CN104852084A - Preparation method of lithium ion battery polymer electrolyte - Google Patents

Preparation method of lithium ion battery polymer electrolyte Download PDF

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Publication number
CN104852084A
CN104852084A CN201510160097.7A CN201510160097A CN104852084A CN 104852084 A CN104852084 A CN 104852084A CN 201510160097 A CN201510160097 A CN 201510160097A CN 104852084 A CN104852084 A CN 104852084A
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electrophoretic deposition
polymer electrolyte
electrolyte
lithium ion
ion battery
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CN201510160097.7A
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CN104852084B (en
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肖围
缪畅
高林
颜学敏
梅平
洪泽勇
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Yangtze University
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Yangtze University
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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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 a lithium ion battery polymer electrolyte, wherein the method comprises the steps as follows: (1) adding a polymer matrix, a pore forming substance and an inorganic additive to an organic solvent under a stirring condition to form uniform transparent solution, and then reducing pressure and standing the solution to remove bubbles, and then coating to obtain a primary membrane; (2) placing the obtained primary membrane in a dispersed electrolyte solution, controlling electrophoretic deposition voltage, electrophoretic deposition current and electrophoretic deposition time, obtaining an electrophoretic deposition polymer electrolyte membrane after performing vacuum drying at the temperature of 60 DEG C; and (3) placing the prepared polymer electrolyte membrane in a liquid electrolyte in a vacuum glove box to activate to prepare the target product polymer electrolyte. The lithium ion battery polymer electrolyte prepared by the invention can be used for effectively improving ionic conductivity at room temperature of a system and mechanical property of a membrane layer, and has excellent electrochemical performance, stable cycle performance, and simple and practicable preparation technology.

Description

A kind of preparation method of lithium ion battery polymer electrolyte
Technical field:
The present invention relates to a kind of preparation method of lithium ion battery polymer electrolyte, belong to lithium ion battery material and preparation method thereof technical field.
Background technology:
Polymer dielectric mainly plays a part in two in lithium-ion battery system, and one is the both positive and negative polarity as membrane separation battery, and to prevent the situation of short circuit, two is for battery system provides passage to move back and forth for lithium ion.Obviously to meet above-mentioned two conditions, prepared electrolyte must be made simultaneously to possess stronger mechanical performance and conductivity at room temperature, the good interface compatibility with battery material will be had in addition.For current present Research, often focus on and solve in a certain characteristic issues, and inhibit the practicality of polymer dielectric to develop.Contain trace due to it or not containing liquid electrolyte, make polymer dielectric become the focus solving battery safety research at present, therefore very urgent to its research.
In order to overcome polymer dielectric Problems existing preferably, adopting it means such as doping and modification to meet service condition, and then improving electrolytical practicality.Visible design invents one can meet ionic conductivity and electrochemical stability window demand, and the development of polymer dielectric film preparation technology to whole lithium ion battery industry that also can meet practical safety in production requirement has great meaning.
Summary of the invention:
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of lithium ion battery polymer electrolyte, the method of solution cast film formation-paraphase-electrophoretic deposition associating is adopted to prepare lithium ion battery polymer dielectric, effectively can improve the conductivity at room temperature of system and the mechanical performance of rete, there is electrochemical performance, stable cycle performance, the feature that preparation is simple.
The present invention realizes above-mentioned purpose by following technical solution.
The preparation method of a kind of lithium ion battery polymer electrolyte provided by the invention, comprises the steps:
(1), by polymeric matrix, pore creating material and inorganic additive join under agitation in organic solvent, after forming homogeneous transparent solution, decompression is coated with after leaving standstill removing bubble, i.e. obtained primary membrane;
(2), by obtained primary membrane be placed in scattered electrolyte solution, control electrophoretic deposition voltage, electrophoretic deposition electric current and electrophoretic deposition time, after 60 DEG C of vacuumizes, namely obtain electrophoretic deposition polymer dielectric film;
(3), by obtained polymer dielectric film in vacuum glove box, be placed in liquid electrolyte to activate, i.e. obtained target product polymer dielectric;
In step (1), reactant mass ratio is: polymeric matrix: pore creating material: inorganic additive: organic solvent=80 ~ 200:5 ~ 10:0.8 ~ 2:400 ~ 1000; Reaction temperature is 20 ~ 100 DEG C, and the reaction time is 2 ~ 12 hours;
Described polymeric matrix is any mixture of one or two or more kinds in polymethyl acrylate, polyvinyl alcohol, polyacrylamide, polyimides, SPSF and hydroxylated cellulose;
Described pore creating material is any mixture of one or two or more kinds in carbonic hydroammonium, urea, polyethylene glycol;
Described inorganic additive is any mixture of one or two or more kinds in titanium dioxide, zirconium dioxide, ceria metal oxide;
Described organic solvent is any mixture of one or two or more kinds in acetone, DMF, DMA, chloroform;
In step (2), described electrolyte solution is any mixture of one or two or more kinds in the carbon nano-tube weak solution of graphene oxide, acidifying; ;
Described electrophoretic deposition voltage is 6 ~ 20V;
Described electrophoretic deposition electric current is 10 ~ 100mA;
The described electrophoretic deposition time is 2 ~ 60min;
Described electrolyte concentration is 0.5 ~ 5mg/mL;
In step (3), described liquid electrolyte is LiPF 6-EC/DMC/EMC, LiTFSI-PC/DMC, LiBF 4-EMIBF 4in any mixture of one or two or more kinds;
Described soak time is 5 ~ 25min.
The present invention has following beneficial effect compared with prior art:
The present invention adopts the method for solution cast film formation-paraphase-electrophoretic deposition associating to prepare lithium ion battery polymer dielectric.First adopting casting film-forming-phase inversion method to prepare polymer primary membrane, immersed in suitable electrolyte solution subsequently, by regulating and controlling the parameter of electrophoretic deposition process, preparing polymer dielectric film.Adopt solution electrophoresis techniques of deposition film, the microporous film layers of ionic conduction can be applicable at primary membrane surface deposition one deck, effective conductivity at room temperature of raising system and the mechanical performance of rete.The polymer dielectric conductivity at room temperature prepared by the present invention is up to 3.4mS/cm, and its hot strength is increased to 20Mpa, and the button cell be assembled into lithium cobaltate cathode and graphite cathode all has good compatibility and cyclical stability.
Accompanying drawing illustrates:
Fig. 1 is the SEM figure of No. 2 samples in embodiment 1, and wherein (A) is shiny surface, and (B) is matsurface.
Fig. 2 is the specific capacity-efficiency cyclic curve figure of No. 2 samples in embodiment 2.
Fig. 3 is charging and discharging curve figure under the different multiplying of No. 3 samples in embodiment 3.
Embodiment:
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1:
Appropriate polymethyl acrylate, urea and nano titanium oxide etc. are joined the N of 200 parts when stirring according to the mass ratio of 10:1:1, in dinethylformamide solution, treat that it forms homogeneous transparent solution (colloidal sol), decompression is coated with after leaving standstill removing bubble, namely obtains primary membrane after a period of time.The primary membrane obtained is placed in the graphene oxide weak solution of 2mg/mL, control certain electrophoretic voltage (6,9,12,18V), be that 40mA carries out electrophoretic deposition and operates about 15min at electric current, with deionized water purification membrane layer surface after electrophoresis completes, namely 60 DEG C of vacuumize a period of times obtain electrophoretic deposition polymer dielectric film.The polymer dielectric film adopting electrophoretic deposition to prepare is placed in containing LiPF in vacuum glove box 6organic liquid electrolyte in activate 15min and namely obtain target product polymer dielectric.
The polymer dielectric of gained is assembled into SS/PE/SS simulated battery and Li/LiPF 6/ LiCoO 2button cell, adopt AC impedence method and rate charge-discharge operation to investigate its conductivity at room temperature and electrochemical stability performance respectively, its result is as shown in table 1.
Table 1: the experiment condition of example 1 and result
Embodiment 2:
Appropriate polymethyl acrylate, urea and nano titanium oxide etc. are joined the N of 200 parts when stirring according to the mass ratio of 10:1:1, in dinethylformamide solution, treat that it forms homogeneous transparent solution (colloidal sol), decompression is coated with after leaving standstill removing bubble, namely obtains primary membrane after a period of time.The primary membrane obtained is placed in the graphene oxide weak solution of 2mg/mL, control certain electrophoretic current (10,40,80,100mA), be that 9V carries out electrophoretic deposition and operates about 15min at voltage, with deionized water purification membrane layer surface after electrophoresis completes, namely 60 DEG C of vacuumize a period of times obtain electrophoretic deposition polymer dielectric film.The polymer dielectric film adopting electrophoretic deposition to prepare is placed in containing LiPF in vacuum glove box 6organic liquid electrolyte in activate 15min and namely obtain target product polymer dielectric.
The polymer dielectric of gained is assembled into SS/PE/SS simulated battery and Li/LiPF 6/ LiCoO 2button cell, adopt AC impedence method and rate charge-discharge operation to investigate its conductivity at room temperature and electrochemical stability performance respectively, its result is as shown in table 2.
Table 2: the experiment condition of example 2 and result
Embodiment 3:
Appropriate polymethyl acrylate, urea and nano titanium oxide etc. are joined the N of 200 parts when stirring according to the mass ratio of 10:1:1, in dinethylformamide solution, treat that it forms homogeneous transparent solution (colloidal sol), decompression is coated with after leaving standstill removing bubble, namely obtains primary membrane after a period of time.The primary membrane obtained is placed in the graphene oxide weak solution of 2mg/mL, be 9V at electrophoretic voltage, electric current is carry out electrophoretic deposition operation different time (5,10,15 and 25min) under the condition of 40mA, with deionized water purification membrane layer surface after electrophoresis completes, namely 60 DEG C of vacuumize a period of times obtain electrophoretic deposition polymer dielectric film.The polymer dielectric film adopting electrophoretic deposition to prepare is placed in containing LiPF in vacuum glove box 6organic liquid electrolyte in activate 15min and namely obtain target product polymer dielectric.
The polymer dielectric of gained is assembled into SS/PE/SS simulated battery and Li/LiPF 6/ C button cell, adopt AC impedence method and rate charge-discharge operation to investigate its conductivity at room temperature and electrochemical stability performance respectively, its result is as shown in table 3.
Table 3: the experiment condition of example 3 and result
Embodiment 4:
Appropriate polymethyl acrylate, urea and nano titanium oxide etc. are joined the N of 200 parts when stirring according to the mass ratio of 10:1:1, in dinethylformamide solution, treat that it forms homogeneous transparent solution (colloidal sol), decompression is coated with after leaving standstill removing bubble, namely obtains primary membrane after a period of time.The primary membrane obtained is placed in variable concentrations (0.5,1.0,2.0,4.0mg/mL) graphene oxide weak solution, be 9V at electrophoretic voltage, electric current is carry out electrophoretic deposition operation 15min under the condition of 40mA, with deionized water purification membrane layer surface after electrophoretic deposition completes, namely 60 DEG C of vacuumize a period of times obtain electrophoretic polymer dielectric film.The polymer dielectric film adopting electrophoretic deposition to prepare is placed in containing LiPF in vacuum glove box 6organic liquid electrolyte in activate 15min and namely obtain target product polymer dielectric.
By the apparent state of the polymer dielectric of gained and be assembled into SS/PE/SS simulated battery, adopt AC impedence method to investigate its conductivity at room temperature, its result is as shown in table 4.
Table 4: the experiment condition of example 4 and result
Note: "--" represents because condition does not allow, and does not do this test
Embodiment 5:
The carbon nano-tube weak solution that the electrolyte solution that the present embodiment is used as different from Example 1 is acidifying, other implementation condition is identical with embodiment 1.

Claims (3)

1. a preparation method for lithium ion battery polymer electrolyte, is characterized in that comprising the steps:
(1), by polymeric matrix, pore creating material and inorganic additive join under agitation in organic solvent, after forming homogeneous transparent solution, decompression is coated with after leaving standstill removing bubble, i.e. obtained primary membrane;
(2), by obtained primary membrane be placed in scattered electrolyte solution, control electrophoretic deposition voltage, electrophoretic deposition electric current and electrophoretic deposition time, after 60 DEG C of vacuumizes, namely obtain electrophoretic deposition polymer dielectric film;
(3), by obtained polymer dielectric film in vacuum glove box, be placed in liquid electrolyte to activate, i.e. obtained target product polymer dielectric;
In step (1), reactant mass ratio is: polymeric matrix: pore creating material: inorganic additive: organic solvent=80 ~ 200:5 ~ 10:0.8 ~ 2:400 ~ 1000; Reaction temperature is 20 ~ 100 DEG C, and the reaction time is 2 ~ 12 hours;
Described polymeric matrix is any mixture of one or two or more kinds in polymethyl acrylate, polyvinyl alcohol, polyacrylamide, polyimides, SPSF and hydroxylated cellulose;
Described pore creating material is any mixture of one or two or more kinds in carbonic hydroammonium, urea, polyethylene glycol;
Described inorganic additive is any mixture of one or two or more kinds in titanium dioxide, zirconium dioxide, ceria metal oxide;
Described organic solvent is any mixture of one or two or more kinds in acetone, DMF, DMA, chloroform;
In step (2), described electrolyte solution is any mixture of one or two or more kinds in the carbon nano-tube weak solution of graphene oxide, acidifying;
In step (3), described liquid electrolyte is LiPF 6-EC/DMC/EMC, LiTFSI-PC/DMC, LiBF 4-EMIBF 4in any mixture of one or two or more kinds.
2. the preparation method of a kind of lithium ion battery polymer electrolyte according to claim 1, is characterized in that described electrophoretic deposition voltage is 6 ~ 20V; Described electrophoretic deposition electric current is 10 ~ 100mA; The described electrophoretic deposition time is 2 ~ 60min; Described electrolyte concentration is 0.5 ~ 5mg/mL.
3. the preparation method of a kind of lithium ion battery polymer electrolyte according to claim 2, is characterized in that described soak time is 5 ~ 25min.
CN201510160097.7A 2015-04-07 2015-04-07 A kind of preparation method of lithium ion battery polymer electrolyte Active CN104852084B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105350054A (en) * 2015-11-25 2016-02-24 哈尔滨工业大学 Method for modifying nano-carbon material on surface of secondary battery diaphragm through electrophoretic deposition
CN105810981A (en) * 2016-04-21 2016-07-27 常州大学 Ion-selective polymer composite film and preparation method thereof
CN109585917A (en) * 2018-12-11 2019-04-05 广东永邦新能源股份有限公司 A kind of polymer dielectric and preparation method thereof and the battery including the polymer dielectric
CN116036870A (en) * 2023-01-16 2023-05-02 江苏大学 Polyphenylene sulfide lithium extraction membrane and electrochemical activation method thereof

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* Cited by examiner, † Cited by third party
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JP2002042792A (en) * 2000-07-31 2002-02-08 Denso Corp Method for manufacturing battery electrode with solid electrolyte layer
CN102035043A (en) * 2009-09-25 2011-04-27 上海比亚迪有限公司 Polymer porous membrane, preparation method thereof, polymer electrolyte, polymer battery and preparation method of battery
CN103972584A (en) * 2013-02-04 2014-08-06 苏州宝时得电动工具有限公司 Electrolyte carrier membrane, electrolyte, preparation method of two and lithium ion battery
CN104056306A (en) * 2014-06-09 2014-09-24 南京师范大学 Nerve conduit material having topological structure and modified by CNT/conducting polymer composite coating and preparation method of nerve conduit material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002042792A (en) * 2000-07-31 2002-02-08 Denso Corp Method for manufacturing battery electrode with solid electrolyte layer
CN102035043A (en) * 2009-09-25 2011-04-27 上海比亚迪有限公司 Polymer porous membrane, preparation method thereof, polymer electrolyte, polymer battery and preparation method of battery
CN103972584A (en) * 2013-02-04 2014-08-06 苏州宝时得电动工具有限公司 Electrolyte carrier membrane, electrolyte, preparation method of two and lithium ion battery
CN104056306A (en) * 2014-06-09 2014-09-24 南京师范大学 Nerve conduit material having topological structure and modified by CNT/conducting polymer composite coating and preparation method of nerve conduit material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105350054A (en) * 2015-11-25 2016-02-24 哈尔滨工业大学 Method for modifying nano-carbon material on surface of secondary battery diaphragm through electrophoretic deposition
CN105810981A (en) * 2016-04-21 2016-07-27 常州大学 Ion-selective polymer composite film and preparation method thereof
CN105810981B (en) * 2016-04-21 2019-06-04 常州大学 A kind of ion selectivity composite membrane of polymer and preparation method thereof
CN109585917A (en) * 2018-12-11 2019-04-05 广东永邦新能源股份有限公司 A kind of polymer dielectric and preparation method thereof and the battery including the polymer dielectric
CN116036870A (en) * 2023-01-16 2023-05-02 江苏大学 Polyphenylene sulfide lithium extraction membrane and electrochemical activation method thereof
CN116036870B (en) * 2023-01-16 2023-09-26 江苏大学 Polyphenylene sulfide lithium extraction membrane and electrochemical activation method thereof

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