WO2001091220A1 - Electrolyte polymere hybride fabrique par un procede de pulverisation, pile secondaire au lithium contenant cet electrolyte et procedes de fabrication correspondants - Google Patents

Electrolyte polymere hybride fabrique par un procede de pulverisation, pile secondaire au lithium contenant cet electrolyte et procedes de fabrication correspondants Download PDF

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WO2001091220A1
WO2001091220A1 PCT/KR2000/000513 KR0000513W WO0191220A1 WO 2001091220 A1 WO2001091220 A1 WO 2001091220A1 KR 0000513 W KR0000513 W KR 0000513W WO 0191220 A1 WO0191220 A1 WO 0191220A1
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polymer electrolyte
hybrid polymer
poly
hybrid
solution
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PCT/KR2000/000513
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Kyung Suk Yun
Byung Won Cho
Won Il Cho
Hyung Sun Kim
Un Seok Kim
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Korea Institute Of Science And Technology
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Priority to PCT/KR2000/000513 priority Critical patent/WO2001091220A1/fr
Publication of WO2001091220A1 publication Critical patent/WO2001091220A1/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
    • H01M10/04—Construction or manufacture in general
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/426—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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • H01M2300/0088—Composites
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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
    • H01M50/44—Fibrous 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
    • 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
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/188—Processes of manufacture
    • 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

  • the present invention relates to a hybrid polymer electrolyte fabricated by a spray method, a lithium secondary battery using the same and its fabrication method.
  • Lithium secondary batteries are typified by a lithium ion battery and a lithium polymer battery.
  • a lithium ion battery uses a polyethylene (hereinafter referred to as "PE”) or polypropylene (hereinafter referred to as "PP”) separator film besides an electrolyte. Because it is difficult to fabricate the lithium ion battery by laminating electrodes and separator films in a flat-plate shape, it is fabricated by rolling the electrodes with separator films and by inserting them into a cylindrical or rectangular casing (D. Linden, Handbook of Batteries, McGraw-Hill Inc., New York (1995)). The lithium ion battery was developed by SONY Company in Japan and has been widely used all over the world; however, it has problems such as instability of the battery, intricacy of its fabrication process, restriction on battery shape and limitation of capacity.
  • PE polyethylene
  • PP polypropylene
  • a lithium polymer battery uses a polymer electrolyte having two functions, as a separator film and as an electrolyte at the same time, and it is now being viewed with keen interest as a battery being able to solve all of the problems.
  • the lithium polymer battery has an advantage in view of productivity because the electrodes and a polymer electrolyte can be laminated in a flat-plate shape and its fabrication process is similar to a fabrication process of a polymer film.
  • a conventional polymer electrolyte is mainly prepared with polyethylene oxide (hereinafter referred to as "PEO"), but its ionic conductivity is merely 10 “8 S/cm at room temperature, and accordingly it can not be used commonly.
  • PEO polyethylene oxide
  • K. M. Abraham et al. and D. L. Chua et al. disclose a polymer electrolyte of a gel type polyacrylonitrile (hereinafter referred to as "PAN") group in U.S. Patent No. 5,219,679 and in U.S. Patent No.5,240,790 respectively.
  • the gel type PAN group polymer electrolyte is prepared by injecting a solvent compound (hereinafter referred to as an "organic electrolyte solution”) prepared with a lithium salt and organic solvents, such as ethylene carbonate and propylene carbonate, etc., into a polymer matrix.
  • a solvent compound hereinafter referred to as an "organic electrolyte solution”
  • organic solvents such as ethylene carbonate and propylene carbonate, etc.
  • A. S. Gozdz et al. discloses a polymer electrolyte of hybrid type polyvinylidenedifluoride (hereinafter referred to as "PVdF") group in U.S. Patent No. 5,460,904.
  • the polymer electrolyte of the hybrid type PVdF group is prepared by fabricating a polymer matrix having a porosity not greater than submicron and then injecting an organic electrolyte solution into the small pores into the polymer matrix. It has advantages in that its compatibility with the organic electrolyte solution is good, the organic electrolyte solution injected into the small pores is not leaked so as to be safe in. use, and the polymer matrix can be prepared in the atmosphere because the organic electrolyte solution is injected later.
  • PMMA polymethylmethacrylate
  • a polymer electrolyte of a polyvinylchloride (hereinafter referred to as "PVC") group which has good mechanical strength and has an ionic conductivity of 10 "3 S/cm at room temperature
  • PVC polyvinylchloride
  • it has disadvantages in that its low-temperature characteristic is poor and its contact resistance is high. Accordingly, development of a polymer electrolyte having a good adhesion with electrodes, good mechanical strength, good low- and high- temperature characteristics, and good compatibility with an organic electrolyte solution for a lithium secondary battery, etc. has been required.
  • Figures 1 a to 1 c illustrate embodiments of a spray method by an electrostatic induction.
  • Figures 2a and 2b illustrate the fabrication of a porous polymer matrix using a spraying machine.
  • Figures 3a to 3c illustrate process flow for fabricating lithium secondary batteries according to the present invention.
  • Figure 4 is a graph illustrating charge/discharge characteristics of the lithium secondary batteries of Examples 1-6 and Comparative Examples 1 and 2.
  • Figures 5a and 5b are graphs illustrating low- and high-temperature characteristics of the lithium secondary batteries of Example 2 and Comparative Example 2.
  • Figures 6a and 6b are graphs illustrating high-rate discharge characteristics of the lithium secondary batteries of Example 2 and Comparative Example 2.
  • the present invention relates to a hybrid polymer electrolyte comprising a porous polymer matrix in particlulate or fibrous form, or a combination thereof, having a diameter of 1-3000nm and a polymer electrolyte incorporated into the porous polymer matrix.
  • the present invention relates to a hybrid polymer electrolyte obtained by dissolving a polymer in an organic solvent, fabricating a porous polymer matrix in particulate or fibrous form, or a combination thereof, having a diameter of 1-3000nm by a spray method and then injecting a polymer electrolyte solution, in which a polymer, a plasticizer and an organic electrolyte solution are mixed and dissolved with each other, into the pores in the polymer matrix.
  • hybrid polymer electrolyte means an electrolyte in which a polymer electrolyte is incorporated into a porous polymer matrix.
  • Polymer electrolyte solution means a solution in which a polymer, which is incorporated into a porous polymer matrix, is dissolved in a mixture of a plasticizer and an organic electrolyte solution.
  • organic electrolyte solution means a solution in which a lithium salt is dissolved in an organic solvent, which does not affect characteristics of electrodes.
  • polymer electrolyte generically means an organic electrolyte solution and a polymer incorporated into the porous polymer matrix.
  • a porous polymer matrix fabricated by a spray method has a form in which particles or fibers, or a combination thereof having a diameter of 1 nm - 3000nm are built up three-dimensionally. Due to the small diameter of the particles or fibers, the ratio of surface area to volume and the void ratio are very high compared to those of a conventional electrolyte. Therefore, due to the high void ratio, the content of electrolyte impregnated is large and the ionic conductivity is increased, and due to the large surface area, the contact area with the electrolyte can be increased and the leakage of electrolyte can be minimized in spite of the high void ratio.
  • the examples of the polymer used for forming a porous polymer matrix can include polyethylene, polypropylene, cellulose, cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, polyvinylpyrrolidone- vinylacetate, poly[bis(2-(2-methoxyethoxyethoxy))phosphagene], poly- ethyleneimide, polyethyleneoxide, polyethylenesuccinate, polyethylenesulfide, poly(oxymethylene-oligo-oxyethylene), polypropyleneoxide, polyvinylacetate, polyacrylonitrile, poly(acrylonitrile-co-methylacrylate), polymethylmethacrylate, poly(methylmethacrylate-co-ethylacrylate), polyvinylchloride, poly(vinylidene- chloride-co-acrylonitrile), polyvinylidenedifluoride, poly(vinylidenefluoride-co- hexafluoropropylene) or mixtures thereof.
  • polymer matrix it is preferable to have a thickness of 1 ⁇ m - 100 ⁇ m, more
  • the of the particles and fibers of the polymer forming a porous polymer matrix is preferably adjusted in the range of 1 nm - 3000 nm, more preferably 10 nm - 1000nm, and most preferably 50 nm - 500 nm.
  • the polymer incorporated into the porous polymer matrix functions as a polymer electrolyte, and examples of the polymer can include polyethylene, polypropylene, cellulose, cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, polyvinylpyrrolidone-vinylacetate, poly[bis(2-(2- methoxyethoxyethoxy))phosphagene], polyethyleneimide, polyethyleneoxide, polyethylenesuccinate, polyethylenesulfide, poly(oxymethylene-oligo- oxyethylene), polypropyleneoxide, polyvinylacetate, polyacrylonitrile, poly- (acrylonitrile-co-methylacrylate), polymethylmethacrylate, poly(methyl- methacrylate-co-ethylacrylate), polyvinylchloride, poly(vinylidenechloride-co- acrylonitrile), polyvinylidenedifluoride, poly(vinylidenefluo ⁇ ' de-co-hexa
  • the lithium salt incorporated into the porous polymer matrix there is no specific limitation on the lithium salt incorporated into the porous polymer matrix.
  • the preferable examples of the lithium salt can include LiPF 6 , LiCIO 4 , LiAsF 6 , LiBF 4 and LiCF 3 SO 3 , and among them LiPF 6 is more preferable.
  • the organic solvent used in the organic electrolyte solution can include ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate or mixtures thereof.
  • an additional solvent such as methyl acetate, methyl propionate, ethyl acetate, ethyl propionate, butylene
  • the hybrid polymer electrolyte of the present invention can further include a filling agent in order to improve the porosity and mechanical strength.
  • a filling agent can include TiO 2 , BaTiO 3 , Li 2 O, LiF, LiOH, Li 3 N, BaO, Na 2 O, MgO, Li 2 CO 3 , LiAIO 2 , SiO 2 , AI 2 O 3 , PTFE or mixtures thereof. It is preferable that the content of the filling agent is generally below 20% by weight of the total hybrid polymer electrolyte.
  • the present invention also relates to a fabrication method for a hybrid polymer electrolyte.
  • the fabrication method comprises a step of melting or dissolving in an organic solvent a polymer for forming a porous polymer matrix, a step of forming a porous polymer matrix by a spray method, and a step of injecting a polymer electrolyte solution into the obtained porous polymer matrix.
  • the step of melting or dissolving a polymer for forming a porous polymer matrix is achieved by melting a polymer with heating, or by mixing a polymer in a suitable organic solvent and then stirring the mixture at a raised temperature, to obtain a clear polymeric solution.
  • a polymer is dissolved in an organic solvent
  • the possible organic solvents used are not particularly limited on condition that they can dissolve the polymer substantially and be applicable to a spray method.
  • a solvent which might influence on the characteristics of the battery can even be used, because the solvent is almost completely removed while fabricating a porous polymer matrix by a spray method.
  • the step of forming a porous polymer matrix is achieved by a spray method.
  • the porous polymer matrix can be obtained by filling a polymeric melt or polymeric solution for forming a porous polymer matrix into a barrel of a spray machine and then spraying the polymeric melt or polymeric solution onto a metal plate or Mylar film using a nozzle at a constant rate.
  • the polymeric melt or polymeric solution can be sprayed directly onto the electrode.
  • a thickness of the porous polymer matrix can be adjusted by changing a spray speed and time, and as described before, a preferable thickness range is 1 - 100 ⁇ m.
  • the polymeric melt or polymeric solution when spraying the polymeric melt or polymeric solution using a nozzle, the polymeric melt or polymeric solution can be sprayed by electrostatic induction.
  • Embodiments of spraying by electrostatic induction include the following methods. One method is that a nozzle and an electrode are connected to be each given an electrical potential in order that the polymeric melt or polymeric solution coming out from the nozzle has an electrostatic charge ( Figure 1a). Another method is that an additional electrode for electrostatic induction is located between a nozzle and an electrode in order to charge the polymeric melt or polymeric solution sprayed through a nozzle ( Figure 1 b). Another method is to combine the above two methods ( Figure 1c).
  • FIGS. 2a and 2b illustrate the fabrication methods of a porous polymer matrix using a spray machine.
  • Figure 2a illustrates the fabrication method by spraying all together using a nozzle to form a polymer matrix.
  • Figure 2b illustrates the fabrication method by spraying sporadically and continually using separately installed nozzles to form a multi-layered polymer matrix.
  • a porous polymer matrix using two or more polymers can be obtained by the following methods.
  • One method is by heating/melting or dissolving in an organic solvent two or more polymers, filling the obtained polymeric melt or solution into a barrel of a spray machine and then spraying the melt or solution using a nozzle, to fabricate a porous polymer separator film.
  • Another method is by heating/melting or dissolving in an organic solvent two or more polymers respectively, filling the obtained melts or solutions into separate barrels of a spray machine and then spraying the respective melts or solutions using nozzles, to fabricate a porous polymer matrix.
  • the hybrid polymer electrolyte is obtained by injecting a polymer electrolyte solution into the porous polymer matrix fabricated by a spray method.
  • a polymer electrolyte solution by dissolving a polymer in a mixture of an organic electrolyte solution and a plasticizer
  • the obtained polymer electrolyte solution is injected into the porous polymer matrix by die-casting, to obtain the hybrid polymer electrolyte.
  • the examples of the organic electrolyte solution used for a polymer electrolyte solution can include propylene carbonate, butylene carbonate, 1 ,4- butyrolactone, diethyl carbonate, dimethyl carbonate, 1 ,2-dimethoxyethane, 1 ,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, ethylene carbonate, ethylmethyl carbonate, N,N-dimethylformamide, N,N-dimethylacetarnide, N- methyl-2-pyrrolidone, polyethylenesulforane, tetraethylene glycol dimethyl ether, acetone, alcohol or mixtures thereof.
  • the kind of plasticizer is not particularly limited.
  • the preferable weight ratio of a polymer, plasticizer and organic electrolyte solution used for a polymer electrolyte solution is in the range of 1 : 1 - 20 : 1 - 20.
  • the present invention also relates to a fabrication method for a lithium secondary battery comprising the above-described hybrid polymer electrolyte.
  • Figures 3a to 3c illustrate the fabrication process in detail.
  • Figure 3a illustrates a fabrication process for a battery, comprising inserting a hybrid polymer electrolyte, which is prepared by incorporating a polymer electrolyte solution into a porous polymer matrix fabricated by a spray method, between an anode and a cathode, making the electrolytes and the electrodes into one body by a certain heat lamination process, inserting the resulting plate into a battery casing after laminating or rolling it, injecting an organic electrolyte solution into the battery casing, and then finally sealing the casing.
  • a hybrid polymer electrolyte which is prepared by incorporating a polymer electrolyte solution into a porous polymer matrix fabricated by a spray method, between an anode and a cathode, making the electrolytes and the electrodes into one body by
  • Figure 3b illustrates a fabrication process for a battery, comprising coating a hybrid polymer electrolyte onto both sides of a cathode or an anode, adhering an electrode having opposite polarity to the coated electrode onto the hybrid polymer electrolyte, making the electrolytes and the electrodes into one body by a certain heat lamination process, inserting the resulting plate into a battery casing after laminating or rolling it, injecting an organic electrolyte solution into the battery casing, and then finally sealing the battery casing.
  • Figure 3c illustrates a fabrication process for a battery, comprising coating a hybrid polymer electrolyte onto both sides of one of two electrodes and onto one side of the other electrode respectively, adhering the electrodes closely together as the hybrid polymer electrolytes are faced to each other, making the electrolytes and the electrodes into one body by a certain heat lamination process, inserting the resulting plate into a battery casing after laminating or rolling it, injecting an organic electrolyte solution into the battery casing, and then finally sealing the battery casing.
  • the anode and cathode used for the lithium secondary battery are fabricated in the same way as in the conventional method, such as by mixing an appropriate amount of active materials, conducting materials and bonding agents with an organic solvent, casting the resulting mixture onto both sides of a copper or aluminum foil plate grid, and then drying and compressing all of them.
  • An anode active material comprises one or more material selected from the group consisting of graphite, cokes, hard carbon, tin oxide and lithiated compounds thereof.
  • a cathode active material is one or more material selected from the group consisting of LiCIO 2 , LiNiO 2 , LiNiCoO 2 , LiMn 2 O 4 , V 2 O 5 or V 6 O 13 .
  • Metallic lithium or lithium alloys can also be used for an anode in the present invention.
  • Example 1 1 -1 Fabrication of a porous polymer matrix
  • Example 1 -2 The hybrid polymer electrolyte fabricated in Example 1 -2 was inserted between a graphite anode and a LiCoO 2 cathode, and the resulting plates
  • Terminals were cut so as to be 3 cm x 4 cm in size and laminated. Terminals were
  • Example 2-1 the polymer electrolyte solution was cast onto the porous polymer matrix obtained in Example 2-1 by die-casting in order to generate a hybrid polymer electrolyte on both sides of a graphite anode.
  • Example 2-2 obtained in Example 2-2.
  • the resulting plate was cut so as to be 3 cm x 4 cm
  • Example 3-1 the polymer electrolyte solution was cast onto the porous polymer matrix obtained in Example 3-1 by die-casting in order to generate a hybrid polymer electrolyte on one side of a LiCoO 2 cathode.
  • Example 4 x 4 cm in size and then laminated. Terminals were welded on to the electrodes, and then the laminated plate was inserted into a vacuum casing. A 1M LiPF 6 solution in EC-DMC was injected into the casing, and then the casing was vacuum-sealed to fabricate a lithium secondary battery.
  • Example 4
  • Example 4-1 The processes in Examples 4-1 and 4-2 were applied to one side of a LiCoO 2 cathode instead of to both sides of a graphite anode, to fabricate a LiCoO 2 cathode coated with a hybrid polymer electrolyte on one side of it.
  • the LiCoO 2 cathode obtained in Example 4-3 was adhered onto both sides of the graphite anode obtained in Example 4-2 so as to face the hybrid polymer electrolytes to each other. The resulting plate was made into
  • Example 5 A 1 M LiPF 6 solution in EC-DMC was injected into the casing, and then the casing was vacuum-sealed to fabricate a lithium secondary battery.
  • Example 5 A 1 M LiPF 6 solution in EC-DMC was injected into the casing, and then the casing was vacuum-sealed to fabricate a lithium secondary battery.
  • DMA solution as a plasticizer, 0.5g of PAN (prepared by Polyscience Company, molecular weight of about 150,000), 2g of polyvinylidenedifluoride (Atochem Kynar 761 ) and 0.5g of PMMA (prepared by Polyscience Company) were added. The resulting mixture was blended for 12 hours and heated at
  • Example 5-1 the porous polymer matrix obtained in Example 5-1 by die-casting in order to fabricate a graphite anode coated with a hybrid polymer electrolyte on both sides of it.
  • the processes in Examples 5-1 and 5-2 were applied to one side of a LiCoO 2 cathode instead of to both sides of a graphite anode, to fabricate a LiCoO 2 cathode coated with a hybrid polymer electrolyte on one side of it.
  • the LiCoO 2 cathode obtained in Example 5-3 was adhered onto both sides of the graphite anode obtained in Example 5-2 so as to face the hybrid polymer electrolytes to each other. The resulting plate was made into
  • a 1 M LiPF 6 solution in EC-DMC was injected into the casing, and then the casing was vacuum-sealed to fabricate a lithium secondary battery.
  • Example 6-4 The LiCoO 2 cathode obtained in Example 6-3 was adhered onto both sides of the graphite anode obtained in Example 6-2 so as to face the hybrid polymer electrolytes to each other. The resulting plate was made into
  • a lithium secondary battery was fabricated by laminating electrodes and separator films in order of an anode, a PE separator film, a cathode, a
  • PE separator film and an anode inserting the resulting laminated plate into a vacuum casing, injecting a 1 M LiPF 6 solution in EC-DMC into the casing, and then finally vacuum-sealing the casing.
  • a lithium secondary battery was fabricated by laminating, in order, a graphite anode, an electrolyte, a Li CoO 2 cathode, an electrolyte and a graphite anode, welding terminals onto the electrodes, inserting the laminated plate into a vacuum casing, injecting a 1 M LiPF 6 solution in EC-DMC into the casing and then finally vacuum-sealing the casing.
  • Example 7 Charge/discharge characteristics of the lithium secondary batteries obtained in Examples 1 - 6 and Comparative Examples 1 and 2 were tested, and Figure 4 shows the results.
  • the tests for obtaining the charge/discharge characteristics were performed by a charge/discharge method of, after charging the batteries with a C/2 constant current and 4.2V constant voltage, discharging with a C/2 constant current, and the electrode capacities and cycle life based on the cathode were tested.
  • Figure 4 shows that the electrode capacities and cycle life of the lithium secondary batteries of Examples 1 - 6 were improved compared to the lithium secondary batteries of Comparative Examples 1 and 2.
  • the lithium secondary battery of Comparative Example 2 exhibited low capacities such as 87% at 1 C discharge and 56% at 2C discharge based on the value of C/5 discharge. Accordingly, it was discovered that the high rate discharge characteristic of the lithium secondary battery of Example 2 was better than that of the lithium secondary battery of Comparative Example 2.

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Abstract

La présente invention concerne un nouvel électrolyte polymère hybride, une pile secondaire au lithium contenant ledit électrolyte, et les procédés de fabrication correspondants. Plus spécifiquement, cette invention concerne l'électrolyte polymère hybride renfermant, d'une part, une matrice polymère poreuse sous forme de particules, de fibres ou d'un mélange correspondant d'un diamètre compris entre 1 et 3000 nm, d'autre part, des polymères et des solutions d'électrolyte organiques de sel de lithium dissous incorporées dans ladite matrice polymère poreuse. L'électrolyte polymère hybride présente des avantages, telles qu'une meilleure adhérence aux électrodes, une meilleure résistance mécanique, un meilleur rendement à des températures basses et élevées, une meilleure compatibilité avec des électrolytes organiques d'une pile secondaire au lithium, ledit électrolyte pouvant être utilisé dans la fabrication de piles secondaires au lithium.
PCT/KR2000/000513 2000-05-22 2000-05-22 Electrolyte polymere hybride fabrique par un procede de pulverisation, pile secondaire au lithium contenant cet electrolyte et procedes de fabrication correspondants WO2001091220A1 (fr)

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EP1422780A1 (fr) * 2002-10-30 2004-05-26 Nissan Motor Co., Ltd. Pile à polymère et procédé associé
CN111129578A (zh) * 2018-10-30 2020-05-08 三星电子株式会社 混杂电解质、各自包括其的电极和锂电池、及其制造方法
JP2021514108A (ja) * 2018-02-11 2021-06-03 中国科学院蘇州納米技術与納米倣生研究所Ｓｕｚｈｏｕ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｎａｎｏ−Ｔｅｃｈ Ａｎｄ Ｎａｎｏ−Ｂｉｏｎｉｃｓ（Ｓｉｎａｎｏ），Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ 固体電解質、並びにその調製方法及び応用
CN114824646A (zh) * 2022-03-21 2022-07-29 惠州锂威电子科技有限公司 一种复合油基隔膜及其制备方法和二次电池
CN116219562A (zh) * 2022-11-21 2023-06-06 盐城优和博新材料有限公司 一种超高分子量聚乙烯纤维的湿法纺丝方法及设备

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1422780A1 (fr) * 2002-10-30 2004-05-26 Nissan Motor Co., Ltd. Pile à polymère et procédé associé
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JP2021514108A (ja) * 2018-02-11 2021-06-03 中国科学院蘇州納米技術与納米倣生研究所Ｓｕｚｈｏｕ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｎａｎｏ−Ｔｅｃｈ Ａｎｄ Ｎａｎｏ−Ｂｉｏｎｉｃｓ（Ｓｉｎａｎｏ），Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ 固体電解質、並びにその調製方法及び応用
JP7083043B2 (ja) 2018-02-11 2022-06-09 中国科学院蘇州納米技術与納米倣生研究所 固体電解質、並びにその調製方法及び応用
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CN111129578A (zh) * 2018-10-30 2020-05-08 三星电子株式会社 混杂电解质、各自包括其的电极和锂电池、及其制造方法
CN111129578B (zh) * 2018-10-30 2024-06-04 三星电子株式会社 混杂电解质、各自包括其的电极和锂电池、及其制造方法
CN114824646A (zh) * 2022-03-21 2022-07-29 惠州锂威电子科技有限公司 一种复合油基隔膜及其制备方法和二次电池
CN116219562A (zh) * 2022-11-21 2023-06-06 盐城优和博新材料有限公司 一种超高分子量聚乙烯纤维的湿法纺丝方法及设备
CN116219562B (zh) * 2022-11-21 2024-01-19 盐城优和博新材料有限公司 一种超高分子量聚乙烯纤维的湿法纺丝方法及设备

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