WO2024172275A2 - Électrolyte solide polymère et batterie entièrement solide le comprenant - Google Patents

Électrolyte solide polymère et batterie entièrement solide le comprenant Download PDF

Info

Publication number
WO2024172275A2
WO2024172275A2 PCT/KR2023/021436 KR2023021436W WO2024172275A2 WO 2024172275 A2 WO2024172275 A2 WO 2024172275A2 KR 2023021436 W KR2023021436 W KR 2023021436W WO 2024172275 A2 WO2024172275 A2 WO 2024172275A2
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
chemical formula
polymer
polymer solid
layer
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.)
Ceased
Application number
PCT/KR2023/021436
Other languages
English (en)
Korean (ko)
Other versions
WO2024172275A3 (fr
Inventor
오경석
이상영
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.)
University Industry Foundation UIF of Yonsei University
Original Assignee
University Industry Foundation UIF of Yonsei University
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 University Industry Foundation UIF of Yonsei University filed Critical University Industry Foundation UIF of Yonsei University
Priority claimed from KR1020230189199A external-priority patent/KR102906688B1/ko
Publication of WO2024172275A2 publication Critical patent/WO2024172275A2/fr
Publication of WO2024172275A3 publication Critical patent/WO2024172275A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/38—Esters containing sulfur
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a solid electrolyte comprising a zwitterionic polymer and an all-solid-state battery employing the same.
  • Solid electrolytes can be classified into polymer solid electrolytes or inorganic solid electrolytes depending on their material, and in particular, inorganic solid electrolytes can secure high ionic conductivity, so there have been many attempts to apply them.
  • inorganic solid electrolytes have limitations in that they are difficult to commercialize due to chemical instability, high interfacial resistance with electrodes, and high temperature/high pressure conditions required during cell manufacturing and operation.
  • polymer solid electrolytes have advantages over inorganic solid electrolytes in terms of flexibility, lightness, and processability.
  • polymer solid electrolytes have problems such as low ion conductivity and lithium ion yield compared to conventional liquid electrolytes and inorganic solid electrolytes, and their low electrochemical window makes it difficult to combine with high-voltage cathode materials.
  • ionic polymer materials such as cationic polymers and anionic polymers, but ionic conductivity is still not sufficient, and even if ionic conductivity is improved somewhat, there is a limitation in that compatibility with high-capacity cathode materials is low.
  • One aspect of the present invention aims to provide a polymer solid electrolyte capable of simultaneously realizing excellent ionic conductivity and electrochemical stability and a method for producing the same.
  • One aspect of the present invention provides a polymer solid electrolyte comprising a zwitterionic polymer and a metal salt, the zwitterionic polymer including a structural unit derived from a zwitterionic compound represented by the following chemical formula 1.
  • p is an integer from 1 to 20, preferably an integer from 3 to 15, more preferably an integer from 5 to 13, most preferably 6 or 11;
  • q is an integer from 1 to 20, preferably an integer from 1 to 10, more preferably an integer from 1 to 6, most preferably 2 or 3;
  • X + is , or and
  • R 2 to R 5 are each independently hydrogen or (C1-C7) alkyl, or R 2 and R 3 , and R 4 and R 5 may be connected to each other to form an alicyclic ring or an aromatic ring;
  • Y - is , or and
  • R 6 is fluoro or fluoro(C1-C7)alkyl.
  • the above zwitterionic compound can be represented by the following chemical formula 2 or 3.
  • R 11 is fluoro or fluoro(C1-C7)alkyl
  • R 1 , X + , p and q are the same as defined in the above chemical formula 1.
  • p may be an integer from 10 to 20
  • q may be an integer from 1 to 7.
  • the above zwitterionic compounds can be represented by the following chemical formulas 4 to 6.
  • R 1 is hydrogen or methyl
  • n is an integer from 1 to 7;
  • X + is , , or and
  • R 6 and R 7 are each independently hydrogen or (C1-C7) alkyl.)
  • the above zwitterionic polymer and metal salt may be included in a weight ratio of 1:0.05 to 1.5.
  • the above metal salt may be a lithium salt.
  • Another aspect of the present invention provides a method for producing a polymer solid electrolyte, comprising the steps of: producing a solid electrolyte slurry composition by mixing a zwitterionic compound represented by the following chemical formula 1, a metal salt, and an organic solvent; and applying the solid electrolyte slurry composition to a substrate and thermally polymerizing the zwitterionic compound.
  • R 1 , X + , Y - , p and q are the same as defined in the above chemical formula 1.
  • the above solid electrolyte slurry composition may contain a zwitterionic compound and a metal salt in a molar ratio of 1:0.1 to 2.
  • the above solid electrolyte slurry composition may contain 5 to 30 parts by weight of an organic solvent per 100 parts by weight of a zwitterionic compound.
  • the above polymerization may be a thermal polymerization performed under conditions of 110 to 150°C.
  • Another aspect of the present invention provides an all-solid-state battery comprising the polymer solid electrolyte.
  • the above-described all-solid-state secondary battery according to one embodiment includes a cathode layer, a solid electrolyte layer, and a cathode layer, and the solid electrolyte layer may include the polymer solid electrolyte according to one embodiment.
  • the above-mentioned positive electrode layer is impregnated with the above-mentioned polymer solid electrolyte according to one embodiment, and the above-mentioned positive electrode layer and the solid electrolyte layer may be integrated with each other.
  • the thickness of the above solid electrolyte layer may be 30 to 100 ⁇ m.
  • the above negative electrode layer includes a negative electrode current collector and a negative electrode active material layer, and the negative electrode active material layer may be lithium metal.
  • An all-solid-state battery employing a polymer solid electrolyte according to one aspect of the present invention can simultaneously satisfy excellent battery performance and life characteristics.
  • the polymer solid electrolyte according to one embodiment has the advantages of high ionic conductivity that can be operated at room temperature, excellent interfacial compatibility with electrodes, and superior mechanical strength.
  • the polymer solid electrolyte according to one embodiment has high oxidation stability, excellent miscibility with high-capacity positive electrode materials such as NCM811, and excellent interfacial stability with lithium metal negative electrodes, and excellent processability, so that it can be advantageous for commercialization.
  • Figure 1 illustrates the results of analysis of the life characteristics of the all-solid-state lithium metal batteries of Example 1 and Comparative Example 1.
  • Figure 2 illustrates the results of analysis of the life characteristics of the all-solid-state lithium metal batteries of Example 3 and Comparative Example 2.
  • Figure 3 illustrates the results of analysis of the life characteristics of the all-solid-state lithium metal batteries of Example 4 and Comparative Example 3.
  • the numerical range used in this specification includes the lower and upper limits and all values within that range, the increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of the upper and lower limits of the numerical range defined in different shapes. Unless otherwise specifically defined herein, values outside the numerical range that may arise due to experimental error or rounding of values are also included in the defined numerical range.
  • alkyl refers to an organic radical derived from an aliphatic hydrocarbon by the removal of one hydrogen, and may include both straight-chain and branched forms. Examples of such alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, ethylhexyl, and the like.
  • fluoroalkyl as used herein means alkyl in which at least one hydrogen is replaced with a fluoro group (-F).
  • One aspect of the present invention provides a polymer solid electrolyte capable of implementing excellent ionic conductivity and electrochemical stability.
  • the polymer solid electrolyte may include a zwitterionic polymer and a metal salt including a structural unit derived from a zwitterionic compound represented by the following chemical formula 1.
  • p is an integer from 1 to 20, preferably an integer from 3 to 15, more preferably an integer from 5 to 13, most preferably 6 or 11;
  • q is an integer from 1 to 20, preferably an integer from 1 to 10, more preferably an integer from 1 to 6, most preferably 2 or 3;
  • X + is , or and
  • R 2 to R 5 are each independently hydrogen or (C1-C7) alkyl, or R 2 and R 3 , and R 4 and R 5 may be connected to each other to form an alicyclic ring or an aromatic ring;
  • Y - is , or and
  • R 6 is fluoro or fluoro(C1-C7)alkyl.
  • the polymer solid electrolyte may include a zwitterionic polymer matrix manufactured using a zwitterionic compound represented by the chemical formula 1 as a monomer, and a metal salt uniformly distributed in the polymer matrix.
  • the zwitterionic polymer and the metal salt may be included in a weight ratio of 1:0.05 to 1.5, or a weight ratio of 1:0.1 to 1.5, or a weight ratio of 1:0.5 to 1.5, or a weight ratio of 1:1 to 1.5.
  • a polymer solid electrolyte according to one aspect can simultaneously realize excellent ion dissociation degree, mobility, and stability by including a zwitterionic polymer and a metal salt prepared from a zwitterionic compound satisfying the structural characteristics described above.
  • the compound represented by the chemical formula 1 when the compound represented by the chemical formula 1 has only a cationic group or an anionic group, there is a problem that the ion conductivity and lithium ion yield of the polymer solid electrolyte manufactured therefrom are significantly reduced.
  • the compound represented by the chemical formula 1 when the compound represented by the chemical formula 1 has a short-chain alkylene group in which p is 6 or less, the mechanical strength and stability of the polymer solid electrolyte may be significantly reduced, making it difficult to achieve the effect intended by the present invention.
  • the zwitterionic compound represented by the chemical formula 1 may be represented by the following chemical formula 2 or 3.
  • R 11 is fluoro or fluoro(C1-C7)alkyl
  • R 1 , X + , p and q are the same as defined in the above chemical formula 1.
  • p may be an integer from 10 to 20
  • q may be an integer from 1 to 7, and when the above ranges are satisfied, the mechanical properties of the polymer solid electrolyte may be further improved.
  • X + may be selected from the following structural formula.
  • R 6 to R 9 are each independently hydrogen or (C1-C7) alkyl.
  • the R 11 may be fluoro or perfluoro(C1-C7)alkyl.
  • the zwitterionic compound can be represented by the following chemical formulas 4 to 6.
  • R 1 is hydrogen or methyl
  • n is an integer from 1 to 7;
  • X + is , , or and
  • R 6 and R 7 are each independently hydrogen or (C1-C7) alkyl.)
  • the above zwitterionic compound may be, for example, selected from the following structures, but is not necessarily limited thereto.
  • the above metal salt may be a lithium salt
  • the lithium salt may be, for example, one or more selected from lithium chloride (LiCl), lithium bromide (LiBr), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(pentafluoroethanesulfonyl)imide (LiBETI).
  • LiCl lithium chloride
  • LiBr lithium bromide
  • LiBF 4 lithium tetrafluoroborate
  • LiPF 6 lithium hexafluorophosphate
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • LiBETI lithium bis(pentafluoro
  • lithium bis(fluorosulfonyl)imide LiFSI
  • lithium bis(trifluoromethanesulfonyl)imide LiTFSI
  • lithium bis(pentafluoroethanesulfonyl)imide LiBETI
  • one aspect of the present invention provides a method for producing the above-described polymer solid electrolyte.
  • a method for producing a polymer solid electrolyte comprises the steps of: (a) mixing a zwitterionic compound represented by the following chemical formula 1, a metal salt, and an organic solvent to produce a solid electrolyte slurry composition; and (b) applying the solid electrolyte slurry composition to a substrate and polymerizing a zwitterionic compound.
  • R 1 , X + , Y - , p and q are the same as defined in the above chemical formula 1.
  • the method for manufacturing a polymer solid electrolyte according to one embodiment can, by satisfying the above steps, make the distribution of the metal salt included in the polymer solid electrolyte very even, and further improve the ion conductivity of the polymer solid electrolyte and the interfacial compatibility with the electrode.
  • the solid electrolyte when the solid electrolyte is manufactured by first polymerizing the zwitterionic compound and then introducing a metal salt, it may be difficult to evenly distribute the metal salt, and the ionic conductivity of the solid electrolyte and the interfacial compatibility with the electrode may deteriorate.
  • the above solid electrolyte slurry composition may include a zwitterionic compound and a metal salt in a molar ratio of 1:0.1 to 0.5, or a molar ratio of 1:0.1 to 3, or a molar ratio of 1:0.5 to 2.
  • the above solid electrolyte slurry composition may contain 5 to 30 parts by weight, or 5 to 20 parts by weight, or 10 to 20 parts by weight of an organic solvent with respect to 100 parts by weight of a zwitterionic compound.
  • the above solid electrolyte slurry composition is a curable composition, and a solid electrolyte can be manufactured through a curing (polymerization) reaction.
  • the curing reaction may be performed by photocuring, thermal curing, or a combination thereof, and may be performed by appropriately changing it according to the purpose.
  • the organic solvent may be used without limitation as long as it can dissolve the zwitterion compound, and for example, may be an alcohol-based organic solvent selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, and 2-ethylhexyl alcohol, and specifically, ethanol may be used, but is not limited thereto.
  • the above solid electrolyte slurry composition may further include an initiator, and may further include a photoinitiator or a thermal initiator depending on the curing method.
  • the initiator may be any known initiator without limitation, and examples of the photoinitiator may be selected from, but are not limited to, acetophenone compounds, benzophenone compounds, triazine compounds, benzoin compounds, imidazole compounds, xanthone compounds, phosphine compounds, and oxime compounds.
  • Examples of the thermal initiator may be selected from, but are not limited to, benzoyl peroxide (BPO), dicumyl peroxide (DCP), azobisisobutyronitrile (AIBN).
  • the polymerization in step (b) may be thermal polymerization, and the thermal polymerization may be performed at a temperature in the range of 50 to 300°C, or 50 to 200°C, or 100 to 200°C, or 110 to 150°C using a heating device such as an oven.
  • one aspect of the present invention provides an all-solid-state battery including the polymer solid electrolyte.
  • the all-solid-state battery can be manufactured with a structure known in the art using conventional manufacturing methods and materials in the art.
  • An all-solid-state battery includes a cathode layer and a cathode layer, and includes a solid electrolyte layer between the cathode layer and the cathode layer, and the solid electrolyte layer may include a polymer solid electrolyte according to one embodiment.
  • the above-mentioned positive electrode layer may include a positive electrode collector and a positive electrode active material layer formed on the positive electrode collector.
  • the positive electrode active material layer may have a polymer solid electrolyte impregnated in pores according to one aspect, and the positive electrode layer and the solid electrolyte layer may be integrated with each other.
  • the thickness of the solid electrolyte layer may be 10 to 100 ⁇ m, or 30 to 100 ⁇ m, or 30 to 80 ⁇ m, and here, the thickness of the solid electrolyte layer means the thickness of a section where the positive electrode active material layer and the solid electrolyte are not mixed and only the polymer solid electrolyte according to one embodiment exists.
  • An all-solid-state battery may be manufactured by including the steps of (S1) applying a cathode material slurry composition to one surface of a cathode current collector, drying and rolling to manufacture a cathode active material layer having pores formed therein; (S2) impregnating the cathode active material layer with a solid electrolyte slurry composition according to one embodiment and thermally polymerizing it to manufacture a cathode layer impregnated with a polymer solid electrolyte and a solid electrolyte layer integrated with the cathode layer; and (S3) laminating the cathode layer impregnated with the polymer solid electrolyte and the anode layer.
  • Non-limiting examples of the positive electrode current collector may include a foil made of aluminum, nickel, or a combination thereof, and the positive electrode material slurry may include a solvent, a binder, a conductive agent, a dispersant, etc., in addition to the positive electrode active material, if necessary.
  • the above cathode active material may be a conventional cathode active material used in this technical field, and non-limiting examples thereof include lithium cobalt oxide composite oxide (LiCoO 2 ), spinel crystal type lithium manganese oxide composite oxide (LiMn 2 O 4 ), lithium manganese oxide composite oxide (LiMnO 2 ), lithium nickel oxide composite oxide (LiNiO 2 ), lithium iron phosphate (LiFePO 4 ), lithium manganese phosphate (LiMnPO 4 ), lithium cobalt phosphate (LiCoPO 4 ), lithium iron pyrophosphate (Li 2 FeP 2 O 7 ), lithium niobate composite oxide (LiNbO 2 ), lithium iron oxide composite oxide (LiFeO 2 ), lithium magnesium oxide composite oxide (LiMgO 2 ), lithium cuprate composite oxide (LiCuO 2 ), and lithium zinc oxide composite oxide.
  • LiCoO 2 lithium cobalt oxide composite oxide
  • LiMn 2 O 4 lithium manganese oxide composite
  • the polymer solid electrolyte according to one aspect has the advantage of excellent compatibility with high-capacity cathode materials such as NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ).
  • conductive agent carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, etc.; conductive fibers such as carbon fibers and metal fibers; metal powders such as fluorinated carbon, aluminum, and nickel powders; conductive whiskies such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives, etc. can be used, but there is no particular limitation as long as it has conductivity and does not cause a chemical change in the battery.
  • the above binder polymer may include one or more selected from the group consisting of nitrile butadiene rubber, polyethylene glycol, polyacrylonitrile, polyvinyl chloride, polymethyl methacrylate, polypropylene oxide, polydimethylsiloxane, polyvinylidene fluoride, polyvinylidene carbonate, and polyvinylpyrrolidinone, and preferably one or more selected from the group consisting of polyvinylidene fluoride, polyvinylidene carbonate, and polyethylene glycol, but is not limited thereto.
  • the above negative electrode layer may include a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector.
  • Non-limiting examples of the negative electrode current collector may be selected from a foil manufactured by copper, gold, nickel, or a copper alloy, or a combination thereof.
  • the negative electrode active material layer may be any one or more selected from the group consisting of any one carbon selected from soft carbon, hard carbon, artificial graphite, natural graphite, expanded graphite, carbon fiber, non-graphitizable carbon, carbon black, carbon nanotubes, acetylene black, Ketjen black, graphene, fullerene, activated carbon, and meso carbon microbeads; any one metal selected from silicon, tin, lithium, aluminum, silver, bismuth, indium, germanium, lead, platinum, titanium, zinc, manganese, cadmium, cerium, copper, cobalt, nickel, and iron; an alloy comprising two or more of the above metals; and an oxide of one or more of the above metals; and preferably, lithium metal, but is not limited thereto.
  • the polymer solid electrolyte according to one aspect has excellent interfacial stability with a lithium metal negative electrode and effectively suppresses the dendrite growth phenomenon, thereby overcoming the limitations of conventional solid electrolytes.
  • one aspect of the present invention provides a device comprising an all-solid-state battery according to various aspects or embodiments of the present invention, wherein the device is selected from a communication device, a transportation device, and an energy storage device.
  • the zwitterionic compound (Ac11Py3TFSI) obtained in the above Preparation Example 1, LiBETI, and benzoyl peroxide (BPO) were mixed in ethanol to prepare a solid electrolyte slurry composition.
  • the zwitterionic compound (1) and LiBETI were in a molar ratio of 1:1.5, ethanol was 10 wt% of the zwitterionic compound (1), and BPO was 1 wt% of the zwitterionic compound.
  • a cathode material slurry was prepared by adding N-methylpyrrolidone to a cathode material content of 40 wt% at a weight ratio of cathode active material (NCM811)/conductive material (carbon black)/binder (polyvinylidene fluoride, PVDF) of 94/3/3.
  • the cathode material slurry was applied to an aluminum (Al) thin film having a thickness of 18 ⁇ m using a doctor blade, dried with hot air at 80 ° C., and then vacuum-dried at 120 ° C. for 24 hours to form a cathode active material layer having a thickness of 20 ⁇ m.
  • the solid electrolyte slurry composition obtained above was impregnated into the cathode active material layer, rolled with a roll press at 80 ° C., and thermally polymerized in an oven at 110 ° C. to prepare a cathode layer impregnated with a polymer solid electrolyte and a 30 ⁇ m thick solid electrolyte layer integrated with the cathode layer.
  • an all-solid-state lithium metal battery was manufactured by laminating a 50 ⁇ m thick lithium metal negative electrode layer rolled on an 8 ⁇ m thick copper foil current collector.
  • a polymer solid electrolyte and an all-solid-state lithium metal battery were manufactured in the same manner as in Example 1, except that the zwitterionic compound (Ac11Py3SO 3 ) manufactured in Manufacturing Example 2 was used instead of the zwitterionic compound (Ac11Py3TFSI) manufactured in Manufacturing Example 1.
  • a polymer solid electrolyte and an all-solid-state lithium metal battery were manufactured in the same manner as in Example 1, except that the zwitterionic compound (Ac11Im3TFSI) manufactured in Manufacturing Example 3 was used instead of the zwitterionic compound (Ac11Py3TFSI) manufactured in Manufacturing Example 1.
  • a polymer solid electrolyte and an all-solid-state lithium metal battery were manufactured in the same manner as in Example 1, except that the zwitterionic compound (Ac6Py3TFSI) manufactured in Manufacturing Example 4 was used instead of the zwitterionic compound (Ac11Py3TFSI) manufactured in Manufacturing Example 1.
  • a polymer solid electrolyte and an all-solid-state lithium metal battery were manufactured in the same manner as in Example 1, except that the zwitterionic compound ( Ac11Im2CO2 ) manufactured in Manufacturing Example 5 was used instead of the zwitterionic compound (Ac11Py3TFSI) manufactured in Manufacturing Example 1.
  • An all-solid-state lithium metal battery was manufactured in the same manner as in Example 1, except that lithium iron phosphate (LFP, LiFePO 4 ) was used instead of NCM811 as the cathode active material.
  • LFP lithium iron phosphate
  • LiFePO 4 lithium iron phosphate
  • An all-solid-state lithium metal battery was manufactured in the same manner as in Example 1, except that overlithiated oxide (OLO, Li 1.2 Mn 0.528 Co 0.096 Ni 0.176 O 2 ) was used instead of NCM811 as the cathode active material.
  • OLO overlithiated oxide
  • a polymer solid electrolyte and an all-solid-state lithium metal battery were obtained in the same manner as in Example 1, except that polyethylene glycol diacrylate (PEGDA, number average molecular weight 20,000 g/mol) was used instead of the zwitterionic compound (Ac11Py3TFSI) prepared in Manufacturing Example 1.
  • PEGDA polyethylene glycol diacrylate
  • Ac11Py3TFSI zwitterionic compound
  • An all-solid-state lithium metal battery of Comparative Example 2 was manufactured in the same manner as Comparative Example 1, except that lithium iron phosphate (LFP, LiFePO 4 ) was used instead of NCM811 as the cathode active material.
  • LFP lithium iron phosphate
  • LiFePO 4 lithium iron phosphate
  • An all-solid-state lithium metal battery of Comparative Example 3 was manufactured in the same manner as in Comparative Example 1, except that overlithiated oxide (OLO, Li 1.2 Mn 0.528 Co 0.096 Ni 0.176 O 2 ) was used instead of NCM811 as the cathode active material.
  • OLO overlithiated oxide
  • the polymer solid electrolytes manufactured in the above examples and comparative examples were overlapped between two identical stainless steel foils to manufacture an ion conductivity measurement cell, and the ion conductivity of the polymer solid electrolyte was measured. Based on EIS (Electrochemical Impedance Spectroscopy) analysis, the impedance was measured and the ion conductivity was calculated by applying an AC amplitude of 10 mV and a frequency range of 0.1 mHz to 3 MHz at room temperature. The results are shown in Table 1 below.
  • the polymer solid electrolytes manufactured in the above examples and comparative examples were laminated between two identical lithium metal foils to manufacture a lithium ion yield measurement cell, and a DC voltage of 10 mV was applied at room temperature for 1 hour.
  • the impedance values before and after the DC voltage was applied were measured to calculate the lithium ion yield. The results are shown in Table 1 below.
  • Example 1 Lithium ion yield
  • Example 2 (Ac11Py3SO 3 ) 0.11 0.65 Comparative Example 1 (PEGDA) 0.048 0.47
  • Example 2-1 (Ac11Im3TFSI) 0.093
  • Example 2-2 (Ac6Py3TFSI) 0.089
  • Example 2-3 (Ac11Im2CO 2 ) 0.076
  • the all-solid-state lithium metal batteries to which the zwitter polymer solid electrolyte of the examples was applied all exhibited an excellent capacity retention rate of 80% or more, regardless of the type of the cathode active material.
  • the all-solid-state lithium metal batteries to which the polymer solid electrolyte of the comparative examples was applied showed significantly reduced capacity retention rates of 44.1% (Comparative Example 1) and 30.1% (Comparative Example 2), and in particular, in the case of Comparative Example 3 to which the OLO cathode active material was applied, it was confirmed that the capacity was not expressed after 5 cycles.
  • the life characteristics of the all-solid-state lithium metal batteries to which the polymer solid electrolytes manufactured in Examples 2-1 to 2-3 were applied were observed under the same conditions as above by repeating the charge/discharge cycles 500 (LFP), 250 (NCM811), and 100 (OLO), and it was confirmed that all of the all-solid-state lithium metal batteries manufactured in these Examples stably implemented an excellent capacity retention rate of 80% or more regardless of the type of positive electrode active material.
  • the zwitterionic polymer solid electrolyte according to one embodiment of the present invention not only has high ionic conductivity that can be operated at room temperature, but also has excellent miscibility with high-capacity cathode materials such as NCM811 and OLO and excellent interfacial stability with a lithium metal anode, and thus has excellent life characteristics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention concerne un électrolyte solide polymère, qui peut simultanément mettre en œuvre une excellente conductivité ionique et une excellente stabilité électrochimique, ainsi qu'une batterie entièrement solide le comprenant.
PCT/KR2023/021436 2023-02-13 2023-12-22 Électrolyte solide polymère et batterie entièrement solide le comprenant Ceased WO2024172275A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2023-0018994 2023-02-13
KR20230018994 2023-02-13
KR1020230189199A KR102906688B1 (ko) 2023-02-13 2023-12-22 고분자 고체전해질 및 이를 포함하는 전고체 전지
KR10-2023-0189199 2023-12-22

Publications (2)

Publication Number Publication Date
WO2024172275A2 true WO2024172275A2 (fr) 2024-08-22
WO2024172275A3 WO2024172275A3 (fr) 2025-06-19

Family

ID=92420199

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2023/021436 Ceased WO2024172275A2 (fr) 2023-02-13 2023-12-22 Électrolyte solide polymère et batterie entièrement solide le comprenant

Country Status (1)

Country Link
WO (1) WO2024172275A2 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6081392B2 (ja) * 2013-04-04 2017-02-15 本田技研工業株式会社 電解質−正極構造体及びそれを備えるリチウムイオン二次電池
KR102278613B1 (ko) * 2019-12-27 2021-07-16 한국에너지기술연구원 가공성이 향상된 고체형 고분자 전해질 및 그의 제조방법
CN112615049B (zh) * 2020-12-21 2023-01-03 中创新航技术研究院(江苏)有限公司 固态电解质及包含它的电池
CN112968210A (zh) * 2021-02-24 2021-06-15 珠海中科先进技术研究院有限公司 一种两性离子液体凝胶电解质及其制备方法和应用
EP4324043A4 (fr) * 2021-04-12 2025-10-08 The Regents Of Univ Of California Zwitterions inspirés des liquides ioniques ayant une conductivité et un nombre de transport élevés

Also Published As

Publication number Publication date
WO2024172275A3 (fr) 2025-06-19

Similar Documents

Publication Publication Date Title
WO2020197278A1 (fr) Batterie secondaire au lithium
WO2021101174A1 (fr) Solution d'électrolyte non aqueux pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant
WO2020060295A1 (fr) Composition pour électrolyte polymère en gel et batterie rechargeable au lithium comprenant un électrolyte polymère en gel formé à partir de cette dernière
WO2017171442A1 (fr) Composition pour électrolyte polymère en gel, électrolyte polymère en gel produit avec ladite composition et élément électrochimique comportant ledit électrolyte
WO2014116082A1 (fr) Composition pour électrolyte polymère en gel et batterie secondaire au lithium comprenant celle-ci
WO2019164164A1 (fr) Solution électrolytique pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant
WO2021040388A1 (fr) Solution électrolytique non aqueuse et batterie secondaire au lithium la comprenant
WO2021060811A1 (fr) Procédé de fabrication de batterie auxiliaire
WO2021066462A1 (fr) Électrolyte non aqueux et batterie secondaire au lithium le comprenant
WO2021040392A1 (fr) Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant
WO2022019642A1 (fr) Composition de précurseur d'électrolyte polymère solide, électrolyte polymère solide et batterie tout solide le comprenant
WO2020036336A1 (fr) Électrolyte pour batterie secondaire au lithium
WO2015064987A1 (fr) Pile rechargeable au lithium
WO2015170786A1 (fr) Électrolyte organique et batterie au lithium utilisant cet électrolyte
WO2020222469A1 (fr) Électrolyte non aqueux pour batterie secondaire au lithium, et batterie secondaire au lithium le comprenant
WO2024219784A1 (fr) Électrolyte solide comprenant une structure organique covalente, et batterie entièrement solide comprenant celui-ci
WO2020009505A1 (fr) Électrolyte pour accumulateur au lithium et accumulateur au lithium le comprenant
WO2017057968A1 (fr) Électrolyte non aqueux et batterie secondaire au lithium le comprenant
WO2021225359A1 (fr) Électrolyte solide à base de polymère ayant une résistance mécanique améliorée, son procédé de préparation et batterie secondaire au lithium comprenant un électrolyte solide
WO2023219474A1 (fr) Électrolyte non aqueux et batterie secondaire au lithium le comprenant
WO2020149677A1 (fr) Solution d'électrolyte non aqueux pour accumulateur au lithium et accumulateur au lithium comprenant cette dernière
WO2020149705A1 (fr) Électrolyte pour acumulateur au lithium et acumulateur au lithium comprenant ledit électrolyte
WO2024038942A1 (fr) Additif d'électrolyte pour batterie secondaire, électrolyte non aqueux pour batterie secondaire au lithium le comprenant, et batterie secondaire au lithium le comprenant
WO2022158749A1 (fr) Additif pour électrolyte de batterie au lithium, électrolyte organique le comprenant et batterie au lithium comprenant un électrolyte
WO2018131952A1 (fr) Solution d'électrolyte non aqueux et batterie secondaire au lithium la comprenant

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: 23923074

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23923074

Country of ref document: EP

Kind code of ref document: A2