CN104852084B - A kind of preparation method of lithium ion battery polymer electrolyte - Google Patents
A kind of preparation method of lithium ion battery polymer electrolyte Download PDFInfo
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- CN104852084B CN104852084B CN201510160097.7A CN201510160097A CN104852084B CN 104852084 B CN104852084 B CN 104852084B CN 201510160097 A CN201510160097 A CN 201510160097A CN 104852084 B CN104852084 B CN 104852084B
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- electrophoretic deposition
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- polymer dielectric
- lithium ion
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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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- 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 present invention relates to a kind of preparation method of lithium ion battery polymer electrolyte is it is characterised in that comprise the steps：(1), polymeric matrix, pore creating material and inorganic additive are added in organic solvent under agitation, after forming homogeneous transparent solution, decompression standing is coated with after removing bubble, that is, primary membrane is obtained；(2), obtained primary membrane is placed in scattered electrolyte solution, controls electrophoretic deposition voltage, electrophoretic deposition electric current and electrophoretic deposition time, electrophoretic deposition polymer dielectric film after 60 DEG C of vacuum drying, is obtained；(3), obtained polymer dielectric film is placed in vacuum glove box activation in liquid electrolyte, that is, target product polymer dielectric is obtained.The lithium ion battery polymer dielectric of present invention preparation, can effectively improve the conductivity at room temperature of system and the mechanical performance of film layer, have electrochemical performance, stable cycle performance, the feature that preparation is simple.
Description
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 its system
Preparation Method technical field.
Background technology：
Polymer dielectric acts on of both acting primarily as in lithium-ion battery system, and one is as barrier film split cell
Both positive and negative polarity, with prevent short circuit situation, two be for battery system provide passage migrate back and forth for lithium ion.Obviously to expire
Sufficient above-mentioned two condition it is necessary to make prepared electrolyte be provided simultaneously with stronger mechanical performance and conductivity at room temperature,
Additionally to have with battery material preferable interface compatibility.For current present Research, often focus on solution
In a certain characteristic issues, and inhibit the practical development of polymer dielectric.Because it contains micro or does not contain liquid electrolyte
Liquid, so that polymer dielectric becomes the current focus solving battery safety research, is therefore studied very urgent to it.
For the problem preferably overcoming polymer dielectric to exist, it is met using means such as doping and modifications makes
With condition, and then improve the practicality of electrolyte.It can be seen that design invents, one kind can meet ionic conductivity and electrochemistry is steady
Determine window requirements, the polymer dielectric film preparation technology that also can meet practical safety in production requirement is to whole lithium ion battery row
The development of industry has great meaning.
Content of the invention：
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of lithium ion battery polymer electrolyte
Preparation method, lithium ion battery electrostrictive polymer is prepared using the united method of solution cast film formation paraphase electrophoretic deposition
Xie Zhi, can effectively improve the conductivity at room temperature of system and the mechanical performance of film layer, have electrochemical performance, cyclicity
Can be stable, the feature that preparation is simple.
The present invention is to realize above-mentioned purpose by following technical solution.
A kind of preparation method of lithium ion battery polymer electrolyte that the present invention provides, comprises the steps：
(1), polymeric matrix, pore creating material and inorganic additive are added in organic solvent under agitation, are formed
After homogeneous transparent solution, decompression standing is coated with after removing bubble, that is, primary membrane is obtained；
(2), obtained primary membrane is placed in scattered electrolyte solution, controls electrophoretic deposition voltage, electrophoresis
Deposition current and electrophoretic deposition time, electrophoretic deposition polymer dielectric film after 60 DEG C of vacuum drying, is obtained；
(3), obtained polymer dielectric film is placed in vacuum glove box activation in liquid electrolyte, that is, is obtained
Target product polymer dielectric；
In step (1), reactant quality 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 response time is 2～12 hours；
Described polymeric matrix is polymethyl acrylate, polyvinyl alcohol, polyacrylamide, polyimides, SPSF
Any mixture with one of hydroxylated cellulose or more than two kinds；
Described pore creating material is any mixture of one of ammonium hydrogen carbonate, carbamide, Polyethylene Glycol or more than two kinds；
Described inorganic additive is one of titanium dioxide, zirconium dioxide, ceria metal-oxide or two kinds
Above any mixture；
Described organic solvent be one of acetone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, chloroform or
More than two kinds of any mixture；
In step (2), described electrolyte solution is graphene oxide, one of the CNT weak solution of acidifying
Or two kinds of mixture；
Described electrophoretic deposition voltage is 6～20V；
Described electrophoretic deposition electric current is 10～100mA；
The described electrophoretic deposition time is 2～60min；
Described concentration of electrolyte solutions is 0.5～5mg/mL；
In step (3), described liquid electrolyte is LiPF6-EC/DMC/EMC、LiTFSI-PC/DMC、LiBF4-
EMIBF4In any one system；
Described soak time is 5～25min.
The present invention has the advantages that compared with prior art：
The present invention is prepared for lithium ion battery polymerization using solution cast film formation-united method of paraphase-electrophoretic deposition
Thing electrolyte.It is prepared for polymer primary membrane initially with casting film-forming-phase inversion method, be subsequently dipped in suitable electrolyte solution
In, by regulating and controlling the parameter of electrophoretic deposition process, prepare polymer dielectric film.Using solution electrophoresis techniques of deposition film,
Can primary membrane surface deposit one layer of suitable ionic conduction microporous film layers, effectively improve system conductivity at room temperature and
The mechanical performance of film layer.The polymer dielectric conductivity at room temperature prepared by the present invention is up to 3.4mS/cm, its stretching
Intensity increases to 20Mpa, and the button cell being assembled into lithium cobaltate cathode and graphite cathode is respectively provided with the good compatibility and follows
Ring stability.
Brief description:
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.
Specific embodiment：
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
By appropriate polymethyl acrylate, carbamide and nano titanium oxide etc. according to 10:1:1 mass ratio is in the feelings of stirring
It is added under condition in 200 parts of DMF solution, treat that it forms homogeneous transparent solution (colloidal sol), decompression standing is removed
It is coated with after removing bubble, after a period of time, obtain primary membrane.Will be dilute molten for graphene oxide that the primary membrane obtaining is placed in 2mg/mL
In liquid, control certain electrophoretic voltage (6,9,12,18V), be that 40mA carries out electrophoretic deposition and operates about 15min, electrophoresis in electric current
After the completion of deionized water clean film surface, 60 DEG C vacuum drying a period of time obtain final product electrophoretic deposition polymer dielectric film.
The polymer dielectric film prepared using electrophoretic deposition is placed in containing LiPF in vacuum glove box6Organic liquid electrolyte
Middle activation 15min obtains final product target product polymer dielectric.
The polymer dielectric of gained is assembled into SS/PE/SS simulated battery and Li/LiPF6/LiCoO2Button cell, point
Do not operate to investigate its conductivity at room temperature and electrochemically stable performance, its result using AC impedence method and rate charge-discharge
As shown in table 1.
Table 1：The experiment condition of example 1 and result
Embodiment 2：
By appropriate polymethyl acrylate, carbamide and nano titanium oxide etc. according to 10:1:1 mass ratio is in the feelings of stirring
It is added under condition in 200 parts of DMF solution, treat that it forms homogeneous transparent solution (colloidal sol), decompression standing is removed
It is coated with after removing bubble, after a period of time, obtain primary membrane.Will be dilute molten for graphene oxide that the primary membrane obtaining is placed in 2mg/mL
In liquid, control certain electrophoretic current (10,40,80,100mA), be that 9V carries out electrophoretic deposition operation about 15min in voltage, electric
After the completion of swimming, deionized water cleans film surface, and 60 DEG C of vacuum drying a period of times obtain final product electrophoretic deposition polymer dielectric
Film.The polymer dielectric film prepared using electrophoretic deposition is placed in containing LiPF in vacuum glove box6Organic liquid electricity
In solution liquid, activation 15min obtains final product target product polymer dielectric.
The polymer dielectric of gained is assembled into SS/PE/SS simulated battery and Li/LiPF6/LiCoO2Button cell, point
Do not operate to investigate its conductivity at room temperature and electrochemically stable performance, its result using AC impedence method and rate charge-discharge
As shown in table 2.
Table 2：The experiment condition of example 2 and result
Embodiment 3：
By appropriate polymethyl acrylate, carbamide and nano titanium oxide etc. according to 10:1:1 mass ratio is in the feelings of stirring
It is added under condition in 200 parts of DMF solution, treat that it forms homogeneous transparent solution (colloidal sol), decompression standing is removed
It is coated with after removing bubble, after a period of time, obtain primary membrane.Will be dilute molten for graphene oxide that the primary membrane obtaining is placed in 2mg/mL
In liquid, it is 9V in electrophoretic voltage, electric current is for carrying out electrophoretic deposition operation different time (5,10,15 and under conditions of 40mA
25min), after the completion of electrophoresis, deionized water cleans film surface, and 60 DEG C of vacuum drying a period of times obtain final product electrophoretic deposition polymerization
Thing dielectric film.The polymer dielectric film prepared using electrophoretic deposition is placed in containing LiPF in vacuum glove box6Have
In machine liquid electrolyte, activation 15min obtains final product target product polymer dielectric.
The polymer dielectric of gained is assembled into SS/PE/SS simulated battery and Li/LiPF6/ C button cell, adopts respectively
Operate to investigate its conductivity at room temperature and electrochemically stable performance, its result such as table with AC impedence method and rate charge-discharge
Shown in 3.
Table 3：The experiment condition of example 3 and result
Embodiment 4：
By appropriate polymethyl acrylate, carbamide and nano titanium oxide etc. according to 10:1:1 mass ratio is in the feelings of stirring
It is added under condition in 200 parts of DMF solution, treat that it forms homogeneous transparent solution (colloidal sol), decompression standing is removed
It is coated with after removing bubble, after a period of time, obtain primary membrane.By the primary membrane obtaining be placed in variable concentrations (0.5,1.0,2.0,
In graphene oxide weak solution 4.0mg/mL), it is 9V in electrophoretic voltage, electric current carries out electrophoretic deposition behaviour under conditions of 40mA
Make 15min, after the completion of electrophoretic deposition, deionized water cleans film surface, 60 DEG C of vacuum drying a period of times obtain final product electrophoresis polymerization
Thing dielectric film.The polymer dielectric film prepared using electrophoretic deposition is placed in containing LiPF in vacuum glove box6Have
In machine liquid electrolyte, activation 15min obtains final product target product polymer dielectric.
By the apparent state of the polymer dielectric of gained and its be assembled into SS/PE/SS simulated battery, using AC impedance
Investigating its conductivity at room temperature, its result is as shown in table 4 for method.
Table 4：The experiment condition of example 4 and result
Note：" -- " expression is not allowed due to condition, does not do this test
Embodiment 5：
The electrolyte solution that the present embodiment is used as different from Example 1 is the CNT weak solution of acidifying, its
His implementation condition is same as Example 1.
Claims (3)
1. a kind of preparation method of lithium ion battery polymer electrolyte is it is characterised in that comprise the steps：
(1), polymeric matrix, pore creating material and inorganic additive are added in organic solvent under agitation, are formed uniformly
After clear solution, decompression standing is coated with after removing bubble, that is, primary membrane is obtained；
(2), obtained primary membrane is placed in scattered electrolyte solution, controls electrophoretic deposition voltage, electrophoretic deposition
Electric current and electrophoretic deposition time, electrophoretic deposition polymer dielectric film after 60 DEG C of vacuum drying, is obtained；
(3), obtained polymer dielectric film is placed in vacuum glove box activation in liquid electrolyte, that is, target is obtained
Resulting polymer electrolyte；
In step (1), reactant quality 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 response time is 2～12 hours；
Described polymeric matrix is polymethyl acrylate, polyvinyl alcohol, polyacrylamide, polyimides, SPSF and hydroxyl
Any mixture of one of base cellulose or more than two kinds；
Described pore creating material is any mixture of one of ammonium hydrogen carbonate, carbamide, Polyethylene Glycol or more than two kinds；
Described inorganic additive is one of titanium dioxide, zirconium dioxide, ceria metal-oxide or more than two kinds
Any mixture；
Described organic solvent is one of acetone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, chloroform or two kinds
Above any mixture；
In step (2), described electrolyte solution is graphene oxide, one of the CNT weak solution of acidifying or two
The mixture planted；
In step (3), described liquid electrolyte is LiPF6-EC/DMC/EMC、LiTFSI-PC/DMC、LiBF4-EMIBF4In
Any one system.
2. a kind of preparation method of lithium ion battery polymer electrolyte according to claim 1 is it is characterised in that described
Electrophoretic deposition voltage be 6～20V；Described electrophoretic deposition electric current is 10～100mA；The described electrophoretic deposition time be 2～
60min；Described concentration of electrolyte solutions is 0.5～5mg/mL.
3. a kind of preparation method of lithium ion battery polymer electrolyte according to claim 2 is it is characterised in that described
Soak time be 5～25min.
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| CN105350054B (en) * | 2015-11-25 | 2017-12-08 | 哈尔滨工业大学 | A kind of method that the nano-carbon material modification of secondary battery membrane surface is realized by electrophoretic deposition |
| 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 |
| CN109585917B (en) * | 2018-12-11 | 2022-02-08 | 广东永邦新能源股份有限公司 | Polymer electrolyte, preparation method thereof and battery comprising polymer electrolyte |
| 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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| CN102035043B (en) * | 2009-09-25 | 2014-02-12 | 上海比亚迪有限公司 | Polymer porous membrane, preparation method thereof, polymer electrolyte, polymer battery and preparation method of battery |
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