WO2012128460A2 - Matériau d'application de film séparateur utilisant un polymère dérivé de moules et procédé de fabrication associé, et matériau pour empêcher le thermo-rétrécissement et procédé de fabrication associé - Google Patents

Matériau d'application de film séparateur utilisant un polymère dérivé de moules et procédé de fabrication associé, et matériau pour empêcher le thermo-rétrécissement et procédé de fabrication associé Download PDF

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WO2012128460A2
WO2012128460A2 PCT/KR2012/000455 KR2012000455W WO2012128460A2 WO 2012128460 A2 WO2012128460 A2 WO 2012128460A2 KR 2012000455 W KR2012000455 W KR 2012000455W WO 2012128460 A2 WO2012128460 A2 WO 2012128460A2
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Prior art keywords
separator
resin
secondary battery
present
preventing heat
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PCT/KR2012/000455
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English (en)
Korean (ko)
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WO2012128460A3 (fr
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최장욱
박정기
이용민
류명현
이동진
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한국과학기술원
한밭대학교 산학협력단
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Priority claimed from KR1020110054319A external-priority patent/KR101198493B1/ko
Application filed by 한국과학기술원, 한밭대학교 산학협력단 filed Critical 한국과학기술원
Publication of WO2012128460A2 publication Critical patent/WO2012128460A2/fr
Publication of WO2012128460A3 publication Critical patent/WO2012128460A3/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M50/454—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • 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 membrane coating agent using a mussel-derived polymer, a method for manufacturing the same, a heat shrink prevention agent, and a method for manufacturing the same, and more particularly, a compatibility with an electrolyte and a low contact angle without damaging pores of the membrane substrate in a relatively simple process.
  • the present invention using a mussel-derived polymer capable of producing a high output battery and a high capacity battery by improving the impregnating ability of the electrolyte by improving the surface properties of the present invention, and further preventing the heat shrinkage of the separator is a membrane coating agent using the mussel-derived polymer. And a method for producing the same, a heat shrink preventing agent and a method for producing the same.
  • the lithium secondary battery is manufactured by using a metal oxide such as LiCoO 2 as a cathode active material and a carbon material as a cathode active material, a porous separator between the anode and the cathode, and a non-aqueous electrolyte having a lithium salt such as LiPF 6 . .
  • lithium ions of the positive electrode active material are released and inserted into the carbon layer of the negative electrode, and during discharge, lithium ions of the negative electrode carbon layer are released and inserted into the positive electrode active material, wherein the non-aqueous electrolyte solution is lithium ions between the negative electrode and the positive electrode. It acts as a medium for moving the.
  • a lithium secondary battery should basically be stable in the operating voltage range of the battery and have a performance capable of transferring ions at a sufficiently high speed.
  • the porous separator is a 10-30 ⁇ m thick polymer membrane having a porous structure located between the positive electrode and the negative electrode, and isolates the positive electrode and the negative electrode, and prevents an electrical short circuit between the two poles. It serves to pass.
  • the separator itself does not electrochemically participate in the battery reaction, but affects battery performance and safety due to physical properties such as wettability with the electrolyte and degree of microporosity.
  • a non-aqueous organic solvent such as ethylene carbonate, dimethyl carbonate, diethyl carbonate, and propylene carbonate is mainly used as the non-aqueous electrolyte mainly used in the secondary battery.
  • These electrolytes are polar solvents that are polar enough to effectively dissolve and dissociate electrolyte salts, and are aprotic solvents without active hydrogen, and are often high in viscosity and surface tension due to extensive interactions within the electrolyte.
  • the electrolyte has a low affinity with an electrolyte having a hydrophilic property. It has a low content characteristic, which results in increasing the overall resistance of the battery, there is a problem in that it is not suitable for high output, high capacity battery by the continuous reduction of capacity and high rate charge-discharge characteristics according to the cycle.
  • the general porous membrane is poor in water permeability compared to the hydrophilic material, even if the membrane having the same pore ( ⁇ ) due to the unique hydrophobic properties. Therefore, it is necessary to hydrophilize the surface of the hydrophobic material to increase its water permeability.
  • Korean Patent Publication No. 2008-0106870 discloses a method of coating the surface of the hydrophobic polymer membrane with a hydrophilic polymer, and Korean Patent Publication No.
  • 2008-0061049 discloses hydrophilization of the surface of the hydrophobic polymer membrane, but in terms of practical technology through Hydrophilization into the internal pores is quite difficult, and due to the problem of high cost, the actual commercialization is difficult.
  • electrochemical devices such as lithium secondary batteries have problems not only with the above-described safety problems but also with the separators currently used.
  • currently produced lithium secondary batteries and lithium ion polymer batteries generally use a polyolefin-based separator to prevent short circuit between the positive electrode and the negative electrode.
  • polyolefin-based membranes have their original size at a high temperature due to the properties of the membrane material, for example, the characteristics and processing characteristics of the polyolefin-based melt, usually at 200 or less, and the stretching process to control pore size and porosity. It has the disadvantage of heat shrinking. Therefore, when the battery rises to a high temperature due to internal / external stimulation, it is more likely that the positive electrode and the negative electrode are shorted to each other due to shrinkage or melting of the separator, and thus, the battery may show a great risk of explosion due to the release of electrical energy. do. Therefore, it is essential to develop a membrane that does not undergo heat shrinkage at high temperatures.
  • the present invention has been made to solve the above problems and to solve the technical problem that is required in the prior art, the problem to be solved by the present invention is a hydrophilic membrane in a simple method without damaging the pores of the hydrophobic porous membrane It is to provide a separator coating agent and a method for manufacturing the same, a separator comprising the same, a method for producing the same and an electrochemical device including the same.
  • the present invention is a method for preparing a separator coating comprising a compound of Formula 1, wherein the method comprises the step of dissolving the compound of Formula 1 in a solution of pH 7 to 11 It provides a method for producing a coating.
  • R 1 , R 2 , R 3 , R 4 and R 5 is thiol, primary amine, secondary amine, nitrile, aldehyde, respectively. , Imidazole, azide, halide, polyhexamethylene dithiocarbonate, hydroxyl, carboxylic acid, carboxylic ester ) Or one selected from the group consisting of carboxamides, and R 1 , R 2 , R 3 , R 4 and R 5 except hydrogen are hydrogen)
  • the compound causes a polymerization reaction at a pH of 7 or more
  • the separator is a separator for an electrochemical device
  • the electrochemical device may be a secondary battery or a capacitor.
  • the present invention also provides a separator coating prepared according to the method described above. '
  • the present invention is a separator, the separator is a porous substrate; And it provides a separator characterized in that it comprises a compound of formula 1 coated on the surface or inside of the porous substrate.
  • R 1 , R 2 , R 3 , R 4 and R 5 is thiol, primary amine, secondary amine, nitrile, aldehyde, respectively. , Imidazole, azide, halide, polyhexamethylene dithiocarbonate, hydroxyl, carboxylic acid, carboxylic ester ) Or one selected from the group consisting of carboxamides, and R 1 , R 2 , R 3 , R 4 and R 5 except hydrogen are hydrogen)
  • the present invention also provides a method for preventing heat shrinkage of a polyolefin separator of a lithium secondary battery, wherein the method includes coating a polymer polymerized with the compound of Formula 1 on the polyolefin separator to a polyolefin separator of a lithium secondary battery.
  • the method includes coating a polymer polymerized with the compound of Formula 1 on the polyolefin separator to a polyolefin separator of a lithium secondary battery.
  • R 1 , R 2 , R 3 , R 4 and R 5 is thiol, primary amine, secondary amine, nitrile, aldehyde, respectively. , Imidazole, azide, halide, polyhexamethylene dithiocarbonate, hydroxyl, carboxylic acid, carboxylic ester ) Or one selected from the group consisting of carboxamides, and R 1 , R 2 , R 3 , R 4 and R 5 except hydrogen are hydrogen)
  • the present invention is also a method for preventing heat shrinkage of a polyolefin separator of a lithium secondary battery.
  • R 1 , R 2 , R 3 , R 4 and R 5 is thiol, primary amine, secondary amine, nitrile, aldehyde, respectively. , Imidazole, azide, halide, polyhexamethylene dithiocarbonate, hydroxyl, carboxylic acid, carboxylic ester ) Or one selected from the group consisting of carboxamides, and R 1 , R 2 , R 3 , R 4 and R 5 except hydrogen are hydrogen)
  • the present invention can improve the surface properties such as compatibility with the electrolyte and low contact angle without damaging the pores of the membrane substrate by a simple process. Therefore, through this, the impregnation ability of the electrolyte is improved, and there is an advantage that the production of a high output battery and a high capacity battery is possible.
  • FIG. 1 is a schematic diagram of a method for producing a porous polyethylene separator coated with polydopamine according to an embodiment of the present invention.
  • Figure 2 is a schematic diagram of the polymerization mechanism (mechanism) of the polydopamine polymer formed from dopamine in accordance with an embodiment of the present invention.
  • Figure 4 is a SEM photograph of the surface of the porous polyethylene separator prepared in Comparative Example and Example.
  • FIG. 7 is a DSC result of measuring thermal properties of polyethylene separators prepared in Comparative Examples and Examples (DSC, heating rate: 10 ° C./min).
  • FIG. 12 is a photograph of the polyethylene membrane exposed to a high temperature environment according to the embodiment and the comparative example of the membrane coated mussel-derived polymer according to the present invention.
  • the electrochemical device used in the present invention is based on the anode / cathode, and includes all of any device including an electrolyte and a separator, for example, a secondary battery, a capacitor and the like.
  • the microporous separator which is mainly used as a separator for a secondary battery, which is an electrochemical device, has a problem in that the impregnation ability of the electrolyte is poor due to the hydrophobic surface characteristic, making it unsuitable for high output and high capacity secondary batteries. Therefore, the present invention uses a mussel-derived polymer as a coating agent to improve the surface properties on the surface of the conventional microporous separator substrate, and by coating this, the impregnating ability of the electrolyte is improved to implement a secondary battery capable of high output and high capacity.
  • mussels Since mussels produce and secrete special water-insoluble adhesives, mussels have been studied as potential raw materials for effective water-resistant bio-adhesives. Mussels are firmly attached to the surface of the water through a squeegee that extends from the foot, and the ends of each stool contain a water-resistant adhesive that allows the adhesive plaque to be fixed to a wet solid surface (Waite et al., Biology Review 58: 209-231 (1983). In addition, mussel-derived adhesive polymers are harmless to humans and do not cause an immune response, and thus may be used as adhesives for medical use (Dove et al., Journal of American Dental Association. 112: 879 (1986)).
  • the present invention uses such a mussel-derived polymer as a membrane coating agent, thereby improving both the containing properties and the wettability of the electrolyte.
  • Formula 1 is a chemical structure of the membrane coating agent using the mussel-derived polymer according to the present invention.
  • R 1 , R 2 , R 3 , R 4, and R 5 may be a thiol, a primary amine, a second amine, a nitrile, or an aldehyde, respectively.
  • the present invention provides a hydrophilic property to the separator without damaging the pores of the hydrophobic porous separator by coating a coating agent, such as the formula (1) in a simple method.
  • a coating agent such as the formula (1)
  • the method of manufacturing a hydrophilized porous separator capable of producing a high output battery and a high capacity battery by improving the impregnation ability of the electrolyte by improving the surface properties such as compatibility with the electrolyte and a low contact angle, and a separator for a lithium secondary battery, and The used lithium secondary battery can be provided.
  • the membrane coating agent according to the present invention comprises a distilled water-based buffer and the compound represented by the formula (1), alcohol, such as methanol may be optionally added according to the description of the porous membrane.
  • alcohol such as methanol
  • the compound represented by Chemical Formula 1 is a dopamine-based material, and the dopamine-based material is spontaneously polymerized into polydopamine, a mussel-derived polymer, in a weak base environment (pH 8.5). Form a thin polymer layer on the surface of the, the coating thickness of the separator may range from 0.001 to 1 ⁇ m.
  • the polydopamine formed in the separator according to the present invention not only possesses excellent chemical stability, but also effectively converts the hydrophobic surface property into hydrophilicity without damaging the pores of the microporous membrane substrate due to the thin polymer coating thickness of about 50 nm. You can expect. Dopamine was also used in a cheap and environmentally friendly distilled water-based buffer (10 mM tris buffer solution, pH 8.5) in place of expensive and environmentally harmful everyday organic solvents. This is because in order to form a polydopamine coating layer, which is a mussel-derived polymer, the solution must be kept at a weak base (pH 8.5).
  • the porous substrate of the separator according to the present invention is an olefin resin, a fluorine resin, a polyester resin, a cellulose resin, a polyamide resin, a polyimide resin, a polysulfone resin, a polyacrylonitrile resin, a polyacetal system Resin, polycarbonate-based resin, vinylidene fluoride-based resin, glass fiber to the inorganic composite may be in the form of a single or multiple layers, the pore size of the porous substrate is in the range of 0.001 to 1000 ⁇ m, porosity is 5 to 95% Range, thickness may range from 1 to 1000 ⁇ m.
  • a porous polyethylene membrane Asahi Kasei, 20 ⁇ m, porosity: 40%
  • Figure 1 is a schematic diagram of a manufacturing procedure of the hydrophilic membrane of the present invention.
  • a porous membrane having a hydrophilic property may be obtained.
  • the impregnation method may be a variety of methods such as pressure coating method, spin coating method, spray method or roller coating method in addition to the general immersion coating method, all belong to the scope of the present invention.
  • Figure 2 shows the chemical reaction characteristics occurring in the membrane coating using dopamine.
  • the membrane coating agent using the dopamine may be spontaneous polymerization reaction under weak base conditions (pH 8.5) to form a polydopamine polymer derived from mussels. Therefore, the pH condition of the solution in which the compound of Formula 1 is dissolved according to the present invention is preferably 7 to 11, and more preferably 7 to 9, which is a weak base condition in which the compound of Formula 1 is spontaneously polymerized.
  • Porous polyethylene membrane (Asahi Kasei, 20 ⁇ m, porosity: 40%) was washed once with acetone and dried for 24 hours in a vacuum oven at room temperature.
  • the resulting polydopamine polymer is coated on the surface of the membrane substrate impregnated with the membrane coating agent.
  • the surface of the membrane substrate impregnated with the membrane coating agent using dopamine has a dark brown color.
  • the polydopamine coating is known to be formed in a very thin thickness, it can be confirmed through the comparative example and the example of FIG. 4 that the coating was effectively coated without pore damage of the microporous membrane substrate.
  • XPS of the membrane surface was measured in order to confirm the presence of the coating of polydopamine in detail, and as shown in FIG. 5, new nitrogen (N1s) and oxygen (O1s) peaks, which were not present in the comparative example, were generated in Examples. It could be confirmed.
  • the porous membrane coated with the polydopamine polymer according to the present invention has the inherent mechanical strength (Instron, tensile rate: 1 cm / min) and pyrolysis characteristics (DSC, heating) of the existing porous membrane substrate. Rate: 10 ° C / min) was confirmed that not inhibited.
  • the porous separator coated with the polydopamine polymer according to the present invention effectively provides the hydrophilic surface property to the conventional porous separator of the hydrophobic surface property.
  • the conventional hydrophobic porous membrane exhibits a contact angle of 108 °, but the contact angle of the separator according to the present invention was 39 °, the contact angle was greatly reduced (contact angle between the droplet and the membrane substrate, 0.5 ⁇ l ).
  • Table 1 shows the characteristics change of the separator according to the polydopamine coating, referring to this, it can be seen that the porous membrane coated with the polydopamine polymer according to the present invention shows an improved electrolyte impregnation amount and ion conductivity compared to the conventional porous separator have.
  • the present invention also provides an electrochemical cell consisting of an electrode assembly wherein the porous separator is interposed between an anode and a cathode, the electrochemical cell provides electricity through an electrochemical reaction, for example, it may be an electrochemical secondary battery or an electrochemical capacitor.
  • Figure 11 shows the output characteristics of the secondary battery, for charging the lithium secondary battery with a current value of 1C for output characteristics analysis, 10 cycles at a current value of 1C, 3C, 6C, 9C, 12C, 15C, 1C Discharged.
  • the porous separator coated with the polydopamine polymer according to the present invention showed significantly improved output characteristics compared to the conventional porous separator. This is thought to be due to the excellent ionic conductivity retention by reducing electrolyte leakage at high rate driving due to the improved compatibility and wettability with the electrolyte as mentioned above.
  • the porous membrane coated with the polydopamine polymer according to the present invention may bring variety in selecting an electrolyte solution.
  • the present invention has discovered a new effect that the mussel-derived polymer according to the above-described method acts as a heat shrink inhibitor of the separator, which will be described through the following experimental example.
  • Porous polyethylene membranes (Asahi Kasei, 20, porosity: 40%) that were not surface treated with polydopamine were stored at 140 for 1 hour at high temperature.
  • FIG. 12 is a photograph of the polyethylene membrane exposed to a high temperature environment according to the embodiment and the comparative example of the membrane coated mussel-derived polymer according to the present invention.
  • d is less shrunk in the separator of the polydopamine-coated example than the comparative example separator on the right side.
  • the degree of shrinkage of the polyolefin separator coated with polydopamine is about half that of the uncoated separator.
  • the present invention generates a heat shrinkage prevention effect by coating the mussel-derived polymer on the surface of the separator as described above.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un film séparateur poreux hydrophile qui utilise un procédé d'application d'un polymère dérivé de moules, et une cellule électrochimique qui comprend le film séparateur poreux hydrophile. Le film séparateur poreux enduit de polydopamine selon la présente invention est écologique et le procédé de fabrication est un procédé de fabrication économique. De même, comme le polymère appliqué fournit efficacement une aptitude hydrophile sans endommager les pores du film séparateur, le film séparateur poreux peut améliorer l'aptitude d'utilisation avec un électrolyte et les performances d'imprégnation de l'électrolyte par l'intermédiaire d'une capacité de mouillage améliorée afin de produire une cellule à haut rendement et une cellule à haute capacité.
PCT/KR2012/000455 2011-03-23 2012-01-18 Matériau d'application de film séparateur utilisant un polymère dérivé de moules et procédé de fabrication associé, et matériau pour empêcher le thermo-rétrécissement et procédé de fabrication associé WO2012128460A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20110025603 2011-03-23
KR10-2011-0025603 2011-03-23
KR10-2011-0054319 2011-06-07
KR1020110054319A KR101198493B1 (ko) 2011-06-07 2011-06-07 홍합유래 고분자를 이용한 폴리올레핀 분리막의 열수축 방지방법, 이에 의하여 열 수축 특성이 향상된 폴리올레핀 분리막과 이를 포함하는 리튬이차전지

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WO2012128460A2 true WO2012128460A2 (fr) 2012-09-27
WO2012128460A3 WO2012128460A3 (fr) 2012-11-22

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Cited By (4)

* Cited by examiner, † Cited by third party
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DE102014208145B3 (de) * 2014-04-30 2015-09-03 Robert Bosch Gmbh Batteriezelle mit einer beschichteten Elektrode sowie deren Herstellung
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CN104051691A (zh) * 2014-06-06 2014-09-17 中国第一汽车股份有限公司 一种基于聚多巴胺的改性复合聚合物隔膜的制备方法
CN104037380A (zh) * 2014-06-10 2014-09-10 中国第一汽车股份有限公司 一种基于聚多巴胺的改性聚合物颗粒隔膜的制备方法
WO2020179998A1 (fr) * 2019-03-06 2020-09-10 삼성에스디아이주식회사 Séparateur, son procédé de préparation et batterie auxiliaire le comprenant
KR20200108144A (ko) * 2019-03-06 2020-09-17 삼성에스디아이 주식회사 세퍼레이터, 이의 제조방법, 및 이를 포함한 이차전지
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