WO2001091219A1 - Batterie secondaire au lithium, comprenant un film de separation polymere poreux, qui est produit selon un procede de pulverisation, et son procede de production - Google Patents

Batterie secondaire au lithium, comprenant un film de separation polymere poreux, qui est produit selon un procede de pulverisation, et son procede de production Download PDF

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Publication number
WO2001091219A1
WO2001091219A1 PCT/KR2000/000512 KR0000512W WO0191219A1 WO 2001091219 A1 WO2001091219 A1 WO 2001091219A1 KR 0000512 W KR0000512 W KR 0000512W WO 0191219 A1 WO0191219 A1 WO 0191219A1
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WIPO (PCT)
Prior art keywords
lithium secondary
secondary battery
separator film
porous polymer
polymeric
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PCT/KR2000/000512
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English (en)
Korean (ko)
Inventor
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/KR2000/000512 priority Critical patent/WO2001091219A1/fr
Publication of WO2001091219A1 publication Critical patent/WO2001091219A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—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
    • H01M10/05—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
    • H01M10/058—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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with 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
    • H01M10/05—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
    • H01M2300/0088—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 lithium secondary battery comprising a porous polymer separator film fabricated by a spray method, and to its fabrication method.
  • 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.
  • the early lithium secondary batteries were fabricated by using metallic lithium or a lithium alloy as an anode.
  • the cycle characteristic of the secondary battery using metallic lithium or a lithium alloy is lowered significantly due to dendrite formation on the anode as a result of repeated charging and discharging of the battery.
  • a lithium ion battery is proposed in order to solve the problem caused by the dendrite.
  • the lithium ion battery developed by SONY Company in Japan and widely used all over the world comprises a cathode active material, an anode active material, an organic electrolyte solution and a separator film.
  • the separator film functions to prevent 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 still has problems such as instability, intricacy of the fabrication process, restriction of battery shape and limitation of capacity. There have been attempts to solve those 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, 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 polymer electrolytes can be laminated in a flat-plate shape and its fabrication process is similar to the 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.
  • a polymer electrolyte of a gel type polyacrylonitrile (hereinafter referred to as "PAN") group was disclosed in U.S. Patent No. 5,219,679 to K. M. Abraham et al. and U.S. Patent No.5,240,790 to D. L. Chua et al.
  • the gel type PAN group polymer electrolyte is prepared by injecting an organic 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.
  • PVdF polyvinylidenedifluoride
  • PMMA polymethylmethacrylate
  • PVC polyvinylchloride
  • an object of the present invention is to provide a new lithium secondary battery having advantages of both a lithium ion battery and a lithium polymer battery.
  • Another object of the present invention is to provide a lithium secondary battery having good adhesion with electrodes, good mechanical strength, good low- and high-temperature characteristics, and good compatibility with an organic electrolyte solution used for a lithium secondary battery.
  • Figures 1a to 1c illustrate embodiments of a spray method by an electrostatic induction.
  • Figures 2a and 2b illustrate the fabrication of a porous polymer separator film 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 1-5 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 lithium secondary battery comprising a porous polymer separator film fabricated by a spray method, and to its fabrication method. More particularly, it relates to a lithium secondary battery comprising a cathode active material, an anode active material, an organic electrolyte solution in which a lithium salt is dissolved, and a porous polymer separator film, wherein the porous polymer separator film is characterized as being one fabricated by a spray method.
  • a porous polymer separator film fabricated by a spray method has a form in which particles or fibers, or a combination thereof with a diameter of 1-3000nm is built up three dimensionally. Due to the small diameter of the fibers, the ratio of surface area to volume and the void ratio are very high compared to those of a conventional separator film. Therefore, due to the high void ratio of the porous polymer separator film, 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 to fabricate batteries.
  • DBP which is used in the conventional process of Bellcore Co. is not used, there is no problem of residual DBP.
  • the process for fabrication of a porous polymer separator film by a spray method comprises a step of obtaining a polymeric melt or polymeric solution and a step of fabricating a separator film using the obtained polymeric melt or polymeric solution.
  • the step of obtaining a polymeric melt or polymeric solution can be achieved by heating/melting a polymer or polymer mixture, or dissolving a polymer or polymer mixture in a suitable organic solvent. If a polymer is dissolved in an organic solvent, the possible organic solvent used are not particularly limited on condition that they can dissolve the polymer substantially and be applicable to a spray method. In addition, 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 separator by a spray method.
  • an organic solvent examples 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-dimethylacetamide, N-methyl-2-pyrrolidone, polyethylenesulfolane, tetraethylene glycol dimethyl ether, acetone, alcohol or mixtures thereof.
  • the dissolving step will now be described in more detail.
  • the polymer and an organic solvent are mixed in a 1 :1-1 :20 ratio by weight and the resulting mixture is stirred at a temperature range of 20-150°C for 30 minutes to 24 hours to obtain a clear polymeric solution.
  • the temperature and stirring time may be changed in accordance with the types of polymers.
  • the examples of the polymer used for forming the porous polymer separator film 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), polypropylene-oxide, polyvinylacetate, polyacrylonitrile, poly(acrylonitrile-co-methylacrylate), polymethylmethacrylate, poly(methylmethacrylate-co-ethylacrylate), poly-vinylchloride, poly(vinylidenechloride-co-acrylonitrile), polyvinylldenedifluoride, poly(vinylidenefluoride-co-hexafluoropropylene) or mixtures thereof.
  • the step of fabricating a separator film with the obtained polymeric melt or polymeric solution can be achieved by filling the polymeric melt or polymeric solution into a barrel of a spray machine and then spraying the polymeric melt or polymeric solution onto a metal plate or Mylar film electrode using a nozzle at a suitable rate.
  • the polymeric melt or polymeric solution can be sprayed directly onto the electrode.
  • 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.
  • 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 a static electricity (Figure 1a).
  • Another method is that an additional electrode for electrostatic induction is located between the nozzle and an electrode to charge polymeric melt or polymeric solution sprayed by the nozzle ( Figure 1b).
  • Another method combines the above two methods ( Figure 1c).
  • FIGS. 2a and 2b illustrate the fabrication of a porous polymer separator film using a spray machine.
  • Figure 2a illustrates the fabrication method by spraying all together using a nozzle to get a highly porous polymer separator film
  • Figure 2b illustrates the fabrication method by spraying sporadically and continually using separately installed nozzles to get a multi-layered porous polymer separator film.
  • the thickness of the porous polymer separator film can be adjusted by changing the spray rate and spray time.
  • the thickness of the separator film ranges from 1 ⁇ m to 100 ⁇ m, more preferably, from 5 ⁇ m to 70 ⁇ m, and most preferably, from 10 ⁇ m to 50 ⁇ m.
  • the diameter of the polymer forming the porous polymer separator film is adjusted in the range of 1 nm - 3000 nm. A more preferable diameter range is 10 nm - 1000nm, and the most preferable diameter range is 50 nm - 500 nm.
  • the porous polymer separator film fabricated by a spray method can comprise two or more polymers and can be fabricated by the following methods.
  • One method is by heating/melting two or more polymers or dissolving two or more polymers in an organic solvent, filling the resulting melts or solution into a barrel of a spray machine and then spraying the melts or solution using a nozzle to fabricate the porous polymer separator film.
  • Another method is by heating/melting each of two or more polymers separately or dissolving two or more polymers in an organic solvent respectively, filling the resulting melts or solutions into the separate barrels of a spray machine, and then spraying the respective melts or solutions using nozzles to fabricate the porous polymer separator film.
  • the porous polymer separator film of the present invention can additionally include a filling agent in order to improve the porosity and mechanical strength.
  • a filling agent are 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 , Al 2 O 3 , PTFE or mixtures thereof. It is preferable that the content of the filling agent is below 20% by weight of the porous separator film.
  • Lithium salts used in the lithium secondary battery of the present invention are the same as generally used in the lithium secondary battery, such as LiPF 6 , LiCIO 4 , LiAsF 6 , LiBF and LiCF 3 SO 3 , and among them LiPF 6 is more preferable.
  • Examples of an organic solvent used in the organic electrolyte solution are 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, butylenecarbonate, ⁇ -butyrolactone, 1 ,2-dimethoxyethane, 1 ,2-dimethoxy-ethane, dimethylacetamide, tetrahydrofuran or mixtures thereof, can be added to the above organic solvent.
  • Typical anode and cathode active materials used in the lithium secondary battery in the prior art can be used in the lithium secondary battery of the present invention.
  • the anode active material include graphite, cokes, hard carbon, tin oxide and lithiated compounds thereof, metallic lithium, and lithium alloys.
  • the cathode active material are LiClO 2 , LiNiO 2 , LiNiCoO 2 , LiMn 2 O , V 2 O 5 or V 6 O ⁇ 3 .
  • the lithium secondary battery of the present invention can further comprise conducting materials and binding agents.
  • the anode and cathode of the lithium secondary battery are typically fabricated by mixing a certain amount of active materials, conducting materials and binding agents with an organic solvent, casting the resulting mixture on both sides of a copper or aluminum foil plate grid, and then drying and compressing all of them.
  • FIG. 3a illustrates a process to fabricate a battery, comprising inserting a porous polymer separator film 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 process to fabricate a lithium secondary battery, comprising coating a porous polymer separator film by spraying polymeric melts or polymeric solutions directly onto both sides of a cathode or anode, adhering the electrode having opposite polarity to the coated electrode onto the porous polymer separator film, 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 process to fabricate a lithium secondary battery, comprising coating a porous polymer separator film by spraying polymeric melts or polymeric solutions directly onto both sides of one of two electrodes and onto one side of the other electrode respectively, adhering the electrodes closely together as the porous polymer separator films 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.
  • Example 2 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 casing, and the casing was then finally vacuum-sealed to give a lithium secondary battery.
  • Example 2 A 1 M LiPF 6 solution in EC-DMC was injected into the casing, and the casing was then finally vacuum-sealed to give a lithium secondary battery.
  • Example 2-2 A LiCoO 2 cathode was adhered onto the porous polymer separator film obtained in Example 2-1. The resulting plate was 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 casing, and the casing was then finally vacuum-sealed to give a lithium secondary battery.
  • Example 3 3-1) 20g of polyvinylidenefluoride (Kynar 761) was added to 100g of dimethylacetamide, and the mixture was stirred at room temperature for 24 hours to give a clear polymeric solution. The resulting polymeric solution was filled into the barrel of a spray machine and sprayed on one side of a LiCoO 2 cathode using a nozzle at a constant rate, to fabricate a LiCoO 2 cathode coated with a porous polymer separator film of 50 ⁇ m thickness on one side of it.
  • Example 3-1 The LiCoO 2 cathode obtained in Example 3-1 was adhered to both sides of the graphite anode obtained in Example 2-1 so as to face the porous polymer separator films to each other.
  • the resulting plate was made into one body by heat lamination at 110°C and then cut so as to be 3 cm x 4 cm in size and 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 the casing was then finally vacuum-sealed to give a lithium secondary battery.
  • Example 4-2 The process described In Example 4-1 was 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 porous polymer separator films on one side of it.
  • Example 4-3 The LiCoO 2 cathode obtained in Example 4-2 was adhered to both sides of the graphite anode obtained in Example 4-1 so as to face the porous polymer separator films to each other.
  • the resulting plate was made into one body by heat lamination at 110°C and then cut so as to be 3 cm x 4 cm in size and laminated. Terminals were welded on to the electrodes and then the laminated plate was inserted into a vacuum casing.
  • a 1M LiPF ⁇ solution in EC-DMC was injected into the casing, and the casing was then finally vacuum-sealed to give a lithium secondary battery.
  • Example 5-1 A LiCoO 2 cathode was adhered onto a porous polymer separator film obtained in Example 5-1 and the resulting plate was cut so as to be 3 cm x 4 cm in size and laminated. Terminals were welded on to the electrodes and then the laminated plate was inserted into a vacuum casing. A 1 M LiPF 6 solution in EC-DMC was injected into the casing, and the casing was then finally vacuum-sealed to give a lithium secondary battery.
  • a lithium secondary battery was fabricated by laminating electrodes and separator films in order of anode, PE separator film, cathode, PE separator film and 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 of a graphite anode, the electrolyte, a LiCoO 2 cathode, the electrolyte and a graphite anode, welding terminals on to the electrodes, inserting the resulting laminated plate into a vacuum casing, injecting a 1M LiPF ⁇ solution in EC-DMC into the casing, and then finally vacuum-sealing the casing.
  • the lithium secondary battery of Comparative Example 2 shows low capacities such as 87% at 1C discharge and 56% at 2C discharge based on the value at C/5 discharge. Accordingly, it was discovered that the high rate discharge characteristic of the lithium secondary battery of Example 2 is better than that of the lithium secondary battery of Comparative Example 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une batterie secondaire au lithium et son procédé de production. Cette invention concerne notamment une batterie secondaire au lithium, qui comprend un film de séparation polymère poreux, ainsi que son procédé de production. Le procédé de production dudit film de séparation poreux consiste a) à faire fondre au moins un polymère ou à dissoudre au moins un polymère avec des solvants organiques, afin d'obtenir au moins une matière fondue polymère ou au moins une solution polymère; b) à ajouter la matière fondue polymère ou la solution polymère dans des récipients d'une machine à pulvériser; et c) à pulvériser la matière fondue polymère ou la solution polymère sur un substrat, par utilisation d'une buse, afin de former un film de séparation poreux. La batterie secondaire au lithium selon cette invention présente avantageusement une meilleure adhésion aux électrodes, une bonne résistance mécanique, une meilleure efficacité à basses et hautes températures, ainsi qu'une meilleure compatibilité avec des électrolytes organiques d'une batterie secondaire au lithium.
PCT/KR2000/000512 2000-05-22 2000-05-22 Batterie secondaire au lithium, comprenant un film de separation polymere poreux, qui est produit selon un procede de pulverisation, et son procede de production WO2001091219A1 (fr)

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US7585587B2 (en) * 2002-12-27 2009-09-08 Bridgestone Corporation Separator for non-aqueous electrolyte cell
US7790320B2 (en) 2004-10-22 2010-09-07 Celgard Llc Battery separator with Z-direction stability
US7829242B2 (en) 2004-10-21 2010-11-09 Evonik Degussa Gmbh Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries
US20110281150A1 (en) * 2004-02-09 2011-11-17 Lg Chem, Ltd. Organic/inorganic composite porous film and electrochemical device prepared thereby
EP2851974A4 (fr) * 2012-05-17 2015-11-04 Toyota Motor Co Ltd Procédé de fabrication d'une cellule
US9570727B2 (en) 2004-10-22 2017-02-14 Celgard Llc Battery separator with Z-direction stability
CN108511665A (zh) * 2018-04-26 2018-09-07 广东永邦新能源股份有限公司 一种用于太阳能锂电池的耐温隔膜及太阳能锂电池
CN109546205A (zh) * 2018-06-13 2019-03-29 上海大学 采用有机无机复合凝胶聚合物电解质的锂离子电池的制备方法
CN111916617A (zh) * 2019-05-10 2020-11-10 湖南农业大学 一种纤维素基功能化隔膜及其制备方法和应用

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US8163441B2 (en) 2004-10-21 2012-04-24 Evonik Degussa Gmbh Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries
US7829242B2 (en) 2004-10-21 2010-11-09 Evonik Degussa Gmbh Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries
KR101060859B1 (ko) * 2004-10-22 2011-08-31 셀가드 엘엘씨 Ｚ－방향 안정성을 갖는 전지 분리막
US7790320B2 (en) 2004-10-22 2010-09-07 Celgard Llc Battery separator with Z-direction stability
US9570727B2 (en) 2004-10-22 2017-02-14 Celgard Llc Battery separator with Z-direction stability
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CN108511665A (zh) * 2018-04-26 2018-09-07 广东永邦新能源股份有限公司 一种用于太阳能锂电池的耐温隔膜及太阳能锂电池
CN108511665B (zh) * 2018-04-26 2021-05-04 广东永邦新能源股份有限公司 一种用于太阳能锂电池的耐温隔膜及太阳能锂电池
CN109546205A (zh) * 2018-06-13 2019-03-29 上海大学 采用有机无机复合凝胶聚合物电解质的锂离子电池的制备方法
CN111916617A (zh) * 2019-05-10 2020-11-10 湖南农业大学 一种纤维素基功能化隔膜及其制备方法和应用

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