WO2003012896A1 - Separateur poreux et procede de fabrication - Google Patents

Separateur poreux et procede de fabrication Download PDF

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Publication number
WO2003012896A1
WO2003012896A1 PCT/KR2001/001825 KR0101825W WO03012896A1 WO 2003012896 A1 WO2003012896 A1 WO 2003012896A1 KR 0101825 W KR0101825 W KR 0101825W WO 03012896 A1 WO03012896 A1 WO 03012896A1
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WO
WIPO (PCT)
Prior art keywords
polymer
porous
separator
layer
binder
Prior art date
Application number
PCT/KR2001/001825
Other languages
English (en)
Inventor
Hea-Tak Kim
Hyo-Rang Kang
Seok-Gyun Chang
Jin-Young Hong
Chang-Wee Kwon
Original Assignee
Newturn Energy Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Newturn Energy Co., Ltd. filed Critical Newturn Energy Co., Ltd.
Publication of WO2003012896A1 publication Critical patent/WO2003012896A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a porous separator applicable to an electro chemical cell and a method of manufacturing the same, and more particularly, to a porous separator on which a polymer binder component is dispersed at the surface portion thereof and a method of manufacturing the same.
  • An electric reduction of an active material of a cathode and an oxidation of an active material of an anode is induced during discharging of a charged cell or battery, and as the result electrons flow from the anode to the cathode through an external circuit for generating current.
  • An electrolytic layer is present between the cathode and anode to prevent an internal flow of the electrons, which is called as an electric short, and to impart an ion transmission between the cathode and anode.
  • the electrolytic layer should be made from a non-electron conductive material and transmit ions during discharging for a primary battery and during charging and discharging for a secondary battery.
  • the electrolytic layer should be electro chemically and chemically stable with respect to the cathode and anode.
  • an electrolytic layer is manufactured by filling a porous layer called as a separator with aqueous or non-aqueous electrolyte containing salts.
  • a porous layer called as a separator
  • porous polyethylene, polypropylene, rayon paper, pulp paper, glass fiber paper, and the like can be used.
  • the separator is positioned as a porous free standing film between the cathode and anode.
  • the separator is commonly manufactured by stretching a plastic film through repeating heating and cooling, or by extracting a soluble plasticizer or a filter from the plastic film, or through a plasma oxidation of the plastic film.
  • U.S. Pat. Nos. 5,691,005 and 5,597,659 disclose a method of using a separator matrix by impregnating pores of a separator with a gel electrolyte having an ionic conductivity.
  • the separator should be porous, chemically stable, and flexible, thin and economic and have a good mechanical strength. These characteristics are essential in improving the cell capacity and rate capability in a winding-type or stacking-type cell. Meantime, an electrode and an electrolyte should make a uniform contact in order to obtain a good cell performance. When the contact is not uniform, the electro chemical reaction at the electrode becomes non-uniform and the capacity and cyclelife is reduced. Generally, when the polyolefin porous separator is used, the contact between the electrode and the separator is kept through a physical pressure. For the cell having the winding-type structure, the contact between the electrode and the separator is kept through a winding tension and for the Prismatic winding cell, an additional pressure by an external can is applied. However, when the contact between the electrode and the separator is kept only through a physical pressure, the shape of the cell is limited and therefore, a cell having various structures and areas cannot be manufactured.
  • the interface between the electrode and the electrolytic layer can be kept uniformly without any physical pressure because the gel or polymer electrolyte has an adhesive strength to the electrode.
  • Various methods for manufacturing the gel has been suggested. A laminating method of the polymer electrolyte through heating, a gelling method after impregnating a battery including a porous separator with an electrolytic solution which can form the gel, etc. can be illustrated.
  • a light and thin battery can be manufactured because the interface between the electrode and the electrolytic layer is kept stable and an energy density per weight and/or volume can be improved when comparing with a battery manufactured by using a metal can such as an aluminum pouch as for an external wrapper.
  • Japanese Patent Laid-Open Publication No. Hei 1-089054 discloses a method of adhering a cathode and anode onto a porous separator after coating a binder resin solution onto the porous separator. According to this method, the electrodes are adhered to the separator coated with the binder resin solution before an evaporation of a solvent and the solvent is evaporated at a temperature range of about 80°C or less. After evaporating the solvent, pores are formed at the resin layer and a binding layer having a porous structure is manufactured.
  • the preparation of the electrolyte and the adhering process of the electrode should be continuously implemented.
  • the adhering strength and the minute structure of the binding layer changes according to the evaporating degree of the solvent, a continuous manufacture of cells having a uniform structure is difficult.
  • U.S. Pat. Nos. 5,691,005 Mitsubishi Electric Corp.
  • 5,597,659 Mitsubishi Electric Corp.
  • some disadvantages are as follows. The electrolytic solution is evaporated and the physical properties of the separator manufactured by this method changes during storing. In addition, the cell should be manufactured within a drying room.
  • Japanese Patent Laid-Open Publication No. Hei 10-162802 discloses a cell manufactured by impregnating a non-woven fabric or an insulating porous film with a liquid polymer material base on polyacrylonitrile to manufacture a separator and then positioning thus obtained separator between a cathode and anode.
  • U.S. Pat. Nos. 5,853,916 (Motorola), 5,716,421 (Motorola), 5,834,135 (Motorola), 5,681,357 (Motorola) and 5,688,293 (Motorola) disclose a separator composed of a non-gelling porous layer and a gelling polymer layer and a secondary battery manufactured by using the same. In this case, a mechanical strength is accomplished and a short induced from a contact of the cathode and anode is prevented by the non-gelling porous separator layer as a non-active material which has a low affinity to an electrolytic solution.
  • the gelling layer positioned at one or both surface of the porous separator has a good affinity to the electrolytic solution and imparts an adhesive power to the electrode.
  • the gelling layer is formed through coating onto the separator, and so, the electrolytic solution is impregnated into the cell through diffusion into the gelling layer.
  • a polymer binder component such as PVdF is sprayed onto an electrode and then, a porous separator is compressed with heat to adhere the electrode and separator.
  • the binder component present at the contacting surface of the electrode and the separator facilitates a good adhering strength between them.
  • the spraying of the binder component onto the electrode might induce a non-uniform surface of an electrode.
  • the sprayed material might be present at the inner portion of the electrode as well as at the surface portion of the porous electrode.
  • Another object of the present invention is to provide a method of manufacturing a cell by which an adhering between a separator and an electrode is advantageous through employing the above-described porous separator.
  • Still further another object of the present invention is to provide an electro chemical cell having a high capacitance and a good lifetime characteristic through employing the above-described porous separator.
  • a porous separator comprising a porous polymer layer and a polymer binder substantially uniformly dispersed on 1-80% range of a surface portion of the porous polymer layer.
  • a porous polymer layer which may be used in the present invention, a porous polyolefin layer, a porous polyvinylidene fluoride layer, a rayon paper, a pulp paper, a porous polytetrafluoroethylene layer, a polyester non-woven fabric, a glass fiber paper, a porous inorganic layer etc. may be mentioned. These may be used alone or in combination thereof.
  • the other object of the present invention is accomplished by a method of manufacturing a porous polymer comprising the steps of coating a solution containing a polymer binder onto a porous polymer layer and removing a solvent.
  • the coating method a spraying method, a dipping method, a doctor blade method, a silk screen printing, an ink jet printing, etc. can be applied.
  • the further another object of the present invention is accomplished by a method of manufacturing an electro chemical cell of an energy storage system. A solution containing a polymer binder is coated onto a porous polymer layer. Then, a solvent is removed to manufacture a porous separator. Then, the porous separator is attached onto an electrode.
  • the still further another object of the present invention is accomplished by an electro chemical cell comprising a cathode, an anode positioned from the cathode with a predetermined distance and a porous separator provided between the cathode and anode.
  • the porous separator includes a porous polymer layer and a polymer binder substantially uniformly dispersed on a surface portion of the porous polymer layer.
  • the electro chemical cell also includes an electrolyte which could not dissolve the polymer binder.
  • the porous separator including a porous polymer layer and a polymer binder component uniformly dispersed on the surface of the porous polymer layer is used for the manufacture of an electro chemical cell.
  • Various kinds of cells having various shapes can be advantageously manufactured and an impregnation of an electrolyte is advantageous. Further, adhering strength between an electrode and a separator is improved to heighten a capacity and improve a cyclelife characteristic of thus manufactured cell.
  • FIGS. IA & IB illustrate a separator on which a binder is dispersed according to the present invention, in which FIG. 1 A is a schematic planar view and FIG. IB is a schematic cross-sectional view;
  • FIGS. 2A-2D illustrate structures of electro chemical cells using a separator according to the present invention, in which FIG. 2A corresponds to a unit cell, FIG. 2B corresponds to a bi-cell, FIG. 2C corresponds to an integrated cell of unit cells and FIG. 2D corresponds to an integrated cell of bi-cells;
  • FIG. 3 is a graph illustrating a cycle characteristic of a battery manufactured by using an electrode according to Example 1 ;
  • FIG. 4 is a graph illustrating a cycle characteristic of a battery manufactured by using an electrode according to Example 2; and FIG. 5 is a graph illustrating a cycle characteristic of a battery manufactured by using an electrode according to Example 3.
  • the separator suggested by the present invention includes a porous polymer layer and a polymer binder dispersed on the surface of the porous polymer.
  • the porous polymer layer has a good mechanical strength as a separator used for a general energy storage system, and also has minute pores therein so as to be filled with an electrolyte to accomplish an ionic conductive characteristic.
  • the polymer binder dispersed on the surface of the porous polymer layer is attached to an electrode and the porous polymer layer to keep a stable contact between the electrode and the porous separator.
  • the polymer binder material adheres to the electrode at a room temperature or under a heated condition, and the adhered state is kept after an impregnation of a cell with an electrolyte.
  • the porous separator has a mechanical strength and an electro chemical stability, and is impregnated with an electrolyte.
  • FIGS. IA & IB illustrate a separator on which a binder is dispersed according to the present invention, in which FIG. 1 A is a schematic planar view and FIG. IB is a schematic cross-sectional view.
  • a polymer binder 12 is uniformly dispersed on a porous polymer layer 10 and space is formed between the polymer binders 12.
  • the polymer binder material is not uniformly coated onto the surface of the separator however, the polymer binder material is present on the surface of the separator through a dispersion state. Since the polymer binder material is partially dispersed on the surface of the separator, a space is provided after adhering the electrode and the separator through the binder. Through the space formed between the electrode and the separator, an electrolyte can be impregnated into the separator and the electrode.
  • the porous polymer layer used in the present invention includes a generally used polymer/separator used for a battery and a capacitor.
  • the porous polymer layer should have a good mechanical strength to prevent an electric short due to an electric contact between a cathode and an anode and an electro chemical and thermal stability.
  • an electrolyte should be advantageously impregnated into the porous polymer layer.
  • the polymer layer used for the present invention includes all of the separators generally used for a battery and a capacitor.
  • a porous polyolefin layer preferably, a porous polyvinylidene fluoride layer, a rayon paper, a pulp paper, a porous polytetrafluoroethylene layer, a polyester non-woven fabric, a glass fiber paper and a porous inorganic layer can be used.
  • the polymer binder material a material which could not be dissolved into an electrolyte and has a good adhering strength with the porous polymer layer and the electrode and an electro chemical and thermal stability, may be used.
  • the polymer binder material includes all of the binders used for an electrode for a general battery and capacitor (condenser).
  • polymer material used for a polymer electrolyte also can be used as for the polymer binder material.
  • a butadiene-based rubber of polymer material including a polyacrylonitrile-butadiene rubber (NBR), a polystyrene-butadiene rubber (SBR), a poly (styrene-butadiene-styrene) rubber (SBS), an acrylonitrile-butadiene-styrene rubber (ABS) and polybutadien; a synthetic or natural rubber including a polydimethyl siloxane, polyisoprene, polychloroprene, polyisobutylene and ethylene-propylene rubber; an acryl-based resin including poly (alkyl acrylate), poly (alkyl methacrylate), poly (alkyl ethacrylate), a copolymer thereof and a mixture thereof; a polyester-based polymer including polyethylene oxide, polyoxymethylene, polypropylene oxide, a copolymer thereof, a blend thereof; a polyvinylether-based polymer including polyvinyl
  • a copolymer thereof and a mixture thereof also can be used. More preferably, the rubber-based polymer, acryl-based resin, fluoride-based polymer and chloride-based polymer can be used.
  • the polymer binder solution a solution in which the polymer is completely dissolved in a solvent or a dispersion in which the polymer is minutely dispersed in the solution can be used.
  • the polymer chain is mixed in a molecular scale with the solvent according to the solubility of the polymer component with respect to the solvent.
  • concentrated and minute particles of the polymer component are present in the solution. The size of the particles does not exceed lOO m.
  • the polymer component When the polymer is completely dissolved into the solution to prepare the polymer binder solution, the polymer component should have a high solubility with respect to the solvent. In addition, it is preferable that the coated solvent is easily removed by vacuum or heat. When the polymer component is dispersed into a solution, the solution is required to have a good dispersion degree with respect to the polymer component, even though the solution could not completely dissolve the polymer component. When a selection of the solution having the required property is difficult, a surfactant could be added to assist the dispersion of the polymer into the solution.
  • the dispersion of the polymer is possible when a polarity difference between the polymer and a solvent is not small.
  • Solvents having both non-polar and polar parts such as ethanol, isopropyl alcohol, etc. are appropriately used because these solvents can disperse both non-polar and polar polymers.
  • the surfactants almost all the surfactants including anionic surfactant, cationic surfactant, neutral surfactant and zwitter-ionic surfactant can be used. According to the kind and amount added of the surfactant, the size of the polymer particles is determined. When the amount added of the surfactant exceeds a critical micell concentration (CMC), a dispersion phase of the polymer is formed.
  • CMC critical micell concentration
  • an appropriate amount of the surfactant is dependent on the kind of the surfactant and solvent, however, the preferred amount is in the range of about 0.01-5% by weight based on the total amount of the solution.
  • a rubber-based binder dispersion can be obtained by adding 0.01-2% by weight of sodium dodecyl benzene sulfonate. If the surfactant is not added, the rubber-based binder is not dispersed into water but is precipitated.
  • Adhering temperature of the porous separator on which the binder is dispersed with an electrode is determined by the glass transition temperature, melting point and cross-linking temperature of the polymer binder material. For example, since the glass transition temperature of the rubber-based binder is lower than room temperature, compression with pressure at a room temperature enables the attachment of the porous separator with the electrode. When one of the amorphous polymer including the fluoride-based polymer, chloride-based polymer and polyacrylate-based polymer is used as for the polymer binder, compression with pressure at a temperature above the room temperature enables the attachment of the porous separator with the electrode. When polystyrene is used as for the polymer binder, compression with pressure at a temperature above the glass transition temperature of the polystyrene (106°C) enables the attachment of the porous separator with the electrode.
  • the polymer binder material is not dissolved into an electrolyte and more preferably is swelled by the electrolyte to keep a gel phase.
  • the polymer binder is swelled by the electrolyte, a surface resistance is lowered because the binder phase does not block an ion transmission.
  • the polymer is swelled excessively, the adherence between the electrode and the separator is reduced and the surface adherence might be weakened.
  • the polymer material is preferably swelled by the electrolyte to about 0-5 times of the weight of the polymer material. When the swelling of the polymer exceeds 5 times of the weight thereof, the adherence of the electrode with the separator becomes weak.
  • the polymer binder is swelled by the electrolyte to about 0.2-3 times of the weight of the polymer.
  • the adhering temperature should not exceed the melting point of the porous separator.
  • the porous separator is made from the amorphous polymer, it is preferable that the adhering temperature does not exceed the glass transition temperature of the separator.
  • a polymer solution is prepared by dispersing or dissolving the polymer binder material into a solvent.
  • prepared dispersion or solution is dispersed on the polymer layer according to one of the following methods.
  • acetone, methanol, ethanol, isopropyl alcohol, tetrahydrofurane, acetonitrile, and the like can be used preferably.
  • the spraying process needs not be implemented under de-humidified atmosphere.
  • the spraying is preferably implemented under the de-humidified atmosphere.
  • the dispersion of the polymer binder material is coated on the porous polymer layer by using a doctor blade method. After volatilizing the solvent, the binder material is dispersed on the surface of the polymer layer.
  • the polymer layer is dipped into a dispersion of the binder to implement a dip coating. Then, the solvent is volatilized to obtain a polymer layer on which the binder material is dispersed. Similar solvents used for the implementation of the spraying method can be used for implementing the dipping method. However, different from the spraying method, a solvent of which boiling point is lower than 30°C can be used. However, the upper limit of the boiling point of the solvent is 200°C or lower.
  • solvents such as ethanol, water, isopropyl alcohol, tapineol, N-methyl pyrrolidone, and the like can be appropriately used. These solvents have an appropriate viscosity for the application of the screen printing and ink jet printing.
  • the polymer binder is coated on the porous polymer layer so that 1-80% of the surface of the porous polymer layer is covered. If less than one percent of the surface of the porous polymer layer is covered, a uniform attachment of the electrode with the separator is not accomplished. When more than 80% of the surface of the porous polymer layer is covered, an impregnation of an electrolyte into the electrode and the separator is difficult. More preferably, the polymer binder is coated so that 3-20% of the surface of the porous polymer layer is covered. Now, an electro chemical cell is manufactured by using the porous separator on which the polymer binder is dispersed.
  • FIGS. 2A-2D illustrate structures of electrochemical cells using a separator according to the present invention, in which FIG. 2A corresponds to a unit cell, FIG. 2B corresponds to a bi-cell, FIG. 2C corresponds to an integrated cell of unit cells and FIG. 2D corresponds to an integrated cell of bi-cells.
  • a porous separator 10 is positioned between a cathode 16 and an anode 14 to obtain a unit cell (FIG. 2A) and an integrated cell (FIG. 2C) or a winding-type cell is obtained by repeatedly integrating the unit cells.
  • Unexplained reference numerals 18 and 20, respectively, designate a current collector of anode and a current collector of cathode.
  • two separators are attached on both sides of the anode and then, two cathode are attached on both sides of the separators to obtain a bi-cell (FIG. 2B) and an integrated cell of the bi-cells (FIG. 2D) can be obtained by integrating the bi-cells.
  • the integration or winding of the electrode with the separator is preferably implemented under a de-humidified atmosphere, however, could be implemented under a normal atmosphere from which humidity is not removed.
  • an electrolyte is injected into the cell to fill the electrode and separator with the electrolyte.
  • the electrolyte is rapidly impregnated into the electrode and separator and is used to swell the polymer binder. After that, the cell is put into a can or a pack and a sealing is implemented to complete the manufacture of the cell.
  • the porous separator of the present invention can be diversely applied for the manufacture of a primary battery, a secondary battery, a capacitor, etc. More preferably, the porous separator can be used for the manufacture of a cell for a lithium secondary battery which employs a cathode made by using LiCoO 2 ,
  • porous separator also can be used for the manufacture of a cell employing a cathode containing sulfur or an organic sulfide compound.
  • Polybutadiene-styrene rubber was dispersed into water into which a surfactant had been added.
  • the concentration of the polymer component was 8% by weight.
  • the rubber solution was sprayed on a porous polypropylene separator (celgard 3501 ; trade name manufactured by Hoechst) by using a spray gun.
  • the rubber deposited separator passed through a drying furnace to evaporate water and then was dried in a vacuum oven of 60°C for one day to remove residual solvent.
  • Thus manufactured separator had a characteristic of adhering to cathode and anode at the room temperature.
  • LiCoO 2 active material was used as for the cathode and MCMB active material was used as for the anode.
  • FIG. 3 is a graph illustrating a cycle characteristic of a battery manufactured by using an electrode according to Example 1. Both of charging rate and discharging rate were 1.0C when measured at the room temperature.
  • Polybutylmethacrylate was dissolved into acetone so that the concentration of thus prepared solution was 10% by weight.
  • Polybutylmethacrylate solution was sprayed on a porous polypropylene separator (celgard 3501 ; trade name manufactured by Hoechst) by using a spray gun.
  • a porous polypropylene separator celgard 3501 ; trade name manufactured by Hoechst
  • polybutylmethacrylate deposited separator passed through a drying furnace to remove acetone.
  • separator polybutylmethacrylate was uniformly dispersed.
  • the polybutylmethacrylate binder material did not exhibit an adhering property at a room temperature, however, exhibited that at a temperature of 60°C or over.
  • An integrated cell was obtained by compressing the separator, a cathode and an anode with pressure at 80°C.
  • LiCo0 2 active material was used for the manufacture of the cathode and MCMB active material was used for the manufacture of the cathode.
  • FIG. 4 is a graph illustrating a cycle characteristic of a battery manufactured by using an electrode according to Example 2. Both of the charging rate and discharging rate were 1.0C when measured at the room temperature. ⁇ Example 3>
  • the polymer binder solution described in Example 1 was sprayed on one surface of a separator and the polymer binder solution described in Example 2 was sprayed on the other surface of the separator.
  • a cathode was attached on one side where polybutadiene-styrene rubber had been dispersed and an anode was attached on the other side where polybutylmethacrylate had been dispersed to obtain an integrated-type cell.
  • the anode and the separator were compressed with heat at 80°C and the cathode and the separator were compressed with pressure at a room temperature.
  • LiCoO 2 active material was used for the manufacture of the cathode and MCMB active material was used for the manufacture of the anode.
  • FIG. 5 is a graph illustrating a cycle characteristic of a battery manufactured by using an electrode according to Example 3. Both charging rate and discharging rate were 1.0C when measured at room temperature.
  • the reason why different binders were used at both sides of the polymer layer as in Example 3 is that the adhering strength to the cathode and anode is different according to the polymer.
  • the electro chemical stability range at the cathode and that at the anode are different. Accordingly, even though the polymer component has a good electro chemical stability and a good adhering strength to the cathode, the same polymer component might have a weak electro chemical stability and a weak adherence to the anode.
  • a polymer material having a good electro chemical stability and a good adhering strength to anode is dispersed on the surface of the separator to obtain a good performance.
  • a polymer binder material imparts an adherence between an electrode and a separator according to the present invention.
  • the polymer binder material is coated by various methods such as a spraying method on a separator and then the solvent is completely evaporated before attaching with an electrode. That is, a separator on which a binder component is uniformly dispersed is manufactured and then, thus obtained separator is attached to an electrode. Therefore, there's no problem that the structure of the binder layer is changed after forming the separator.
  • a resin solution is coated on the polymer layer and the solvent contained therein is evaporated and then the binder layer is attached to the electrode according to the present invention. Therefore, no deviation on an internal structure of a cell according to the difference of the evaporation rate of the solvent occurs during the attachment of the binder and electrode.
  • the separator described in the present invention does not contain an electrolyte but is composed on a porous polymer layer and a polymer binder component. Therefore, the physical property of the separator due to the evaporation of the electrolyte does not change. In addition, the manufacture of the separator or the assembling of the cell needs not to be implemented under a dried room and so the productivity is good. Meantime, the polymer material is mixed with a solvent and then is coated on the porous separator according to the present invention. Therefore, the binder material is not present at the inner portion of the separator but is present at the surface portion of the separator. In addition, not the whole surface of the separator is coated with the binder material but the binder material is dispersed on a partial portion of the surface. Accordingly, the impregnation of the electrolyte is advantageous.
  • the rubber or binder component is not coated on the whole surface of the separator but is uniformly dispersed according to the present invention. Therefore, the electrolyte is easily impregnated into the inner portion of the separator and the electrode through the portion where the binder component is not present by means of a capillary phenomenon. Further, when the binder component is dispersed on the separator as described in the present invention, the binder component is positioned on uniform surface of the separator and so, almost all amount of the binder component is present above the contacting surface with an electrode to exhibit a good adhering strength.

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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
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  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

Cette invention concerne un séparateur poreux sur lequel est dispersé un liant qui facilite la fixation d'une électrode, ainsi que le procédé de fabrication correspondant. On enduit tout d'abord une couche polymère poreuse d'une solution renfermant un liant polymère. On retire ensuite le solvant pour fabriquer le séparateur. Le liant confère une bonne force d'adhérence entre l'électrode et le séparateur. Par ailleurs, une solution électrolytique peut facilement imprégner la zone comprise entre l'électrode et le séparateur via un espace dont le liant est absent. Une cellule électrochimique fabriquée au moyen du séparateur de l'invention présente une capacité élevée et une durée de cycle stable.
PCT/KR2001/001825 2001-07-27 2001-10-29 Separateur poreux et procede de fabrication WO2003012896A1 (fr)

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KR2001/45444 2001-07-27
KR1020010045444A KR20030010406A (ko) 2001-07-27 2001-07-27 다공성 격리막 및 이의 제조방법

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004107479A1 (fr) 2003-05-30 2004-12-09 Lg Chem, Ltd. Batterie au lithium rechargeable mettant en application un separateur revetu partiellement par un gel polymere
US7759004B2 (en) * 2003-12-12 2010-07-20 Panasonic Corporation Electrode for lithium ion secondary batteries, lithium ion secondary battery using the same, and method for manufacturing the battery
EP2248209A2 (fr) * 2008-01-30 2010-11-10 LG Chem, Ltd. Séparateur destiné à faire progresser une force unie à une électrode et dispositif électrochimique le contenant
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US8277691B2 (en) 2008-05-05 2012-10-02 Ada Technologies, Inc. High performance carbon nanocomposites for ultracapacitors
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CN103715384A (zh) * 2013-09-30 2014-04-09 河南师范大学 锂离子电池复合隔膜及其制备方法
EP2874203A1 (fr) * 2013-11-19 2015-05-20 Samsung SDI Co., Ltd. Séparateur pour batterie au lithium, batterie au lithium comprenant celui-ci et procédé de fabrication de la batterie au lithium
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WO2017210405A1 (fr) * 2016-06-01 2017-12-07 Daramic, Llc Séparateurs améliorés pour accumulateurs au plomb-acide, accumulateurs perfectionnés et procédés associés
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CN109273646A (zh) * 2018-09-28 2019-01-25 青岛大学 一种制备聚碳酸酯包覆的锂离子电池隔膜的方法
EP3471187A4 (fr) * 2016-08-12 2019-07-31 LG Chem, Ltd. Assemblage d'électrodes dans lequel une électrode et un film de séparation sont partiellement liés
WO2021256905A1 (fr) * 2020-06-18 2021-12-23 주식회사 엘지에너지솔루션 Procédé de fabrication de séparateur et séparateur ainsi fabriqué

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KR100948267B1 (ko) * 2007-11-14 2010-03-18 한국원자력연구원 실록산이 그라프팅된 다공성 분리막, 이의 제조방법 및이를 적용한 리튬 2차전지
KR100985185B1 (ko) * 2008-05-19 2010-10-05 주식회사 에스 피 씨 사무용 펀치
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JP2006525624A (ja) * 2003-05-30 2006-11-09 エルジー・ケム・リミテッド ゲル状ポリマーで部分コートされたセパレータ膜を用いたリチウム二次電池
EP1631998A4 (fr) * 2003-05-30 2009-04-22 Lg Chemical Ltd Batterie au lithium rechargeable mettant en application un separateur revetu partiellement par un gel polymere
WO2004107479A1 (fr) 2003-05-30 2004-12-09 Lg Chem, Ltd. Batterie au lithium rechargeable mettant en application un separateur revetu partiellement par un gel polymere
US7759004B2 (en) * 2003-12-12 2010-07-20 Panasonic Corporation Electrode for lithium ion secondary batteries, lithium ion secondary battery using the same, and method for manufacturing the battery
US8284539B2 (en) 2006-08-02 2012-10-09 Ada Technologies, Inc. High performance ultracapacitors with carbon nanomaterials and ionic liquids
US8377583B2 (en) 2008-01-30 2013-02-19 Lg Chem, Ltd. Separator for providing a uniting force to electrode and electrochemical cell containing the same
JP2011512005A (ja) * 2008-01-30 2011-04-14 エルジー・ケム・リミテッド 電極に対する結着性が改善したセパレータ及びこれを備えた電気化学素子
CN101926024A (zh) * 2008-01-30 2010-12-22 株式会社Lg化学 用于改进与电极的结合力的隔膜以及含有所述隔膜的电化学装置
EP2248209A2 (fr) * 2008-01-30 2010-11-10 LG Chem, Ltd. Séparateur destiné à faire progresser une force unie à une électrode et dispositif électrochimique le contenant
EP2248209A4 (fr) * 2008-01-30 2013-01-23 Lg Chemical Ltd Séparateur destiné à faire progresser une force unie à une électrode et dispositif électrochimique le contenant
CN103928650A (zh) * 2008-01-30 2014-07-16 株式会社Lg化学 用于改进与电极的结合力的隔膜以及含有所述隔膜的电化学装置
EP2927993A1 (fr) * 2008-01-30 2015-10-07 Lg Chem, Ltd. Séparateur pour dispositif électrochimique
JP2014239042A (ja) * 2008-01-30 2014-12-18 エルジー・ケム・リミテッド 電極に対する結着性が改善したセパレータ及びこれを備えた電気化学素子
US8236446B2 (en) 2008-03-26 2012-08-07 Ada Technologies, Inc. High performance batteries with carbon nanomaterials and ionic liquids
US8277691B2 (en) 2008-05-05 2012-10-02 Ada Technologies, Inc. High performance carbon nanocomposites for ultracapacitors
US9543584B2 (en) 2010-06-16 2017-01-10 Lg Chem, Ltd. Binder for secondary battery providing excellent cycle property
US9276247B2 (en) 2011-04-06 2016-03-01 Lg Chem, Ltd. Separator and electrochemical device comprising the same
CN103460444A (zh) * 2011-04-06 2013-12-18 株式会社Lg化学 隔膜及包含该隔膜的电化学装置
CN103688388B (zh) * 2011-07-22 2017-12-26 罗伯特·博世有限公司 用于蓄能器的分离器和蓄能器
WO2013013867A1 (fr) * 2011-07-22 2013-01-31 Robert Bosch Gmbh Séparateur pour accumulateur d'énergie et accumulateur d'énergie
JP2014523630A (ja) * 2011-07-22 2014-09-11 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング エネルギー蓄積器用のセパレータおよびエネルギー蓄積器
CN103688388A (zh) * 2011-07-22 2014-03-26 罗伯特·博世有限公司 用于蓄能器的分离器和蓄能器
US10673043B2 (en) 2011-07-22 2020-06-02 Robert Bosch Gmbh Separator for an energy store and an energy store
CN102399381A (zh) * 2011-10-11 2012-04-04 沈阳理工大学 一种高耐磨性碳微球-橡胶复合材料及其制备方法
CN102399381B (zh) * 2011-10-11 2013-04-10 沈阳理工大学 一种高耐磨性碳微球-橡胶复合材料及其制备方法
US10033024B2 (en) 2011-11-11 2018-07-24 Lg Chem, Ltd. Separator and electrochemical device having the same
EP2779275A4 (fr) * 2011-11-11 2016-03-02 Séparateur et dispositif électrochimique comprenant ledit séparateur
US20130244080A1 (en) * 2012-03-16 2013-09-19 Samsung Sdi Co., Ltd. Separator for lithium secondary battery
US20190140242A1 (en) * 2012-07-26 2019-05-09 Asahi Kasei E-Materials Corporation Separator for Electricity Storage Device, Laminate and Porous Film
US10811659B2 (en) 2012-07-26 2020-10-20 Asahi Kasei E-Materials Corporation Separator for electricity storage device, laminate and porous film
US10153473B2 (en) 2012-07-26 2018-12-11 Asahi Kasei E-Materials Corporation Separator for electricity storage device, laminate and porous film
US11814483B2 (en) 2012-08-01 2023-11-14 Samsung Sdi Co., Ltd. Separation membrane comprising coating layer, method of preparing same, and battery using same
US20150155542A1 (en) * 2012-08-01 2015-06-04 Samsung Sdi Co., Ltd. Separation membrane comprising coating layer and battery using same
US9627691B2 (en) 2013-02-07 2017-04-18 Ada Technologies, Inc. Metalized, three-dimensional structured oxygen cathode materials for lithium/air batteries and method for making and using the same
CN103715384A (zh) * 2013-09-30 2014-04-09 河南师范大学 锂离子电池复合隔膜及其制备方法
CN105684190A (zh) * 2013-10-25 2016-06-15 Lg化学株式会社 用于在分离膜上涂覆粘性粘结剂的方法
EP2874203A1 (fr) * 2013-11-19 2015-05-20 Samsung SDI Co., Ltd. Séparateur pour batterie au lithium, batterie au lithium comprenant celui-ci et procédé de fabrication de la batterie au lithium
US9825270B2 (en) 2013-11-19 2017-11-21 Samsung Sdi Co., Ltd. Separator for lithium battery, lithium battery including the same, and method of manufacturing the lithium battery
CN104659311B (zh) * 2013-11-19 2020-10-23 三星Sdi株式会社 隔板、其制造方法、包括其的锂电池和制造锂电池的方法
CN104659311A (zh) * 2013-11-19 2015-05-27 三星Sdi株式会社 隔板、其制造方法、包括其的锂电池和制造锂电池的方法
WO2017209748A1 (fr) * 2016-06-01 2017-12-07 Daramic, Llc Séparateurs hybrides améliorés pour batteries au plomb
CN109478624A (zh) * 2016-06-01 2019-03-15 达拉米克有限责任公司 用于铅酸电池的改进的隔板、改进的电池及相关方法
WO2017210405A1 (fr) * 2016-06-01 2017-12-07 Daramic, Llc Séparateurs améliorés pour accumulateurs au plomb-acide, accumulateurs perfectionnés et procédés associés
EP3471187A4 (fr) * 2016-08-12 2019-07-31 LG Chem, Ltd. Assemblage d'électrodes dans lequel une électrode et un film de séparation sont partiellement liés
US10826039B2 (en) 2016-08-12 2020-11-03 Lg Chem, Ltd. Electrode assembly including electrode and separator partially bonded to each other
CN109273646A (zh) * 2018-09-28 2019-01-25 青岛大学 一种制备聚碳酸酯包覆的锂离子电池隔膜的方法
WO2021256905A1 (fr) * 2020-06-18 2021-12-23 주식회사 엘지에너지솔루션 Procédé de fabrication de séparateur et séparateur ainsi fabriqué

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