CN105322120A - Preparation method of water-based PVDF coating slurry of gel diaphragm for lithium-ion battery - Google Patents

Preparation method of water-based PVDF coating slurry of gel diaphragm for lithium-ion battery Download PDF

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Publication number
CN105322120A
CN105322120A CN201510653818.8A CN201510653818A CN105322120A CN 105322120 A CN105322120 A CN 105322120A CN 201510653818 A CN201510653818 A CN 201510653818A CN 105322120 A CN105322120 A CN 105322120A
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CN
China
Prior art keywords
pvdf
water
ion battery
lithium
preparation
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Pending
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CN201510653818.8A
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Chinese (zh)
Inventor
毛赢超
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Individual
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Individual
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Priority to CN201510653818.8A priority Critical patent/CN105322120A/en
Publication of CN105322120A publication Critical patent/CN105322120A/en
Priority to CN201610871634.3A priority patent/CN106159317A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • 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
    • H01M50/403—Manufacturing processes of separators, 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the 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
    • H01M50/411—Organic material
    • 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

Abstract

The invention relates to a preparation method of water-based PVDF coating slurry of a gel diaphragm for a lithium-ion battery. According to the method, by a phase-transfer catalysis method, PVDF, polyether silicone oil and hydroxyl silicone oil are blended, grafted and modified at the ratio; the hydrophily, the wettability and the crystalline state are improved; and the environment-friendly and safe water-based PVDF slurry is prepared through the processes of solubilizing, modifying, emulsifying, dispersing, micelle balance, catalytic phase inversion and the like. The water-based PVDF slurry contains hydroxyl; compared with solvent type PVDF slurry, the hydroxyl is stable in system, uniform in dispersion and friendly to environment, and is easy to form a covalent bond together with an active electrode material; the viscoelasticity, the wettability and the liquid absorption rate are obviously improved; the water-based PVDF slurry is non-toxic in production, free of waste and free of pollution, and can be widely applied to coating modification of a lithium-ion battery pole plate and the diaphragm; and improvement of the overall performance of the lithium-ion battery is facilitated.

Description

A kind of preparation method of lithium ion battery gelatin membrane water-based PVDF coating paste
Technical field
The present invention relates to the preparation method of a kind of lithium ion battery gelatin membrane of lithium ion battery material technical field water-based PVDF coating paste.
Background technology
It is high that lithium ion battery has energy density, has extended cycle life, and self-discharge rate is little, and the advantage such as memory-less effect and environmental protection, is widely used in portable electric appts, electric tool, the aspect such as motor vehicle and energy storage.
Barrier film is interior layer assembly crucial in lithium ion battery.The capacity of battery, cycle performance and charging and discharging currents density, high temperature resistant and high strength, the key performances such as safety guarantee all have direct relation with barrier film.
Conventional lithium ion battery separator is first-selected mainly with polyolefin PP, PE material.Along with the development of lithium ion battery industry and application market, the combination property of battery and security performance require more and more higher.Ceramic-coated separator, PVDF gel coat barrier film, polymer dielectric film etc. emerge in succession, application market.Water-based system PVDF gelatin membrane coating paste effectively can ensure that it is produced and the environmental requirement of environment at lithium ion battery, and pollution-free, without the three wastes, high safety, also improves the combination property of lithium ion battery simultaneously.
Summary of the invention
The object of this invention is to provide a kind of preparation method of lithium ion battery gelatin membrane water-based PVDF coating paste.The barrier film that the PVDF coating paste of this kind of water-based system is made can have good cohesive force to the active material pole piece of lithium ion battery, the fine and close consolidation of the active material configuration of pole piece can be made, evenly, safety, is conducive to forming SEI film at height than negative material surface, has good ionic conductivity, improve electrochemical stability, optimize the compatibility with other water-based system materials, compatibility, concertedness.Water-based system PVDF gelatin membrane coating paste more can improve the combination property of lithium ion battery than the application of traditional solvent-borne PVDF slurry.
For achieving the above object, the technical solution adopted in the present invention is as follows: phase transfer catalysis process
A kind of preparation method of lithium ion battery gelatin membrane water-based PVDF coating paste: the first step, first by hemicrystalline hydrophobic material PVDF and polyether silicone oil, hydroxy silicon oil is blended by a certain percentage, is dissolved in acetone, in isopropyl alcohol equal solvent, obtain transparent comparatively viscous solution.Add polyether silicone oil, hydroxy silicon oil, reduce the degree of crystallinity of PVDF, improve hydrophily and wettability and the Swelling Capacity to electrolyte, imbibition, liquid-keeping property, can prevent the electrolyte loss in barrier film, keeps conductance stability.Second step, adds the graft modification of PEGME polyethylene glycol monomethyl ether by the viscous solution of obtained for the first step [PVDF+ polyether silicone oil, hydroxy silicon oil], add a certain amount of deionized water uniform stirring, after certain hour, by the acetone in mixed solution, isopropanol solvent extracts and collects.3rd step; [the horizontal hydrochlorate of the anion emulsifier detergent alkylate+nonionic wetting dispersing agent APES+high molecular surfactant] of certain formula ratio is combined HLB equilibrium valve, the emulsifying dispersant that homogeneous is uniformly mixed.4th step; The mixing and emulsifying dispersant of stirring is joined slowly [the PVDF+ polyether silicone oil of stirring, hydroxy silicon oil+PEGME polyethylene glycol monomethyl ether] mixed aqueous solution in, carry out sufficient phase transfer catalysis (PTC), form the large molecular gel coating paste of stable water-based PVDF.
It, by the effect of surfactant, is changed into the application of the water-based system slurry of environmental protection by PVDF by the mode of the solvent pulping material of traditional non-environmental protection.Protect environment, ensure the health of employee.
Specific implementation method
The first step; First by PVDF [10--70wt%] and polyether silicone oil [3--30wt%], hydroxy silicon oil [2--20wt%] co-blended stirs, and fully stirs 2 hours, be dissolved in acetone under 80 degree, in isopropanol solvent, obtain transparent or sub-translucent thickness mixing material.Second step; In the viscous solution that the first step is obtained, add PEGME polyethylene glycol monomethyl ether [0.5--5wt%], fully stir graft modification, and gradation adds deionized water [5--20%] on a small quantity, simultaneously uniform stirring 2 hours [rotating speed 60 revs/min].Afterwards, extract and collect solvent acetone, isopropyl alcohol, continuing to stir [PVDF+ polyether silicone oil, hydroxy silicon oil] hydration mixing material.3rd step; By formula by [anion emulsifier dodecyl benzene sulfonate [1--5wt%], nonionic wetting dispersing agent APES [1--2.5wt%], high molecular surfactant PEG400 [0.5--2.5wt%], deionized water [5--20wt%] is blended, carry out homogeneous at normal temperatures and stir into emulsion dispersion liquid [rotating speed 60 revs/min, 15 minutes].4th step; The emulsion dispersion liquid that 3rd step obtains is joined slowly [the PVDF+ polyether silicone oil that second step continues stirring, hydroxy silicon oil] in hydration mixing material, carry out emulsion dispersion, carry out sufficient phase transfer catalysis (PTC), after high-speed stirred 2--3 hour, decelerate to 60 revs/min and vacuumize froth breaking, stopping after 30 minutes stirring, form stable water-based PVDF large molecular gel barrier film coating paste.

Claims (1)

1. the present invention relates to a kind of preparation method of lithium ion battery gelatin membrane water-based PVDF coating paste, claim is as follows:
Adopt phase transfer catalysis process by hemicrystalline hydrophobic material PVDF [10--70wt%] and polyether silicone oil [3--30wt%], hydroxy silicon oil [2--20wt%] is mixed to join anion emulsifier dodecyl benzene sulfonate [1--5wt%], nonionic wetting dispersing agent APES [1--2.5wt%], sufficient micella balance is carried out in the emulsion dispersion system that high molecular surfactant PEG400 [0.5--2.5wt%] forms, phase transfer catalysis (PTC), be prepared into the preparation method of stable water-based system PVDF large molecular gel barrier film coating paste.
CN201510653818.8A 2015-10-08 2015-10-08 Preparation method of water-based PVDF coating slurry of gel diaphragm for lithium-ion battery Pending CN105322120A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201510653818.8A CN105322120A (en) 2015-10-08 2015-10-08 Preparation method of water-based PVDF coating slurry of gel diaphragm for lithium-ion battery
CN201610871634.3A CN106159317A (en) 2015-10-08 2016-09-30 The lithium ion battery preparation method of gelatin membrane aqueous PVDF coating paste

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510653818.8A CN105322120A (en) 2015-10-08 2015-10-08 Preparation method of water-based PVDF coating slurry of gel diaphragm for lithium-ion battery

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CN201610871634.3A Pending CN106159317A (en) 2015-10-08 2016-09-30 The lithium ion battery preparation method of gelatin membrane aqueous PVDF coating paste

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CN107507956A (en) * 2017-07-28 2017-12-22 山东嘉寓润峰新能源有限公司 Lithium ion battery slurry coating process
CN107528026A (en) * 2016-06-21 2017-12-29 住友化学株式会社 Layered product
CN107998905A (en) * 2017-12-20 2018-05-08 宋永秀 A kind of preparation method of the good small aperture ceramic film of surface integrity
CN111341974A (en) * 2020-03-13 2020-06-26 江苏厚生新能源科技有限公司 PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof, PVDF coated layer and lithium battery
CN111599969A (en) * 2020-05-29 2020-08-28 东莞市溢兴新材料科技有限公司 PVDF (polyvinylidene fluoride) -coated lithium ion battery diaphragm and preparation method thereof
US11038208B2 (en) 2017-12-19 2021-06-15 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery
US11094997B2 (en) 2017-05-29 2021-08-17 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery
US11158907B2 (en) 2017-12-19 2021-10-26 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery
US11158883B2 (en) 2017-12-19 2021-10-26 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery
US11205799B2 (en) 2017-12-19 2021-12-21 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery

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CN109244322B (en) * 2018-09-18 2021-10-22 武汉惠强新能源材料科技有限公司 Water-based coating for lithium ion battery diaphragm and preparation method and application thereof
CN112625517A (en) * 2021-01-15 2021-04-09 惠州市昌达胶粘制品有限公司 Shading waterproof nano coating

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KR100903180B1 (en) * 2006-05-22 2009-06-17 주식회사 엘지화학 Method of Controlling Coating-Quantity of Separator for Lithium-ion Polymer Battery
CN102931369A (en) * 2012-10-16 2013-02-13 能一郎科技股份有限公司 High-safety gel polymer film and preparation method thereof
KR101723994B1 (en) * 2014-02-21 2017-04-06 주식회사 포스코 Separator, method of manufacturing the same, lithium polymer secondary battery including the same, and method of manufacturing lithium polymer secondary battery using the same
CN104282865B (en) * 2014-09-03 2017-01-11 深圳中兴创新材料技术有限公司 Preparation method of gel polymer coating composite membrane, and battery diaphragm
CN104966848A (en) * 2015-06-19 2015-10-07 储盈新能源科技（上海）有限公司 Polymer for lithium ion battery, preparation method of polymer, lithium ion battery gel electrolyte and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN107528026A (en) * 2016-06-21 2017-12-29 住友化学株式会社 Layered product
US11094997B2 (en) 2017-05-29 2021-08-17 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery
CN107507956A (en) * 2017-07-28 2017-12-22 山东嘉寓润峰新能源有限公司 Lithium ion battery slurry coating process
CN107507956B (en) * 2017-07-28 2020-02-07 山东嘉寓润峰新能源有限公司 Lithium ion battery slurry coating process
US11038208B2 (en) 2017-12-19 2021-06-15 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery
US11158907B2 (en) 2017-12-19 2021-10-26 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery
US11158883B2 (en) 2017-12-19 2021-10-26 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery
US11205799B2 (en) 2017-12-19 2021-12-21 Sumitomo Chemical Company, Limited Nonaqueous electrolyte secondary battery
CN107998905A (en) * 2017-12-20 2018-05-08 宋永秀 A kind of preparation method of the good small aperture ceramic film of surface integrity
CN107998905B (en) * 2017-12-20 2020-11-13 绍兴凯达纺织装饰品有限公司 Method for repairing macropores or cracks on surface of ceramic membrane
CN111341974A (en) * 2020-03-13 2020-06-26 江苏厚生新能源科技有限公司 PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof, PVDF coated layer and lithium battery
CN111599969A (en) * 2020-05-29 2020-08-28 东莞市溢兴新材料科技有限公司 PVDF (polyvinylidene fluoride) -coated lithium ion battery diaphragm and preparation method thereof

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Application publication date: 20160210