CN104466242A - 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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- CN104466242A CN104466242A CN201410746874.1A CN201410746874A CN104466242A CN 104466242 A CN104466242 A CN 104466242A CN 201410746874 A CN201410746874 A CN 201410746874A CN 104466242 A CN104466242 A CN 104466242A
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- sponge
- gel polymer
- polymer electrolyte
- electrolyte
- substrate carrier
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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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- Condensed Matter Physics & Semiconductors (AREA)
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- Manufacturing & Machinery (AREA)
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- 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 ionic conductivity that the existing liquid electrolyte of lithium ion battery gel polymer electrolyte is high, has again the security and stability of solid polymer electrolyte, is the important directions that is further enhanced of performance of lithium ion battery and guarantee.But current gel polymer electrolyte cannot be applied in lithium ion battery product, this is because the mechanical property of gel polymer electrolyte film and dimensional space stability do not reach the factorial praluction requirement of large area film forming all the time.Therefore, the gel polymer electrolyte with excellent mechanical performances and dimensional space stability is prepared in research is the extremely the most urgent problem in this field.At present, modal solution adds various inorganic nano-filler, as clay, ceramic particle and metal oxide.This method improves mechanical property and the dimensional space stability of gel polymer electrolyte to a certain extent really, but various inorganic filler price is not low, adds electrolytical cost undoubtedly.In addition, inorganic filler scattering problem in the electrolyte can not get solving thoroughly all the time, also limit this method and can only improve gel polymer electrolyte mechanical property and dimensional space stability to a certain extent.Therefore, add inorganic filler as cast aside and reach and improve this method of object, Expand Thinking, opening brand-new method, to solve problem must be the new opportunity 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, therefore, has the advantages that surface area is large and quality is light.Sponge material abundance, mature preparation process are simple, therefore, in price on the market inexpensively.
The present invention, with utilizing sponge internal porous hole and the feature be communicated with that intermeshes, with it for medium carrier provides mechanical support, prepares gel polymer electrolyte wherein, obtains lithium ion battery sponge matrix carrier gel polymer dielectric.Content proposed by the invention, there is not yet any relevant research report.
Summary of the invention
The technical problem solved
In order to thoroughly solve gel polymer electrolyte film due to poor mechanical property with dimensional space stability is not good and cause cannot this root problem of large area batch production film forming, for the exploitation of gel polymer electrolyte lithium-ion battery product provides feasibility, the present invention is that medium carrier provides mechanical support to prepare gel polymer electrolyte with sponge.
Technical scheme
The present invention, using sponge as mechanical support medium carrier, prepares gel polymer electrolyte wherein, obtains lithium ion battery sponge matrix carrier gel polymer dielectric.
Lithium ion battery sponge matrix carrier gel polymer dielectric of the present invention and preparation method thereof, its technical characteristic is: described sponge is with the standby porous, expanded material of hardness within the scope of 20 °-40 ° of raw material polyurethane; Described polymer is the homopolymers of polyethers, polyacrylate, polypropylene nitrile, Kynoar class, group of polyphosphazenes and polyvinyl acetate, copolymer or mixture; Lithium salts in described liquid electrolyte and plasticizer are respectively the mixture of one or both different ratio in lithium perchlorate, lithium hexafluoro phosphate and are one or more mixed solutions in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate.
Lithium ion battery sponge matrix carrier gel polymer dielectric of the present invention and preparation method thereof, is characterized in that: concrete steps are as follows:
(1) polymer is dissolved in solvent under room temperature, stirs and obtain uniform solution;
(2) dry sponge of thickness within the scope of 30 μm-500 μm is immersed in the solution obtained, after its maximum absorbent solution, taken out with tweezers, solvent is volatilized from sponge, obtain sponge matrix carrier polymer compound, then at 40 DEG C-80 DEG C, be placed in vacuum drying oven remove trace solvent;
(3) the dry sponge medium carrier polymer complex obtained being immersed concentration in glove box is 1molL
-1in liquid electrolyte, treat that it absorbs maximum liquid electrolyte, when polymer forms gel, just prepare sponge matrix carrier gel polymer dielectric.
Solvent described in step (1) is one or more different ratio mixed solutions in oxolane, acetone, dimethyl formamide.
Beneficial effect
The invention has the beneficial effects as follows, with this low price of sponge and the porous material be easy to get for medium carrier is to prepare lithium ion battery gel polymer electrolyte, thoroughly solve gel polymer electrolyte film due to poor mechanical property and dimensional space stability not good causing can not large area film forming and affect this problem of factorial praluction.
Accompanying drawing explanation
Fig. 1 is the process chart of sponge matrix carrier gel polymer dielectric.
Embodiment
In order to prepare sponge matrix carrier gel polymer dielectric, this invention takes following execution mode:
Embodiment 1:
(1) polymethyl methacrylate is dissolved in acetone under room temperature, stirs and obtain uniform solution;
(2) be that the dry sponge of 120 μm is immersed in the solution obtained by thickness, after its maximum absorbent solution, taken out with tweezers, solvent is volatilized from sponge, obtain sponge matrix carrier polymethyl methacrylate compound, then at 50 DEG C, be placed in vacuum drying oven remove trace solvent;
(3) the dry sponge medium carrier polymethyl methacrylate compound obtained being immersed concentration in glove box is 1molL
-1in lithium perchlorate propene carbonate liquid electrolyte, treat that it absorbs maximum liquid electrolyte, when polymer forms gel, just prepare sponge matrix carrier gel polymethyl methacrylate electrolyte, called after system 1.
Embodiment 2:
(1) polyacrylonitrile is dissolved in acetone under room temperature, stirs and obtain uniform solution;
(2) be that the dry sponge of 250 μm is immersed in the solution obtained by thickness, after its maximum absorbent solution, taken out with tweezers, solvent is volatilized from sponge, obtain sponge matrix carrier polyacrylonitrile compound, then at 60 DEG C, be placed in vacuum drying oven remove trace solvent;
(3) the dry sponge medium carrier polyacrylonitrile compound obtained being immersed concentration in glove box is 1molL
-1in lithium perchlorate dimethyl carbonate liquid electrolyte, treat that it absorbs maximum liquid electrolyte, when polymer forms gel, just prepare sponge matrix carrier gel polyacrylonitrile electrolyte, called after system 2.
Embodiment 3:
(1) will gather (methyl methacrylate-vinylacetate) copolymer is dissolved in oxolane under room temperature, stirs and obtains uniform solution;
(2) be that the dry sponge of 350 μm is immersed in the solution obtained by thickness, after its maximum absorbent solution, taken out with tweezers, solvent is volatilized from sponge, obtain poly-(methyl methacrylate-vinylacetate) compound of sponge matrix carrier, then at 70 DEG C, be placed in vacuum drying oven remove trace solvent;
(3) poly-for the dry sponge medium carrier obtained (methyl methacrylate-vinylacetate) compound being immersed concentration in glove box is 1molL
-1in lithium hexafluoro phosphate dimethyl carbonate liquid electrolyte, treat that it absorbs maximum liquid electrolyte, just prepare sponge matrix carrier gel poly-(methyl methacrylate-vinylacetate) electrolyte when polymer forms gel, called after system 3.
Embodiment 4:
(1) polyethylene glycol oxide and polymethyl acrylate blend (mass ratio 1: 1) are dissolved in oxolane under room temperature, stir and obtain uniform solution;
(2) be that the dry sponge of 450 μm is immersed in the solution obtained by thickness, after its maximum absorbent solution, taken out with tweezers, solvent is volatilized from cellulose membrane, obtain sponge matrix carrier polyethylene glycol oxide and polymethyl methacrylate compound, then at 80 DEG C, be placed in vacuum drying oven remove trace solvent;
(3) the dry sponge medium carrier polyethylene glycol oxide obtained and polymethyl methacrylate compound being immersed concentration in glove box is 1molL
-1in lithium hexafluoro phosphate ethylene carbonate and propene carbonate (volume ratio is 3: 7) liquid electrolyte, treat that it absorbs maximum liquid electrolyte, polymer just prepares sponge matrix carrier gel polyethylene glycol oxide and polymethyl methacrylate electrolyte, called after system 4 when forming gel.
Carry out performance test to four kinds of system electrolytes, the results listed in the following table.
Claims (3)
1. sponge matrix carrier gel polymer dielectric and preparation method thereof, is characterized in that: described sponge is with the standby porous, expanded material of hardness within the scope of 20 °-40 ° of raw material polyurethane; Described polymer is the homopolymers of polyethers, polyacrylate, polypropylene nitrile, Kynoar class, group of polyphosphazenes and polyvinyl acetate, copolymer or mixture; Lithium salts in described liquid electrolyte and plasticizer are respectively the mixture of one or both different ratio in lithium perchlorate, lithium hexafluoro phosphate and are one or more mixed solutions in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate.
2. sponge matrix carrier gel polymer dielectric and preparation method thereof as claimed in claim 1, is characterized in that: concrete steps are as follows:
(1) polymer is dissolved in solvent under room temperature, stirs and obtain uniform solution;
(2) dry sponge of thickness within the scope of 30 μm-500 μm is immersed in the solution obtained, after its maximum absorbent solution, taken out with tweezers, solvent is volatilized from sponge, obtain with sponge matrix carrier polymer compound, then at 40 DEG C-80 DEG C, be placed in vacuum drying oven remove trace solvent;
(3) the dry sponge medium carrier polymer complex obtained being immersed concentration in glove box is 1molL
-1in liquid electrolyte, treat that it absorbs maximum liquid electrolyte, when polymer forms gel, just prepare sponge matrix carrier gel polymer dielectric.
3. method as claimed in claim 2, is characterized in that: the solvent described in step (1) is one or more different ratio mixed solutions in oxolane, acetone, dimethyl formamide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410746874.1A CN104466242B (en) | 2014-12-09 | 2014-12-09 | Sponge substrate carrier gel polymer electrolyte and preparation method thereof |
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| CN201410746874.1A CN104466242B (en) | 2014-12-09 | 2014-12-09 | Sponge substrate carrier gel polymer electrolyte and preparation method thereof |
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| CN104466242A true CN104466242A (en) | 2015-03-25 |
| CN104466242B CN104466242B (en) | 2017-04-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355978A (en) * | 2015-10-16 | 2016-02-24 | 西南石油大学 | Xylogen matrix gel polymer electrolyte and preparation method therefor |
| 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 |
| CN114199427A (en) * | 2021-12-09 | 2022-03-18 | 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 |
-
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 |
|---|
| 郝冬梅等: ""增塑剂对聚氨醋型固体电解质离子导电性能的影响"", 《中国塑料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355978A (en) * | 2015-10-16 | 2016-02-24 | 西南石油大学 | Xylogen matrix gel polymer electrolyte and preparation method therefor |
| 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 |
| CN114199427A (en) * | 2021-12-09 | 2022-03-18 | 华东师范大学 | High-linearity conductive coating sponge piezoresistive sensor and preparation method thereof |
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| CN104466242B (en) | 2017-04-26 |
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