WO2001091221A1 - Electrolyte polymere composite fabrique par un procede de pulverisation, accumulateur au lithium comprenant ledit elecrolyte polymere et leurs procedes de fabrication - Google Patents

Electrolyte polymere composite fabrique par un procede de pulverisation, accumulateur au lithium comprenant ledit elecrolyte polymere et leurs procedes de fabrication Download PDF

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Publication number
WO2001091221A1
WO2001091221A1 PCT/KR2000/000514 KR0000514W WO0191221A1 WO 2001091221 A1 WO2001091221 A1 WO 2001091221A1 KR 0000514 W KR0000514 W KR 0000514W WO 0191221 A1 WO0191221 A1 WO 0191221A1
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polymer electrolyte
composite polymer
solution
poly
lithium secondary
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PCT/KR2000/000514
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English (en)
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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/KR2000/000514 priority Critical patent/WO2001091221A1/fr
Publication of WO2001091221A1 publication Critical patent/WO2001091221A1/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
    • H01M10/05—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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0431—Cells with wound or folded electrodes
    • 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
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • 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
    • 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
    • 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
    • H01M2300/0088—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • 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 composite polymer electrolyte, a lithium secondary battery using the same, and to 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. Recently, a gel or hybrid type polymer electrolyte having an ionic conductivity above 10 "3 S/cm at room temperature has been developed.
  • 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 PAN-group polymer matrix.
  • A. S. Gozdz et al. discloses a polymer electrolyte of hybrid type polyvmylidenedifluoride (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 in the polymer matrix. It has advantages in that its compatibility with an 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 fabricated in the atmosphere because the organic electrolyte solution is injected later.
  • PMMA polymer electrolyte
  • PVC polyvinylchloride
  • Figures 1a to 1c illustrate embodiments of a spray method by an electrostatic induction.
  • Figures 2a and 2b illustrate fabrication methods of a polymer electrolyte matrix using a spray machine.
  • FIGS 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 composite polymer electrolyte comprising a polymer electrolyte matrix in particulate or fibrous form, or a combination thereof having a diameter of 1-3000nm and a polymer electrolyte incorporated into the polymer electrolyte matrix.
  • the present invention relates to a composite polymer electrolyte obtained by dissolving a polymer in a mixture of a plasticizer and an organic electrolyte solution, fabricating a polymer electrolyte 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.
  • composite polymer electrolyte means an electrolyte in which a polymer electrolyte is incorporated into a polymer electrolyte matrix.
  • Polymer electrolyte matrix means a matrix comprising a polymer, an organic solvent and a lithium salt.
  • the polymer electrolyte matrix can be fabricated by dissolving a polymer for forming the matrix in a mixture of an organic electrolyte solution dissolving a lithium salt and a plasticizer, and then spraying the obtained solution (hereinafter, it is referred to as a "polymeric solution") onto a metal plate, a Mylar film or electrodes.
  • Polymer electrolyte solution means a solution which dissolves a polymer to be incorporated into the polymer electrolyte matrix in a mixture of an organic electrolyte solution and a plasticizer.
  • Polymer electrolyte generically means an organic electrolyte solution and a polymer incorporated into the polymer electrolyte matrix.
  • a polymer electrolyte matrix fabricated by a spray method has a form in which particles or fibers, or a combination thereof with a diameter of 1- 3000nm are built up three-dimensionally. Due to the small diameter, 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 amount 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 fabrication equipment and processes can be simplified, and the fabrication time can be shortened because the final product is fabricated in the form of a film directly, and accordingly the economic efficiency is high and as well the fabrication of the film is easy.
  • the particles or fibers, or combination thereof are built up to form a structure having pores of effective size, closed pores can not be formed structurally, and there is no possibility of closing the pores during the lamination process applied in order to fabricate batteries.
  • DBP which is used in the conventional process of Bellcore Co. for forming pores, is not used, there is no problem of residual DBP.
  • the examples of the polymer for forming the polymer electrolyte matrix 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), polyvinylldenedifluoride, poly(vinylidenefluoride-co- hexafluoropropylene) or mixtures thereof.
  • electrolyte matrix it is preferable to be 1 ⁇ m - 100 ⁇ m, more preferably 5 ⁇ m
  • fibers forming the polymer electrolyte 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 polymers incorporated into the polymer electrolyte matrix function 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, poly- ethyleneoxide, polyethylenesuccinate, polyethylenesulfide, poly(oxy- methylene-oligo-oxyethylene), polypropyleneoxide, polyvinylacetate, polyacrylonitrile, poly(acrylonitrile-co-methylacrylate), polymethylmethacrylate, poly(methylmethacrylate-co-ethylacrylate), polyvinylchloride, poly(vinylidene- chloride-co-acrylonitrile), polyvinylldenedifluoride, poly(vinylidenefluoride-co- he
  • Examples of an organic electrolyte solution used in the polymer electrolyte matrix and the polymer electrolyte can include ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate or mixtures thereof.
  • an additional solvent selected from the group consisting of methyl acetate, methyl propionate, ethyl acetate, ethyl propionate, butylene
  • lithium salt used for the organic electrolyte solution can include LiPF 6 , LiCIO 4 , LiAsF 6 , LiBF 4 or UCF 3 SO 3 . Among them LiPF 6 is more preferable.
  • the lithium salt is not particularly limited to the above-mentioned examples.
  • the examples of the plasticizer used for the fabrication of the polymer electrolyte matrix and the polymer electrolyte solution can include propylene carbonate, butylene carbonate, 1 ,4-butyrolactone, diethyl carbonate, dimethyl carbonate, 1 ,2-dimethoxyethane, 1 ,3-dimethyl-2-imidazolidinone, dimethyl- sulfoxide, ethylene carbonate, ethylmethyl carbonate, N,N-dimethyl- formamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, polyethylene- sulforane, tetraethylene glycol dimethyl ether, acetone, alcohol or mixtures thereof.
  • the kind of plasticizer is not particularly limited to the above examples.
  • the composite polymer electrolyte of the present invention can additionally include a filling agent in order to improve the porosity and mechanical strength.
  • a filling agent can include TiO 2 , BaTiO 3 ,
  • the content of the filling agent is typically below 20% by weight of the total composite polymer electrolyte.
  • the present invention relates to a fabrication method of a composite polymer electrolyte.
  • the method comprises a step of obtaining a polymeric solution in which a polymer is dissolved in a mixture of a plasticizer and an organic electrolyte solution, a step of fabricating a polymer electrolyte matrix by a spray method, and a step of injecting a polymer electrolyte solution into the fabricated polymer electrolyte matrix.
  • the step of obtaining a polymeric solution can be achieved by dissolving a polymer in a mixture of a plasticizer and an organic electrolyte solution and then raising the temperature of the mixture to obtain a clear polymeric solution.
  • the possible plasticizer used for obtaining the polymeric solution is not particularly limited on condition that it can dissolve the polymer substantially and be applicable to a spray method.
  • a plasticizer which might influence on the characteristics of the battery can even be used, because it is almost completely removed while fabricating a polymer electrolyte matrix by a spray method.
  • the step of fabricating a polymer electrolyte matrix can be achieved by a spray method.
  • the polymer electrolyte matrix can be obtained by filling the polymeric solution for forming the polymer electrolyte matrix into a barrel of a spray machine and then spraying the polymeric solution using a nozzle at a constant rate onto a metal plate or Mylar film.
  • the polymeric solution can be sprayed directly onto electrodes.
  • the thickness of the polymer electrolyte matrix can be adjusted by changing a spray speed and time, and the preferable thickness range is 1 - 100 ⁇ m as mentioned before.
  • the polymeric solution when spraying the polymeric solution using a nozzle, the polymeric solution can be sprayed by electrostatic induction.
  • Embodiments of spraying by electrostatic induction can 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 solution coming out from the nozzle has an electrostatic charge ( Figure 1a).
  • a variety of methods can be applied in spraying a polymeric solution using a nozzle. Examples can include a method of spraying the polymeric solutions all together, and another method of installing the spraying nozzles separately and then spraying the respective polymeric solutions sporadically and continually to get a multi-layered polymer electrolyte matrix.
  • Figures 2a and 2b illustrate the fabrication of a polymer matrix using a spray machine.
  • Figure 2a illustrates the fabrication method by spraying all together using a nozzle to get a polymer matrix
  • Figure 2b illustrates the fabrication method by spraying sporadically and continually using separately installed nozzles to get a multi-layered polymer matrix.
  • the polymer electrolyte matrix using two or more polymers can be obtained by the following methods.
  • One method is that two or more polymers are dissolved in a mixtures of a suitable plasticizer and organic electrolyte solution, and the obtained solution is filled into a barrel of a spray machine and sprayed using a nozzle, to fabricate the polymer electrolyte matrix.
  • Another method is that two or more polymers are dissolved respectively in a mixture of a suitable plasticizer and organic electrolyte solution, and the obtained solutions are filled into separate barrels of a spray machine respectively and sprayed using different nozzles, to fabricate the polymer electrolyte matrix.
  • the composite polymer electrolyte is obtained by injecting a polymer electrolyte solution into the polymer electrolyte matrix fabricated by a spray method.
  • a polymer is dissolved in a mixture of an organic electrolyte solution and a plasticizer to give a polymer electrolyte solution, and the obtained polymer electrolyte solution is injected into the polymer electrolyte matrix by die-casting.
  • the weight ratio of a polymer, plasticizer and organic electrolyte solution used for the polymer electrolyte solution is preferably in the range of 1 : 1 - 20 : 1 - 20, and the kinds are the same as mentioned before.
  • FIG. 3a illustrates a fabrication process for a battery comprising inserting a composite polymer electrolyte, obtained by incorporating a polymer electrolyte solution into a polymer electrolyte 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.
  • Figure 3b illustrates a fabrication process for a battery comprising coating a composite polymer electrolyte onto both sides of a cathode or anode; adhering an electrode having opposite polarity to the coated electrode onto the composite 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 composite polymer electrolyte onto both sides of one of two electrodes and onto one side of the other electrode respectively; adhering the electrodes closely together so the composite 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 for the lithium secondary battery are fabricated in the same way as in the conventional method, such as by mixing a certain 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.
  • the anode active material consists of a material selected from the group consisting of graphite, cokes, hard carbon, tin oxide and lithiated compounds thereof.
  • the cathode active material is a material selected from the group consisting of LiCIO 2 , LiNiO 2 , LiNiCoO 2 , LiMn 2 O 4 , V 2 O 5 and V 6 O 13 .
  • Metallic lithium or lithium alloys can also be used for the anode in the present invention.
  • Example 1-1 the polymer electrolyte solution was cast onto the polymer electrolyte matrix fabricated in Example 1-1 by die-casting, to fabricate a composite polymer electrolyte in which the polymer electrolyte solution was incorporated into the polymer electrolyte matrix.
  • Example 1-3 Fabrication of a lithium secondary battery
  • the composite polymer electrolyte fabricated in Example 1-2 was inserted between a graphite anode and a LiCoO 2 cathode, and the resulting
  • Example 2 A 1M LiPF 6 solution in EC-DMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery.
  • Example 2 A 1M LiPF 6 solution in EC-DMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery.
  • electrolyte matrix film having a thickness of 50 ⁇ m.
  • Example 2-2 the polymer electrolyte solution was cast onto the polymer electrolyte matrix obtained in Example 2-1 by die-casting, to generate a composite polymer electrolyte on both sides of the graphite anode 2-3) A LiCoO 2 cathode was adhered onto the composite polymer electrolyte obtained in Example 2-2. The resulting plate was cut so as to be
  • Example 3 A 1M LiPF 6 solution in EC-DMC was injected into the vacuum casing, and the casing was then vacuum-sealed to fabricate a lithium secondary battery.
  • Example 3 A 1M LiPF 6 solution in EC-DMC was injected into the vacuum casing, and the casing was then vacuum-sealed to fabricate a lithium secondary battery.
  • Example 3-1 the polymer electrolyte solution was cast onto the polymer electrolyte matrix obtained in Example 3-1 by die-casting, to generate a composite polymer electrolyte on one side of a LiCo0 2 cathode.
  • Example 3-2 The LiCoO 2 cathode obtained in Example 3-2 was adhered onto both sides of the graphite anode obtained in Example 2-2 so as to face the composite polymer electrolytes to each other.
  • the resulting plate was made
  • Example 4 4-2) 2g of an oligomer of polyethylene glycol diacrylate (hereinafter referred to as "PEGDA", prepared by Aldrich Company, molecular weight of 742) and 3g of polyvinylidenedifluoride (Atochem Kynar 761) were added to 20g of 1 M LiPF 6 solution in EC-DMC. The resulting mixture was blended enough to be homogeneous for 3 hours and then cast onto the polymer electrolyte matrix obtained in Example 4-1.
  • PEGDA polyethylene glycol diacrylate
  • Atochem Kynar 761 polyvinylidenedifluoride
  • An ultraviolet lamp having a power of 100W was irradiated onto the polymer electrolyte matrix for about 1.5 hours in order to induce polymerization of the oligomer, to fabricate a composite polymer electrolyte in which a polymer electrolyte was incorporated into a polymer electrolyte matrix.
  • Example 4-3 The composite polymer electrolyte fabricated in Example 4-2 was inserted between a graphite anode and a LiCoO 2 cathode, and then the
  • resulting plates were cut so as to be 3 cm x 4 cm in size and laminated.
  • Terminals were welded on to the electrodes, and the laminated plate was inserted into a vacuum casing.
  • a 1 M LiPF 6 solution in EC-DMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery. Comparative Examples
  • 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 1M LiPF 6 solution in EC-DMC into the casing, and then vacuum-sealing the casing.
  • a lithium secondary battery was fabricated by laminating, in order, a graphite anode, an electrolyte, a LiCoO 2 cathode, an electrolyte and a graphite anode, welding terminals on to the electrodes, inserting the resulting laminated plate into a vacuum casing, injecting a 1M LiPF 6 solution in EC-DMC into the casing, and then finally vacuum-sealing the casing.
  • Example 1 Battery of Example 1 had an outstanding characteristic of 91 % even at -10°C.
  • Example 7 High rate discharge characteristics of the lithium secondary batteries of Example 1 and Comparative Example 2 were tested, and Figures 6a and 6b illustrate the results (wherein Figure 6a is for Example 1 and Figure 6b is for Comparative Example 2).
  • the tests for obtaining the high rate discharge characteristics of the lithium secondary batteries were performed by a charge/discharge method of, after charging the lithium batteries with a C/2 constant current and 4.2 V constant voltage, discharging while varying the constant current to C/5, C/2,1C and 2C.
  • the lithium secondary battery of Example 1 exhibited capacities such as 99% at C/2 discharge, 96% at 1C discharge and 90% at 2C discharge based on the value of C/5 discharge.
  • 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 1 was better than that of the lithium secondary battery of Comparative Example 2.

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Abstract

L'invention concerne un nouvel électrolyte polymère composite, un accumulateur au lithium comprenant ledit électrolyte polymère composite et leurs procédés de fabrication. L'invention porte, notamment, sur l'électrolyte polymère composite comprenant une matrice d'électrolyte polymère poreuse constituée de particules, de fibres ou de mélange de celles-ci possédant un diamètre de 1 à 3 000 nm, des polymères et des solutions électrolytiques organiques dissoutes dans du sel de lithium, incorporées à la matrice polymère poreuse. L'électrolyte polymère composite de l'invention est avantageux en ce qu'il adhère mieux aux électrodes, qu'il possède une meilleure résistance mécanique, qu'il est plus efficace aux températures basses et élevées, qu'il présente une meilleure compatibilité avec les électrolytes organiques de l'accumulateur au lithium et qu'il peut être appliqué à la fabrication d'accumulateurs au lithium.
PCT/KR2000/000514 2000-05-22 2000-05-22 Electrolyte polymere composite fabrique par un procede de pulverisation, accumulateur au lithium comprenant ledit elecrolyte polymere et leurs procedes de fabrication WO2001091221A1 (fr)

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WO2008093125A1 (fr) * 2007-02-02 2008-08-07 G24 Innovations Limited Injection de fluides
CN107069082A (zh) * 2017-01-16 2017-08-18 中南大学 一种糖类改性导锂聚合物/无机杂化电解质及其应用
CN109860720A (zh) * 2019-01-30 2019-06-07 浙江锋锂新能源科技有限公司 一种复合电解质层的制备方法和固态电池
CN111799514A (zh) * 2020-07-11 2020-10-20 浙江锋锂新能源科技有限公司 一种固态电池用正极片或负极片的制备方法、固态电池用正极片或负极片、固态电池

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