CN104124415A - Composite gel polymer electrolyte as well as preparation method and application thereof - Google Patents
Composite gel polymer electrolyte as well as preparation method and application thereof Download PDFInfo
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- CN104124415A CN104124415A CN201310156428.0A CN201310156428A CN104124415A CN 104124415 A CN104124415 A CN 104124415A CN 201310156428 A CN201310156428 A CN 201310156428A CN 104124415 A CN104124415 A CN 104124415A
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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
- 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
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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
- H01M10/058—Construction or manufacture
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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
- H01M2300/0085—Immobilising or gelification of 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a composite gel polymer electrolyte. The composite gel polymer electrolyte comprises a composite gel polymer electrolyte membrane and an electrolyte solution adsorbed on the composite gel polymer electrolyte membrane, wherein the composite gel polymer electrolyte membrane comprises a support body, and poly (butyl methacrylate-acrylonitrile) and polyvinylidene fluoride, which are adsorbed in the support body, a polyethylene film, a polypropylene film, a polypropylene-ethylene-propylene three-layer composite diaphragm or a non-woven fabric is adopted as the support body, the electrolyte solution comprises lithium hexafluorophosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, the mass ratio of ethylene carbonate to dimethyl carbonate to methyl ethyl carbonate is (0.5-2):(0.5-2):(0.5-2), and the molar concentration of lithium hexafluorophosphate is 0.5-2mol/L. The composite gel polymer electrolyte has good electrolyte adsorptive property and ion transmission property and high electrical conductivity; the electrolyte solution is prepared from components with reasonable ratio so that interface stability of the gel polymer electrolyte and metal lithium is high.
Description
Technical field
The present invention relates to lithium ion battery field, particularly relate to a kind of plural gel polymer dielectric and preparation method thereof and application.
Background technology
Gel polymer electrolyte (GPE), owing to combining the features such as liquid electrolyte conductivity height and solid electrolyte fail safe are good simultaneously, is deeply probed into by researcher all the time.Many polymer as GPE matrix have now been reported, as Kynoar (PVDF), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyethylene glycol oxide (PEO), polyvinyl chloride (PVC) etc.But according to research, find that above-mentioned matrix still exists some defects: (1) is compared with liquid electrolyte, gel electrolyte conductivity is at room temperature not ideal enough, (2) interface stability of gel electrolyte and desirable negative material-lithium is not fine, makes gel polymer electrolyte be difficult to meet user demand.
Summary of the invention
Based on this, be necessary low for existing gel polymer electrolyte conductivity, poor with the interface stability of lithium metal problem, provide a kind of conductivity higher, with the good plural gel polymer dielectric film of interface stability of lithium metal.
Further, provide a kind of method for preparing gel polymer electrolyte and application.
A kind of plural gel polymer dielectric, comprise plural gel polyelectrolyte membranes and be adsorbed in the electrolyte on described plural gel polymer dielectric film, described plural gel polymer dielectric film comprises supporter and is adsorbed in poly-(butyl methacrylate-acrylonitrile) and the Kynoar in described supporter, described supporter is polyethylene film, polypropylene screen, three layers of composite diaphragm of polypropylene-ethylene-propylene or nonwoven fabrics, described electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, described ethylene carbonate, the mass ratio of dimethyl carbonate and methyl ethyl carbonate is 0.5～2:0.5～2:0.5～2, the molar concentration of described lithium hexafluoro phosphate is 0.5～2mol/L.
In an embodiment, the mass ratio of described poly-(butyl methacrylate-acrylonitrile) and Kynoar is 1～6:1～6 therein.
A plural gel method for preparing polymer electrolytes, comprises the following steps:
Provide support body, described supporter is polyethylene film, polypropylene screen, three layers of composite diaphragm of polypropylene-ethylene-propylene or nonwoven fabrics;
Described supporter is soaked 5～20 minutes in poly-(butyl methacrylate-acrylonitrile) solution, take out and dry, the supporter after being dried;
Supporter after described oven dry is soaked 5～20 minutes in Kynoar solution, take out and dry, obtain plural gel polymer dielectric film;
Described plural gel polymer dielectric film is soaked 1～2 hour in electrolyte, obtain plural gel polymer dielectric; Wherein, described electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, the mass ratio of described ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 0.5～2:0.5～2:0.5～2, and the molar concentration of described lithium hexafluoro phosphate is 0.5～2mol/L.
Therein in an embodiment, the compound method of described poly-(butyl methacrylate-acrylonitrile) solution is: in the first protective gas atmosphere, to gather (butyl methacrylate-acrylonitrile) and be dissolved in the first solvent, in 30～80 ℃ of return stirrings 0.5～5 hour; The compound method of described Kynoar solution is: in the second protective gas atmosphere, Kynoar is dissolved in the second solvent, in 30～80 ℃ of return stirrings 0.5～5 hour.
In an embodiment, described the first solvent is selected from least one in acetone, N-N dimethyl formamide and oxolane therein; Described the second solvent is selected from least one in acetone, N-N dimethyl formamide and oxolane.
In an embodiment, the mass percentage concentration of described poly-(butyl methacrylate-acrylonitrile) solution is 1～6% therein; The mass percentage concentration of described Kynoar solution is 1～6%.
Therein in an embodiment, described described plural gel polymer dielectric film is soaked in electrolyte to the operation of 1～2 hour before, also comprise described plural gel polymer dielectric film in 30～55 ℃ of steps of dry 5～24 hours.
A lithium ion battery, comprises battery container, positive pole, negative pole and above-mentioned plural gel polymer dielectric; Wherein,
Described positive pole, negative pole and plural gel polymer dielectric are contained in described battery container, and described plural gel polymer dielectric is between described positive pole and negative pole.
In an embodiment, the material of described positive pole is high cobalt acid lithium, inferior LiMn2O4, LiFePO4 or LiNi therein
1/3co
1/3mn
1/3o
2, the material of described negative pole is Delanium or coke phase carbon microbeads.
A preparation method for lithium ion battery, comprises the following steps:
Above-mentioned plural gel polymer dielectric is reeled and is assembled into battery core with anodal, negative pole;
Battery core, 50～65 ℃ of vacuumizes 15～20 hours, is sealed, changed into and obtain lithium ion battery.
In above-mentioned plural gel polymer dielectric, because supporter has adsorbed poly-(butyl methacrylate-acrylonitrile) and Kynoar, make plural gel polymer dielectric film have the microcellular structure being cross-linked with each other, the hole with mutual perforation, thereby there is good electrolyte absorption property and ion transmission performance, thereby can improve conductivity; And electrolyte adopts suitable component and proportioning to make the interface stability of this gel polymer electrolyte and lithium metal better in this electrolyte.
Accompanying drawing explanation
Fig. 1 is the flow chart of the plural gel method for preparing polymer electrolytes of an embodiment;
Fig. 2 is preparation method's the flow chart of the lithium ion battery of an embodiment;
Fig. 3 is the ac impedance measurement figure of the plural gel polymer dielectric of embodiment 1 preparation;
Fig. 4 (a) is the single P(BMA-AN of comparative example 1 preparation) the SEM figure of polymer dielectric;
Fig. 4 (b) is the SEM figure of the plural gel polymer dielectric of embodiment 3 preparations;
Fig. 5 is the linear scan figure of the plural gel polymer dielectric of embodiment 4 preparations;
Fig. 6 is the thermogravimetric analysis figure of the plural gel polymer dielectric of embodiment 5 preparations.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
The plural gel polymer dielectric of one execution mode, comprises plural gel polyelectrolyte membranes and is adsorbed in the electrolyte on plural gel polymer dielectric film.
Plural gel polymer dielectric film comprises supporter and is adsorbed in poly-(butyl methacrylate-acrylonitrile) (P (BMA-AN)) and the Kynoar (PVDF) in supporter.
Supporter is polyethylene film (PE), polypropylene screen (PP), three layers of composite diaphragm of polypropylene-ethylene-propylene (PP-PE-PP) or nonwoven fabrics.Wherein, three layers of composite diaphragm of polypropylene-ethylene-propylene (PP-PE-PP) refer to that polypropylene screen, polyethylene film and polypropylene screen stack gradually the composite membrane of formation.
Supporter plays supporting role on the one hand, make the mechanical strength of plural gel polymer dielectric higher, on the other hand, the supporter that this different materials forms can adsorb poly-(butyl methacrylate-acrylonitrile) (P (BMA-AN)) and Kynoar (PVDF) and the plural gel polymer dielectric film of formation loose structure preferably.The gel polymer electrolyte film being formed by supporter, poly-(butyl methacrylate-acrylonitrile) (P (BMA-AN)) and Kynoar (PVDF) has higher mechanical strength, and can comprehensively gather the advantage of (butyl methacrylate-acrylonitrile) (P (BMA-AN)) and Kynoar (PVDF).
The thickness of supporter is preferably 0.015～0.030mm.
Poly-(butyl methacrylate-acrylonitrile) (P (BMA-AN)) and Kynoar (PVDF) are adsorbed in supporter jointly, the plural gel polymer dielectric film forming has the microcellular structure being cross-linked with each other, the hole with mutual perforation, thereby there is good electrolyte absorption property and ion transmission performance, thereby can improve conductivity.
Preferably, the mass ratio of poly-(butyl methacrylate-acrylonitrile) (P (BMA-AN)) and Kynoar (PVDF) is 1～6:1～6.
Electrolyte comprises lithium hexafluoro phosphate (LiPF
6), ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC).Wherein, the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 0.5～2:0.5～2:0.5～2, and the molar concentration of lithium hexafluoro phosphate is 0.5～2mol/L.
Above-mentioned electrolyte adopts suitable component and proportioning, is conducive to improve the interface stability of this plural gel polymer dielectric and lithium metal.
In above-mentioned plural gel polymer dielectric, because supporter has adsorbed poly-(butyl methacrylate-acrylonitrile) and Kynoar, make plural gel polymer dielectric film have the microcellular structure being cross-linked with each other, the hole with mutual perforation, thereby there is good electrolyte absorption property and ion transmission performance, thereby can improve conductivity; And electrolyte adopts suitable component and proportioning to make the interface stability of this gel polymer electrolyte and lithium metal better in this electrolyte.
This plural gel polymer dielectric is applied in lithium ion battery, can improves the performance of lithium ion battery.Lithium ion battery can lithium-ion button battery, and this lithium-ion button battery can be for electronic product as electronic dictionary, wrist-watch, calculator etc.; Can be other lithium ion batteries, such as Soft Roll polymer Li-ion battery etc.
Refer to Fig. 1, the plural gel method for preparing polymer electrolytes of an execution mode, comprises the following steps:
Step S101: provide support body, supporter is polyethylene film, polypropylene screen, three layers of composite diaphragm of polypropylene-ethylene-propylene or nonwoven fabrics.
Supporter can strengthen the mechanical strength of plural gel polymer dielectric, for suitability for industrialized production provides condition.
The thickness of supporter is preferably 0.015～0.030mm.
Step S102: supporter is soaked 5～20 minutes in poly-(butyl methacrylate-acrylonitrile) solution, take out and dry, the supporter after being dried.
The compound method of poly-(butyl methacrylate-acrylonitrile) solution is: in the first protective gas atmosphere; to gather (butyl methacrylate-acrylonitrile) is dissolved in the first solvent; in 30～80 ℃ of return stirrings 0.5～5 hour, gathered (butyl methacrylate-acrylonitrile) solution.
The first protective gas can be nitrogen or inert gas.The mass percentage concentration of poly-(butyl methacrylate-acrylonitrile) solution is preferably 1～6%.The first solvent is at least one in acetone, N-N dimethyl formamide and oxolane preferably.
Supporter is soaked in poly-(butyl methacrylate-acrylonitrile) solution, and poly-(butyl methacrylate-acrylonitrile) solution is adsorbed on supporter, takes out and dries, the supporter after being dried.In supporter after oven dry, the first solvent evaporates, poly-(butyl methacrylate-acrylonitrile) forms micropore in supporting body surface.
The method of drying is that air blast is dried.Air blast is dried and the solvent evaporating can be blown away, pore-forming better effects if.
Step S103: the supporter after drying is soaked 5～20 minutes in Kynoar solution, take out and dry, obtain plural gel polymer dielectric film;
The compound method of Kynoar solution is: in the second protective gas atmosphere, Kynoar is dissolved in the second solvent, in 30～80 ℃ of return stirrings 0.5～5 hour, obtains Kynoar solution.
The second protective gas can be nitrogen or inert gas.The mass percentage concentration of Kynoar solution is 1～6%.The second solvent is selected from least one in acetone, N-N dimethyl formamide and oxolane.
Supporter after drying is soaked in Kynoar solution, carry out secondary immersion, Kynoar solution can be filled up in the micro cellular voids that become, the aperture of the plural gel polymer dielectric film that the process of again drying obtains is less, hole is more, therefore the plural gel polymer dielectric film making has the fabulous microcellular structure being cross-linked with each other, has the hole of mutual perforation, thereby has good electrolyte absorption property and ion transmission performance.
The method of drying is that air blast is dried.Air blast is dried and the solvent evaporating can be blown away, pore-forming better effects if.
Step S104: plural gel polymer dielectric film is soaked 1～2 hour in electrolyte, obtain plural gel polymer dielectric; Wherein, electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 0.5～2:0.5～2:0.5～2, and the molar concentration of lithium hexafluoro phosphate is 0.5～2mol/L.
Preferably, before plural gel polymer dielectric film being soaked in electrolyte to the operation of 1～2 hour, can also by plural gel polymer dielectric film in 30～55 ℃ dry 5～24 hours.Object is further to remove supporter residual solvent when poly-(butyl methacrylate-acrylonitrile) solution, Kynoar solution soak.
Plural gel polymer dielectric film is immersed under anhydrous and oxygen free condition and carries out in electrolyte, for example, can in glove box, carry out.
Electrolyte comprises lithium hexafluoro phosphate (LiPF
6), ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC).Wherein, the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 0.5～2:0.5～2:0.5～2, and the molar concentration of lithium hexafluoro phosphate is 0.5～2mol/L.
Above-mentioned plural gel method for preparing polymer electrolytes is soaked in supporter successively in poly-(butyl methacrylate-acrylonitrile) solution and Kynoar solution and forms the gel polymer electrolyte film with the micropore that is cross-linked with each other, then this gel polymer electrolyte film is soaked in and in electrolyte, obtains gel polymer electrolyte.Be soaked in poly-(butyl methacrylate-acrylonitrile) solution and on supporter, form microcellular structure, secondary is soaked in Kynoar solution, in the hole that new Kynoar solution can be filled up become, the aperture of the micropore of the plural gel polymer dielectric film that the process of again drying obtains is less, the hole advantages that make this plural gel polymer dielectric film combine poly-(butyl methacrylate-acrylonitrile) and Kynoar more, there is the fabulous microcellular structure being cross-linked with each other, splendid absorbent and ion transmission performance, superior performance.
And above-mentioned plural gel method for preparing polymer electrolytes technique is simple, the time is short, and efficiency is high, with the existing hardware compatibility of preparing liquid lithium ionic cell, has reduced the cost of suitability for industrialized production.
The lithium ion battery of one execution mode, comprises battery container, positive pole, negative pole and above-mentioned plural gel polymer dielectric.
Wherein, positive pole, negative pole and plural gel polymer dielectric are contained in battery container, and gel polymer electrolyte is between described positive pole and negative pole.
In the present embodiment, the material of described positive pole is preferably high cobalt acid lithium (LiCoO
2), inferior LiMn2O4 (LiMn
2o
4), LiFePO4 (LiFePO
4) or LiNi
1/3co
1/3mn
1/3o
2, the material of described negative pole is preferably Delanium or coke phase carbon microbeads.
Because above-mentioned plural gel polymer dielectric conductivity is higher, better with the interface stability of lithium metal, make the better performances of this lithium ion battery.
Refer to Fig. 2, the preparation method of the lithium ion battery of an execution mode, comprises the following steps:
Step S201: above-mentioned plural gel polymer dielectric film is reeled and is assembled into battery core with anodal, negative pole;
Adopt winding process to be assembled into battery core at plural gel polymer dielectric film and anodal, negative pole, wherein positive pole is drawn with aluminium pole ears spot welding, and negative pole is drawn with the spot welding of nickel lug.
Step S202: battery core, 50～65 ℃ of vacuumizes 15～20 hours, is sealed, changed into and obtain lithium ion battery.
By battery core 50～65 ℃ of vacuumizes 15～20 hours, the battery core of drying is placed in aluminum plastic film bag, in glove box, inject pre-closedtop after electrolyte, then with vacuum sealer, seal, during sealing, reserved ballonet in bag, changes into after standing 15～20 hours, after end to be changed, the gas that changes into generation enters sealing again after air bag, obtains lithium ion battery.
Preparation method's technique of this lithium ion battery is simple, owing to having adopted above-mentioned plural gel polymer dielectric, prepares the lithium ion battery that performance is higher.
Below in conjunction with specific embodiment, the present invention will be described.
Embodiment 1
Prepare plural gel polymer dielectric
(1) in nitrogen atmosphere, P (BMA-AN) is dissolved in oxolane, in 45 ℃ of return stirrings 4 hours, poly-(butyl methacrylate-acrylonitrile) solution that preparation mass percentage concentration is 3%;
(2) in nitrogen atmosphere, PVDF is dissolved in acetone, in 45 ℃ of return stirrings 4 hours, the Kynoar solution that preparation mass percentage concentration is 3%;
(3) using polypropylene (PP) film that thickness is 0.015mm as supporter, supporter is soaked in resulting poly-(butyl methacrylate-acrylonitrile) solution of step (1), after 10 minutes, take out, supporter after air blast is dried, again the supporter after drying is soaked in the resulting Kynoar solution of step (2), after 10 minutes, take out, air blast is dried, and obtains plural gel polymer dielectric film.
(4) plural gel polymer dielectric film is cut into after suitable size, is placed in vacuum drying chamber vacuumize at 45 ℃ and, after 15 hours, transfers to rapidly glove box (Mikrouna Super12201750).Plural gel polymer dielectric film was immersed in electrolyte after 1 hour, obtained plural gel polymer dielectric.Wherein, electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, and the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 0.5:1:2, and the molar concentration of lithium hexafluoro phosphate is 0.5mol/L.
Embodiment 2
Prepare plural gel polymer dielectric
(1) in nitrogen atmosphere, P (BMA-AN) is dissolved in oxolane, in 30 ℃ of return stirrings 5 hours, poly-(butyl methacrylate-acrylonitrile) solution that preparation mass percentage concentration is 6%;
(2) in nitrogen atmosphere, PVDF is dissolved in oxolane, in 30 ℃ of return stirrings 5 hours, the Kynoar solution that preparation mass percentage concentration is 6%;
(3) using polyethylene film (PE) that thickness is 0.020mm as supporter, supporter is soaked in resulting poly-(butyl methacrylate-acrylonitrile) solution of step (1), after 5 minutes, take out, supporter after air blast is dried, again the supporter after drying is soaked in the resulting Kynoar solution of step (2), after 5 minutes, take out, air blast is dried, and obtains plural gel polymer dielectric film.
(4) plural gel polymer dielectric film is cut into after suitable size, is placed in vacuum drying chamber vacuumize at 30 ℃ and, after 24 hours, transfers to rapidly glove box (Mikrouna Super12201750).Plural gel polymer dielectric film was immersed in electrolyte after 2 hours, obtained plural gel polymer dielectric.Wherein, electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, and the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 0.5:2:1, and the molar concentration of lithium hexafluoro phosphate is 1mol/L.
Embodiment 3
Prepare plural gel polymer dielectric
(1) in nitrogen atmosphere, P (BMA-AN) is dissolved in acetone and the N-N dimethyl formamide mixed solvent that 1:1 mixes by volume, in 80 ℃ of return stirrings 0.5 hour, poly-(butyl methacrylate-acrylonitrile) solution that preparation mass percentage concentration is 4%;
(2) in nitrogen atmosphere, PVDF is dissolved in acetone and the N-N dimethyl formamide mixed solvent that 2:1 mixes by volume, in 80 ℃ of return stirrings 0.5 hour, the Kynoar solution that preparation mass percentage concentration is 3%;
(3) using polypropylene (PP) film that thickness is 0.020mm as supporter, supporter is soaked in resulting poly-(butyl methacrylate-acrylonitrile) solution of step (1), after 20 minutes, take out, supporter after air blast is dried, again the supporter after drying is soaked in the resulting Kynoar solution of step (2), after 20 minutes, take out, air blast is dried, and obtains plural gel polymer dielectric film.
(4) plural gel polymer dielectric film is cut into after suitable size, is placed in vacuum drying chamber vacuumize at 55 ℃ and, after 3 hours, transfers to rapidly glove box (Mikrouna Super12201750).Plural gel polymer dielectric film was immersed in electrolyte after 1.5 hours, obtained plural gel polymer dielectric.Wherein, electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, and the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 0.5:1.5:0.5, and the molar concentration of lithium hexafluoro phosphate is 1.5mol/L.
Embodiment 4
Prepare plural gel polymer dielectric
(1) in nitrogen atmosphere, P (BMA-AN) is dissolved in oxolane, in 45 ℃ of return stirrings 5 hours, poly-(butyl methacrylate-acrylonitrile) solution that preparation mass percentage concentration is 3%;
(2) in nitrogen atmosphere, PVDF is dissolved in acetone, in 65 ℃ of return stirrings 5 hours, the Kynoar solution that preparation mass percentage concentration is 5%;
(3) using polypropylene (PP) film that thickness is 0.025mm as supporter, supporter is soaked in resulting poly-(butyl methacrylate-acrylonitrile) solution of step (1), after 5 minutes, take out, supporter after air blast is dried, again the supporter after drying is soaked in the resulting Kynoar solution of step (2), after 10 minutes, take out, air blast is dried, and obtains plural gel polymer dielectric film.
(4) plural gel polymer dielectric film is cut into after suitable size, is placed in vacuum drying chamber vacuumize at 30 ℃ and, after 24 hours, transfers to rapidly glove box (Mikrouna Super12201750).Plural gel polymer dielectric film was immersed in electrolyte after 2 hours, obtained plural gel polymer dielectric.Wherein, electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, and the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 2:0.5:0.5, and the molar concentration of lithium hexafluoro phosphate is 1.7mol/L.
Embodiment 5
Prepare plural gel polymer dielectric
(1) in nitrogen atmosphere, P (BMA-AN) is dissolved in oxolane, in 55 ℃ of return stirrings 2 hours, poly-(butyl methacrylate-acrylonitrile) solution that preparation mass percentage concentration is 4%;
(2) in nitrogen atmosphere, PVDF is dissolved in acetone, in 55 ℃ of return stirrings 2 hours, the Kynoar solution that preparation mass percentage concentration is 4%;
(3) using polypropylene (PP) film that thickness is 0.015mm as supporter, supporter is soaked in resulting poly-(butyl methacrylate-acrylonitrile) solution of step (1), after 20 minutes, take out, supporter after air blast is dried, again the supporter after drying is soaked in the resulting Kynoar solution of step (2), after 5 minutes, take out, air blast is dried, and obtains plural gel polymer dielectric film.
(4) plural gel polymer dielectric film is cut into after suitable size, is placed in vacuum drying chamber vacuumize at 30 ℃ and, after 24 hours, transfers to rapidly glove box (Mikrouna Super12201750).Plural gel polymer dielectric film was immersed in electrolyte after 2 hours, obtained plural gel polymer dielectric.Wherein, electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, and the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 1:1:1, and the molar concentration of lithium hexafluoro phosphate is 2mol/L.
Embodiment 6
Prepare plural gel polymer dielectric
(1) in nitrogen atmosphere, P (BMA-AN) is dissolved in oxolane, in 65 ℃ of return stirrings 3 hours, poly-(butyl methacrylate-acrylonitrile) solution that preparation mass percentage concentration is 5%;
(2) in nitrogen atmosphere, PVDF is dissolved in acetone, in 35 ℃ of return stirrings 3 hours, the Kynoar solution that preparation mass percentage concentration is 5%;
(3) using three layers of composite diaphragm of polypropylene-ethylene-propylene that thickness is 0.025mm as supporter, supporter is soaked in resulting poly-(butyl methacrylate-acrylonitrile) solution of step (1), after 5 minutes, take out, supporter after air blast is dried, again the supporter after drying is soaked in the resulting Kynoar solution of step (2), after 20 minutes, take out, air blast is dried, and obtains plural gel polymer dielectric film.
(4) plural gel polymer dielectric film is cut into after suitable size, is placed in vacuum drying chamber vacuumize at 30 ℃ and, after 24 hours, transfers to rapidly glove box (Mikrouna Super12201750).Plural gel polymer dielectric film was immersed in electrolyte after 2 hours, obtained plural gel polymer dielectric.Wherein, electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, and the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 2:0.5:2, and the molar concentration of lithium hexafluoro phosphate is 2mol/L.
Comparative example 1
Prepare single P(BMA-AN) polymer dielectric
In step (1), only has single P (BMA-AN), in step (2), supporter polyethylene (PE) only soaks once in P (BMA-AN) gel solution, other parameters are all identical with embodiment 1, and the electrolyte preparing is single P(BMA-AN) polymer dielectric.
Performance characterization
ac impedance measurement
The plural gel polymer dielectric of embodiment 1 preparation is placed between two metal lithium sheet, carries out AC impedance test.As shown in Figure 3, semicircle in figure is the charge-transfer resistance between metal lithium sheet, by the test of different time, just can reflect the variation of the charge-transfer resistance value of the negative pole that plural gel polymer dielectric and the lithium metal of take are representative, can reflect the interface compatibility of this gel-form solid polymer electrolyte and negative pole.Shown in Fig. 1, the interface compatibility of the negative material that the plural gel polymer dielectric of this embodiment 1 preparation and the lithium metal of take are representative can be fabulous.
scanning electron microscope analysis
Single P(BMA-AN to comparative example 1 preparation) the plural gel polymer dielectric of polymer dielectric film and embodiment 3 preparations carries out scanning electron microscope analysis, result as shown in Figure 4, (a) figure is the single P(BMA-AN of comparative example 1 preparation) the SEM figure of polymer dielectric film, (b) figure be that the SEM of the plural gel polymer dielectric prepared of embodiment 3 schemes.By SEM, scheme, can obviously find out the P(BMA-AN of (a) figure) polymer dielectric film becomes porosity low, and pore-forming is single; (b) in figure, plural gel polymer dielectric becomes porosity high, and has multilayer pore-forming state, and obviously the plural gel polymer dielectric in (b) figure can receive more electrolyte, thereby improves conductance.
linear scan
Under room temperature, the plural gel polymer dielectric of embodiment 4 preparations is placed between metal lithium sheet and stainless steel substrates (SS) electrode and carries out linear scan, Fig. 5 is that the plural gel polymer dielectric open circuit voltage of embodiment 4 preparations is to the linear scan figure of 6V.From scheming, the decomposition voltage of the plural gel polymer dielectric of embodiment 4 preparations reaches 5.4V, for now popular high-voltage positive electrode material provides usage platform.
thermogravimetric analysis
Plural gel polymer dielectric to embodiment 5 preparations carries out thermogravimetric analysis.As shown in Figure 6, the decomposition temperature of the plural gel polymer dielectric of embodiment 5 preparations, up to 330 ℃, can be used as a kind of high-temperature behavior material to result.
Embodiment 7
The application of plural gel polymer dielectric
The plural gel polymer dielectric of embodiment 1 is pressed to positive electrode (LiCoO successively
2, LiMn
2o
4, LiFePO
4, LiNi
1/3co
1/3mn
1/3o
2), the order of gel polymer electrolyte, negative material (Delanium or coke phase carbon microbeads (MCMB)), in glove box, be assembled into button cell.This battery can be for daily electronic product as electronic dictionary, wrist-watch, calculator etc.
Embodiment 8
The preparation of Soft Roll polymer Li-ion battery
The plural gel polymer dielectric of embodiment 1 is pressed to positive electrode (LiCoO successively
2, LiMn
2o
4, LiFePO
4, LiNi
1/3co
1/3mn
1/3o
2), the order of gelatin polymer film and negative material (Delanium or coke phase carbon microbeads (MCMB)) adopts winding process to be assembled into battery core.
Positive pole is drawn with aluminium pole ears spot welding, and negative pole is drawn with the spot welding of nickel lug.Battery core is taken out after dry 18 hours in 55 ℃ of vacuum drying chambers.The battery core of oven dry is placed in to aluminum plastic film bag, in glove box, injects pre-closedtop after electrolyte, then with vacuum sealer sealing, reserved ballonet in bag during sealing.
After standing 6 hours, change into, after end to be changed, a small amount of gas that changes into generation enters sealing again after air bag, obtains Soft Roll polymer Li-ion battery.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a plural gel polymer dielectric, it is characterized in that, comprise plural gel polyelectrolyte membranes and be adsorbed in the electrolyte on described plural gel polymer dielectric film, described plural gel polymer dielectric film comprises supporter and is adsorbed in poly-(butyl methacrylate-acrylonitrile) and the Kynoar in described supporter, described supporter is polyethylene film, polypropylene screen, three layers of composite diaphragm of polypropylene-ethylene-propylene or nonwoven fabrics, described electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, described ethylene carbonate, the mass ratio of dimethyl carbonate and methyl ethyl carbonate is 0.5～2:0.5～2:0.5～2, the molar concentration of described lithium hexafluoro phosphate is 0.5～2mol/L.
2. plural gel polymer dielectric according to claim 1, is characterized in that, the mass ratio of described poly-(butyl methacrylate-acrylonitrile) and Kynoar is 1～6:1～6.
3. a plural gel method for preparing polymer electrolytes, is characterized in that, comprises the following steps:
Provide support body, described supporter is polyethylene film, polypropylene screen, three layers of composite diaphragm of polypropylene-ethylene-propylene or nonwoven fabrics;
Described supporter is soaked 5～20 minutes in poly-(butyl methacrylate-acrylonitrile) solution, take out and dry, the supporter after being dried;
Supporter after described oven dry is soaked 5～20 minutes in Kynoar solution, take out and dry, obtain plural gel polymer dielectric film;
Described plural gel polymer dielectric film is soaked 1～2 hour in electrolyte, obtain plural gel polymer dielectric; Wherein, described electrolyte comprises lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, the mass ratio of described ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 0.5～2:0.5～2:0.5～2, and the molar concentration of described lithium hexafluoro phosphate is 0.5～2mol/L.
4. plural gel method for preparing polymer electrolytes according to claim 3, it is characterized in that, the compound method of described poly-(butyl methacrylate-acrylonitrile) solution is: in the first protective gas atmosphere, to gather (butyl methacrylate-acrylonitrile) and be dissolved in the first solvent, in 30～80 ℃ of return stirrings 0.5～5 hour; The compound method of described Kynoar solution is: in the second protective gas atmosphere, Kynoar is dissolved in the second solvent, in 30～80 ℃ of return stirrings 0.5～5 hour.
5. plural gel method for preparing polymer electrolytes according to claim 4, is characterized in that, described the first solvent is selected from least one in acetone, N-N dimethyl formamide and oxolane; Described the second solvent is selected from least one in acetone, N-N dimethyl formamide and oxolane.
6. plural gel method for preparing polymer electrolytes according to claim 3, is characterized in that, the mass percentage concentration of described poly-(butyl methacrylate-acrylonitrile) solution is 1～6%; The mass percentage concentration of described Kynoar solution is 1～6%.
7. plural gel method for preparing polymer electrolytes according to claim 3, it is characterized in that, described described plural gel polymer dielectric film is soaked in electrolyte to the operation of 1～2 hour before, also comprise described plural gel polymer dielectric film in 30～55 ℃ of steps of dry 5～24 hours.
8. a lithium ion battery, is characterized in that, comprises the plural gel polymer dielectric described in battery container, positive pole, negative pole and claim 1 or 2; Wherein,
Described positive pole, negative pole and plural gel polymer dielectric are contained in described battery container, and described plural gel polymer dielectric is between described positive pole and negative pole.
9. lithium ion battery according to claim 8, is characterized in that, the material of described positive pole is high cobalt acid lithium, inferior LiMn2O4, LiFePO4 or LiNi
1/3co
1/3mn
1/3o
2, the material of described negative pole is Delanium or coke phase carbon microbeads.
10. a preparation method for lithium ion battery, is characterized in that, comprises the following steps:
Plural gel polymer dielectric described in claim 1 or 2 is reeled and is assembled into battery core with anodal, negative pole;
Battery core, 50～65 ℃ of vacuumizes 15～20 hours, is sealed, changed into and obtain lithium ion battery.
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| CN113130982A (en) * | 2019-12-30 | 2021-07-16 | 北京卫蓝新能源科技有限公司 | Preparation method of high-liquid-retention electrolyte and application of high-liquid-retention electrolyte in lithium battery |
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