[go: up one dir, main page]

WO2025105607A1 - Batterie rechargeable entièrement solide - Google Patents

Batterie rechargeable entièrement solide Download PDF

Info

Publication number
WO2025105607A1
WO2025105607A1 PCT/KR2024/004871 KR2024004871W WO2025105607A1 WO 2025105607 A1 WO2025105607 A1 WO 2025105607A1 KR 2024004871 W KR2024004871 W KR 2024004871W WO 2025105607 A1 WO2025105607 A1 WO 2025105607A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
solid
secondary battery
state secondary
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/KR2024/004871
Other languages
English (en)
Korean (ko)
Inventor
이재준
이은경
김재민
이건욱
이시은
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung SDI Co Ltd
Original Assignee
Samsung SDI Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samsung SDI Co Ltd filed Critical Samsung SDI Co Ltd
Publication of WO2025105607A1 publication Critical patent/WO2025105607A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—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
    • 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
    • H01M4/36—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
    • H01M4/362—Composites
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • 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
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • 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
    • 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 is being 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.
  • the above solid electrolyte layer is,
  • the above first solid electrolyte and the second solid electrolyte are in the form of particles, and an average particle diameter (D50) of the first solid electrolyte is smaller than the average particle diameter (D50) of the second solid electrolyte, and an all-solid-state secondary battery is provided.
  • An all-solid-state secondary battery according to one embodiment can exhibit improved battery performance by including a solid electrolyte having high lithium ion conductivity.
  • Figure 1 is a cross-sectional view schematically illustrating an all-solid-state secondary battery according to one embodiment.
  • Figure 2 is a cross-sectional view schematically illustrating an all-solid-state secondary battery according to another 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.
  • 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).
  • an all-solid-state secondary battery includes a cathode, an anode, and a solid electrolyte layer disposed between the cathode and the anode, wherein the solid electrolyte layer includes: a first solid electrolyte layer disposed in contact with the cathode and including a first solid electrolyte and a carbon composite; and a second solid electrolyte layer disposed in contact with the cathode and including a second solid electrolyte; wherein the first solid electrolyte and the second solid electrolyte are in the form of particles, and an average particle diameter (D50) of the first solid electrolyte is smaller than an average particle diameter (D50) of the second solid electrolyte.
  • D50 average particle diameter
  • 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 above all-solid-state secondary battery (100) may further include an elastic layer (500) on the outer side of at least one of the positive electrode (200) and the negative electrode (400).
  • FIG. 1 illustrates one electrode assembly including a cathode (400), a solid electrolyte layer (300), and a cathode (200), but an all-solid-state secondary battery may be manufactured by stacking two or more electrode assemblies.
  • the 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 positive electrode/solid electrolyte layer/negative electrode/solid electrolyte layer/positive electrode, or a laminated battery in which the structure of the unit cell is repeated.
  • the shape of the above-described 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-described all-solid-state secondary battery can be applied to large-sized batteries used in electric vehicles, etc.
  • the above-described 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-described all-solid-state secondary battery can be used in various fields, such as portable electronic devices.
  • a solid electrolyte layer (300) includes a first solid electrolyte layer (310) arranged in contact with a negative electrode (400) and including a first solid electrolyte and a carbon composite; and a second solid electrolyte layer (320) arranged in contact with a positive electrode (200) and including a second solid electrolyte.
  • first solid electrolyte and the second solid electrolyte are each in the form of particles, and the average particle diameter (D50) of the first solid electrolyte is smaller than the average particle diameter (D50) of the second solid electrolyte.
  • first solid electrolyte having a relatively small average particle size By applying a first solid electrolyte having a relatively small average particle size to the first solid electrolyte layer (310) in contact with the cathode (400), pores can be reduced and a conductive path can be easily formed.
  • second solid electrolyte having a relatively large average particle size to the second solid electrolyte layer (320) in contact with the cathode (200), ion conductivity at the interface with the cathode and ion conductivity within the solid electrolyte layer can be increased.
  • An all-solid-state secondary battery includes a double-layered solid electrolyte layer, and by controlling the particle size of the solid electrolyte included in each solid electrolyte layer, the occurrence of a section where contact between electrolyte particles does not occur can be minimized. Accordingly, the path through which lithium ions can move can be optimized, thereby increasing lithium ion conductivity and improving the overall characteristics of the battery.
  • the average particle size (D50) of the first solid electrolyte may be 0.1 ⁇ m to 2.0 ⁇ m, for example, 0.1 ⁇ m to 1.5 ⁇ m, 0.1 ⁇ m to 1.0 ⁇ m, or 0.5 ⁇ m to 1.0 ⁇ m.
  • the average particle diameter (D50) of the second solid electrolyte may be 2.0 ⁇ m to 5.0 ⁇ m, for example, 2.0 ⁇ m to 4.0 ⁇ m, or 2.5 ⁇ m to 3.0 ⁇ m.
  • the average particle diameter (D50) of the first and second solid electrolytes may be measured from an electron microscope image.
  • the particle size distribution may be obtained by measuring the size (diameter or length of the major axis) of about 20 particles in a scanning electron microscope image, and D50 may be calculated from this.
  • the average particle diameter (D50) of each of the first solid electrolyte and the second solid electrolyte included in the solid electrolyte layer may be larger than the average particle diameter (D50) of the solid electrolyte included in the positive electrode (200).
  • the energy density of the all-solid-state secondary battery can be maximized while increasing the mobility of lithium ions, thereby improving the overall performance.
  • the average particle diameter (D50) of the solid electrolyte included in the positive electrode (200) may be 0.1 ⁇ m to 1.9 ⁇ m, or 0.1 ⁇ m to 1.0 ⁇ m, or 0.1 ⁇ m to 0.5 ⁇ m.
  • the energy density of the all-solid-state secondary battery can be maximized while the transfer of lithium ions is facilitated, thereby suppressing resistance and thus improving the overall performance of the all-solid-state secondary battery.
  • the first solid electrolyte layer (310) includes a carbon composite.
  • the carbon composite is a material that can improve conductivity and increase lithium ion conductivity.
  • the phenomenon of the conductive path being disconnected after a charge/discharge cycle can be prevented, and the battery performance, such as implementing high capacity and high efficiency, can be improved.
  • the above carbon composite includes a carbon-based material and metal particles, and may be in the form of a composite in which the metal particles are dispersed within the carbon-based material, between the carbon-based materials, on the surface of the carbon-based material, or in two or more of these locations.
  • a metal may be supported on the carbon-based material.
  • the carbonaceous material may include amorphous carbon, crystalline carbon, or a mixture thereof.
  • the amorphous carbon may include carbon black, vapor-grown carbon fibers (VGCF), acetylene black (AB), activated furnace black, or a combination thereof.
  • the crystalline carbon may include natural graphite, artificial graphite, carbon nanotubes (CNT), graphene, or a combination thereof.
  • the crystalline carbon may be amorphous, plate-like, flake-like, spherical, or fibrous.
  • the metal particles may include silicon, silver, zinc, tin or a combination thereof.
  • the content of the metal particles may be 5 wt% to 40 wt%, and the content of the carbon-based material may be 60 to 95 wt%. In the above range, the metal may be evenly dispersed in the carbon-based material and well complexed.
  • the carbon composite may be included in an amount of 1 wt% to 20 wt% based on the total weight of the first solid electrolyte layer, for example, 5 wt% to 20 wt%, or 5 wt% to 10 wt%.
  • the lithium ion conductivity may be significantly improved by minimizing the section where contact between solid electrolyte particles does not occur while improving conductivity.
  • the types of the first solid electrolyte and the second solid electrolyte are not particularly limited, and may be the same or different.
  • the average particle diameters (D50) may be different due to differences in monomers or compositions, and can be applied regardless as long as the average particle diameter of the first solid electrolyte is smaller than the average particle diameter of the second solid electrolyte.
  • the first solid electrolyte and the second solid electrolyte may each independently be an inorganic solid electrolyte such as a sulfide-based solid electrolyte or an oxide-based solid electrolyte, or a solid polymer electrolyte.
  • the above solid electrolyte may be a sulfide-based solid electrolyte having excellent ion conductivity, an oxide-based inorganic solid electrolyte, or a combination thereof.
  • the above sulfide-based solid electrolyte is, 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, Zn, or Ga), Li 2 S-GeS 2 , Li 2 S-SiS 2 -Li 3 Examples include PO 4 , Li 2 S
  • the above sulfide-based solid electrolyte 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 in a molar ratio of 50:50 to 80:20. 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 , B 2 S 3 , etc. can be further included to further improve the ionic conductivity.
  • mechanical milling is a method of mixing starting materials by placing them in a reactor and vigorously stirring them with a ball mill, etc. to make the starting materials fine particles.
  • the starting materials can be mixed in a solvent to obtain a solid electrolyte as a precipitate.
  • additional calcination can be performed after mixing. If additional calcination is performed, the crystals of the solid electrolyte can become more solid.
  • the solid electrolyte may be an argyrodite-type sulfide-based solid electrolyte.
  • the sulfide-based solid electrolyte may be, for example, Li a M b P c S d A e (wherein a, b, c, d, and e are all 0 to 12, M is Ge, Sn, Si, or a combination thereof, and A is one of F, Cl, Br, or I), and specifically, Li 3 PS 4 , Li 7 P 3 S 11 , Li 6 PS 5 Cl, Li 6 PS 5 Br, Li 6 PS 5 I, and the like.
  • These sulfide-based solid electrolytes have high ionic conductivity close to the ionic conductivity of general liquid electrolytes at room temperature, which is in the range of 10 -4 to 10 -2 S/cm, and thus can form a close bond between the positive active material and the solid electrolyte without causing a decrease in ionic conductivity, and further can form a close interface between the electrode layer and the solid electrolyte layer.
  • An all-solid-state battery including the same can have improved battery performance, such as rate characteristics, Coulombic efficiency, and cycle life characteristics.
  • the above sulfide-based solid electrolyte may be amorphous or crystalline, or may be a mixture of the two.
  • the above 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 2 O 3 , Al 2 O 3 , TiO 2 , SiO 2 , lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li
  • each of the first solid electrolyte layer and the second solid electrolyte layer may further include an alkali metal salt, and/or an ionic liquid, and/or a conductive polymer.
  • 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-based lithium salt
  • the imide-based 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 ).
  • the lithium salt may maintain or improve ionic conductivity by appropriately maintaining chemical reactivity with the ionic liquid.
  • 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 ) 2 N-, (C 2 F 5 SO 2 )(CF 3 SO 2 )N-, and (CF
  • 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.
  • the thickness of the first solid electrolyte layer (310) and the thickness of the second solid electrolyte layer (320) 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 10 ⁇ m to 200 ⁇ m, for example, 10 ⁇ m to 150 ⁇ m, 10 ⁇ m to 100 ⁇ m, or 20 ⁇ m to 80 ⁇ m.
  • the thickness of the second solid electrolyte layer may be 10 ⁇ m to 200 ⁇ m, for example, 10 ⁇ m to 150 ⁇ m, 10 ⁇ m to 100 ⁇ m, or 20 ⁇ m to 80 ⁇ m.
  • the above solid electrolyte layer (300) may be in the form of a free-standing film.
  • a free-standing film may mean one that can maintain its shape by itself without a separate support structure (e.g., a substrate such as a film or glass).
  • the above self-supporting membrane-type solid electrolyte layer can be manufactured by coating first and second solid electrolyte layers on a release film, laminating and pressing the first solid electrolyte layer and the second solid electrolyte layer so that they are in contact, and then removing the release film.
  • the device includes a cathode current collector (201) and a cathode active material layer (203) positioned on the cathode current collector, and the cathode active material layer (203) includes a cathode active material and a solid electrolyte, and may optionally include a binder and/or a conductive material.
  • the second solid electrolyte layer described above may be referred to as a surface in contact with the cathode active material layer (203).
  • 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 positive electrode 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 oxide (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 oxide
  • the positive electrode active material may include, for example, a lithium nickel-based oxide represented by the following chemical formula 1, a lithium cobalt-based oxide represented by the following chemical formula 2, a lithium iron phosphate-based compound represented by the following chemical formula 3, a cobalt-free lithium nickel-manganese-based oxide represented by the following chemical formula 4, 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 above positive electrode active material may be 1 ⁇ m to 25 ⁇ m, for example, 3 ⁇ m to 25 ⁇ m, 1 ⁇ m to 20 ⁇ m, 1 ⁇ m to 18 ⁇ m, 3 ⁇ m to 15 ⁇ m, or 5 ⁇ m to 15 ⁇ m.
  • the positive electrode active material may include small particles having an average particle diameter (D50) of 1 ⁇ m to 9 ⁇ m and large particles having an average particle diameter (D50) of 10 ⁇ m to 25 ⁇ m.
  • the mixing ratio of the small particles and the large particles may be a weight ratio of about 10:90 to 40:60.
  • 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 realize 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 polyhedral or irregular.
  • 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. Within the content range, the binder can sufficiently exhibit adhesive ability without deteriorating battery performance.
  • 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. In the above content range, the conductive material can improve electrical conductivity without deteriorating battery performance.
  • Aluminum foil may be used as the above positive electrode collector, but is not limited thereto.
  • An anode (400) for an all-solid-state secondary battery includes an anode current collector (401) and an anode active material layer (403) positioned on the anode current collector (401).
  • the anode active material layer includes an anode active material and may further include a binder and/or a conductive material.
  • the first solid electrolyte layer (310) described above may be referred to as a surface that is in contact with the anode active material layer (403).
  • the negative electrode 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 in weight ratio.
  • 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 the 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 first solid electrolyte layer (310) can be said to be a surface that comes into 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 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 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.
  • An Ag/C composite is 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 is added to 2 g of an NMP solution containing 7 wt% of polyvinylidene fluoride binder and mixed to prepare a cathode coating layer composition.
  • This is applied to a SUS current collector using a bar coater, vacuum-dried, and rolled to prepare a deposition-type cathode in which a cathode coating layer is formed on the current collector.
  • a cathode composition is 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 azirodite-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 OA solvent.
  • the prepared cathode composition is coated on a cathode current collector using a bar coater and vacuum dried, thereby preparing a cathode in which a cathode active material layer is formed on the current collector.
  • a first solid electrolyte having an average particle diameter of about 1 ⁇ m (Li 6 PS 5 Cl, Mitsui Co.), a carbon composite (Denka Black, Denka Co.), and a dispersant are added to a binder solution in which an acrylic binder is dissolved in an octyl acetate (OA) solvent and stirred to prepare a first solid electrolyte layer slurry.
  • the first solid electrolyte layer slurry contains 92 wt% of the first solid electrolyte, 6 wt% of the carbon composite, 1.3 wt% of the binder, and 0.7 wt% of the dispersant.
  • the prepared first solid electrolyte layer slurry is cast on a polyethylene terephthalate (PET) release film with a thickness of about 50 ⁇ m and dried at room temperature to prepare a first solid electrolyte layer.
  • PET polyethylene terephthalate
  • a second solid electrolyte (Li 6 PS 5 Cl, Mitsui) having an average particle diameter of about 3 ⁇ m and a dispersant are added to a binder solution in which an acrylic binder is dissolved in an octyl acetate (OA) solvent and stirred to prepare a second solid electrolyte layer slurry.
  • the second solid electrolyte layer slurry contains 98 wt% of the second solid electrolyte, 1.3 wt% of the binder, and 0.7 wt% of the dispersant.
  • the prepared second solid electrolyte layer slurry is cast on a polyethylene terephthalate (PET) release film with a thickness of about 50 ⁇ m and dried at room temperature to prepare a second solid electrolyte layer.
  • PET polyethylene terephthalate
  • a first solid electrolyte layer is laminated on the negative electrode so that the negative active material layer of the manufactured negative electrode is in contact with the first solid electrolyte layer.
  • a second solid electrolyte layer is laminated on the first solid electrolyte layer.
  • a positive electrode is laminated on the second solid electrolyte layer so that the second solid electrolyte layer is in contact with the positive electrode active material layer.
  • An assembly in which a cathode, a first solid electrolyte layer, a second solid electrolyte layer, and a cathode are sequentially laminated 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 is about 40 ⁇ m.
  • An all-solid-state secondary battery is manufactured in the same manner as in Example 1, except that the average particle size of the first solid electrolyte included in the first solid electrolyte layer is about 2 ⁇ m.
  • An all-solid-state secondary battery is manufactured in the same manner as in Example 1, except that the average particle size of the second solid electrolyte included in the second solid electrolyte layer is about 2 ⁇ m.
  • An all-solid-state secondary battery is manufactured in the same manner as in Example 1, except that the first solid electrolyte layer does not include a carbon composite and the first solid electrolyte layer slurry contains 98 wt% of the first solid electrolyte, 1.3 wt% of a binder, and 0.7 wt% of a dispersant.
  • An all-solid-state secondary battery is manufactured in the same manner as in Example 2, except that the first solid electrolyte layer does not include a carbon composite and the first solid electrolyte layer slurry contains 98 wt% of the first solid electrolyte, 1.3 wt% of a binder, and 0.7 wt% of a dispersant.
  • An all-solid-state secondary battery is manufactured in the same manner as in Example 3, except that the first solid electrolyte layer does not include a carbon composite and the first solid electrolyte layer slurry contains 98 wt% of the first solid electrolyte, 1.3 wt% of a binder, and 0.7 wt% of a dispersant.
  • Second solid electrolyte layer First solid electrolyte (average particle size) With or without carbon complex Second solid electrolyte (average particle size)
  • Example 1 Li 6 PS 5 Cl (1 ⁇ m) you Li 6 PS 5 Cl (3 ⁇ m)
  • Example 2 Li 6 PS 5 Cl (2 ⁇ m) you Li 6 PS 5 Cl (3 ⁇ m)
  • Example 3 Li 6 PS 5 Cl (1 ⁇ m) you Li 6 PS 5 Cl (2 ⁇ m) Comparative Example 1 Li 6 PS 5 Cl (1 ⁇ m) radish Li 6 PS 5 Cl (3 ⁇ m) Comparative Example 2 Li 6 PS 5 Cl (2 ⁇ m) radish Li 6 PS 5 Cl (3 ⁇ m) Comparative Example 3 Li 6 PS 5 Cl (1 ⁇ m) radish Li 6 PS 5 Cl (2 ⁇ m)
  • the ratio (%) of the discharge amount to the charge amount is calculated as the charge/discharge efficiency and is shown in Table 2 below.

Landscapes

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

Abstract

L'invention concerne une batterie rechargeable entièrement solide comprenant une électrode négative, une électrode positive et une couche d'électrolyte solide disposée entre l'électrode négative et l'électrode positive, la couche d'électrolyte solide comprenant : une première couche d'électrolyte solide disposée en contact avec l'électrode négative et comprenant un premier électrolyte solide et un composite de carbone ; et une seconde couche d'électrolyte solide disposée en contact avec l'électrode positive et comprenant un second électrolyte solide, le premier électrolyte solide et le second électrolyte solide se présentant sous la forme de particules, le diamètre de particule moyen (D50) du premier électrolyte solide étant inférieur au diamètre de particule moyen (D50) du second électrolyte solide.
PCT/KR2024/004871 2023-11-14 2024-04-11 Batterie rechargeable entièrement solide Pending WO2025105607A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2023-0157631 2023-11-14
KR1020230157631A KR20250071060A (ko) 2023-11-14 2023-11-14 전고체 이차 전지

Publications (1)

Publication Number Publication Date
WO2025105607A1 true WO2025105607A1 (fr) 2025-05-22

Family

ID=95742848

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2024/004871 Pending WO2025105607A1 (fr) 2023-11-14 2024-04-11 Batterie rechargeable entièrement solide

Country Status (2)

Country Link
KR (1) KR20250071060A (fr)
WO (1) WO2025105607A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130085564A (ko) * 2011-12-22 2013-07-30 비나텍주식회사 연성 구조의 슈퍼 커패시터 및 이의 제조 방법
US20160336617A1 (en) * 2015-05-15 2016-11-17 Seiko Epson Corporation Solid electrolyte battery, electrode assembly, composite solid electrolyte, and method for producing solid electrolyte battery
US20180159169A1 (en) * 2015-10-30 2018-06-07 Lg Chem, Ltd. Polymer electrolyte having multi-layer structure, and all-solid battery comprising same
KR20230009312A (ko) * 2021-07-08 2023-01-17 도요타 지도샤（주） 전고체전지 및 전고체전지의 제조방법
JP2023101001A (ja) * 2019-11-11 2023-07-19 三星エスディアイ株式会社 全固体二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130085564A (ko) * 2011-12-22 2013-07-30 비나텍주식회사 연성 구조의 슈퍼 커패시터 및 이의 제조 방법
US20160336617A1 (en) * 2015-05-15 2016-11-17 Seiko Epson Corporation Solid electrolyte battery, electrode assembly, composite solid electrolyte, and method for producing solid electrolyte battery
US20180159169A1 (en) * 2015-10-30 2018-06-07 Lg Chem, Ltd. Polymer electrolyte having multi-layer structure, and all-solid battery comprising same
JP2023101001A (ja) * 2019-11-11 2023-07-19 三星エスディアイ株式会社 全固体二次電池
KR20230009312A (ko) * 2021-07-08 2023-01-17 도요타 지도샤（주） 전고체전지 및 전고체전지의 제조방법

Also Published As

Publication number Publication date
KR20250071060A (ko) 2025-05-21

Similar Documents

Publication Publication Date Title
WO2023171890A1 (fr) Batteries rechargeables entièrement solide
WO2024117675A1 (fr) Batterie à l'état solide
WO2024214921A1 (fr) Batterie rechargeable tout solide et son procédé de préparation
WO2024262755A1 (fr) Membrane électrolytique solide et batteries rechargeables tout solide
WO2025105602A1 (fr) Batterie rechargeable tout solide
WO2024262724A1 (fr) Batterie rechargeable tout solide
WO2025084526A1 (fr) Électrolyte solide, et électrode positive et batterie rechargeable tout solide le comprenant
WO2024210303A1 (fr) Matériau actif d'électrode négative, son procédé de préparation, électrode négative pour batterie rechargeable tout solide, et batterie rechargeable tout solide
WO2024101792A1 (fr) Couche d'électrode positive pour batterie secondaire entièrement solide, son procédé de fabrication et batterie secondaire entièrement solide la comprenant
WO2024058371A1 (fr) Électrode positive pour batterie rechargeable tout solide, et batterie rechargeable tout solide
WO2025105607A1 (fr) Batterie rechargeable entièrement solide
WO2025063415A1 (fr) Batterie rechargeable entièrement solide
WO2024191031A1 (fr) Membrane à électrolyte solide et batterie rechargeable tout solide
WO2024162637A1 (fr) Électrode positive pour batteries rechargeables entièrement solides et batteries rechargeables entièrement solides
WO2025014029A1 (fr) Électrolyte solide, son procédé de préparation, et membrane électrolytique solide et batteries rechargeables tout solide le comprenant
WO2025146872A1 (fr) Électrolyte solide, et membrane d'électrolyte solide et batterie rechargeable tout solide le comprenant
WO2024242273A1 (fr) Membrane à électrolyte solide et batterie rechargeable tout solide
WO2025105604A1 (fr) Électrode positive pour batteries rechargeables entièrement solides et batteries rechargeables entièrement solides
WO2025121560A1 (fr) Batterie rechargeable tout solide
WO2025095240A1 (fr) Batterie rechargeable tout solide
WO2025188001A1 (fr) Électrode positive pour batterie rechargeable tout solide et batterie rechargeable tout solide
WO2025244212A1 (fr) Batterie rechargeable tout solide
WO2025105608A1 (fr) Membrane électrolytique solide, électrode et batterie rechargeable tout solide
WO2025023411A1 (fr) Batterie rechargeable tout solide
WO2025127251A1 (fr) Batterie rechargeable entièrement solide

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: 24891556

Country of ref document: EP

Kind code of ref document: A1