WO2000038263A1 - Electrolytes solides microporeux et procedes de preparation - Google Patents

Electrolytes solides microporeux et procedes de preparation Download PDF

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Publication number
WO2000038263A1
WO2000038263A1 PCT/KR1999/000798 KR9900798W WO0038263A1 WO 2000038263 A1 WO2000038263 A1 WO 2000038263A1 KR 9900798 W KR9900798 W KR 9900798W WO 0038263 A1 WO0038263 A1 WO 0038263A1
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Prior art keywords
electrolyte
film
absorbent
solvent
solid electrolyte
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PCT/KR1999/000798
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English (en)
Korean (ko)
Inventor
Dong Hun Jang
Sa Heum Kim
Han Jun Kim
Sung Min Hong
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Finecell Co., Ltd.
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Application filed by Finecell Co., Ltd. filed Critical Finecell Co., Ltd.
Priority to JP2000590241A priority Critical patent/JP2002543554A/ja
Priority to EP99960009A priority patent/EP1171927A4/fr
Publication of WO2000038263A1 publication Critical patent/WO2000038263A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • 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 an electrolyte film usable in rechargeable cells. More particularly, it relates to a provision of pathways for ions mobile between a cathode and an anode during repeated charge and discharge of rechargeable cells by introducing liquid components and lithium salts (hereinafter, both are referred to as "liquid electrolytes") to an electrolyte film having microporous structures and containing an absorbent.
  • liquid electrolytes liquid components and lithium salts
  • Electrochemical cells include three essential components, i.e., cathode, anode and electrolyte.
  • materials for said anode are typically compounds in which lithium metal or lithium ions can be intercalated, preferably carbon and polymer materials.
  • materials for said cathode are typically materials in which lithium ions can be intercalated.
  • oxide compounds or polymer materials such as lithium cobalt oxide (Li x Co0 2 ), lithium nickel oxide (Li x Ni0 2 ), lithium nickel cobalt oxide (Li x Ni y C ⁇ -y ⁇ 2), spinel type lithium manganese oxide (Li x Mn 2 ⁇ 4) and manganese dioxide (Mn0 2 ) can be used.
  • the introduction of a liquid electrolyte to said electrolyte film can lead to the formation of an ion conductive matrix.
  • Electrochemical cells using polymer electrolytes have some advantages over ones using liquid electrolytes in that i) they have less leakage risk of liquid; ii) they have excellent electrochemical stability, which makes it possible to manufacture various types of cells; and iii) they make the automation of the manufacturing process easy.
  • polymers such as polyoxyethylene may have metal ionic conductivity in case that they contain polar heterologous atoms capable of electric interaction with metal ions
  • polymer electrolytes since the fact that polymers such as polyoxyethylene may have metal ionic conductivity in case that they contain polar heterologous atoms capable of electric interaction with metal ions was found, research on ion conductive polymers, i.e., polymer electrolytes has been actively conducted.
  • pure polymers such as polyoxyethylene have very low ionic conductivity of 10 "8 S/cm or so at room temperature, they have a demerit in that they should be approached to the temperature of approximately 100°C in order to show ionic conductivity of approximately 10 "4 S/cm applicable to electrochemical cells. For this reason, the main stream of the research on polymer electrolytes was concentrated on the improvement of conductivity.
  • Blonsky et al proposed a method for manufacturing an electrolyte having increased conductivity of 10 "3 S/cm by introducing phosphazene linkages to the mam chain of the polymers (./. Am. Chem. Soc, 106, 6854 (1984)).
  • said electrolyte has lower conductivity and poor mechanical strength.
  • gel-type electrolytes disclosed in US Patent 5,219,679 contain liquid electrolytes in their polymer backbones, and thus demonstrate conductivity close to that of liquid electrolytes while exhibiting properties of polymers in their mechanical properties, suggesting the possibility of commercialization to rechargeable battery.
  • the cell of said patent doesn't need a separate activation procedure of adding a liquid electrolyte, but contains some amount of liquid electrolytes which were incorporated during the manufacture of the polymer electrolytes (a mixture of polymer solution and liquid electrolyte was subjected to casting).
  • 5,219,679 have problems in that they contain polymers such as polyacrylonitrile which are reactive to lithium metal, and thus the reaction products between electrolytes and lithium electrode come to be accumulated during the storage and use period of the cell, resulting in a constant increase in interfacial resistance.
  • These electrolytes which use polymethylmethacrylate as a polymer component have little reactivity with the surface of lithium, and thus have a merit in that the resistance increase phenomenon on the surface of electrode during the storage is insignificant.
  • the liquid electrolytes are added after electrolyte film is prepared, it is necessary for the inside of the electrolyte film to have sites capable of absorbing liquid components therein or driving force making the liquid component possible to be penetrated thereinto.
  • dibutyl phthalate is added as a plasticizer in the step of preparing electrolyte film, and after the assembly of cell is complete, the plasticizer is extracted by the use of an organic solvent such as alcohol or ether to form sites for liquid component being absorbed.
  • an organic solvent such as alcohol or ether
  • the electrolyte film of the said solid electrolyte consists of an absorbent and a polymer binder under dried condition.
  • the polymer binder has more or less dense structure.
  • the solid electrolyte of which the stereo structure of the electrolyte film is changed is need.
  • the present invention desires to solve the above mentioned problems encountered in the process for the preparation of a solid electrolyte which comprise of adding an absorbent capable of absorbing liquid electrolytes to a polymer matrix to form an electrolyte film, and after the assembly of the battery.
  • the present invention introduces microporous structures to the polymer matrix while maintaining the mechanical strength of the electrolyte film as it is, which facilitates the absorption of the liquid electrolyte, which in turn improves the lithium ionic conductivity of the solid electrolyte.
  • electrolyte film used in the specification refers to an electrolyte film which is dried condition and does not contain any liquid electrolytes.
  • solid electrolytes used in the specification means said electrolyte film having ionic conductivity by incorporating liquid electrolytes thereto. Although the solid electrolytes are not in a complete solid state since they contain liquid electrolytes, they are called “solid electrolytes” in order to be distinguished from the liquid electrolytes because the basic backbone of solid electrolytes starts from the electrolyte film at a solid state.
  • absorbent used in the specification means materials capable of absorbing liquid electrolytes or of increasing the ability of the solid electrolytes absorbing liquid electrolytes.
  • the process for assembling batteries refers to binding a cathode and an anode, which are separately prepared, with an inte ⁇ osed electrolyte film in the manner of lamination or pressing.
  • the electrolyte film is prepared by one of the said methods, liquid electrolytes are added after the assembly of battery, which can minimize the restriction on dehumidifying conditions in the process.
  • the sites capable of absorbing liquid electrolytes are already formed in the course of manufacturing the electrolyte film and thus there is no need for the procedure of extracting a plasticizer. Therefore, the method has some advantages in that it simplifies the process, which not only reduces the production cost but also makes the automation process easy and improves the yield.
  • the polymer matrix comes to have microporous structures, which facilitates the transfer of the liquid electrolyte, which in turn improves the lithium ionic conductivity of the solid electrolyte with the same amount of absorbent.
  • the solid electrolytes according to the present invention comprise an electrolyte film containing an inorganic absorbent and consisting of microporous structures, and an ion conductive liquid electrolyte.
  • Said electrolyte film can be preferably prepared by means of a phase inversion method.
  • Examples of such method include wet process and dry process
  • the wet process refers to a process for the preparation of an electrolyte film, which comprises the steps of dissolving a mixture of an absorbent and a polymer binder in a solvent for the polymer binder, making the resulting solution to a film form, exchanging the solvent with a non-solvent for the polymer binder, and then drying the resulting material to form an electrolyte film
  • the dry process refers to a process for the preparation of an electrolyte film, which comprises the steps of mixing a mixture of an absorbent and a polymer binder with a solvent for dissolving the polymer binder, a non-solvent which does not dissolve the polymer binder, a pore former and a wetting agent, making the resulting mixture into a film form, and drying the resulting film completely
  • the solid electrolyte of the present invention can be prepared by introducing an absorbent capable of absorbing the liquid electrolyte or increasing the abso ⁇ tion ability to the mside of the electrolyte film to form a porous electrolyte film matrix and then injecting an liquid electrolyte thereto
  • prepared solid electrolyte has lithium ionic conductivity of approximately 1 to 3 x 10 "3 S/cm at room temperature.
  • absorbents capable of absorbing liquid electrolytes or increasing the abso ⁇ tion ability include organic materials such as porous polymers and inorganic materials such as mineral particles.
  • porous polymer absorbents polypropylene, polyethylene, polystyrene and polyurethane to which porosity is introduced by means of net type polymer wherein bulky functional groups are introduced to branched chains or by means of adjusting the parameters of the process according to the present invention can be used.
  • Natural polymers such as wood powder, pulp, cellulose and cork may also be used.
  • inorganic absorbents it is possible to use one or two or more particles selected from the group consisting of mineral particles, synthetic oxide compounds particles and mesoporous molecular sieves.
  • mineral particles include mineral particles having phyllosilicate structures such as clay, paragonite, montmorillonite and mica.
  • synthetic oxide compounds particles include zeolite, porous silica and porous alumina.
  • mesoporous molecular sieves include mesoporous molecular sieves made of oxide compounds such as silica/polymer substance and having a pore diameter in 2 to 30 nm.
  • Said mineral particles, synthetic oxide compounds particles and mesoporous molecular sieves may be used in the form of a mixture wherein two or more absorbents selected from the above mentioned absorbents are combined.
  • Said inorganic absorbents have better mechanical, thermal and electrochemical stability as compared to organic absorbents such as porous polymers, and thus the performance properties of the rechargeable cells utilizing inorganic absorbents are better than those of the rechargeable cells utilizing organic absorbents.
  • the organic absorbents differ from the electrolyte films or polymer binders of composite electrodes in their mechanical and thermal behaviors, and thus the rechargeable cells utilizing these organic absorbents show significant reduction in their discharge capacity during repeated charge and discharge as compared to the rechargeable cells utilizing inorganic absorbents.
  • absorbents consisting of organic materials such as polymers with low melting points or deteriorating mechanical strength may lose their abso ⁇ tion ability in the course of pressing or lamination procedures.
  • the use of organic absorbents such as polymers may be beneficial to the performance of electrolyte films or solid electrolytes themselves, but it may be very difficult to maintain their original performance when cells are fabricated by means of the pressing or lamination method.
  • the transfer of polymer chains directly affects the ionic conductivity in general polymer electrolytes, the effect of temperature on ionic conductivity becomes significant. Particularly, at low temperatures, the transfer of polymer chains is weakened, which significantly reduces the ionic conductivity, thereby resulting in severe deterioration in the performance of the cells.
  • the use of absorbents as in the present invention increases the ionic conductivity.
  • the effect of temperature becomes less unlike the properties of general polymer electrolytes.
  • the electrolytes have some merits in that the resistance against ignition or explosion is improved as compared to the electrolytes containing a large amount of organic material such as polymers.
  • the amount of absorbents added is 30 to 95 % by weight and preferably, 50 to 90 % by weight based on the weight of the dried state electrolyte film which does not contain liquid electrolyte. If the added amount exceeds 95 % by weight, the mechanical strength of the electrolyte film formed falls. If the amount is not more than 30 % by weight, the ability to absorb liquid electrolyte decreases.
  • the particle size of absorbents is preferably not more than 40 ⁇ m, more preferably, not more than 20 ⁇ m so as not to decrease the mechanical strength and the uniformity of the electrolyte film.
  • polymer binders it is possible to use most common polymers.
  • polystyrene resin a mixture of one or two or more polymers selected from the group consisting of copolymers of polyvinylidene fluoride, vinylidene fluoride and hexafluoropropylene, copolymers of vinylidene fluoride and maleic anhydride, polyvmylchloride, polymethylmethacrylate, polymethacrylate, cellulose triacetate, polyurethane, polysulfone, polyether, polyolefine such as polyethylene or polypropylene, polyethylene oxide, polyisobutylene, polybutyldiene, polyvinylalcohol, polyacrylonitrile, polyimide, polyvinyl formal, acrylonit ⁇ lebutyldiene rubber, ethylene- propylene-diene-monomer, tetra(ethylene glycol)diacrylate, polydimethylsiloxane, polycarbonate and polysilicon, or copolymers thereof.
  • the present invention introduces porous structures to the electrolyte film used as a matrix for the solid electrolyte, which facilitates the transfer of liquid electrolyte, and thus improves the lithium ionic conductivity of the solid electrolyte with the use of same amount of absorbent.
  • methods for preparing said porous electrolyte film include the wet process and dry process, as explained above. The wet process is carried out by subjecting electrolyte film component to a casting and reacting the resulting film with a non-solvent to form microporous structures in the polymer matrix.
  • the dry process is carried out by subjecting the electrolyte film components together with a non-solvent for introducing porosity and a pore former to molding to form a microporous electrolyte film.
  • a non-solvent for introducing porosity and a pore former for molding to form a microporous electrolyte film.
  • solvents for dissolving polymer binders a mixture of one or two or more solvents selected from the group consisting of N- methylpyrrolidinone, dimethylformamide, dimethylacetamide, tetrahydrofuran, acetonitrile, cyclohexanone, chloroform, dichloromethane, hexamethylphosphoramide, dimethylsulfoxide, acetone and dioxane.
  • non-solvents for the polymer binder it is possible to use a mixture of one or two or more selected from the group consisting of water, ethanol, ethylene glycol, glycerol, acetone, dichloroemethane, ethylacetate, butanol, pentanol, hexanol and ether.
  • pore formers it is preferred to use a mixture of one or two or more selected from the group consisting of 2-propanol, resorcinol, trifluoroethanol, cyclohexanol, hexafluoroisopropanol, methanol and hemiacetal obtained by the reaction of maleic acid with hexafluoroacetone.
  • nonionic surfactants for example, Triton X-100 (manufactured by Aldrich Company), Igepal DM-710 (manufactured by GAF Company).
  • the liquid electrolytes which contain absorbents and are to be absorbed in electrolyte film, can be prepared by dissolving lithium salt in an organic solvent.
  • the abso ⁇ tion of the liquid electrolytes into electrolyte film is defined as "activation".
  • said organic solvents have high polarity and no reactivity to lithium metal so as to improve the degree of dissociation of ions by raising the polarity of electrolyte and to facilitate ion conduction by lowering local viscosity around ions.
  • organic solvents examples include ethylene carbonate, propylene carbonate, dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate, ⁇ -butyrolactone, dimethylsulfoxide, 1 ,3-d ⁇ oxane, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, N,N- dimethylformamide, diglyme, triglyme and tetraglyme.
  • the organic solvent is used in the form of mixed solutions of two or more solvents consisting of high viscosity solvents and low viscosity solvents.
  • Said lithium salt is preferred to have low lattice energy and a high degree of dissociation.
  • Examples of such lithium salt include
  • LiC(CF 3 S0 2 ) 3 The selective mixtures thereof can also be used.
  • the concentration of the lithium salt is preferably 0.5M to 2M.
  • the liquid electrolyte can be added in an amount of 30 to 90 % by weight, preferably 40 to 85 % by weight, based on the total amount of electrolytes including the liquid electrolyte.
  • the solid electrolyte according to the present invention is characterized by the facts that it is easy to prepare when compared to prior polymer electrolytes; that it has higher ionic conductivity because the conduction of lithium ions proceeds via liquid phase; and that it is not affected by moisture or temperature until it absorbs the liquid electrolyte or it is activated.
  • the solid electrolyte having porous structures according to the present invention can be prepared by five steps, i.e., mixing an absorbent with a polymer binder, dissolution of the resulting mixture, casting, making polymer matrix porous and drying/ activation.
  • an absorbent in powder form (particle size of not more than 40 ⁇ m) and a polymer binder are dry mixed in a closed container.
  • the resulting mixture of the absorbent and the polymer binder is dissolved in a solvent for the polymer binder.
  • the solid content of said mixed solution is preferably 5 to 50 % by weight based on the total weight of the solution. If the content is not more than 5 % by weight, the mechanical strength of the electrolyte film decreases and if the content is more than 50 % by weight, the polymer binder cannot be dissolved sufficiently or the viscosity of the mixed solution becomes large, which is problematic.
  • a magnetic stirrer In order to facilitate the dissolution of the polymer binder and to avoid the agglomeration between absorbent, a magnetic stirrer, a mechanical stirrer, a planetary mixer or a high-speed disperser can be used to stir the mixed solution. While stirring, an ultrasonic stirrer may be adopted to prevent the absorbent from agglomerating or bubbling in the middle of mixing. In addition, if desired, the mixed solution may be subjected to defoaming and filtration steps.
  • the resulting mixture is made in the form of film with a regular thickness.
  • the mixed solution may be poured on a flat glass plate or a Teflon plate and then be subjected to casting so that the resulting products have a regular thickness.
  • the mixed solution may be extracted from a die with a regular space and then coated onto a substrate made of polymer film.
  • the thickness of the film is controlled in the range of 10 to 200 ⁇ m. If the thickness of the film is not more than 10 ⁇ m, the mechanical strength decreases, and if the thickness of the film exceeds 200 ⁇ m, the ionic conductivity decreases, which is not preferable.
  • the film was contacted with a non-solvent for the polymer binder to extract the solvent for the polymer binder.
  • a non-solvent for the polymer binder for example, it is possible to extract the solvent by soaking the film in a non-solvent pool containing a non-solvent. Accordingly, it is preferable to combine a miscible solvent and a non-solvent.
  • the time for soaking the film in a non-solvent pool varies from one minute to one hour depending on the kinds of the solvents and non-solvents. If the time is shorter than the defined time, it is difficult to obtain sufficient porosity. On the contrary, if the time exceeds the defined time, the productivity becomes decreased, which is not preferable.
  • the temperature in the pool is preferably from 10°C to 90°C, more preferably from 20°C to 80°C. If the temperature is lower than that, it is difficult to obtain sufficient porosity. If the temperature is excessively high, the mechanical strength of the electrolyte film decreases, which is not preferable.
  • the liquid electrolyte is introduced thereto.
  • the solid electrolyte having porous structures according to the present invention can be prepared by dry process consisting of four steps, i.e., mixing an absorbent with a polymer binder, adding additives
  • An absorbent in powder form (particle size of not more than 40 ⁇ m) and a polymer binder are dry mixed in a closed container.
  • the resulting mixture of absorbent and the polymer binder is dissolved in a solvent for the polymer binder.
  • a magnetic stirrer In order to facilitate the dissolution of the polymer binder and to avoid the agglomeration between absorbent, a magnetic stirrer, a mechanical stirrer, a planetary mixer or a high-speed disperser can be used to stir the mixed solution. While stirring, an ultrasonic stirrer may be used to prevent the absorbent from agglomerating or foaming in the middle of mixing. In addition, if desired, the mixed solution may be subjected to defoaming and filtration steps.
  • a solvent which does not dissolve the polymer binder i.e., a non-solvent is added in an amount range of not causing the precipitation of the polymer binder.
  • pore formers or dipping agents it is preferable to add pore formers or dipping agents.
  • the resulting mixture is molded in the form of film with a regular thickness.
  • the mixed solution may be poured on a flat glass plate or a Teflon plate and then be subjected to casting so that the resulting products have a regular thickness.
  • the mixed solution may be extracted from a die with a regular space and then coated onto a substrate made of polymer film.
  • various other application methods can be selected. It is preferred that the thickness of the film is controlled in the range of 10 to 200 ⁇ m. If the thickness of the film is not more than 10 ⁇ m, the mechanical strength decreases, and if the thickness of the film exceeds 200 ⁇ m, the ionic conductivity decreases, which is not preferable.
  • the resulting electrolyte film is completely dried at 20°C to 200°C and then the liquid electrolyte is introduced thereto.
  • the dry process has a demerit in that a complete dispersing or mixing of the absorbents, polymer binders and additives is comparatively difficult to accomplish.
  • a complete dispersion or mixing is not conducted, (i) it becomes difficult to accomplish an even dispersion of pores or absorbents, (ii) it is not easy to cast into the form of an electrolyte film and (iii) the mechanical strength and reproducibility become decreased.
  • the dry process necessitates the addition of non- solvents in order to form pores and in view of the principle of the dry process, the solvent should be evaporated (dried) prior to the non- solvents so that pores can be formed. If the non-solvents are evaporated prior to the solvents, pores cannot be formed. In this regard, it is essential that the non-solvents should have non-volatile property or higher boiling points than solvents. For this reason, the dry process is likely to have a problem of residual non-solvents. In other words, non- solvents, which have higher boiling point than solvents or are nonvolatile, are difficult to remove completely from the electrolyte film during drying procedure.
  • the present invention is directed to rechargeable cells, particularly to rechargeable lithium cells wherein said porous solid electrolyte is used as an electrolyte.
  • the process for assembling batteries refers to binding a cathode and an anode, which are separately prepared, with an inte ⁇ osed electrolyte film in the manner of lamination, pressing or winding.
  • the electrolyte film is prepared by one of the said methods, liquid electrolytes are added after the assembly of battery, which can minimize the restriction on dehumidifying atmosphere in the process.
  • the sites capable of absorbing liquid electrolytes are already formed in the course of manufacturing the electrolyte film and thus there is no need for the procedure of extracting a plasticizer. Therefore, the method has some advantages in that it simplifies the process, which not only reduces the production cost but also makes the automation process easy and improves the yield.
  • the polymer matrix comes to have microporous structures, which facilitates the transfer of the liquid electrolyte and improves the lithium ionic conductivity of the solid electrolyte with the same amount of absorbent.
  • a cell can be constructed by bonding a cathode and an anode, inte ⁇ osed with the porous electrolyte film prepared from the above-mentioned procedure.
  • the porous electrolyte film contains absorbent powder therein and has porous structures, which make the electrolyte film maintain its condition facilitating the abso ⁇ tion of the liquid electrolyte.
  • the cathode is electrically connected to a cathode current collector; and the anode is electrically connected to an anode current collector.
  • Fig. 1 illustrates a cross sectional view of the rechargeable cell in which the solid electrolyte according to the present invention is used.
  • the solid electrolyte (1 ) contains the absorbent powder (1 1) and the liquid electrolyte, which is absorbed during the activation step.
  • the cathode (2) is electrically connected to a cathode current collector (22) and the anode (3) is electrically connected to an anode current collector (33), respectively.
  • the cathode or anode consists of a current collector and an active material layer.
  • the active material layer comprises of active materials, conducting materials and binders, etc.
  • various additives may be introduced in order to improve the performance of cells.
  • the current collectors, conducting materials, binders and additives, which are contained in the cathode or anode, may be identical or different, depending on desired objectives.
  • the current collectors provide mobile pathways for electrons, which are generated in the oxidation reduction reaction, taking place in the cathode or the anode.
  • As current collectors generally grids, foils, punching foils and etching foils, etc., may be used, depending on the performance or manufacturing processes of the cell.
  • the use of grids can increase the filling rate of the active material, but it may complicate the manufacturing process.
  • the use of foils can improve the performance of the cell and simplify the manufacturing process, but it may deteriorate the compactness of the active materials Copper, aluminum, nickel, titanium, stainless steel, carbon, etc , can be used as current collectors Generally, aluminum is used for the cathode and copper is used for the anode
  • the active materials are the most crucial component of electrochemical cells since they determine the performance of cells m view of the fact that the charge and discharge reaction (or oxidation/reduction reaction) of cells take place on these materials Furthermore, the active materials possess the largest content in the active material layer
  • cathode active materials it is possible to use oxide compounds or sulfide compounds of transition metals, organic compounds, polymer compounds, etc
  • oxide compounds or polymer materials such as lithium cobalt oxide (L ⁇ Co0 2 ).
  • lithium nickel oxide (L ⁇ x N ⁇ 0 2 ), lithium nickel cobalt oxide (L ⁇ x N ⁇ C ⁇ 0 2 ), spmel type lithium manganese oxide (L ⁇ x Mn 2 0 4 ), manganese dioxide (Mn0 2 ), etc
  • alkali metals, alkali earth metals, carbon, oxide compounds or sulfide compounds of transition metals, organic compounds and polymer compounds may be used, preferably carbon or polymer materials can be used It is essential that the active materials should be chosen in accordance with the desired performance or use of cells
  • the conducting materials refer to materials that are added to the cathode or anode m order to improve the electronic conductivity, and are generally carbon Among them, conducting materials are preferably graphite, cokes, activated carbon and carbon black, more preferably graphite and carbon black. One or two or more of conducting materials selected from the above group can be used and there is no difference whether they are synthetic or natural materials.
  • the conducting materials are added in an amount of 3 to 15 % by weight based on the total weight of the electrode materials. If the amount of the conducting materials added is not more than 3 % by weight, the electrical conductivity falls, causing the problem of over voltage. If the amount exceeds 15% by weight, the energy density per unit volume decreases and the side reaction due to the conducting materials become severe.
  • the binders refer to components to be added to enhance the binding ability of the active materials and are generally polymer compounds.
  • the polymer compounds that are used in the preparation of the solid electrolyte film may serve as binders. It is preferable to use binders, which are the same as polymers of the electrolyte film or have miscibility.
  • the binders may be added in an amount of 15 % by weight or less based on the total weight of the electrode materials. If the amount of binders is less than required, the binding ability of the electrodes may decrease. If the amount of binders exceeds 15 % by weight, the processability and porosity of the electrodes decrease.
  • the additives refer to materials, which are added to improve the performance of cells or electrodes and can be chosen within a wide range in accordance with desired performances or use.
  • the additives are added to improve the binding ability with composite electrodes inside or current collectors, to induce the porosity or non-crystallinity of the composite electrodes, to improve the dispersibility of the composite electrode constituting materials or the efficiency of the process for the manufacturing of the electrodes, to prohibit the overcharge/overdischarge of the active materials, to recombine or remove the side reaction products, or to improve the abso ⁇ tion ability of the liquid electrolytes.
  • salts, organic/inorganic compounds, minerals and polymer compounds can be used as additives, and absorbents added to the electrolyte film can be chosen.
  • the porous electrolyte film in a dried solid condition obtained by the above-mentioned process without having the step introducing the liquid electrolyte is assembled with a cathode and an anode prepared separately to form a cell, to which a liquid electrolyte is absorbed to obtain the rechargeable lithium cell.
  • the solid electrolyte should be subjected to an activation step absorbing the liquid electrolyte in order to have a sufficient ionic conductivity for being used. By passing through the activation step, the solid electrolyte comes to be workable as an electrochemical cell. In case that the solid electrolyte fails to pass through the activation step, the ionic conductivity at room temperature decreases drastically, which renders the solid electrolyte itself inappropriate as an electrolyte.
  • the process for the preparation of the cathode and/or anode to be assembled with said electrolyte film is as follows. Each mixture of the cathode or anode materials is kneaded to give slurry. The resulting slurry is made to a thin film by means of casting, coating and screen printing and then the resulting thin film is combined with a current collector by means of pressing or lamination to form a cathode and/or an anode. Alternatively, the slurry may be directly coated on a current collector to form a cathode and/or an anode.
  • a solid electrolyte slurry consisting of an absorbent, a polymer binder and a solvent may be directly applied to form a cell in which an electrolyte film is formed on the electrodes.
  • the binding ability between the electrodes and the electrolyte film may increase.
  • it will be hard to adopt the former method when the electrodes and the electrolyte film do not correspond with each other, or when the electrodes or the electrolyte film are easy to pollute or lose their performance in the course of manufacturing process.
  • electrodes may be contaminated by the non-solvents or pore formers which are used to introduce porous structures, which is problematic.
  • the cell performance may be deteriorated if water is not completely removed by sufficient drying step.
  • the latter method although there is a demerit in that the binding ability between the electrodes and the electrolyte film is weak, there are much better merits in that it simplifies the quality control, process design and equipment used. Therefore, the latter method is preferred to the former one.
  • the electrolyte film prepared by the present invention contains an absorbent and thus has advantages in that it has higher mechanical strength as compared to pure electrolyte films or other electrolyte films containing gel type polymer electrolytes or plasticizers. Accordingly, because the electrolyte film of the present invention shows little change in its shape during the pressing or lamination procedure and has high reproducibility, it has merits in that it can be produced with a low failure rate and on a large scale. Namely, it can be stated that the electrolyte film prepared by the present invention has properties suitable for pressing or lamination methods, which are more advantageous in terms of quality control, process design and equipment used.
  • Figure 1 is a cross sectional view of the cell wherein the solid electrolyte according to the present invention is used.
  • Figure 2 shows graphs demonstrating the experimental results of linear sweep voltammetry to determine the electrochemical stability of the solid electrolyte according to the present invention.
  • Figure 3 shows a variation of discharge capacity of the cell in which the solid electrolyte containing an inorganic absorbent is used as compared to the cell in which polymer absorbent is used with repeated charge and discharge.
  • cathode 22 cathode current collector
  • the solid electrolyte according to the present invention and the process for the preparation of cells by using said solid electrolyte are explained in detail. Firstly, the production of the solid electrolyte and the examination of performances were carried out. In addition, the solid electrolyte is assembled together with the anode and cathode to form a cell and then the procedure to examine the performance of the cell is described.
  • the present invention is not restricted to those examples and various modifications are possible within the scope of the invention.
  • ⁇ ab [amount of the liquid electrolyte absorbed (mg)]/[weight of the electrolyte film (mg)]
  • Paragonite powder and a binder powder were introduced to a 20 ml vial and then dry mixed for approximately 5 minutes with a magnetic stirrer To the resulting mixture 4 ml of N-methyl pyrrolidinone was added and then continuously stirred until the binder was completely dissolved In order to prohibit the absorbent particles from agglomerating with each other, the resulting solution was further subjected to ultrasonic stirring for 30 minutes while stirring.
  • the mixed solution thus prepared was coated onto a glass plate in thickness of 100 ⁇ m. The coated film was soaked in a water bath for 10 minutes, which was removed from the bath and then dried at 40°C for approximately one hour.
  • the porous electrolyte film thus prepared was soaked in a liquid electrolyte solution for approximately 10 minutes After the liquid electrolyte was completely absorbed, the weight change was determined.
  • the ionic conductivity was also determined by the use of an alternate current impedance method. The results are summarized in Table 2.
  • the mixed solution thus prepared was coated onto a glass plate m thickness of 100 ⁇ m.
  • the coated film was dried at 40°C for approximately 2 hours, which was further dried for approximately 6 hours in a vacuum drier set to 50°C.
  • the electrolyte film thus prepared was soaked in an EC/DEC 1M LiPF 6 solution for approximately 10 minutes. After the liquid electrolyte was completely absorbed, the weight change was determined. ⁇ a b value measured by the use of the weight change was 7.5.
  • the conductivity determined at room temperature by an alternate current impedance method was 2.0 x 10° S/cm.
  • the present example differs from Examples 1 to 3 in the fact that a process for forming porous structures was not conducted.
  • the electrolyte film thus prepared was soaked in a liquid electrolyte solution for approximately 10 minutes. After the liquid electrolyte was completely absorbed, the weight change was determined.
  • the conductivity was determined by the use of an alternate current impedance method. Lithium ionic conductivity measured at room temperature was 7.0 x 10 S/cm.
  • the linear sweep voltammetry method was carried out by the use of a stainless steel (#304) as an operating electrode and lithium metal as an opposite electrode and a standard electrode.
  • the electrochemical voltage applied in the linear sweep voltammetry was from an open circuit voltage to 5.5 V.
  • the scan rate of the linear sweep voltammetry was lOmV/sec.
  • the results of the linear sweep voltammetry measured on the porous solid electrolyte prepared by the methods of Example l-(f), l-(j), 1-(1) and 2-(s) are shown as A, B, C and D, respectively, in Fig. 2.
  • an oxide compound cathode, a carbon anode and a solid electrolyte according to the present invention were assembled to fabricate cells, and then the charge and discharge test on thus fabricated cells was carried out.
  • the fabricated cells were in a laminated form and were prepared by lamination of the cathode, anode and electrolyte film to form an assembly, to which a liquid electrolyte was absorbed.
  • the constant current was applied with a rate charging the reversible capacity within 2 hours (C/2 rate) until the cell voltage became 4.2 V, and then the constant voltage of 4.2 V was applied again until the current decreased down to C/10 mA.
  • the discharging current was applied with a rate discharging the voltage down to 2.5 V or 2.75 V within 2 hours (C/2 rate).
  • the charge and discharge experiment was repeated and the change of discharge capacity with the charge and discharge was measured.
  • the cell constitution and the test results are summarized in the following Table 3 and shown in Fig. 3.
  • the solid electrolyte refers to the conditions where a liquid electrolyte is absorbed into an electrolyte film.
  • the solid electrolyte obtained m Example 4 was not applied for cell tests.
  • Fig.3 illustrates the discharge capacity with repeated charge and discharge of the cell obtained by the respective examples in comparison with the first discharge capacity. From the test results, it was confirmed that the use of the solid electrolytes containing inorganic absorbents (Examples 6-v, w, z) shows much better cell performances than that of the solid electrolyte containing organic absorbents such as polymers (Example 6-x). Furthermore, it was also confirmed that the use of solid electrolytes obtained by the wet process according to the present invention (Examples 1 and 2) shows much better cell performances than that of the solid electrolyte obtained by the dry process (Example 6-y).
  • the solid electrolyte containing inorganic absorbent and prepared by the wet process has a much better effect on the total cell performances (charge and discharge performance, etc.), although the electrolyte film or solid electrolyte itself does not show any significant differences in properties (ionic conductivity, mechanical strength, etc.).
  • microporous solid electrolytes according to the present invention are characterized by the following facts: they have high mechanical strength, which makes them suitable to be made into thin films; they have high ionic conductivity corresponding to that of the liquid electrolytes since the microporous structures and absorbents introduced to the polymer matrix facilitate the abso ⁇ tion of the liquid electrolyte and there is no restriction on the transfer of lithium ions; unlike general polymer electrolytes in gel type, they do not require any particular dehumidifying atmosphere since lithium salt, which is easily decomposed by a trace amount of moisture, is not introduced during the manufacturing of the electrolyte films; they have a broad electrochemical potential window since the absorbent therein is electrochemically stable; and they are of ease in automation for mass production due to the simple process for the production of the electrolyte.
  • the microporous solid electrolyte according to the present invention is suitable for being used as an electrolyte for rechargeable lithium cells.
  • the solid electrolytes containing inorganic absorbents also show superior mechanical, thermal and electrochemical stability to those of the solid electrolytes containing organic absorbents, thereby showing less decrease in their discharge capacity during the repeated charge and discharge.
  • the wet process is more efficient and stable than the dry process.
  • the microporous solid electrolyte shows superior performances such as less decrease in their discharge capacity as mentioned above when they are used to form electrochemical cells.

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Abstract

La présente invention concerne un électrolyte solide présentant une bonne conductivité aux ions de lithium en laissant les composants liquides et les sels de lithium être absorbés par le film d'électrolyte contenant des absorbants ajoutés lors de sa préparation et présentant une bonne porosité. La présente invention a également pour objet un procédé de préparation dudit électrolyte et une pile auithium rechargeable utilisant ce dernier. Les matériaux inorganiques utilisés comme absorbants présentent une taille de particule inférieure ou égale à 40 ν. Tout liant de polymère dont la solubilité par rapport à l'électrolyte liquide est faible peut être utilisé. Un procédé par voie humide peut introduire la structure poreuse du film d'électrolyte. L'électrolyte solide selon la présente invention présente une conductivité ionique supérieure à environ 1 à 3 x 10-3 S/cm à température ambiante, et une faible réactivité au métal lithium. Laile est fabriquée à partir de l'électrolyte solide avec des électrodes par des procédés de superposition de couches ou de compression. L'électrolyte liquide, qui est décomposé par l'humidité, est introduit dans la pile juste avant l'emballage. Par conséquent, l'électrolyte solide selon la présente invention n'est pas affecté par les conditions d'humidité et de température pendant la fabrication du film d'électrolyte. En outre, l'électrolyte solide selon l'invention présente de bonnes propriétés thermiques, mécaniques et une bonne stabilité électrochimique, et peut être utilisé comme électrolyte pour les piles au lithium rechargeables.
PCT/KR1999/000798 1998-12-22 1999-12-21 Electrolytes solides microporeux et procedes de preparation WO2000038263A1 (fr)

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JP2001167796A (ja) * 1999-11-30 2001-06-22 Korea Electronics Telecommun リチウム２次電池用高分子電解質
WO2005038946A2 (fr) * 2003-10-14 2005-04-28 Degussa Ag Separateur ceramique destine a des cellules electrochimiques presentant une meilleure conductivite
WO2005038946A3 (fr) * 2003-10-14 2006-02-16 Degussa Separateur ceramique destine a des cellules electrochimiques presentant une meilleure conductivite
US7682740B2 (en) 2004-02-07 2010-03-23 Lg Chem, Ltd. Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same
US20110281171A1 (en) * 2004-02-09 2011-11-17 Lg Chem, Ltd. Organic/inorganic composite porous film and electrochemical device prepared thereby
US20110281172A1 (en) * 2004-02-09 2011-11-17 Lg Chem, Ltd. Organic/inorganic composite porous film and electrochemical device prepared thereby
US9490463B2 (en) 2004-09-02 2016-11-08 Lg Chem, Ltd. Organic/inorganic composite porous film and electrochemical device prepared thereby
US8409746B2 (en) 2004-09-02 2013-04-02 Lg Chem, Ltd. Organic/inorganic composite porous film and electrochemical device prepared thereby
US20170005309A1 (en) * 2004-09-02 2017-01-05 Lg Chem, Ltd. Organic/inorganic composite porous film and electrochemical device prepared thereby
US20070122694A1 (en) * 2005-11-14 2007-05-31 Junichi Yamaki Non-aqueous electrolyte secondary battery
US8741470B2 (en) 2007-04-24 2014-06-03 Lg Chem, Ltd. Electrochemical device having different kinds of separators
US20100297501A1 (en) * 2009-05-22 2010-11-25 Hitachi, Ltd. Negative electrode for lithium secondary battery, and lithium secondary battery using the same
WO2013071043A3 (fr) * 2011-11-10 2013-12-05 Dow Global Technologies Llc Substrats polymères poreux comprenant des particules poreuses
US20170098861A1 (en) * 2012-03-26 2017-04-06 The University Of Tokyo Lithium secondary battery electrolytic solution and secondary battery including said electrolytic solution
US10727499B2 (en) 2014-06-17 2020-07-28 Medtronic, Inc. Semi-solid electrolytes for batteries
US9911984B2 (en) 2014-06-17 2018-03-06 Medtronic, Inc. Semi-solid electrolytes for batteries
CN105336985A (zh) * 2014-08-07 2016-02-17 惠州市鸣曦科技有限公司 高倍率锂离子电解液
US10333173B2 (en) 2014-11-14 2019-06-25 Medtronic, Inc. Composite separator and electrolyte for solid state batteries
US11437649B2 (en) 2014-11-14 2022-09-06 Medtronic, Inc. Composite separator and electrolyte for solid state batteries
US10873106B2 (en) 2016-03-16 2020-12-22 University Of Utah Research Foundation Composite solid electrolytes for lithium batteries
US10587005B2 (en) 2016-03-30 2020-03-10 Wildcat Discovery Technologies, Inc. Solid electrolyte compositions
WO2018051045A1 (fr) 2016-09-19 2018-03-22 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé de realisation d'un dispositif electrochimique et dispositif electro-chimique
US11217823B2 (en) 2016-09-19 2022-01-04 Commissariat à l'Energie Atomique et aux Energies Alternatives Method for fabricating an electrochemical device and electrochemical device
EP4238643A1 (fr) * 2022-03-04 2023-09-06 SK On Co., Ltd. Procédé de fabrication d'un absorbeur, absorbeur et batterie secondaire au lithium comprenant l'absorbeur

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CN1167164C (zh) 2004-09-15
EP1171927A1 (fr) 2002-01-16
KR20000041210A (ko) 2000-07-15
EP1171927A4 (fr) 2004-07-28
JP2002543554A (ja) 2002-12-17
CN1331848A (zh) 2002-01-16
KR100308690B1 (ko) 2001-11-30

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