Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • 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
  • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
  • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
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  • 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
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
• • 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
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
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  • 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
  • H01M4/381—Alkaline or alkaline earth metals elements
  • H01M4/382—Lithium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• • H—ELECTRICITY
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  • 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
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • H—ELECTRICITY
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  • 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
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
• • H—ELECTRICITY
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  • 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
• • H—ELECTRICITY
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  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
• • H—ELECTRICITY
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  • 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
  • H01M2300/0082—Organic polymers
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
  • H01M2300/0091—Composites in the form of mixtures
• • 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
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• This invention relates to solid state electrolyte rechargeable battery in no use of separator which has been efficiently refrained the internal resistance such as interface resistance between a positive active material and a negative active material in case of using a conductive polymer solid electrolyte, a thin film cell, a less dependence on the operating temperature and an excellent safety in case of happening a short circuit. And it will be anticipated greatly in practical applications.
• PCT-WO2004/88671 Patent reference 1
• PCT-WO2010/113971 Patent reference 2
• Patent reference 3 proposes a composite polymer electrolyte composition comprising adding a fluoropolymer to the above composite polymer electrolyte composition as described in Patent reference 1 or Patent reference 2, and the rechargeable battery using this polymer electrolyte composition.
• Patent reference 4 proposes a rechargeable battery in no use of separator, using a composition comprising a conductive polyether polymer and a ceramic whisker.
• this composite polymer electrolyte composition has not sufficient conductivity property and much dependence on the temperature, and also it has a lack of low temperature property since it has a usage restriction because of Tg at higher than zero degree C., that is, this polyether type materials perform as the most excellent property at higher than 60° C.
• Patent reference 5 proposes a solid electrolyte comprising a Garnet solid inorganic electrolyte layer and a polyether polymer conductive polyether layer.
• PCT-WO2013/073038 propose a sintering in the method of descending particle interface resistance between a positive and a negative active materials in case of using only Garnet inorganic solid electrolyte, and a physical processing such as electrode crimping sulfide material such as lithium sulfide to particle interface coated solid electrolyte.
• this method has an excessive loading process in mass production.
• the conductive polymer-solid electrolyte system of rechargeable battery as this invention enables the optimization in practical usages.
• Patent reference 1 PCT-WO2004/088671
• Patent reference 2 PCT-WO2010/113971
• Patent reference 3 PCT-WO2016/0633994
• Patent reference 4 Japanese Patent Kokai No.2002-313424
• Patent reference 5 Japanese Patent Kokai No.2014-238925
• Patent reference 6 PCT-WO2013/073038
• the purpose of this invention is to obtain a conductive polymer solid state electrolyte rechargeable battery in no use of separator, which has a descending effect of particle interface resistance between a positive and a negative active materials in case of using a conductive polymer solid electrolyte, a thin film cell, a less dependence on operating temperature, in other words operating at low temperature and excellent safety in case of happening short circuit.
• the purpose is to achieve providing a solid state electrolyte rechargeable battery in no use of separator comprising a positive electrode/a conductive polymer electrolyte layer/a negative electrode, in which the solid state electrolyte layer is a composition comprising an inorganic solid electrolyte and a polymer electrolyte composition wherein the polymer electrolyte composition is selected from the group consisting of a polymer electrolyte composition (X 1 ) obtained by graft polymerizing or living radical polymerization of a molten salt monomer having a polymerizable functional group and having an onium cation and an anion containing a halogen with a fluoro polymer, and a polymer electrolyte composition comprising (X 1 ) and at least one kind selected from the following (X 2 ) and (X 3 ),
• X 2 a molten salt having an onium cation and an anion containing a halogen, or a molten salt monomer having a polymerizable functional group and having an onium cation and an anion containing a halogen
• X 3 a polymer or copolymer of a molten salt monomer having a polymerizable functional group and having an onium cation. and an anion containing a halogen.
• the purpose is to achieve providing more favorably a solid state electrolyte rechargeable battery in no use of separator as claimed in claim 1 , wherein the solid state rechargeable battery comprising a positive electrode/a conductive polymer solid state electrolyte layer/a negative electrode further contains a polyether polymer partially.
• the positive electrolyte is at least one kind selected from the group consisting Li x Me y O z , LiNixMe y O z , LiCo w Ni x Me y O z and LiMe x P y O z (w, x, y and z is optional positive number; Me is Fe, Co, Ni, Al or Mn) and the negative electrolyte is at last one kind selected from the group consisting of a natural spheroidal graphite, an artificial hard graphite, and a lithium metal foil.
• a solid state electrolyte rechargeable battery in no use of separator has a depression effect of particle interface resistance between a positive and a negative active materials in case of using a conductive polymer solid electrolyte, a thin film cell, a less dependence on temperature and an excellent safety in case of happening short circuit.
• a thickness of the cell becomes thinner, and in case of coating allyl glycidyl ether polymer on the surface of the positive and/or negative electrodes, REDOX resistance makes enhanced.
• polymer electrolyte composition (X 1 ) obtained by graft polymerizing or living radical polymerization of a molten salt monomer having a polymerizable functional group and having an onium cation and an anion containing a halogen with a fluoro polymer is mentioned below.
• a polyvinylidene fluoride polymer or copolymer are preferably raised.
• polyvinylidene fluoride copolymer a copolymer having a unit of vinylidene and a unit specifying
• X is of halogen atom except fluorine atom.
• R 1 and R 2 are hydrogen atom or fluorine atom, each is same or different atom, halogen atom is chlorine atom as the best, bromine atom or iodine atom also.
• X is of halogen atom except fluorine atom.
• R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen atom or fluorine atom, each is same or different atom “n” is 65 to 99 mol %, “m” is 1 to 35 mol %.
• n 99 to 65 mol %
• m 35 to 1 mol %
• n in 65 to 99 mol % and “m” in 1 to 35 mol %.
• the better formula is “n” in 67 to 97 mol % and “m” in 3 to 33 mol %.
• the best formula is “n” in 70 to 90 mol % and “m” in 10 to 30 mol %.
• the said co-polymer is of block polymer or random co-polymer. And other monomers obtaining co-polymer are also utilized in a range of conforming to the purpose of this invention.
• the molecular weight of the said polymer is 30,000 to 2,000,000. better as a mean molecular by weight. And the more preferred molecular by weight is 100,000 to 1,500,000.
• the mean molecular by weight is calculated based on the intrinsic viscosity[ ⁇ ] in an estimated formula.
• the co-polymer of vinylidene fluoride monomer and vinyl monomer containing fluorine and halogen atoms such as chlorine is utilized better.
• the graft polymerization of molten salt monomer is started by occurring easily pulling out halogen atom such as chlorine atom except fluorine atom faster than fluorine atom by a transition metal which is to weaken a connection energy between carbon and halogen with presence of fluorine and halogen atoms such as chlorine in a part of trunk polymer.
• Catalysts in the atom transfer radical polymerization are utilized a transition metal halogen materials as proposed particularly Copper Chloride(I) (CuCl), acetylacetonate copper(II) and Copper Bromide(CuBr)(I) and Copper Iodide(CuI)(I) and its same group.
• Ligand being formed the complex introduces 4,4′-dialkyl-2,2′-bipyridyl(bpy) (alkyl having C 1 to C 8 carbons such as methyl, ethyl, propyl, butyl are preferably raised), Tris(dimethyl aminoethyl)amine(Me 6 -TREN), N,N,N′,N′′,N′′-Pentamethyl diethylenetriamine(PMDETA), N,N,N′,N′-Tetrakis (2-pyridylmethyl)ethylenediamine(TPEN), tris (2-pyridylmethyl) amine(TPMA) and its same group.
• 4,4′-dialkyl-2,2′-bipyridyl(bpy) alkyl having C 1 to C 8 carbons such as methyl, ethyl, propyl, butyl are preferably raised
• the reaction solvent in this invention are utilized to be dissolving the fluoro polymer and as an example N-methyl pyrrolidone, dimethylacetamide, dimethyl sulfoxide, acetone and its same group which dissolve the co-polymer between a polyvinylidene fluoride monomer composition, and a vinyl monomer containing fluorine atom and halogen atom such as chlorine atom.
• This reaction temperature are dependent on kinds of Ligand complex used, ordinarily in the range of 10 to 110° C.
• One of other polymerization methods is utilized also ultraviolet ray with a photo polymerization trigger and is to be irradiated a radiation ray such as electron beam and its same group.
• This electron beam polymerization method is being to obtain a crosslinking reaction on co-polymer itself and to being possibly a grafting reaction on a reinforcing material of the monomer, which are specified well.
• the irradiation volume is controlled preferring in 0.1 to 50 Mrad and 1 to 20 Mrad as more preferred.
• a graft polymerization at range between 2 and 90 mol %, in adjusting the recipe of polymer structure at 98 to 10 mol % as monomer unit and 2 to 90 mol % of the molten salt monomer to meet plastic physical properties aimed as the controlling target.
• a graft ratio of the graft is preferably 40 to 85 mol %, and more preferably 50 to 80 mol %.
• the polymer is of liquid or solid.
• a molten salt monomer having a polymerizable functional group and having an onium cation and anion containing a fluorine with a fluorine containing a polymer of which salt structures are related onium cation having an aliphatic, an alicyclic, an aromatic or a heterocyclic radical, and anion containing fluorine as preferred.
• This onium cation means ammonium cation, phosphonium cation, sulfonium cation, onium cation, or guanidium cation.
• ammonium cation quaternary ammonium cation, heterocyclic ammonium cation such as imidazolium cation, pyridinium cation and piperidinium cation.
• the salt structure consisting of ammonium cation at least one kind selected from ammonium cation group as described below and anion at least one kind selected from anion group as described below.
• Tetra alkyl phosphonium cation (for example 1 to 30 carbon atoms), trimethyl ethyl phosphonium cation, triethyl methyl phosphonium cation, tetra amino phosphonium cation, trialkyl hexadecyl phosphonium cation (alkyl having 1 to 30 carbon atoms), triphenyl benzyl phosphonium cation, phosphonuim derivatives having three alkyl groups in which each alkyl has 1 to 30 carbon atoms. Hexyl trimethyl phosphonium cation, asymmetry trimethyl octyl phosphonium cation,
• anion group containing fluorine anion group containing chlorine atom, anion group containing bromine atom are raised.
• anion group containing fluorine is more preferable to achieve the desired object of this invention
• lithium ion battery including lithium ion capacitor an electrolytic capacitor by reasons of enhancing a thermal stability, Durability properties in REDOX and making wider electric potential window, in which a lithium ion battery containing the above material can be used in the range of 0.7 to 5.5 V of higher voltage and a capacitor containing the above material can be used in the range of less than ⁇ 45° C. of extremely low temperature.
• the above material can be used in paint, adhesive, pressure sensitive adhesive, surface coating agent, shaped articles as additives and further the above material can render the non-conductive layer of anti-static property. Further in case of blending the above material and another resin, good dispersing property and smooth phase on the surface of the shaped articles can be improved.
• Polymeric radicals of the monomer are indicated C—C unsaturated radicals such as vinyl, acryl, methacryl, acrylamide, allyl radicals and its same group, cyclic-ether group as epoxy, oxetane radicals and its same group, cyclic-sulfide group such as tetrahydrothiophene or isocyanate radical and its same group.
• Ammonium cation group having polymeric radicals preferred particularly include Trialkyl aminoethyl methacrylate ammonium, trialkyl aminoethyl acrylate ammonium, trialkyl amino propyl acryl amido ammonium, 1-alkyl-3-vinyl imidazolium, 4-vinyl-1-alkylpyridinium, 1-(4-vinylbenzyl))-3-alkyl imidazolium, 2-(methacryloyloxy) dialkyl ammonium, 1-(vinyl oxyethyl)-3-alkylimidazolium, 1-vinyl imidazolium, 1-allylimidazolium, N-alkyl-N-allyl ammonium, 1-vinyl-3-alkylimidazolium, 1-glycidyl-3-alkyl-imidazolium, N-allyl-N-alkyl pyrrolidinium or quaternary diallyl dialkyl ammonium cations
• Anion group preferred particularly include bis (trifluoro methyl sulfonyl) imide anion, bis (fluoro sulfonyl) amide anion, 2,2,2-trifluoro-N- ⁇ (trifluoromethyl)sulfonyl ⁇ acetoamide anion, bis ⁇ (pentafluoro) sulfonyl ⁇ imide anion, tetra fluoroborate anion, hexafluorophosphate anion, trifluoro methane sulfonyl imide anion and its same group.
• Anions having halogen atom therein are more preferred.
• the molten salt monomer as salt of cation and anion group described above are most preferably included trialykyl aminoethyl methacrylate ammonium bis (fluoro sulfonyl)amide, 2-(methacryloyloxy) dialkyl ammonium bis(fluoro sulfonyl)amide, wherein alkyl is C 1 to C 10 alkyl, N-alkyl-N-allyl ammonium bis (trifluoro methyl sulfonyl) amide wherein alkyl is C 1 to C 10 alkyl, 1-vinyl-3-alkylimidazolium bis(trifluoro methyl sulfonyl)amide wherein alkyl is C 1 to C 10 alkyl, 1-vinyl-3-alkylimidazolium tetrafluoroborate wherein alkyl is C 1 to C 10 alkyl, 4-vinyl-1-alkyl pyridinium bis(trifluoro methyl)
• Graft ratio of the molten salt monomer on the co-polymer described above is preferred in the range of 2 to 90 mol %, more preferred 10 to 85 mol % and the most preferred 20 to 80 mol %.
• the lower range of graft ratio for example, 2 to 40 mol %. preferably 5 to 35 mol %, more preferably 5 to 30 mol % the flexibility such as sponge is obtained, and further an adhesive strength, an elasticity can be improved better.
• the higher range of graft ratio for example, 41 to 90 mol %.
• an adhesive strength is improved better due to the increase of a viscoelasticity, and further a pressure sensitive adhesive strength, an anti-cracking property, a dispersing property of particles such as pigment, a stability on PH, a stability on temperature and a conductivity can be improved better.
• the measure of graft ratio is described in the later Example.
• This graft polymerization of the molten salt monomers is preferred either sole or co-polymerization of the molten salt monomer with other monomers making co-polymerization with the molten salt monomer.
• SEI Solid Electrolyte Interphase
• Vinylidene carbonate vinylene acetate, 2-cyanofuran, 2-thiophenecarbonitrile, acrylonitrile, membrane forming material or solvents
• molten salt having an onium cation and an anion containing fluorine the above mentioned molten salt having ammonium cation group and anion group containing halogen, for example, various ion liquids such as cyclic conjugated ion liquid sharing a cation with two nitrogen, noncyclic aliphatic ion liquid containing alkylammonium or phosphonium, cyclic aliphatic ion liquid containing quaternary ammonium, or pyrrolidinium are raised.
• EMI.FSI 1-ethyl-3-methyl imidazolium bis (fluoro methane sulfonyl) amide
• EMI.TFSI 1-ethyl-3-methylimidazoliumbis(trifluoro methane sulfonyl) amide
• BMI.FSI 1-butyl-3-methylimidazoliumbis(fluoro methane sulfonyl) amide
• a homo polymer of the abovementioned molten salt monomer is preferably raised.
• homo-polymers of monomers such as 1-alkyl-3-vinyl imidazolium cation (AVI), 4-vinyl-1-alkylpyridinium cation, 1-(4-vinylbenzyl))-3-alkyl imidazolium cation, 1-(vinyloxy ethyl)-3-alkylimidazolium cation, 1-vinyl imidazolium cation, quaternary diallyl dialkyl ammonium cation (DAA),
• AVI 1-alkyl-3-vinyl imidazolium cation
• 4-vinyl-1-alkylpyridinium cation 1-(4-vinylbenzyl))-3-alkyl imidazolium cation
• 1-(vinyloxy ethyl)-3-alkylimidazolium cation 1-vinyl imidazolium cation
• DAA quaternary diallyl dialkyl ammonium c
• Hydroxy alkyl methacrylate are preferable. Further copolymers of the above mentioned molten salt monomers and other co-monomer are utilized.
• the monomers other than the molten salt monomer are utilized within the range not hindered and within the range of forming polymer matrix.
• homopolymers and copolymers are obtained by radical polymerization using azo catalyst (AIBN), peroxide catalyst (BPO), or by cation polymerization using Lewis acid, Bronsted acid, or by living radical polymerization using azo catalyst AIBN, BPO.
• AIBN azo catalyst
• BPO peroxide catalyst
• living radical polymerization is preferable.
• the amount of polymer electrolyte composition (X 1 ) is 5 to 90 wt. %, preferably 10 to 75 wt. % based on the total amount of a molten salt monomer (X 2 ) and/or homopolymer or copolymer of a molten salt monomer (X 3 ).
• a conductivity, an adhesiveness and the durability are increased.
• one or more are utilized.
• a charge transfer ion source supporting salt
• the conductivity and durability of conductivity are preferably improved.
• lithium salt is typically utilized wherein it is more preferred lithium salt consisting of lithium cation and anion having fluorine atom.
• TIO stannic tin indium oxide
• Alkylene in tetra alkylene glycol dialkyl ether which is a pair of ion transfer source means of having 1 to 30 carbon atoms such as methylene, ethylene, propylene, and alkyl in TAGDAE means alkyl having 1 to 30 carbon atoms such as methyl, ethyl, propyl.
• TAGDAE tetra alkylene glycol dialkyl ether
• TAGDAE tetra ethylene glycol dimethyl ether
• the amount of TAGDAE is of 0.2 to 60 mol % to the polymeric electrolyte composition X 1 , preferably 0.4 to 50 mol %.
• This supporting salt is used in the polymer electrolyte composition, and also the later mentioned Garnet material and polyether polymer as needed.
• the various solvents are used in the polymer electrolyte composition.
• the solvent dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, dimethyl acetoamide, acetone, acetonitrile and mixture thereof are raised.
• the inorganic solid electrolyte used in the composition is described as below.
• Garnet material Garnet material, NASICON type crystal structure, sulfide material are used.
• Garnet material is more preferable among them, first the Garnet material is described.
• oxide solid electrolyte such as LLZ, LLT, are raised more preferably.
• Li 0.33 La 0.55 TiO 3 (Cubic phase), Li 0.33 La 0.55 TiO 3 (Tetragonal phase), Li 5 La 3 Ta 2 O 12 , Li 6 La 3 Ta 1.5 Y 0.5 O 12 are raised.
• the Garnet ones are not limited to these materials, and the Garnet material substituted each transition metal to other metal element are used in this invention.
• the LAGP and the LATP solid electrolyte is raised as mentioned below.
• Li 3 PO 4 Li 4 SiPO 4 , Li 4 SiPO 4 —Li3PO 4 , Li 3 BO 4 are raised.
• Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 is raised.
• the oxide compound such as La x Li y TiO z is raised.
• Li 2 S.P 2 S 5 Li 3.25 P 0.95 S 4 , Li 3.2 P 0.96 S 4 , Li 4 P 2 S 6 , Li 7 P 3 S 11 are raised.
• the descending effect of particle interface resistance can be rendered and also the generation of toxic gas can be reduced.
• This embodiment means coating, laminating or impregnating a polyether polymer to the surface of a negative electrode, impregnating a polyether polymer to the surface of a positive electrode, coating or laminating a polyether polymer to the surface of a electrolyte layer, or containing a polyether polymer in a negative electrode, a positive electrode and an electrolyte layer.
• the embodiment of coating, laminating or impregnating a polyether polymer to the surface of a negative electrode is preferable.
• polyether polymer partially crosslinked polyether polymer is preferable, and cross linked polymer of (1) a polyether obtained by ring-opening polymerizing an allyl glycidyl ether with ethylene oxide and (2) a polyether polyol poly(metha) acrylate polyether polymer obtained by acylating the terminal of three functional polyether polyol obtained by adding glycerin to ethylene oxide with (metha) acryl acid is most preferable.
• a molten salt and lithium salt are added to a copolymer of glycidyl ether having radical polymerizable allyl group in the side chain and alkylene oxide, and by heating it a molten salt and lithium salt are taken in the polymer matrix
• crosslinked polyether polymer the crosslinked polymer of a) polyether polymer having at least one
• R means hydrogen or alkyl having not more than 4 of carbon atom
• polyether polyol poly(metha)acrylate is preferable.
• polyether polymer electrolyte phase has an excellent mechanical strength, and a thin electrolyte layer can be obtained.
• the total thickness of the battery can be thin.
• a polyether polymer electrolyte has an excellent affinity to electrode and the integration of the polyether polymer and the electrolyte active material can be done.
• the interface resistance of the active material particle can be reduced through the polyether polyol. Especially by using polyether polyol, the interface resistance of lithium foil negative electrode can be reduced remarkably.
• the typical example of monomer corresponding to formula 2 is ethylene oxide.
• alkylene oxide such as propylene oxide (PO), butylene oxide (BO) can be used with ethylene oxide.
• Polymer added ethylene oxide to the terminal of PO or BO in the random polymer of PO-BO is preferable.
• Polymer added BO to the terminal of EO or PO in the random polymer of EO-PO, or polymer added PO to the terminal of EO or BO in the random polymer of EO-PO can be used,
• A-Component is produced by ring-opening polymerizing a mixture of glycidyl ether corresponding to formula 1 and a monomer containing alkylene oxide corresponding formula.
• the mixture of monomers can contain other glycidyl ether such as methyl glycidyl ether, ethylene glycol or polyethylene glycol monomethyl glicidyl ether.
• the mixture having 70 to 95 mol % of ethylene oxide, especially 70 to 90 mol % and all glycidyl ether having allyl group and/or not allyl group as remaining unit is preferable.
• the a) component having 50,000 to 200,000 of number average molecular is preferable.
• B-Component is produced by acylating the terminal of OH group of polyoxy alkylene polyol having more than 2 functional group with reactive derivatives of acrylic acid or methacrylic acid such as acid chloride.
• the polyoxy alkylene polyol having more than 2 functional group is produced by well known method, for example by random or block addition polymerizing alkylene oxide such as ethylene oxide, ethylene oxide-propylene oxide, or butylene oxide by using polyhydric alcohol such ethylene glycol, glycerin, trimethylol propane or pentaerythritol as an initiator.
• the number of mols added, based on one OH group of hydric alcohol is not more than 35, particularly not more than 10.
• the process for forming a layer or film of polyether polymer the process for solving a) component, b) component and lithium salt in non-proton organic solvent, coating or casting this solution to electrode active material layer and then curing it by heating or photo polymerization is raised.
• acetonitrile, cyclic carbonate, lactone, cyclic ether, nitrile, chain ether, chain ester of carboxylic acid, chain carbonate, sulfolane, dimethyl sulfoxide, N.N-dimethyl formamide, especially ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate and the mixture thereof are preferable.
• the ratio of A-Component/B-Component (A/B) is preferably 1/5 to 5/1.
• physical and rheological property can be adjusted from gel having soft and excellent adhesiveness to gel corresponding to comparative hard solid polymer electrolyte.
• polyethylene glycol dialkyl or dialkenyl ether, or diepoxy polyethylene glycol can be added to the solution before polymerization.
• the amount of the plasticizer is preferably not more than 50 wt. % of the crosslinked polyether polymer.
• the polyether polymer preferably contains 2 to 98 wt. % (the residue is polymer electrolyte composition) of the IPN (Internal Penetration) crosslinked polymer comprising a) component and b) component can be preferably contained.
• the higher this ratio the physical and electrical property of the polyether polymer gets closer to the physical and electrical property corresponding to total solid electrolyte.
• the ratio of the crosslinked polymer to the polyether polymer is preferably at least 2 wt. %.
• the ratio is preferably at least 50 wt. %.
• the desired rechargeable battery can be obtained. Further, it is effective to cast the composition comprising inorganic solid electrolyte and polymer electrolyte composition, to make the membrane thereof and to put the membrane between the positive and the negative electrodes and to cure them.
• the temperature at 60 to 100° C. for 5 to 60 minutes is preferable.
• to coat or impregnate the electrolyte on or into the positive and the negative electrodes, respectively is raised, but it is preferable to coat or impregnate only the polymer electrolyte composition containing supporting salt.
• the LIB cell formed by inserting the polymer electrolyte composition-inorganic solid electrolyte between the positive and the negative electrodes, of which polymer electrolyte composition is containing supporting salt is used. This formation method to make inserting the polymer composition-inorganic solid electrolyte phase into the both electrodes is effective to make thinner in the cell form and also helpful to prevent the destruction of this cell structure.
• Polymer conductive component formed in a range of relatively low grafting ratio with the molten salt to fluoropolymer as mentioned above is used for ion conductive binder in manufacturing applications of the both electrodes.
• the solid electrolyte might be substituted as a part of conductive agent in 5 to 20 wt. % to the volume of Ion conductive binder.
• a layer of the polymer electrolyte composition and solid electrolyte phase means a composition comprising polymer electrolyte composition and inorganic solid electrolyte, for example, as the membrane of this composition and also the conductive layer of the composition.
• inorganic solid electrolyte and polymer electrolyte composition in the conductive polymer-inorganic solid electrolyte matrix. It is preferable to contain inorganic solid electrolyte in the positive electrode and the negative electrode respectively in case of aiming the integration (homogenization) of the positive-negative electrodes and the conductive polymer-inorganic solid electrolyte. However, it may not be contained.
• the amount of the inorganic solid electrolyte is 1 to 99 wt. % based on the total amount of a composition (containing supporting salt) comprising polymer electrolyte composition and inorganic solid electrolyte, preferably 40 to 98 wt. %, more preferably 60 to 95 wt. %.
• lithium compound is preferable.
• Li x Me y O z such as LiCoO 2 , LiNiO 2 , LiFeO 2 , LiMnO 3 , LiMn 2 O 4 and LiMn 2 O 4 ; LiNi x Me y O z such as LiNi 0.5 Mn 1.5 O 4 ; LiCo w Ni x Me y Oz such as LiCo 1 Ni 1 Al 1 O 2 , LiCo 13 Ni 13 Mn 13 O 2 : LiFePO 4 , LiCoPO 4 , LiNiPO 4 and LiMnPO 4 are preferable.
• w, x, y, z means optional positive number respectfully, Me means Fe, Co, Ni, Al or Mn.
• Other metal may be contained in lithium compound of these positive electrode. Further as the positive electrode, the other positive electrode may be used.
• a conductive material may be used in addition to the above positive active material.
• the conductive material natural graphite, artificial graphite, hard carbon, MCMB (mesophase small sphere), nanoparticle carbon, carbon nanofiber (VGCF), or carbon nanotube (CNT) are raised.
• polymer electrolyte composition may be used, and the polymer electrolyte composition having a lower graft ratio may be used as a conductive binder.
• carbon material such as natural graphite, artificial graphite, hard carbon, MCMB (mesophase small sphere), LTO (lithium titanate) such as Li 4 Ti 5 O 12 , silicon material such as SiO/graphite or lithium metal foil are raised.
• conductive material natural graphite, artificial graphite, hard carbon, MCMB (mesophase small sphere), nanoparticle carbon, carbon nanofiber (VGCF), or carbon nanotube (CNT) are raised, but in case of using lithium metal foil as the negative electrode, these conductive materials are not needed.
• the active material used in the negative electrode is the same as one used in the positive electrode or different from one used in the positive electrolyte. However the active material used in the negative electrode and the positive electrode is preferably different.
• LIB cell can be obtained in no use of separator, so called, separator-less LIB can be obtained.
• separator-less LIB it is no problem to use the separator, and by using separator having a thin layer of the polymer electrolyte composition to the surface of the separator, practical LIB cell having a constant performance can be obtained.
• ⁇ graft polymer (X 1 ) and a molten salt (X 2 ) and supporting salt ⁇ Positive electrode: LiCo 2 and conductive material ⁇ nanoparticle carbon [Product name: Super C65] produced by Imerys Graphite & Carbon Co. ⁇ : Negative electrode: natural sphere graphite and conductive material ⁇ nanoparticle carbon [Product name: Super P-Li] produced by Imerys Graphite & Carbon Co. ⁇ :
• the solid state electrolyte was prepared by mixing 90 wt. % of the inorganic solid electrolyte Li 7 La 3 Zr 2 O 12 ⁇ Product name [LLZO-PT] prepared by Piotrek Co., Ltd. ⁇ (90 wt. %), and 10 wt.
• the above mixture was heated at 50° C. and for 1 hour and as the result the polymer matrix was formed. Then by using acetonitrile solvent, casting solution having 65 wt. % of the solid content was obtained, and then the casting solution was casted and dried at 80° C. and for 30 minutes.
• the conductive polymer-solid electrolyte membrane having an excellent conductive network and 20 ⁇ m of thickness. The conductivity of this conductive polymer-solid electrolyte membrane was 2.6 ⁇ 10 3 S/cm.
• the conductive polymer solid state electrolyte membrane was laminated on the above negative electrode, and then the negative electrode laminating with Solid-polymer electrolyte was prepared by pressing process. Further, this half cell form was combined with the above positive electrode by pressing process to complete a separator-less rechargeable LIB flat cell in size of 5 ⁇ 5 cm by vacuum sealing process.
• the volumetric energy density of this cell was measured at 25° C., and this cell had a stable performance 31 mAh (117.8 mWh) at 3.8 V of average operating voltage, and this shows descending the interface resistance. Further, 94% to the initial volume showed at the 30 cycle property.
• Conductive polymer-solid electrolyte Garnet (80 wt. %) and (20 wt. %) of polymer electrolyte composition electrolyte composition (X 1 ) having 50 mol % of graft ratio, obtained by graft polymerizing MOETMA-FSI with a vinylidene fluoride copolymer ⁇ vinylidene fluoride copolymer utilized [Product name: Solvay #5130] produced by Solvay Co., ⁇ containing a molten salt (LiFSI) as a supporting salt which is 30 wt. % to the graft polymer (X 1 ).
• a molten salt LiFSI
• Positive electrode LiCo 13 Ni 13 Mn 13 O 2 and conductive material ⁇ nanoparticle carbon [Product name: Super C65] ⁇ .
• LiTFSI as the supporting salt containing 30 wt. % to the polymer electrolyte composition electrolyte composition was impregnated to the surface of the positive electrode.
• Negative electrode natural sphere graphite and conductive material ⁇ nanoparticle carbon [Product name: Super P-Li] ⁇
• the polymer electrolyte composition (X 1 ) containing 20 wt. % of LiFSI as the supporting salt to X 1 was impregnated to the surface of the negative electrode,
• the polymer electrolyte composition (X 1 ) and an allyl glycidyl polyethylene glycol polymer which ratio is 1:1 20 wt. % of the supporting salt (LiFSI) to the above mixture was doped, and then by using acetonitrile, the conductive polymer was diluted. Further, 15 wt. % of the inorganic solid electrolyte (Li 7 La 3 Zr 2 O 12 ) to the total amount of the polymer electrolyte composition (X 1 ) (containing the supported salt) and the above inorganic solid electrolyte was mixed to the above solution, and the mixed solution of 65 wt. % of the solid content was prepared.
• the supporting salt LiFSI
• This mixed solution was impregnated to the surface of the negative electrolyte of natural spheroidal graphite having 1.6 mAh/cm 2 volume capacity, and then it was dried at 80° C. and for 30 minutes. And the negative electrolyte processed with the conductive layer was measured at 3.6 g/cm3 as a press density. The thickness of the conductive layer is of 3 ⁇ m. The thickness was enough to meet a practical performance. This conductive polymer electrolyte was performed at 1.5 ⁇ 10 ⁇ 4 S/cm conductivity.
• the polymer solid state electrolyte as the mixture of Garnet (LLZO-PT), X 1 and LIFSI; containing LiFSI was prepared in the amount of inorganic solid electrolyte was 75 wt. % to the total mixture.
• the casting solution was prepared on 65 wt. % of the solid content.
• the casted film was cured at 80° C. for 30 minutes.
• the membrane of the conductive polymer-solid electrolyte in 20 ⁇ m formed an excellent conductive network to perform superior conductivity.
• This LIB cell was measured at 25° C., and this cell had a stable performance of 37 mAh (144.3 mWh) at 3.9 V as the average operating voltage, and this shows descending the interface resistance. Further, 94% of the initial volume capacity was measured at the 30 cycle property.
• Positive electrolyte LiCoO 2 and conductive material ⁇ nanoparticle carbon [Product name: Super P-Li].
• Negative electrolyte lithium metal foil.
• the positive electrolyte the above LiCoO 2 was used.
• the above conductive polymer solid state electrolyte was prepared the solution in 65 wt. % of solid content. Further, 30 wt. % of supporting salt (LiFSI) was doped. This solution was coated on the surface of the positive electrode in glovebox under the dew point at ⁇ 40° C., and then the surface was cured at 80° C. for 30 minutes. The thickness of the membrane was of 15 ⁇ m.
• One-piece specimen of the positive electrode processed with the conductive polymer-solid electrolyte was prepared.
• lithium metal foil in 200 ⁇ m thickness was used as the negative electrolyte.
• a mixture of the graft polymer (X 1 ), allyl glycidyl polyethylene glycol polymer and inorganic solid electrolyte (LAGP) was prepared, and 20% of supported salt (LiBF 4 ) was formulated to this mixture.
• this conductive polymer as the casting solution was coated on the lithium metal foil in glovebox under the dew point at ⁇ 40° C. to make the thickness of impregnated layer at 2 ⁇ m.
• the separator-less conductive polymer-solid electrolyte LIB flat cell was prepared in the same as Example 1.
• this LIB cell had 32 mAh (118.4 Wh) of stable performance at 3.7 V of average operating voltage, and this shows descending the interface resistance. Further, 95% of the initial volume capacity was measured at the 30 cycle property.
• Conductive polymer-solid electrolyte Garnet-LLZO-PT (90 wt. %) and a polymer electrolyte composition (X 1 ) (10 wt. %) as used in Example 1 (containing supporting salt).
• Positive electrode LiCo 13 Ni 13 Mn 13 O 2 and conductive material ⁇ nanoparticle carbon [Product name: Super 65] ⁇ .
• Negative Electrolyte Lithium Metal Foil.
• the polymer electrolyte composition (X 1 ), allyl glycidyl polyethylene glycol polymer and solid electrolyte (LLZO-PT) were used in positive electrode and negative electrode.
• the above Conductive polymer-solid electrolyte ⁇ the polymer electrolyte composition (X 1 ) and Garnet and the supporting salt (LiFSI) ⁇ were used in the conductive polymer solid electrolyte membrane.
• separator-less solid electrolyte rechargeable battery cell was obtained.
• this LIB cell had 38 mAh (148.2 Wh) of stable performance at 3.9 V as the average operating voltage, and this shows descending the interface resistance. Further 97% of the initial capacity volume was measured at the 30 cycle property.
• Conductive polymer-solid electrolyte Garnet (95 wt. %) and a polymer electrolyte composition (X 1 ) (3 wt. %) as used in Example 1 and supporting salt (LiFSI) (2 wt. %).
• Positive electrode LiFePO 4 and conductive material ⁇ nanoparticle carbon [Product name: Super 65].
• Negative Electrode Lithium Metal Foil.
• this LIB cell had 33 mAh (105.6 mWh) of stable performance at 3.2 V as the average operating voltage and this shows descending the interface resistance. Further 98% of the initial volume capacity was measured at the 30 cycle property.
• Conductive polymer-solid electrolyte Garnet-LLZO-PT (90 wt. %), ⁇ a polymer electrolyte composition (X 1 ) as used in Example 3 and MOETMA-FSI homopolymer (X 3 ) ⁇ (8 wt. %) and ⁇ a molten salt (ion liquid) (MPPy-FSI) (X 2 ) and supporting salt LiFSI) ⁇ (2 wt. %).
• Positive electrode LiCoO 2 and conductive material ⁇ nanoparticle carbon [Product name: Super 65] ⁇ .
• Negative Electrode Lithium Metal Foil.
• the polymer electrolyte composition (X 1 ), molten salt (X 2 ) and supporting salt were used in the positive electrode and the above conductive polymer solid electrolyte ⁇ Garnet, polymer electrolyte composition (X 1 ), molten salt and a molten salt (X 2 ) and homopolymer (X 3 )were used in the conductive polymer electrolyte.
• separator-less solid state electrolyte rechargeable battery cell in which polymer matrix was formed was obtained.
• this LIB cell had 34 mAh (125.8 mWh) of stable performance at 3.7 V as the average operating voltage, and this shows descending the interface resistance. Further 99% of the initial volume capacity was measured at the 30 cycle property.
• Conductive polymer-solid electrolyte Garnet-LLZO-PT, a polymer electrolyte composition (X 1 ) as used in Example 3 and a molten salt (MOETMA-FSI) (X 2 ).
• Positive electrode LiNi 0.5 Mn 1.5 O 4 and conductive material ⁇ nanoparticle carbon [Product name: Super 65] ⁇ .
• Negative Electrolyte Lithium Metal Foil.
• the polymer electrolyte composition (X 1 ) (containing supporting salt) and inorganic solid electrolyte LAGP were used in the positive electrode, and the above conductive polymer solid electrolyte Garnet-LLZO-PT, polymer electrolyte composition (X 1 ), a molten salt of monomer (X 2 ) and supporting salt (LiFSI): the total amount of X 1 , X 2 and LiFSI was 30 wt. % based on the total amount of the above conductive polymer sloid electrolyte ⁇ were used in conductive polymer electrolyte membrane.
• the electrolyte layer comprising the three layers was obtained.
• This layer of 2 ⁇ of the conductive polymer electrolyte did not contain the Garnet, but it may contain the Garnet.
• this LIB cell had 33 mAh (158.4 mWh) of stable performance at 4.8 V as the average operating voltage, and this shows descending the interface resistance. Further 97% of the initial volume capacity was measured at the 30 cycle property.
• Conductive polymer-solid electrolyte sulfide material (Li 2 S.P 2 S 5 ), a polymer electrolyte composition (X 1 ) as used in Example 3, a molten salt (MPPy-FSI) (X 2 ) and supporting salt (LiFSI).
• Positive electrode LiNi 0.5 Mn 1.5 O 4 and conductive material ⁇ nanoparticle carbon [Product name: Super 65].
• Negative Electrode Lithium Metal Foil.
• the polymer electrolyte composition (X 1 ) and supporting salt (LiTFSI) were used in the positive electrode, and by hardening the surface of sulfide material inorganic electrolyte with polymer electrolyte composition (X 1 ) (containing supporting salt) and then by heating this mixture at 50° C. and for 1 hour with a molten salt (MPPy-FSI) (X 2 ) and supporting salt (LiFSI) in which ratio is 1/1, polymer matrix was obtained.
• MPPy-FSI molten salt
• X 2 molten salt
• LiFSI supporting salt
• this LIB cell had 33 mAh (158.4 mWh) of stable performance at 4.8 V as the average operating voltage, and this shows descending the interface resistance.
• this LIB cell had 28 mAh of stable performance at 3.7 V as the average operating voltage, but Li ion transfer coefficient (transport number) at not more than 25° C. was lower, and this did not show descending the interface resistance. Further 89% of the initial volume capacity was measured at the 30 cycle property. However at more than 60° C. the solubility of PEO is increased and also the conductivity is increased.
• This invention is greatly expected as the solid electrolyte rechargeable battery in no use of separator which has a descending effect of particle interface resistance between positive and negative active materials using solid electrolyte, a thin film cell, a little temperature dependence and excellent safety in case of happening short circuit.

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