CN104466242B - Sponge substrate carrier gel polymer electrolyte and preparation method thereof - Google Patents
Sponge substrate carrier gel polymer electrolyte and preparation method thereof Download PDFInfo
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- CN104466242B CN104466242B CN201410746874.1A CN201410746874A CN104466242B CN 104466242 B CN104466242 B CN 104466242B CN 201410746874 A CN201410746874 A CN 201410746874A CN 104466242 B CN104466242 B CN 104466242B
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- sponge
- gel polymer
- electrolyte
- polymer electrolyte
- polymer
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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
- H01M2300/0025—Organic electrolyte
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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
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- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a sponge substrate carrier gel polymer electrolyte and a preparation method thereof. The sponge substrate carrier gel polymer electrolyte is characterized in that sponge is a porous foaming material prepared by polyurethane with the hardness of 20 degrees to 40 degrees; a polymer is a homopolymer, a copolymer or a mixture of polyethers, polyacrylates, polyacrylonitriles, polyvinylidene fluorides, polyphosphazenes and polyvinyl acetates; and lithium salt and a plasticizer in the liquid electrolyte are one of or a mixture of two of lithium perchlorate and lithium hexafluorophosphate with different proportions and one of or mixed solution of a plurality of ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate. According to the process, the sponge firstly forms a compound with the polymer and then absorbs the liquid electrolyte to obtain the sponge substrate carrier gel polymer electrolyte. The sponge substrate carrier gel polymer electrolyte has the beneficial effects that the problem that the current gel polymer electrolyte cannot be subjected to industrialized large-sized film formation is solved, and new opportunity and possibility are provided for development of the electrolyte lithium ion battery products.
Description
Technical field
The present invention relates to lithium ion battery sponge matrix gel polymer electrolyte and preparation method thereof.
Background technology
The lithium ion battery high ionic conductivity of the existing liquid electrolyte of gel polymer electrolyte, has solid polymerization again
The security and stability of thing electrolyte, is important directions and guarantee that performance of lithium ion battery is further enhanced.But, at present
Gel polymer electrolyte cannot be applied in lithium ion battery product, this is because the mechanical property of gel polymer electrolyte film
The factorial praluction requirement of large area film forming is reached with dimensional space stability all the time can not.Therefore, research is prepared with good
The gel polymer electrolyte of good mechanical property and dimensional space stability is the most extremely urgent problem in the field.At present, most
Common solution is the various inorganic nano-fillers of addition, such as clay, ceramic particle and metal-oxide.This method is one
Determine in degree, to improve really the mechanical property and dimensional space stability of gel polymer electrolyte, but various inorganic fillers
Price is not low, undoubtedly increased the cost of electrolyte.In addition, inorganic filler scattering problem in the electrolyte all the time cannot
Thoroughly solve, also limit this method can only improve gel polymer electrolyte mechanical property and size to a certain extent
Spatial stability.Therefore, such as casting aside addition inorganic filler improves purpose this method to reach, and Expand Thinking is opened brand-new
Method carry out the new opportunity that solve problem must be that gel polymer electrolyte is able to apply in lithium ion battery.
Sponge is a kind of porous elastic material, and main component is polyurethane.Sponge inner void intermeshes connection, because
This, with surface area is big and the characteristics of light weight.Sponge material abundance, mature preparation process are simple, therefore, on the market
Price inexpensively.
The present invention with using sponge internal porous hole and intermesh connection the characteristics of, mechanics is provided for medium carrier with which
Support, prepare gel polymer electrolyte wherein, obtain lithium ion battery sponge matrix carrier gel polymer dielectric.
Content proposed by the invention, there is not yet any related research report.
The content of the invention
Technical problem to be solved
In order to thoroughly solve gel polymer electrolyte film as poor mechanical property and dimensional space stability is not good and lead
Cause cannot large area batch production film forming this root problem, the exploitation for gel polymer electrolyte lithium-ion battery product provides
Feasibility, the present invention provide mechanical support to prepare gel polymer electrolyte with sponge as medium carrier.
Technical scheme
The present invention using sponge as mechanical support medium carrier, prepare gel polymer electrolyte wherein, obtain lithium from
Sub- battery sponge matrix carrier gel polymer dielectric.
Lithium ion battery of the present invention sponge matrix carrier gel polymer dielectric and preparation method thereof, its skill
Art is characterised by：The sponge is the porous, expanded material with the standby hardness of raw material polyurethane in the range of 20 ° -40 °；It is described
Polymer is polyethers, polyacrylate, polypropylene nitrile, polyvinylidene fluoride alkenes, group of polyphosphazenes and polyvinyl acetate
Homopolymer, copolymer or mixture；Lithium salts and plasticizer in described liquid electrolyte is respectively lithium perchlorate, hexafluoro phosphorus
The mixture of one or two different ratios in sour lithium and be ethylene carbonate, Allyl carbonate, dimethyl carbonate, carbonic acid two
One or more mixed solution in ethyl ester.
Lithium ion battery of the present invention sponge matrix carrier gel polymer dielectric and preparation method thereof, which is special
Levy and be：Comprise the following steps that：
(1) polymer is dissolved in solvent at room temperature, stirring obtains uniform solution；
(2) dry sponge by thickness in 30 μm of -500 μ m is immersed in the solution for obtaining, and treats that its maximum is inhaled
After receiving solution, it is drawn off with tweezers, makes solvent volatilize from sponge, obtain sponge matrix carrier polymer complex, then at
It is placed at 40 DEG C -80 DEG C in vacuum drying oven and removes trace solvent；
(3) the dry sponge medium carrier polymer complex for obtaining is immersed into concentration in glove box for 1molL-1Liquid
In body electrolyte, treat which absorbs maximum liquid electrolyte, polymer just prepares sponge matrix carrier and coagulates when forming gel
Xanthan polymer electrolyte.
Solvent described in step (1) is tetrahydrofuran, acetone, one or more different ratio in dimethylformamide
Mixed solution.
Beneficial effect
The invention has the beneficial effects as follows, with this low price of sponge and the porous material that is easy to get is prepared as medium carrier
Lithium ion battery gel polymer electrolyte, thoroughly solves gel polymer electrolyte film as poor mechanical property and size are empty
Between stability is not good causes to be unable to large area film forming and affect factorial praluction this problem.
Description of the drawings
Process charts of the Fig. 1 for sponge matrix carrier gel polymer dielectric.
Specific embodiment
In order to prepare sponge matrix carrier gel polymer dielectric, following embodiment is this invention takes：
Embodiment 1：
(1) polymethyl methacrylate is dissolved in acetone at room temperature, stirring obtains uniform solution；
(2) dry sponge that thickness is 120 μm is immersed in the solution for obtaining, after its maximum absorbent solution, is used
Tweezers are drawn off, and make solvent volatilize from sponge, obtain sponge matrix carrier polymethyl methacrylate complex, then at 50
It is placed at DEG C in vacuum drying oven and removes trace solvent；
(3) the dry sponge medium carrier polymethyl methacrylate complex for obtaining is immersed concentration in glove box is
1mol·L-1In lithium perchlorate Allyl carbonate liquid electrolyte, treat which absorbs maximum liquid electrolyte, polymer forms solidifying
Sponge matrix carrier gel polymethyl methacrylate electrolyte is just prepared during glue, system 1 is named as.
Embodiment 2：
(1) polyacrylonitrile is dissolved in acetone at room temperature, stirring obtains uniform solution；
(2) dry sponge that thickness is 250 μm is immersed in the solution for obtaining, after its maximum absorbent solution, is used
Tweezers are drawn off, and make solvent volatilize from sponge, obtain sponge matrix carrier polyacrylonitrile complex, are placed at 60 DEG C
Trace solvent is removed in vacuum drying oven；
(3) the dry sponge medium carrier polyacrylonitrile complex for obtaining is immersed into concentration in glove box for 1molL-1
In lithium perchlorate dimethyl carbonate liquid electrolyte, treat which absorbs maximum liquid electrolyte, polymer is just made when forming gel
It is standby to obtain sponge matrix carrier gel polyacrylonitrile electrolyte, it is named as system 2.
Embodiment 3：
(1) poly- (methyl methacrylate-vinylacetate) copolymer is dissolved in tetrahydrofuran at room temperature, is stirred
To uniform solution；
(2) dry sponge that thickness is 350 μm is immersed in the solution for obtaining, after its maximum absorbent solution, is used
Tweezers are drawn off, and make solvent volatilize from sponge, obtain sponge matrix carrier poly- (methyl methacrylate-vinylacetate)
Complex, is placed in vacuum drying oven at 70 DEG C and removes trace solvent；
(3) by the dry sponge medium carrier for obtaining poly- (methyl methacrylate-vinylacetate) complex in glove
It is 1molL that concentration is immersed in case-1In lithium hexafluoro phosphate dimethyl carbonate liquid electrolyte, treat which absorbs maximum liquid electrolytic
Matter, polymer just prepare sponge matrix carrier gel poly- (methyl methacrylate-vinylacetate) electricity when forming gel
Xie Zhi, is named as system 3.
Embodiment 4：
(1) polyethylene glycol oxide and polymethyl acrylate blend (mass ratio 1: 1) are dissolved in into tetrahydrochysene furan at room temperature
In muttering, stirring obtains uniform solution；
(2) dry sponge that thickness is 450 μm is immersed in the solution for obtaining, after its maximum absorbent solution, is used
Tweezers are drawn off, and make solvent volatilize from cellulose membrane, obtain sponge matrix carrier polyethylene glycol oxide and polymethylacrylic acid
Methyl ester complex, is placed in vacuum drying oven at 80 DEG C and removes trace solvent；
(3) by the dry sponge medium carrier polyethylene glycol oxide for obtaining and polymethyl methacrylate complex in glove box
Middle immersion concentration is 1molL-1Lithium hexafluoro phosphate ethylene carbonate and Allyl carbonate (volume ratio is 3: 7) liquid electrolyte
In, treat which absorbs maximum liquid electrolyte, polymer just prepares sponge matrix carrier gel polyoxygenated when forming gel
Ethylene and polymethyl methacrylate electrolyte, are named as system 4.
Performance test is carried out to four kinds of system electrolytes, the results listed in the following table.
Claims (2)
1. sponge matrix carrier gel polymer dielectric and preparation method thereof, it is characterised in that：Comprise the following steps that：
(1) polymer is dissolved in solvent at room temperature, stirring obtains uniform solution；
(2) dry sponge by thickness in 30 μm of -500 μ m is immersed in the solution for obtaining, and treats that its maximum absorbs molten
After liquid, it is drawn off with tweezers, makes solvent volatilize from sponge, is obtained with sponge matrix carrier polymer complex, then at 40
It is placed in vacuum drying oven at DEG C -80 DEG C and removes trace solvent；
(3) the dry sponge medium carrier polymer complex for obtaining is immersed into concentration in glove box for 1molL-1Liquid electric
Xie Zhizhong, treats which absorbs maximum liquid electrolyte, and polymer just prepares sponge matrix carrier gel and gathers when forming gel
Polymer electrolyte；
The sponge is the porous, expanded material with the standby hardness of raw material polyurethane in the range of 20 ° -40 °；The polymer
For the homopolymerization of polyethers, polyacrylate, polypropylene nitrile, polyvinylidene fluoride alkenes, group of polyphosphazenes and polyvinyl acetate
Thing, copolymer or mixture.
2. the method for claim 1, it is characterised in that：Solvent described in step (1) be tetrahydrofuran, acetone, two
One or more different ratio mixed solution in methylformamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410746874.1A CN104466242B (en) | 2014-12-09 | 2014-12-09 | Sponge substrate carrier gel polymer electrolyte and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410746874.1A CN104466242B (en) | 2014-12-09 | 2014-12-09 | Sponge substrate carrier gel polymer electrolyte and preparation method thereof |
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| Publication Number | Publication Date |
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| CN104466242A CN104466242A (en) | 2015-03-25 |
| CN104466242B true CN104466242B (en) | 2017-04-26 |
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| CN201410746874.1A Expired - Fee Related CN104466242B (en) | 2014-12-09 | 2014-12-09 | Sponge substrate carrier gel polymer electrolyte and preparation method thereof |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355978B (en) * | 2015-10-16 | 2019-04-16 | 西南石油大学 | Lignin matrix gel polymer electrolyte |
| CN110380118A (en) * | 2019-07-18 | 2019-10-25 | 华中科技大学 | A kind of polymer dielectric and its preparation and application with flame retarding function |
| CN114199427B (en) * | 2021-12-09 | 2024-08-13 | 华东师范大学 | High-linearity conductive coating sponge piezoresistive sensor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927923A (en) * | 2006-09-06 | 2007-03-14 | 北京理工大学 | Ion liquid, non-aqueous liquid and polymer electrolyte material based on the same |
| CN101740813A (en) * | 2009-12-16 | 2010-06-16 | 北京理工大学 | Ionic liquid compound electrolyte material |
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2014
- 2014-12-09 CN CN201410746874.1A patent/CN104466242B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927923A (en) * | 2006-09-06 | 2007-03-14 | 北京理工大学 | Ion liquid, non-aqueous liquid and polymer electrolyte material based on the same |
| CN101740813A (en) * | 2009-12-16 | 2010-06-16 | 北京理工大学 | Ionic liquid compound electrolyte material |
Non-Patent Citations (1)
| Title |
|---|
| "增塑剂对聚氨醋型固体电解质离子导电性能的影响";郝冬梅等;《中国塑料》;20050831;第19卷(第8期);第76-80页 * |
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Granted publication date: 20170426 Termination date: 20171209 |