WO2002061872A1 - Polyelectrolyte multicouche et batterie secondaire au lithium renfermant celui-ci - Google Patents

Polyelectrolyte multicouche et batterie secondaire au lithium renfermant celui-ci Download PDF

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WO2002061872A1
WO2002061872A1 PCT/KR2001/000129 KR0100129W WO02061872A1 WO 2002061872 A1 WO2002061872 A1 WO 2002061872A1 KR 0100129 W KR0100129 W KR 0100129W WO 02061872 A1 WO02061872 A1 WO 02061872A1
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group
polymer
polymer electrolyte
electrolyte
lithium secondary
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PCT/KR2001/000129
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English (en)
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Kyung-Suk Yun
Byung-Won Cho
Won-Il Cho
Hyung-Sun Kim
Un-Sek Kim
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Korea Institute Of Science And Technology
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Priority to PCT/KR2001/000129 priority Critical patent/WO2002061872A1/fr
Publication of WO2002061872A1 publication Critical patent/WO2002061872A1/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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • 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
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • 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
    • 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 multi-layered polymer electrolyte and a lithium secondary battery comprising the same. More specifically, the multi- layered polymer electrolyte of the present invention comprises: A) a separator film layer formed of a polymer electrolyte, PP, PE, PVdF or a non-woven fabric; B) a gelled polymer electrolyte layer which is cast onto one or both surfaces of the separator film layer, comprising: a) 5 - 90 wt % of PAN group polymer; b) 5 - 80 wt % of polymer selected from PVdF group polymers and PMMA group polymers; c) 5 - 80 wt % of polymer selected from the group consisting of PVC group polymers and PVdF group polymers; and
  • a lithium secondary battery has been proposed as one energy source in the aspect that the higher integration of energy is possible because the molecular weight of lithium used in a lithium secondary battery is very low, but its density is relatively high.
  • a lithium ion battery was presented in order to solve the problem of dendrite generation.
  • the lithium ion battery developed by SONY Company in Japan and widely used all over the world comprises an anode active material, a cathode active material, an organic electrolyte solution and a separator film.
  • the separator film functions to prevent an internal short-circuiting of the lithium ion battery caused by contacting of a cathode and an anode, and to permeate ions.
  • Separator films generally used at the present time are polyethylene (hereinafter referred to as "PE”) or polypropylene (hereinafter referred to as "PP”) separator films.
  • PE polyethylene
  • PP polypropylene
  • the lithium ion battery using the PE or PP separator film has problems such as instability of a battery, intricacy of its fabrication process, restriction on battery shape and limitation of high capacity. There have been attempts to solve the above-mentioned problems, but there is no clear result until now.
  • 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 stacked 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. 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 in the polymer matrix. It has the advantages 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
  • PVC polyvinylchloride
  • U.S. Patent No. 5,681 ,357, U.S. Patent No. 5, 688,293 and U.S. Patent No. 5,834,135M to Oliver et al. disclose a fabrication method of secondary battery, comprising the steps of placing a separator film obtained by casting a solution, in which a polymer such as PVdF, etc. is dissolved in an organic solvent or an organic electrolyte solution, onto a PP or PE separator film used for a lithium ion battery between an anode and a cathode, making the resultant into one body by a certain heat lamination process and then injecting an organic electrolyte solution into the body.
  • UV ultraviolet
  • a resistance is increased compared with the one in which an organic electrolyte solution is impregnated into the PE separator film because a polymer electrolyte is injected into the pores of the PE separator film. Accordingly, charge and discharge characteristics of the lithium secondary batteries are lowered. In addition, its adhesive force with an electrode is inferior, and therefore, a fabrication of a battery becomes intricate.
  • an object of the present invention is to provide an electrolyte for a lithium secondary battery which is superior in adhesion with electrodes, compatibility with an organic electrolyte solution for a lithium secondary battery, mechanical strength and permeability, etc.
  • Another object of the present invention is to provide a lithium secondary battery comprising said electrolyte.
  • the above and other objects of the present invention can be achieved by providing a multi-layered polymer electrolyte in which a gelled polymer electrolyte showing good adhesion with electrodes, good compatibility with an organic electrolyte solution for a lithium secondary battery, high mechanical strength and permeability, etc. is cast onto one or both surfaces of a separator film, for example, a polymer electrolyte, PP, PE, PVdF, non- woven fabric, etc.
  • a separator film for example, a polymer electrolyte, PP, PE, PVdF, non- woven fabric, etc.
  • a multi-layered electrolyte comprising:
  • Figure 1a and 1b are cross-sectional views illustrating a multi-layered polymer electrolyte according to the present invention.
  • Figure 2a and 2b are cross-sectional views illustrating a lithium secondary battery comprising the multi-layered polymer electrolyte according to the present invention.
  • Figures 3a - 3c are process flow diagrams illustrating fabrication of lithium secondary batteries according to the present invention.
  • Figure 4 is a graph showing charge and discharge characteristics of the lithium secondary batteries of Examples 1 - 6 and Comparative Examples 1 and 2.
  • Figure 5a is a graph showing high-temperature characteristics of the lithium secondary battery obtained in Example 2
  • Figure 5b is a graph showing high-temperature characteristics of the lithium secondary battery obtained in Comparative Example 2.
  • Figure 6a is a graph showing high-rate discharge characteristics of the lithium secondary battery obtained in Example 2
  • Figure 6b is a graph showing high-rate discharge characteristics of the lithium secondary battery obtained in Comparative Example 2.
  • the present invention relates to a multi-layered polymer electrolyte and a lithium secondary battery comprising the same.
  • Said multi-layered polymer electrolyte comprises:
  • the PAN group polymers used in the present invention are superior in adhesion with electrodes and ion conductivity.
  • the PVdF group and the PMMA group polymers are superior in compatibility with an organic electrolyte.
  • the PVC group and the PVdF group polymers are superior in mechanical strength. Accordingly, the present invention provides a polymer electrolyte showing superior characteristics.
  • the polymer electrolyte of the present invention can be prepared by casting a combination of polymers having good adhesion with electrodes, good compatibility with an organic electrolyte solution for a lithium secondary battery and high mechanical strength onto one or both surfaces of a separator film.
  • the PAN group polymer is selected from the group consisting of polyacrylonitrile and poly(acrylonithle-methylacrylate)
  • the PMMA group polymer is selected from the group consisting of polymethylmethacrylate, poly(methylmethacrylate-co-ethylacrylate) and poly(methylmethacrylate-co-methacrylic acid)
  • the PVdF group polymer is selected from the group consisting of polyvinylidene difluoride, poly(vinylidene difluoride-hexafluoropropylene)
  • the PVC group polymer is selected from the group consisting of polyvinylchloride and poly(vinyl chloride-co- acrylonitrile).
  • a mixing ratio of a polymer mixture can be varied according to the characteristics required.
  • a ratio of the polymer component a) is increased.
  • compatibility with an organic electrolyte solution is required, a ratio of the polymer component b) is increased.
  • a ratio of the polymer component c) is increased.
  • Lithium salts used in the present invention are the same as generally used in the lithium secondary batteries, such as LiPF 6 , LiCI0 4 , LiAsF 6 , LiBF 4 and LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N. Among them, LiPF 6 is more preferable.
  • Examples of an organic solvent used in the organic electrolyte solution may be 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
  • tetrahydrofuran or mixtures thereof can be added to the above organic solvent.
  • the polymer electrolyte according to the present invention can further comprise a plasticizer, a porous filler, etc.
  • a plasticizer may include N,N-dimethylacetamide
  • the amount of the plasticizer used for the polymer electrolyte is preferably adjusted in the range of 100 - 2000 wt % of the total polymer mixture.
  • the filler examples 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, an organic filler, a polymer filler and mixtures thereof.
  • the filler improves porosity and mechanical strength of the electrolyte.
  • the content of the filler is no more than 20 wt % of the total polymer mixture.
  • a preparation method of the gelled polymer electrolyte layer comprising: a) a step of sufficiently mixing (generally, for 12 hours) 5 - 90 wt % of PAN group function-l polymers, 5 - 80 wt % of function-ll polymers selected from the group consisting of PVdF group and PMMA group polymers and 5 - 80 wt % of function-Ill polymers selected from the group consisting of PVC and PVdF group polymers, and optionally with 100 - 2000 wt % of a plasticizer, 100 - 2000 wt % of an organic electrolyte solution and/or no more than 20 wt % of a porous filler (for example, SiO 2 , etc.) to the above polymer mixture, respectively; b) a step of obtaining a homogeneous solution having a viscosity of 10,000 - 60,000 cps by heating the resulting homogeneous mixture at 80 -
  • Solubility Parameters written by A.F.M. Baton et al. Hilderbrand Parameters are 23.3 - 31.5 MPa 1 2 in PAN, 18.6 - 26.3 MPa 1 2 in PMMA, 12 - 30 MPa 1/2 in P(VdF-HPP) which is a PVdF group polymer, 19.1 - 22.1 MPa 1 2 in PVC. Accordingly, by identifying an suitable plasticizer, solvent and blending condition, a homogeneous gelled polymer electrolyte layer can be prepared.
  • Figure 1a and 1b illustrate cross-sectional structures of a multi-layered polymer electrolyte according to the present invention, in which a gelled polymer electrolyte prepared by the above-described method is cast onto one or both surfaces of a separator film, such as a polymer electrolyte, PP, PE, PVdF and a non-woven fabric, etc.
  • a separator film such as a polymer electrolyte, PP, PE, PVdF and a non-woven fabric, etc.
  • Figure 1a shows a cross- sectional structure of a double-layered polymer electrolyte in which a gelled polymer electrolyte according to the present invention is cast onto one surface of a separator film such as a polymer electrolyte having good mechanical strength, PP, PE, PVdF or a non-woven fabric.
  • Figure 1b shows a cross- sectional structure of a triple-layered polymer electrolyte in which a gelled polymer electrolyte according to the present invention is cast onto both surfaces of a separator film such as a polymer electrolyte having good mechanical strength, PP, PE, PVdF or a non-woven fabric.
  • a separator film such as a polymer electrolyte having good mechanical strength, PP, PE, PVdF or a non-woven fabric.
  • Figure 2a shows a lithium secondary battery having a mono-cell structure in which the multi-layered polymer electrolyte is located between an anode and a cathode.
  • Figure 2b shows a cross-section of a lithium secondary battery having a bi-cell structure.
  • Fabrication processes of lithium secondary batteries using the multi- layered polymer electrolyte are as shown in Figures 3a - 3c. It will now be described in more detail.
  • a solution of gelled polymer electrolyte is cast onto one or both surfaces of a separator film such as a polymer electrolyte, PP, PE, PVdF, a non-woven fabric or the like at a thickness of 1 - 50 ⁇ m, to
  • the obtained multi- layered polymer electrolyte is adhered to both surfaces of the anode or inserted between an anode and a cathode and then adhered, and the
  • the obtained polymer electrolyte is closely adhered to both surfaces of an anode.
  • the doubled-layered polymer electrolyte and anode are made into one body by a lamination process.
  • the resultant is cut so as to be in a predetermined size and then stacked it with a cathode in a predetermined size, to fabricate a lithium secondary battery.
  • a solution of a gelled polymer electrolyte is cast onto both surfaces of a separator film such as a polymer electrolyte, PP, PE, PVdF, a non-woven fabric or the like to obtain a triple-layered polymer electrolyte.
  • the obtained polymer electrolyte is adhered to both surfaces of an anode, and then the triple-layered polymer and anode are made into one body by a lamination process.
  • the resultant is then cut so as to be in predetermined size and then stacked it with a cathode in a predetermined size, to fabricate a lithium secondary battery.
  • a solution of a gelled polymer electrolyte is cast onto both surfaces of a separator film such as a polymer electrolyte, PP, PE, PVdF, a non-woven fabric or the like to obtain a triple-layered polymer electrolyte.
  • the obtained polymer electrolyte is adhered to both surfaces of an anode, and then a cathode is adhered onto the outside parts of the polymer electrolyte.
  • the resultant is then made into one body in a by-cell structure which consists of a cathode/a triple-layered polymer electrolyte/an anode/a triple-layered polymer electrolyte/a cathode by a lamination process.
  • the resulting plate is cut and then stacked, to fabricate a lithium secondary
  • anode and cathode used in lithium secondary batteries are fabricated as in the conventional art by mixing a certain amount of active materials, conducting materials, binders and an organic solvent, casting the resulting mixture onto both sides of a copper or aluminum foil plate grid, and then drying and rolling.
  • an anode consists of one material selected from the group consisting of graphite, cokes, hard carbon, tin oxide and lithiated compounds thereof, metallic lithium or lithium alloys.
  • a cathode consists of one 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 .
  • An organic electrolyte solution used in the fabrication of the battery is a solution selected from the group consisting of a lithium salt-dissolved ethylene carbonate-dimethyl carbonate (EC-DMC) solution, lithium salt- dissolved ethylene carbonate-diethyl carbonate (EC-DEC) solution, lithium salt-dissolved ethylene carbonate-ethyl methyl carbonate(EC-EMC) solution, lithium salt-dissolved ethylene carbonate-propylene carbonate (EC-PC) solution and mixtures thereof, and solutions in which at least one solvent selected from the group consisting of methyl acetate (MA), methyl propionate
  • EC-DMC lithium salt-dissolved ethylene carbonate-dimethyl carbonate
  • EC-DEC lithium salt- dissolved ethylene carbonate-diethyl carbonate
  • EC-EMC lithium salt-dissolved ethylene carbonate-ethyl methyl carbonate
  • EC-PC lithium salt-dissolved ethylene carbonate-propylene carbonate
  • ⁇ -BL butyrolactone
  • DME 1,2-dimethoxyethane
  • DMA dimethylacetamide
  • a plate, a punched plate, an expanded plate and a porous plate can be used as a copper and aluminum grid. If an organic electrolyte solution is injected after stacking, it is preferable to use a punched plate, an expanded plate and a porous plate for efficient electrolyte impregnation.
  • the obtained polymeric solution was cast onto one surface of a PE separator film by a die-casting method to prepare a double-layered polymer electrolyte.
  • the prepared triple-layered polymer electrolyte was closely adhered onto a graphite anode and then joined with the graphite anode by a lamination process. The resultant was cut
  • LiCoO 2 cathode of 2.9 cm x 3.9 cm in size Terminals were welded onto the
  • a LiCoO 2 cathode was then adhered onto both surfaces of the obtained plate.
  • the resultant was cut so as to be 3 cm x 4 cm in size, and then stacked in a bi-cell structure. Terminals were welded onto the electrodes, and then the cell was inserted into a vacuum casing.
  • a 1M LiPF 6 solution in EC-EMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery.
  • the prepared triple-layered polymer electrolyte was closely adhered onto both surfaces of a graphite anode, a LiCoO 2 cathode was adhered onto the both surfaces of the obtained plate, and then the resultant were joined together by a lamination process.
  • the obtained was cut so as to be 3 cm x 4 cm in size and then stacked it in a bi-cell structure. Terminals were welded onto the electrodes and then the cell was inserted into a vacuum casing.
  • a 1 M LiPF 6 solution in EC-EMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery.
  • Example 4 To a mixture of 1g of polyacrylonitrile (available from Polyscience Co., molecular weight of 150,000), 2g of polyvinylidenedifluoride (Atochem Kynar 761) and 1g of polymethylmethacrylate (available from Polyscience Co., molecular weight of 100,000), 25g of 1 M LiPF 6 solution in EC-DMC was added. The resulting mixture was mixed for 12 hours and then heated at 130°C for one hour to give a clear polymeric solution having a viscosity of about 3000 which was suitable for casting. The obtained polymeric solution was cast onto both surfaces of a PE separator film by a die-casting method to prepare a triple-layered polymer electrolyte.
  • polyacrylonitrile available from Polyscience Co., molecular weight of 150,000
  • the prepared triple-layered polymer electrolyte was closely adhered onto both surfaces of a graphite anode and then joined with the graphite anode by a lamination process.
  • the resultant was cut so as to be 3 cm x 4 cm in size, and then it was alternately stacked with a LiCoO 2 cathode of 2.9 cm x 3.9 cm in size. Terminals were welded onto the electrodes, and then the cell was inserted into a vacuum casing.
  • a 1 M LiPF 6 solution in EC-EMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery.
  • Example 5 To a mixture of 1g of polyacrylonitrile (available from Polyscience Co., molecular weight of 150,000), 2g of polyvinylidenedifluoride (Atochem Kynar 761) and 0.1g of TiO 2 , 25g of 1 M LiPF 6 solution in EC-DMC was added. The resulting mixture was mixed for 12 hours and then heated at 130°C for one hour to give a clear polymeric solution having a viscosity of about 3000 which was suitable for casting. The obtained polymeric solution was cast onto both surfaces of a PP separator film by a die-casting method to prepare a triple- layered polymer electrolyte.
  • the prepared triple-layered polymer electrolyte was closely adhered onto both surfaces of a graphite anode and then joined with the graphite anode by a lamination process.
  • the resultant was cut so as to be 3 cm x 4 cm in size, and then it was alternately stacked with a LiCoO 2 cathode of 2.9 cm x 3.9 cm in size. Terminals were welded onto the electrodes and then the cell was inserted into a vacuum casing.
  • a 1M LiPF 6 solution in EC-EMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery.
  • the prepared double-layered polymer electrolyte was closely adhered onto both surfaces of a graphite anode and then joined with the graphite anode by a lamination process.
  • the resultant was cut so as to be 3 cm x 4 cm in size, and then it was alternately stacked with a LiCoO 2 cathode of 2.9 cm x 3.9 cm in size. Terminals were welded onto the electrodes and then the cell was inserted into a vacuum casing.
  • a 1 M LiPF 6 solution in EC-EMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery.
  • the prepared double-layered polymer electrolyte was closely adhered onto both surfaces of a graphite anode and then joined with the graphite anode by a lamination process.
  • the resultant was cut so as to be 3 cm x 4 cm in size, and then it was alternately stacked with a LiCoO 2 cathode of 2.9 cm x 3.9 cm in size. Terminals were welded onto the electrodes and then the cell was inserted into a vacuum casing.
  • a 1 M LiPF 6 solution in EC-EMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery.
  • the resultant was cut so as to be 3 cm x 4 cm in size, and then it was alternately stacked with a LiCoO 2 cathode of 2.9 cm x 3.9 cm in size. Terminals were welded onto the electrodes and then the cell was inserted into a vacuum casing. A 1M LiPF 6 solution in EC-EMC was injected into the vacuum casing, and then the vacuum casing was vacuum-sealed to fabricate a lithium secondary battery.
  • Comparative Example 1 Electrodes and separator films were stacked in order of anode, PE separator film, cathode, PE separator film and anode, terminals were welded onto the electrodes. The obtained cell was inserted into a vacuum casing, a 1 M LiPF 6 solution in EC-EMC was injecting a into the casing, and then the casing was vacuum-sealed, to fabricate a lithium secondary battery.
  • Terminals were welded onto the electrodes, and then the obtained cell was inserted into a vacuum casing.
  • a 1 M LiPF 6 solution in EC-EMC was injected into the casing, and then the casing was vacuum-sealed, to fabricate a lithium secondary battery.
  • Electrode capacities and cycle life based on the cathode of the lithium secondary batteries obtained in Examples 1 - 8 and Comparative Examples 1 and 2 were examined. These tests were performed with a charge/discharge method of charging the batteries with a C/2 constant current and 4.2V constant voltage, and then discharging with a C/2 constant current.
  • Figure 4 shows the results. As shown in Figure 4, the electrode capacities and cycle life of the lithium secondary batteries of Examples 1 - 8 were superior to the lithium secondary batteries of Comparative Examples 1 and 2. In addition, the lithium secondary batteries of Examples 1 - 8 of the present invention exhibited superior characteristics in that their electrode capacities were not reduced regardless of repeated charge and discharge.
  • the multi-layered polymer electrolyte of the present invention can improve the electrode capacities and cycle life of the lithium secondary batteries. Such improvement seems to be resulted from which surface resistance was reduced because adhesive force between the electrodes and the multi-layered polymer electrolyte were good, and an ionic conductivity of the polymer electrolyte was also good.
  • Example 10 High rate discharge characteristics of the lithium secondary batteries obtained in Example 2 and Comparative Example 2 were examined. The examination was performed with a charge/discharge method of charging the lithium batteries with a C/2 constant current and 4.2 V constant voltage, and then discharging them while changing the constant current into C/5, C/2.1C and 2C.
  • Figures 5a and 5b illustrate the results. As shown in Figures 5a and 5b, the lithium secondary battery of Example 1 exhibited capacities of 95% and 90% at 1C and 2C discharge, respectively, based on the value of 0.2C discharge (see Figure 5a). However, the lithium secondary battery of Comparative Example 2 exhibited low capacities of 87% and 56% at 1C and 2C discharge, respectively. Accordingly, it was discovered that the high rate discharge characteristic of the lithium secondary battery of Example 2 was superior to that of the lithium secondary battery of Comparative Example 2.
  • the multi-layered polymer electrolyte according to the present invention is superior in adhesive force and mechanical strength to those of the conventional polymer electrolyte.
  • a lithium secondary battery showing good performances in low- and high-temperature characteristics, high rate discharge characteristic, capacity of battery, cycle life, stability, etc. can be provided. Accordingly, the lithium secondary battery can be applied in various industrial fields such as small electronic appliances, communicating apparatus and electric automobiles, etc.

Abstract

L"invention concerne un polyélectrolyte multicouche et une batterie secondaire au lithium renfermant celui-ci, caractérisé en ce que le polyélectrolyte multicouche comprend A) une couche de séparation formée de polyélectrolyte, PP, PE, PVdF ou d"un non-tissé, la couche de séparation présentant deux surfaces; B) au moins une couche de polyélectrolyte gélifiée disposée sur au moins une surface de la couche de séparation comprenant a) 5 à 90 % en poids de polymère à base de PAN; b) 5 à 80 % en poids d"au moins un polymère choisi dans le groupe comprenant un polymère à base de PVdF et un polymère à base de PMMA; et c) 5 à 80 % en poids d"au moins un polymère choisi dans le groupe comprenant un polymère à base de PVC et un polymère à base de PVdF; et C) une solution d"électrolyte organique dans laquelle un sel de lithium est dissous dans un solvant.
PCT/KR2001/000129 2001-01-31 2001-01-31 Polyelectrolyte multicouche et batterie secondaire au lithium renfermant celui-ci WO2002061872A1 (fr)

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FR2841045A1 (fr) * 2002-06-17 2003-12-19 Electricite De France Accumulateur au lithium
EP1598896A1 (fr) * 2004-04-24 2005-11-23 Electronics and Telecommunications Research Institute Électrolyte à composite polymère contenant une charge inorganique conductrice d'ions lithium pour une battérie secondaire au lithium et méthode de fabrication d'un tel électrolyte
WO2006077325A2 (fr) * 2005-01-24 2006-07-27 Batscap Electrolyte bicouche pour batterie au lithium
CN100365080C (zh) * 2003-08-01 2008-01-30 阿托菲纳公司 基于pvdf的ptc涂料及其在自我调节加热体系的应用
EP2068384A1 (fr) * 2007-11-28 2009-06-10 Samsung SDI Co., Ltd. Électrodes négatives pour batteries au lithium rechargeables, leur procédé de préparation, et batterie au lithium rechargeable les comprenant
US8003262B2 (en) * 2003-08-06 2011-08-23 Mitsubishi Chemical Corporation Nonaqueous electrolyte solution secondary battery separator having defined ratio of average pore diameter to maximum pore diameter and nonaqueous electrolyte solution secondary battery using the same
CN102694203A (zh) * 2012-05-29 2012-09-26 深圳华粤宝电池有限公司 一种凝胶聚合物电解质的制备方法
EP2581977A1 (fr) * 2011-10-11 2013-04-17 Samsung SDI Co., Ltd. Batterie au lithium rechargeable
US8524394B2 (en) 2007-11-22 2013-09-03 Samsung Sdi Co., Ltd. Negative electrode and negative active material for rechargeable lithium battery, and rechargeable lithium battery including same
US8529801B2 (en) 2007-10-02 2013-09-10 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, and negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same
US20140057155A1 (en) * 2012-08-23 2014-02-27 Robert Bosch Gmbh Separator for rechargeable lithium battery
CN107394265A (zh) * 2017-07-21 2017-11-24 中科（淮安）新能源技术开发有限公司 双溶剂分步转相制备聚甲基丙烯酸甲酯凝胶电解质微孔膜的方法
US9911984B2 (en) 2014-06-17 2018-03-06 Medtronic, Inc. Semi-solid electrolytes for batteries
CN107814433A (zh) * 2017-11-01 2018-03-20 陕西科技大学 重金属废水电解处理用聚合物膜修饰电极及其制备方法
CN108682863A (zh) * 2018-06-11 2018-10-19 佛山腾鲤新能源科技有限公司 一种锂电池聚合物凝胶电解质
CN108987650A (zh) * 2018-07-20 2018-12-11 河北金力新能源科技股份有限公司 电池用隔膜及其制备方法和电池
CN109346648A (zh) * 2018-10-15 2019-02-15 苏州清陶新能源科技有限公司 一种阻燃凝胶陶瓷隔膜及其制备方法
US10333173B2 (en) 2014-11-14 2019-06-25 Medtronic, Inc. Composite separator and electrolyte for solid state batteries
US10587005B2 (en) 2016-03-30 2020-03-10 Wildcat Discovery Technologies, Inc. Solid electrolyte compositions
US10903520B2 (en) 2017-06-20 2021-01-26 Lg Chem, Ltd. Multi-layer structure polymer solid electrolylte and all solid-state battery comprising the same
WO2022057189A1 (fr) * 2020-09-15 2022-03-24 江苏时代新能源科技有限公司 Batterie à semi-conducteur, module de batterie, bloc-batterie, et dispositif associé

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WO2003107469A2 (fr) * 2002-06-17 2003-12-24 Electricite De France Service National Accumulateur au lithium
WO2003107469A3 (fr) * 2002-06-17 2004-11-11 Electricite De France Accumulateur au lithium
FR2841045A1 (fr) * 2002-06-17 2003-12-19 Electricite De France Accumulateur au lithium
CN100365080C (zh) * 2003-08-01 2008-01-30 阿托菲纳公司 基于pvdf的ptc涂料及其在自我调节加热体系的应用
US8597836B2 (en) 2003-08-06 2013-12-03 Mitsubishi Chemical Corporation Nonaqueous electrolyte solution secondary battery separator having filler and controlled impurities
US8003262B2 (en) * 2003-08-06 2011-08-23 Mitsubishi Chemical Corporation Nonaqueous electrolyte solution secondary battery separator having defined ratio of average pore diameter to maximum pore diameter and nonaqueous electrolyte solution secondary battery using the same
USRE44264E1 (en) * 2003-12-30 2013-06-04 Electronics And Telecommunications Research Institute Lithium cationic single-ion conducting filler-containing composite polymer electrolyte for lithium secondary battery and method of manufacturing the same
US7399556B2 (en) 2003-12-30 2008-07-15 Electronics And Telecommunications Research Institute Lithium cationic single-ion conducting filler-containing composite polymer electrolyte for lithium secondary battery and method of manufacturing the same
EP1598896A1 (fr) * 2004-04-24 2005-11-23 Electronics and Telecommunications Research Institute Électrolyte à composite polymère contenant une charge inorganique conductrice d'ions lithium pour une battérie secondaire au lithium et méthode de fabrication d'un tel électrolyte
WO2006077325A2 (fr) * 2005-01-24 2006-07-27 Batscap Electrolyte bicouche pour batterie au lithium
WO2006077325A3 (fr) * 2005-01-24 2007-07-05 Batscap Sa Electrolyte bicouche pour batterie au lithium
FR2881275A1 (fr) * 2005-01-24 2006-07-28 Batscap Sa Electrolyte bicouche pour batterie au lthium
US8546022B2 (en) 2005-01-24 2013-10-01 Batscap Bilayer electrolyte for a lithium battery
US8431266B2 (en) 2005-01-24 2013-04-30 Batscap Bilayer electrolyte for a lithium battery
US8529801B2 (en) 2007-10-02 2013-09-10 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, and negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same
US8592083B2 (en) 2007-11-22 2013-11-26 Samsung Sdi Co., Ltd. Negative electrode and negative active material for rechargeable lithium battery, and rechargeable lithium battery including same
US8524394B2 (en) 2007-11-22 2013-09-03 Samsung Sdi Co., Ltd. Negative electrode and negative active material for rechargeable lithium battery, and rechargeable lithium battery including same
JP2009135104A (ja) * 2007-11-28 2009-06-18 Samsung Sdi Co Ltd リチウム２次電池用負極およびこれを含むリチウム２次電池
EP2068384A1 (fr) * 2007-11-28 2009-06-10 Samsung SDI Co., Ltd. Électrodes négatives pour batteries au lithium rechargeables, leur procédé de préparation, et batterie au lithium rechargeable les comprenant
US8734989B2 (en) 2007-11-28 2014-05-27 Samsung Sdi Co., Ltd. Negative electrode for rechargeable lithium battery and rechargeable lithium battery including the same
EP2581977A1 (fr) * 2011-10-11 2013-04-17 Samsung SDI Co., Ltd. Batterie au lithium rechargeable
US10461358B2 (en) 2011-10-11 2019-10-29 Samsung Sdi Co., Ltd. Rechargeable lithium battery
CN102694203A (zh) * 2012-05-29 2012-09-26 深圳华粤宝电池有限公司 一种凝胶聚合物电解质的制备方法
CN102694203B (zh) * 2012-05-29 2014-11-05 深圳华粤宝电池有限公司 一种凝胶聚合物电解质的制备方法
US20140057155A1 (en) * 2012-08-23 2014-02-27 Robert Bosch Gmbh Separator for rechargeable lithium battery
US10700331B2 (en) * 2012-08-23 2020-06-30 Samsung Sdi Co., Ltd. Separator for rechargeable lithium battery
US9911984B2 (en) 2014-06-17 2018-03-06 Medtronic, Inc. Semi-solid electrolytes for batteries
US10727499B2 (en) 2014-06-17 2020-07-28 Medtronic, Inc. Semi-solid electrolytes for batteries
US11437649B2 (en) 2014-11-14 2022-09-06 Medtronic, Inc. Composite separator and electrolyte for solid state batteries
US10333173B2 (en) 2014-11-14 2019-06-25 Medtronic, Inc. Composite separator and electrolyte for solid state batteries
US10587005B2 (en) 2016-03-30 2020-03-10 Wildcat Discovery Technologies, Inc. Solid electrolyte compositions
US10903520B2 (en) 2017-06-20 2021-01-26 Lg Chem, Ltd. Multi-layer structure polymer solid electrolylte and all solid-state battery comprising the same
CN107394265A (zh) * 2017-07-21 2017-11-24 中科（淮安）新能源技术开发有限公司 双溶剂分步转相制备聚甲基丙烯酸甲酯凝胶电解质微孔膜的方法
CN107394265B (zh) * 2017-07-21 2020-06-02 中科（淮安）新能源技术开发有限公司 双溶剂分步转相制备聚甲基丙烯酸甲酯凝胶电解质微孔膜的方法
CN107814433B (zh) * 2017-11-01 2020-09-08 陕西科技大学 重金属废水电解处理用聚合物膜修饰电极及其制备方法
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