and an electron conductive material on a side in contact with the cathode.
  • the region may be referred to as a portion of the solid electrolyte layer that contacts the cathode. Due to the region, the bonding area between the cathode and the solid electrolyte layer can be maximized, and the void at the interface can be minimized.
  • the above solid electrolyte particles may be, for example, sulfide-based solid electrolyte particles having excellent ion conductivity.
  • the above sulfide-based solid electrolyte particles are, for example, Li 2 SP 2 S 5 , Li 2 SP 2 S 5 --LiX (X is a halogen element, for example, I or Cl), Li 2 SP 2 S 5 -Li 2 O, Li 2 SP 2 S 5 -Li 2 O-LiI, Li 2 S-SiS 2 , Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 SB 2 S 3 , Li 2 SP 2 S 5 -Z m S n (m and n are each integers, and Z is Ge, Z
  • Such sulfide-based solid electrolytes can be obtained, for example, by mixing Li 2 S and P 2 S 5 in a molar ratio of 50:50 to 90:10, or a molar ratio of 50:50 to 80:20, and optionally performing a heat treatment. In the above mixing ratio range, a sulfide-based solid electrolyte having excellent ionic conductivity can be produced.
  • other components such as SiS 2 , GeS 2 , and B 2 S 3 can be further included to further improve the ionic conductivity.
  • mechanical milling is a method of putting starting raw materials in a ball mill reactor, vigorously stirring them, and mixing them by pulverizing them.
  • the starting raw materials can be mixed in a solvent to obtain a solid electrolyte as a precipitate.
  • heat treatment is performed after mixing, the crystals of the solid electrolyte can become more solid and the ionic conductivity can be improved.
  • a sulfide-based solid electrolyte can be produced by mixing sulfur-containing raw materials and performing heat treatment twice or more, in which case a sulfide-based solid electrolyte with high ionic conductivity and solidity can be produced.
  • the temperature of the first heat treatment may be, for example, 150°C to 330°C, or 200°C to 300°C
  • the temperature of the second heat treatment may be, for example, 380°C to 700°C, or 400°C to 600°C.
  • the above argyrodite-type sulfides may specifically be 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 , etc.
  • 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 diameter (D50) of the 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 diameter of the solid electrolyte particles may be measured from 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 electronically conductive material may be applied without limitation to any type as long as it is electronically conductive and does not adversely affect the battery, and may include, for example, a carbon-based material, a metal-based material, a conductive polymer, or a combination thereof.
  • the carbon-based material may include, for example, natural graphite, artificial graphite, carbon black, acetylene black, Denka black, Ketjen black, carbon fibers, carbon nanofibers, carbon nanotubes, or a combination thereof.
  • the metal-based material may include Al, Ag, Au, Bi, Cu, Ni, Pd, Pt, Si, Sn, Zn, Zr, or a combination thereof.
  • the conductive polymer may be, for example, a polyphenylene derivative.
  • the above-mentioned electronically conductive material may include, for example, a carbon-metal composite containing a carbon-based material and a metal-based material.
  • the carbon-based material may be an amorphous carbon material
  • the metal-based material may be a lithium-philic metal including Al, Ag, Au, Bi, Pd, Pt, Si, Sn, Zn or a combination thereof.
  • the above electron conductive material may be, for example, in the form of particles.
  • the average particle diameter (D50) of the electron conductive material may be, for example, 10 nm to 200 nm, or 50 nm to 150 nm, or 60 nm to 100 nm.
  • the average particle diameter (D50) of the electron conductive material may be smaller than the average particle diameter (D50) of the solid electrolyte particles existing within the region.
  • the ratio of the average particle diameter (D50) of the electron conductive material to the average particle diameter (D50) of the solid electrolyte particles may be 0.1 or less, and may be 0.01 to 0.1 or 0.2 to 0.09.
  • the average particle size of the above electronic conductive material can be obtained by measuring the size (diameter or length of the major axis) of about 20 particles in a scanning electron microscope image to obtain a particle size distribution and calculating D50 from this.
  • the electron conductive material may be included in an amount of 5 to 10 wt% based on 100 wt% of the total of the solid electrolyte particles and the electron conductive material in the region.
  • the electron conductive material may be included in an amount of 3 to 20 wt% based on 100 volume% of the region, for example, 4 to 15 volume%, or 5 to 10 volume%.
  • the region refers to a portion of the solid electrolyte layer that contacts the negative electrode, and includes the solid electrolyte particles and the electron conductive material.
  • the thickness of the above region can be 10% to 60% of the total thickness of the solid electrolyte layer, for example 15% to 50%, or 20% to 40%.
  • the interfacial resistance between the negative electrode and the solid electrolyte layer can be effectively controlled without deteriorating the performance of the all-solid-state secondary battery.
  • the above solid electrolyte layer may further include a binder in addition to the solid electrolyte.
  • the above region may also further include a binder in addition to the solid electrolyte particles and the electron conductive material.
  • 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,
  • a solid electrolyte layer according to one embodiment may be expressed as a multilayer structure of two or more layers, for example.
  • the multilayer structure may include two layers, or three or more layers, or two or more layers and five or less layers.
  • the solid electrolyte layer may include a first solid electrolyte layer in contact with the negative electrode and a second solid electrolyte layer in contact with the positive electrode.
  • the first solid electrolyte layer includes first solid electrolyte particles and an electron conductive material, which corresponds to the “region” described above.
  • the second solid electrolyte layer may include second solid electrolyte particles and may not include an electron conductive material.
  • the first solid electrolyte and the second solid electrolyte may be the same or different from each other.
  • the first solid electrolyte and the second solid electrolyte may have substantially the same composition and average particle size.
  • the first solid electrolyte and the second solid electrolyte may have substantially the same composition but different average particle sizes.
  • the first solid electrolyte and the second solid electrolyte may be, for example, a sulfide-based solid electrolyte, and among them, may be an argyrodite-type sulfide-based solid electrolyte.
  • the average particle diameter (D50) of the first solid electrolyte particles may be larger than the average particle diameter (D50) of the second solid electrolyte particles.
  • the average particle diameter (D50) of the first solid electrolyte particles may be 2.0 ⁇ m to 5.0 ⁇ m, or 3.0 ⁇ m to 4.0 ⁇ m
  • the average particle diameter (D50) of the second solid electrolyte particles may be 0.1 ⁇ m to 1.5 ⁇ m, or 0.1 ⁇ m to 1.0 ⁇ m, or 0.2 ⁇ m to 0.9 ⁇ m, or less than 1 ⁇ m.
  • the average particle diameter (D50) of the second solid electrolyte particles may be larger than the average particle diameter (D50) of the first solid electrolyte particles.
  • the average particle diameter (D50) of the first solid electrolyte particles may be 0.1 ⁇ m to 1.5 ⁇ m, or 0.1 ⁇ m to 1.0 ⁇ m, or 0.2 ⁇ m to 0.9 ⁇ m, or less than 1 ⁇ m
  • the average particle diameter (D50) of the second solid electrolyte particles may be 2.0 ⁇ m to 5.0 ⁇ m, or 3.0 ⁇ m to 4.0 ⁇ m.
  • the average particle diameter (D50) of the electron conductive material may be smaller than the average particle diameter (D50) of the first solid electrolyte particles, for example, a ratio of the average particle diameter (D50) of the electron conductive material to the average particle diameter (D50) of the first solid electrolyte particles may be 0.1 or less, and may be 0.01 to 0.1 or 0.2 to 0.09. In this case, the bonding area between the negative electrode and the solid electrolyte layer may be further increased, and thus the interfacial resistance may be lowered.
  • the above-described electron conductive material may be included in the first solid electrolyte layer in an amount of 5 wt% to 10 wt% based on 100 wt% of the total of the solid electrolyte particles and the electron conductive material.
  • the electron conductive material may be included in an amount of 3 wt% to 20 wt% based on 100 volume% of the first solid electrolyte layer, for example, 4 wt% to 15 wt%, or 5 wt% to 10 wt%.
  • the thickness of the first solid electrolyte layer and the thickness of the second solid electrolyte layer may be the same or different from each other.
  • the thickness of the first solid electrolyte layer and the thickness of the second solid electrolyte layer may be substantially the same.
  • the thickness of the first solid electrolyte layer may be from 10 ⁇ m to 200 ⁇ m, for example, from 10 ⁇ m to 150 ⁇ m, from 10 ⁇ m to 100 ⁇ m, or from 20 ⁇ m to 80 ⁇ m.
  • the thickness of the second solid electrolyte layer may be from 10 ⁇ m to 200 ⁇ m, for example, from 10 ⁇ m to 150 ⁇ m, from 10 ⁇ m to 100 ⁇ m, or from 20 ⁇ m to 80 ⁇ m.
  • the solid electrolyte layer may further include an oxide-based inorganic solid electrolyte in addition to a sulfide-based solid electrolyte.
  • oxide-based inorganic 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
  • the solid electrolyte layer, or the region, or the first solid electrolyte layer and the second solid electrolyte layer may each independently further include an alkali metal salt, and/or an ionic liquid, and/or a conductive polymer.
  • the above alkali metal salt may be, for example, a lithium salt.
  • the content of the lithium salt in the solid electrolyte layer may be 1 M or more, for example, 1 M to 4 M.
  • the lithium salt may improve ion conductivity by enhancing lithium ion mobility of the solid electrolyte layer.
  • the above lithium salts include , for example, LiSCN , LiN (CN) 2 , Li( CF3SO2 ) 3C , LiC4F9SO3 , LiN( SO2CF2CF3 ) 2 , LiCl, LiF , LiBr, LiI , LiB( C2O4 ) 2 , LiBF4, LiBF3 ( C2F5 ), lithium bis(oxalato) borate (LiBOB), lithium oxalyldifluoroborate (LIODFB), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(trifluoromethanesulfonyl)imide, LiTFSI, LiN( SO2CF3 ) 2 .
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiN(SO 2 F) 2 lithium bis(fluorosulfonyl)imide
  • LiCF 3 SO 3 lithium bis(fluorosulfonyl)imide
  • LiAsF 6 LiSbF 6
  • LiClO 4 LiClO 4 or a mixture thereof.
  • the lithium salt may be an imide type, and for example, the imide type lithium salt may include lithium bis(trifluoro methanesulfonyl)imide (LiTFSI, LiN(SO 2 CF 3 ) 2 ), lithium bis(fluorosulfonyl)imide (LiFSI, LiN(SO 2 F) 2 ).
  • LiTFSI lithium bis(trifluoro methanesulfonyl)imide
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiFSI LiN(SO 2 F) 2
  • the above ionic liquid has a melting point below room temperature and is a salt or room-temperature molten salt that is liquid at room temperature and consists only of ions.
  • the above ionic liquid comprises a) at least one cation selected from ammonium-based, pyrrolidinium-based, pyridinium-based, pyrimidinium-based, imidazolium-based, piperidinium-based, pyrazolium-based, oxazolium-based, pyridazinium-based, phosphonium-based, sulfonium-based, triazolium-based and mixtures thereof, and b) BF 4 - , PF 6 - , AsF 6 - , SbF 6 - , AlCl 4 - , HSO 4 - , ClO 4 - , CH 3 SO 3 - , CF 3 CO 2 - , Cl - , Br - , I - , BF 4 - , SO 4 - , CF 3 SO 3 - , (FSO 2 ) 2 N - , (C 2 F 5 SO 2 )2N - ,
  • the above ionic liquid may be at least one selected from the group consisting of, for example, N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidinium bis(3-trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide.
  • the weight ratio of the solid electrolyte and the ionic liquid can be 0.1:99.9 to 90:10, for example, 10:90 to 90:10, 20:80 to 90:10, 30:70 to 90:10, 40:60 to 90:10, or 50:50 to 90:10.
  • the solid electrolyte layer satisfying the above range can improve the electrochemical contact area with the electrode, thereby maintaining or improving the ionic conductivity. Accordingly, the energy density, discharge capacity, rate characteristics, etc. of the all-solid-state secondary battery can be improved.
  • An anode for an all-solid-state secondary battery includes a current collector and a negative electrode active material layer positioned on the current collector.
  • the negative electrode active material layer includes a negative electrode active material and may further include a binder and/or a conductive material.
  • the above-mentioned region or the first solid electrolyte layer may be referred to as a surface in contact with the negative electrode active material layer.
  • the above negative active material includes a material capable of reversibly intercalating/deintercalating lithium ions, lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.
  • the material capable of reversibly intercalating/deintercalating the lithium ions may include a carbon-based negative electrode active material, for example, crystalline carbon, amorphous carbon, or a combination thereof.
  • crystalline carbon include graphite such as natural graphite or artificial graphite in an amorphous, plate-like, flake-like, spherical, or fibrous form
  • amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, calcined coke, and the like.
  • lithium metal alloy an alloy of lithium and a metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn can be used.
  • a Si-based negative electrode active material or a Sn-based negative electrode active material can be used.
  • the Si-based negative electrode active material silicon, a silicon-carbon composite, SiO x (0 ⁇ x ⁇ 2), a Si-Q alloy (wherein Q is an element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Group 15 elements, Group 16 elements, transition metals, rare earth elements, and combinations thereof, but is not Si), and as the Sn-based negative electrode active material, Sn, SnO 2 , a Sn-R alloy (wherein R is an element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Group 15 elements, Group 16 elements, transition metals, rare earth elements, and combinations thereof, but is not Sn), and the like.
  • the above elements Q and R may be selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof.
  • the negative active material may include silicon-carbon composite particles.
  • the average particle diameter (D50) of the silicon-carbon composite particles may be, for example, 0.5 ⁇ m to 20 ⁇ m.
  • the average particle diameter (D50) is measured by a particle size analyzer and refers to the diameter of particles having a cumulative volume of 50 volume% in a particle size distribution.
  • silicon may be included in an amount of 10 wt% to 60 wt% and carbon may be included in an amount of 40 wt% to 90 wt%.
  • the silicon-carbon composite particles may include, for example, a core including silicon particles, and a carbon coating layer positioned on a surface of the core.
  • the average particle diameter (D50) of the silicon particles in the core may be 10 nm to 1 ⁇ m, or 10 nm to 200 nm.
  • the silicon particles may exist as silicon alone, in the form of a silicon alloy, or in an oxidized form.
  • the oxidized form of silicon can be represented as SiO x (0 ⁇ x ⁇ 2).
  • the thickness of the carbon coating layer can be about 5 nm to 100 nm.
  • the silicon-carbon composite particle may include a core including silicon particles and crystalline carbon, and a carbon coating layer positioned on the surface of the core and including amorphous carbon.
  • the amorphous carbon may not be present in the core but may be present only in the carbon coating layer.
  • the crystalline carbon may be artificial graphite, natural graphite, or a combination thereof, and the amorphous carbon may be formed from coal pitch, mesophase pitch, petroleum pitch, coal oil, petroleum heavy oil, or a polymer resin (phenol resin, furan resin, polyimide resin, etc.).
  • the content of the crystalline carbon may be 10 wt% to 70 wt% with respect to 100 wt% of the silicon-carbon composite particle, and the content of the amorphous carbon may be 20 wt% to 40 wt%.
  • the core may include a void in the central portion.
  • the radius of the void may be 30% to 50% of the radius of the silicon-carbon composite particle.
  • the silicon-carbon composite particles described above can effectively suppress problems such as volume expansion, structural collapse, or particle crushing due to charge and discharge, thereby preventing the phenomenon of conductive path disconnection, realizing high capacity and high efficiency, and are advantageous for use under high voltage or high-speed charging conditions.
  • the above Si-based negative electrode active material or Sn-based negative electrode active material can be used in a mixture with a carbon-based negative electrode active material.
  • the mixing ratio can be 1:99 to 90:10 by weight.
  • the content of the negative active material in the above negative active material layer may be 95 wt% to 99 wt% with respect to the total weight of the negative active material layer.
  • the negative electrode active material layer further includes a binder and may optionally further include a conductive material.
  • the content of the binder in the negative electrode active material layer may be 1 wt% to 5 wt% with respect to the total weight of the negative electrode active material layer.
  • the negative electrode active material layer may include 90 wt% to 98 wt% of the negative electrode active material, 1 wt% to 5 wt% of the binder, and 1 wt% to 5 wt% of the conductive material.
  • the above binder serves to adhere the negative active material particles well to each other and also to adhere the negative active material well to the current collector.
  • the binder may be an insoluble binder, a water-soluble binder, or a combination thereof.
  • the above-mentioned insoluble binders may include polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, ethylene propylene copolymers, polystyrene, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyimide or combinations thereof.
  • the above water-soluble binder may be a rubber-based binder or a polymer resin binder.
  • the rubber-based binder may be selected from styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, fluororubber, and combinations thereof.
  • the polymer resin binder may be selected from polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, ethylene propylene diene copolymer, polyvinyl pyridine, chlorosulfonated polyethylene, latex, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, and combinations thereof.
  • a cellulose-based compound that can provide viscosity as a kind of thickener may be further included.
  • the cellulose-based compound one or more types of carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, or an alkali metal salt thereof may be mixed and used.
  • the alkali metal Na, K or Li may be used.
  • the amount of such thickener used may be 0.1 to 3 parts by weight based on 100 parts by weight of the negative electrode active 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 can 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 including copper, nickel, aluminum, and silver in the form of metal powder or metal fibers; conductive polymers such as polyphenylene derivatives; or conductive materials including mixtures thereof.
  • 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 negative electrode for an all-solid-state secondary battery may be a precipitation-type negative electrode.
  • the precipitation-type negative electrode may mean a negative electrode that does not include a negative electrode active material when the battery is assembled, but in which lithium metal or the like is precipitated or deposited on the negative electrode when the battery is charged, and this serves as a negative electrode active material.
  • FIG. 2 is a schematic cross-sectional view of an all-solid-state secondary battery including a precipitation-type negative electrode.
  • the precipitation-type negative electrode (400') may include a current collector (401) and a negative electrode coating layer (405) positioned on the current collector.
  • An all-solid-state secondary battery including such a precipitation-type negative electrode (400') starts initial charging in a state in which no negative electrode active material exists, and when charging, high-density lithium metal is precipitated or deposited between the current collector (401) and the negative electrode coating layer (405) or on the negative electrode coating layer (405) to form a lithium metal layer (404), which may function as a negative electrode active material.
  • 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 aforementioned region or first solid electrolyte layer can be said to be a surface in contact with the cathode coating layer (405).
  • the above cathode coating layer (405) may be called a lithium electrodeposition induction layer or a cathode catalyst layer, and may include a metal, carbon material, or a combination thereof that acts as a catalyst.
  • 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 mixing ratio of the metal and the carbon material may be, for example, a weight ratio of 1:10 to 2:1.
  • the precipitation of lithium metal can be effectively promoted and the characteristics of the all-solid-state secondary battery can be improved.
  • the above-described negative electrode coating layer (405) may include, for example, a carbon material supported with a catalytic metal, or may include a mixture of metal particles and carbon material particles.
  • the above-described cathode coating layer (405) may include, for example, the above-described lithium-philic metal and amorphous carbon, in which case the precipitation of lithium metal may be effectively promoted.
  • the above-described cathode coating layer (405) may include a composite in which a lithium-philic metal is supported on amorphous carbon.
  • the above cathode coating layer (405) may further include a binder, and the binder may be, for example, a conductive binder.
  • the above cathode coating layer (405) may further include general additives such as fillers, dispersants, and ion conductive agents.
  • the thickness of the 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 above-described precipitated negative electrode (400') may further include, for example, a thin film on the surface of the current collector, that is, between the current collector and the negative electrode coating layer.
  • the thin film may include an element capable of forming an alloy with lithium.
  • the element capable of forming an alloy with lithium may be, for example, gold, silver, zinc, tin, indium, silicon, aluminum, bismuth, etc., and may be composed of one type of these or may be composed of multiple types of alloys.
  • the thin film may further flatten the precipitated form of the lithium metal layer (404) and further improve the characteristics of the all-solid-state secondary battery.
  • the thin film may be formed by, for example, a vacuum deposition method, a sputtering method, a plating method, or the like.
  • the thickness of the thin film may be, for example, 1 nm to 500 nm.
  • the above lithium metal layer (404) may include lithium metal or a lithium alloy.
  • the lithium alloy may be, for example, a Li-Al alloy, a Li-Sn alloy, a Li-In alloy, a Li-Ag alloy, a Li-Au alloy, a Li-Zn alloy, a Li-Ge alloy, or a Li-Si alloy.
  • 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 device comprises a current collector and 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 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.
  • the above cathode active material may be, for example, lithium cobalt oxide (LCO), lithium nickel oxide (LNO), lithium nickel cobalt oxide (NC), lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium nickel manganese oxide (NM), lithium manganese oxide (LMO), or lithium iron phosphate (LFP).
  • LCO lithium cobalt oxide
  • LNO lithium nickel oxide
  • NC lithium nickel cobalt oxide
  • NCA lithium nickel cobalt aluminum oxide
  • NCM lithium nickel cobalt manganese oxide
  • NM lithium nickel manganese oxide
  • LMO lithium manganese oxide
  • LFP lithium iron phosphate
  • the positive electrode active material may include, for example, a lithium nickel-based oxide represented by the following chemical formula 11, a lithium cobalt-based oxide represented by the following chemical formula 12, a lithium iron phosphate-based compound represented by the following chemical formula 13, a cobalt-free lithium nickel-manganese-based oxide represented by the following chemical formula 14, or a combination thereof.
  • M 1 and M 2 are each independently one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zr, and X is one or more elements selected from the group consisting of F, P, and S.
  • 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.
  • M 5 is at least one element selected from the group consisting of Al, B, Ba, Ca, Ce, Cr, Fe, Mg, Mo, Nb, Si, Sn, Sr, Ti, V, W, 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 20 or so 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 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 polyhedral or irregular.
  • 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 solid electrolyte included in the positive electrode active material layer may include a sulfide-based solid electrolyte, an oxide-based solid electrolyte, or a combination thereof, and may be, for example, an argyrodite-type sulfide-based solid electrolyte. Since the solid electrolyte has been described above, a detailed description thereof will be omitted.
  • the solid electrolyte may be included in an amount of 0.1 wt% to 35 wt%, for example, 1 wt% to 35 wt%, 5 wt% to 30 wt%, 8 wt% to 25 wt%, or 10 wt% to 20 wt%.
  • 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.
  • 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 content of the binder in the positive electrode active material layer may be approximately 0.1 wt% to 5 wt% with respect to 100 wt% of the positive electrode active material layer.
  • 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, and silver 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.
  • Aluminum foil may be used as the positive electrode collector, but is not limited thereto.
  • the above-mentioned all-solid-state secondary battery may be a unit cell having a structure of positive electrode/solid electrolyte layer/negative electrode, a bicell having a structure of negative electrode/solid electrolyte layer/positive electrode/solid electrolyte layer/negative electrode, or a laminated battery in which the structure of the unit cell is repeated.
  • 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.
  • 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, vacuum-dried, and rolled to prepare a deposition-type negative electrode in which a negative electrode coating layer was formed on the current collector.
  • the first composition is applied onto the cathode coating layer of the prepared cathode using a blade coater to form a first solid electrolyte layer.
  • the second composition is applied onto the first solid electrolyte layer using a blade coater to form a second solid electrolyte layer, and drying is performed at 80°C for 10 minutes.
  • a cathode composition was prepared by mixing 85 wt% of LiNi 0.9 Co 0.05 Mn 0.05 O 2 cathode active material coated with Li 2 O-ZrO 2 , 13.5 wt% of argyrodite-type solid electrolyte (Li 6 PS 5 Cl), 1.0 wt% of PVdF binder, and 0.5 wt% of carbon nanotube conductive material in an IBIB solvent.
  • the prepared cathode composition was coated on a cathode current collector using a bar coater, and dried in a convection oven at 80° C. for 10 minutes, thereby preparing a cathode having a cathode active material layer formed on the current collector.
  • the positive electrode is laminated on the second solid electrolyte layer such that the positive electrode active material layer touches the second solid electrolyte layer.
  • An assembly in which the negative electrode, the first solid electrolyte layer, the second solid electrolyte layer, and the positive electrode are laminated in that order is inserted into a pouch, sealed, and subjected to a warm isostatic press (WIP) at a high temperature of 85°C and 500 MPa for 30 minutes to manufacture an all-solid-state secondary battery.
  • WIP warm isostatic press
  • the thickness of each of the first solid electrolyte layer and the second solid electrolyte layer was about 50 ⁇ m.
  • An all-solid-state secondary battery was manufactured in substantially the same manner as in Example 1, except that the electronic conductive material introduced into the first solid electrolyte layer in Example 1 was changed to 5 wt% of nano silver particles having an average particle diameter of about 150 nm.
  • An all-solid-state secondary battery was manufactured in substantially the same manner as in Example 1, except that the first solid electrolyte layer was not formed and only the second solid electrolyte layer was formed with twice the thickness.
  • An all-solid-state secondary battery was manufactured in substantially the same manner as in Example 1, except that the second solid electrolyte layer was not formed and only the first solid electrolyte layer was formed with twice the thickness.
  • Cathode current collector 203 Cathode active material layer
  • Negative electrode current collector 403 Negative electrode active material layer
  • Negative coating layer 500 Elastic layer

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Abstract

La présente invention concerne une batterie rechargeable entièrement solide comprenant une électrode négative, une électrode positive et une couche d'électrolyte solide positionnée entre l'électrode négative et l'électrode positive, la couche d'électrolyte solide comportant, sur le côté qui est en contact avec l'électrode négative, une région qui comprend des particules d'électrolyte solide et un matériau conducteur d'électrons.
PCT/KR2024/004363 2023-09-21 2024-04-03 Batterie rechargeable entièrement solide Pending WO2025063415A1 (fr)

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US20170092975A1 (en) * 2015-09-25 2017-03-30 Samsung Electronics Co., Ltd. Composite electrolyte film, electrochemical cell including the composite electrolyte film, and method of preparing the composite electrolyte film
KR20200041189A (ko) * 2018-10-11 2020-04-21 주식회사 엘지화학 고체 전해질막 및 이를 제조하는 방법 및 이를 포함하는 전고체 전지
KR20200113779A (ko) * 2019-03-26 2020-10-07 한국생산기술연구원 하이브리드 고체전해질 시트, 그를 포함하는 전고체 리튬이차전지 및 그의 제조방법
KR20220048298A (ko) * 2020-10-12 2022-04-19 삼성에스디아이 주식회사 전고체이차전지 및 그 제조방법
KR20230132293A (ko) * 2022-03-08 2023-09-15 삼성에스디아이 주식회사 전고체 이차 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170092975A1 (en) * 2015-09-25 2017-03-30 Samsung Electronics Co., Ltd. Composite electrolyte film, electrochemical cell including the composite electrolyte film, and method of preparing the composite electrolyte film
KR20200041189A (ko) * 2018-10-11 2020-04-21 주식회사 엘지화학 고체 전해질막 및 이를 제조하는 방법 및 이를 포함하는 전고체 전지
KR20200113779A (ko) * 2019-03-26 2020-10-07 한국생산기술연구원 하이브리드 고체전해질 시트, 그를 포함하는 전고체 리튬이차전지 및 그의 제조방법
KR20220048298A (ko) * 2020-10-12 2022-04-19 삼성에스디아이 주식회사 전고체이차전지 및 그 제조방법
KR20230132293A (ko) * 2022-03-08 2023-09-15 삼성에스디아이 주식회사 전고체 이차 전지

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