CN100467504C - Preparing method and application of polymer gel electrolyte for lithium ion cell - Google Patents
Preparing method and application of polymer gel electrolyte for lithium ion cell Download PDFInfo
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Abstract
The present invention provides a kind of polymer electrolyte for lithium ion cell and its preparation process and application. The preparation process of the polymer electrolyte includes the following steps: dissolving sodium dodecyl sulfate in deionized water, adding methyl methacrylate, vinyl acetate and dipropenyl phthalate via stirring, and adding sodium sulfate to react to obtain white emulsion; demulsifying the emulsion in Al2(SO4)3 solution via stirring, washing out un-reacted monomer and nitrogen sweeping to obtain white PMMA-VAc powder; dissolving in N, N-dimethyl formamide and adding diethyl carbonate to obtain ropy gel; soaking polyolefin diaphragm or polyolefin non-woven fabric inside the gel and drying to obtain polymer film; and soaking the polymer film in electrolyte solution to obtain the polymer electrolyte.
Description
Technical field
The invention belongs to technical field of electrochemistry, particularly a kind of preparation method of gel state lithium ion battery polymer electrolyte and application thereof.
Background technology
Since lithium ion battery is the nineties in 20th century, used the lithium ion battery of liquid electrolyte since commercialization, to obtain great success.Polymer Li-ion battery (PLIB) is a kind of new type lithium ion battery that grows up gradually on the liquid lithium ionic cell basis, because it can accomplish frivolous conductization and arbitrary shapeization in shape, can guarantee the abundant contact of inside battery, improve the handiness of drawing the battery shape-designing greatly, thereby can cooperate product demand, make the battery of arbitrary shape and capacity, be providing a great convenience property of research and development; Owing to polymer battery security preferably and cycle life are arranged simultaneously, thereby caused people's extensive concern.Polymer Li-ion battery is mainly used in mobile phone at present, aspects such as notebook computer, along with the high speed development of electronic technology and the people requirements at the higher level to portable power source, polymer Li-ion battery will be at electromobile, aspect widespread uses such as pick up camera and military field.
The key part of polymer battery is a polymer dielectric.Polymer dielectric can be divided into gel polymer electrolyte (GPE) and solid polymer electrolyte (SPE) by its form, and its key distinction is that the former contains liquid plasticizer, and the latter does not have.Although developed a lot of polymer dielectrics at present, as polyethers system (mainly being PEO), polyacrylonitrile (PAN) is, polymethacrylate (PMMA) class and polyvinylidene difluoride (PVDF) (PVDF) are etc., but polymer dielectric is still not ideal, has following point: (1) specific conductivity at room temperature is on the low side; (2) physical strength has much room for improvement.Thereby the ionic conductivity and the physical strength that adopt blend, copolymerization and utilize softening agent to become method synthetic polymer ionogen such as micropore to improve polymeric film have become present research direction.Advantages such as gel-type polymer electrolyte is because the ionic conductivity height, and electrochemical stability is good become present research focus.The preparation polymer dielectric film has Bellcore method and phase transfer method at present, because the Bellcore method adopts solvent extraction plasticising, complicated operation, to the environmental requirement height, bring difficulty to large-scale industrial production, though and the polymeric film ionic conductivity height that phase transfer method obtains, bad mechanical property is difficult to be adapted to the battery production process; And the mechanical property of the gel-type polymer electrolyte that obtains at present and liquid retainability can also be difficult to satisfy the high speed development of polymer Li-ion battery.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method of gel state lithium ion battery polymer electrolyte.
Another object of the present invention is to provide the application of above-mentioned gel state lithium ion battery polymer electrolyte in the preparation polymer Li-ion battery.
Purpose of the present invention realizes by following technical proposals: a kind of preparation method of gel state lithium ion battery polymer electrolyte comprises the steps:
(1) at N
2Under the atmosphere, with mass percent is that to join mass percent be to dissolve in 60～75% the deionized water for 1～3% emulsifier sodium lauryl sulfate, add mass percent again and be 25～35% monomer M MA (methyl methacrylate) and VAc (vinyl-acetic ester) and mass percent and be 0.1～0.4% linking agent diallyl phthalate, stir, adding down mass percents at 60～75 ℃ is that 0.1～0.4% initiator Sodium Persulfate reacts; React and obtain white emulsion after 6～10 hours, pouring white emulsion into mass percent is 2～5% Al
2(SO
4)
3Stir breakdown of emulsion in the solution, wash 2～5 times then after, use ethanol successively: the deionized water quality is than being the solvent of 1:1, acetone: the deionized water quality is than for behind the unreacted monomer of solvent flush away of 1:1,60～80 ℃ of following N
2Purged 24～36 hours, and obtained PMMA-VAc (polymethylmethacrylate-vinyl-acetic ester) powder of white.
(2) be that 1～4% PMMA-VAc powder dissolution is 46～50% N in mass percent with mass percent, in-N dimethyl formamide (DMF) or the acetone, and the adding mass percent is that 46～50% softening agent diethyl carbonate (DEC) obtain the heavy-gravity gel.
(3) with polyalkene diaphragm (Celgard, Entek, space portion) or the polyolefine non-woven fabrics be dipped in the gel after 5～20 minutes and take out, drying is 6～12 hours in 60～80 ℃ of air dry ovens, promptly obtain the two-sided polymeric film that contains polymkeric substance, polymeric film is immersed in the electrolytic solution 10～50 minutes, can obtains gel state lithium ion battery polymer electrolyte.
Step (2) also can be carried out as follows: for the further mechanical property that increases the contact between pole piece and strengthen polymeric film, with the PMMA-VAc of mass percent 1～3% and 1～2% PVDF (poly(vinylidene fluoride)) or PTFE (tetrafluoroethylene) or PVP-VA64 (multipolymer of N-V-Pyrol RC (NVP) and vinyl-acetic ester (VAc)) blend, and they are dissolved in mass percent is in 40～46% the acetone or N-Methyl pyrrolidone (NMP) equal solvent, adds mass percent then and is 50～55% softening agent diethyl carbonate (DEC) and obtain the heavy-gravity gel.
MMA (methyl methacrylate) is 9:1～5:5 with VAc (vinyl-acetic ester) mass ratio in the described step (1).
The application of gel state lithium ion battery polymer electrolyte in the preparation polymer Li-ion battery, preparation method according to gel state lithium ion battery polymer electrolyte prepares polymeric film, polymeric film and positive electrode material and the negative material employing winding process of preparation are assembled into electric core, then electric core is taken out after dry 20～30 hours in 70～80 ℃ of vacuum drying ovens, again electric core is placed battery, inject electrolytic solution (1mol/LLiPF
6+ EC+DMC+EMC, EC:DMC:EMC=1:1:1, mass ratio) leave standstill after the sealing and changed in 8 hours, obtain polymer Li-ion battery.
In order to realize the present invention better, the application of gel state lithium ion battery polymer electrolyte in the preparation polymer Li-ion battery, can also adopt following method: the preparation method according to gel state lithium ion battery polymer electrolyte prepares polymeric film, polymeric film and positive electrode material and the negative material employing winding process of preparation are assembled into electric core, positive pole is drawn with aluminium pole ears spot welding, negative pole is drawn with the spot welding of nickel lug, then electric core is taken out after dry 20～30 hours in 70～80 ℃ of vacuum drying ovens, the electric core of oven dry is placed the aluminum plastic film bag, in glove box, inject electrolytic solution (1mol/L LiPF
6+ EC+DMC+EMC, EC:DMC:EMC mass ratio are 1:1:1) after seal in advance, seal with vacuum sealer then, reserve vesicula when sealing in the bag, leave standstill after 8 hours and change into, after the end to be changed, seal once more after the gas that changes into generation enters air bag, obtain the Soft Roll polymer Li-ion battery.
Synthetic PMMA-VAc of the present invention (polymethylmethacrylate-vinyl acetate) powder is in conjunction with containing carbonyl in polymethylmethacrylate (PMMA) unit, oxygen in carbonyl and the carbonic ether softening agent has very strong effect, thereby imbibition ability is strong, simultaneously with advantages such as the good stability of electrode interface and MMA abundant raw material, but its bad mechanical property; And polyvinyl acetate (PVAc) has stronger close-burning characteristics, synthesized polymkeric substance with emulsion polymerization: polymethylmethacrylate-vinyl-acetic ester-P (MMA-VAc), and with this polymer manufacture the novel microporous polymer dielectric that supports of polyolefin film.This polymer dielectric film has splendid micropore crosslinking structure and pick up, and electro-chemical test shows that polymer dielectric has good ion transmission performance and chemical property, can be as the ionogen of polymer Li-ion battery.
The polymer dielectric that the present invention obtains has splendid reticulated structure (to see Fig. 1, Fig. 2), can not only absorb a large amount of electrolytic solution, also the migration for lithium ion provides a passage easily, the ionic conductivity of polymer dielectric is improved greatly, and the transformation efficiency of entire reaction is also up to 97.5%.Simultaneously polymkeric substance is dissolved in organic solvent and adds softening agent and obtain gel, with PE film (Celgard, Entek or UBE space portion) or the polyolefine non-woven fabrics immerse gel and take out after several 10 minutes, do not adopt tens of hours flow processs of traditional vacuum-drying, and adopt forced air drying promptly to obtain polymeric film in 8 hours, be used for doing the coiling battery again, saved the time greatly and become to produce cost, technology is simpler.
The present invention compared with prior art has following advantage and beneficial effect:
Technology of the present invention is simple, and the time is short, and for technology production provides condition, and the polymeric film that obtains has splendid absorbency and liquid-maintaining capacity.The poly-lithium battery of the present invention's preparation, owing to have good consistency and my ionogen of polymkeric substance that good cohesiveness is arranged between polymeric film and positive and negative pole material, positive and negative electrode tightly can be combined, thus the good stability at the polymer lithium ion battery electric utmost point interface that obtains; The adding of linking agent simultaneously makes polymkeric substance that splendid crosslinked reticulated structure be arranged, for the migration of lithium ion provides a passage easily, the ionic conductivity of polymer dielectric improves greatly, and the cycle performance of polymer Li-ion battery and safety performance also improve greatly.
Description of drawings
Fig. 1 is the sem photograph (amplifying 2000 times) of polymeric film.
Fig. 2 is the sem photograph (amplifying 4000 times) of polymeric film.
Fig. 3 is a polymer dielectric at 25 ℃ alternating-current impedance figure.
Fig. 4 is the graphic representation of the DSC/TG (differential thermal/thermogravimetric) of polymeric film.
Fig. 5 adds linking agent and the absorbent comparison diagram that does not add 4% polymeric film of linking agent.
Fig. 6 is the different current discharge graphic representations of polymer battery.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
The synthetic method of gel state lithium ion battery polymer electrolyte:
(1) the monomer M MA and the VAc of polymerization use are analytical pure.Earlier monomer distillation is removed hydroquinone of polymerization retarder before the experiment, wherein the VAc distillation is purified and is carried out under normal pressure, and temperature is 72 ℃; 80 ℃ of underpressure distillation purification MMA.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere, with mass percent is that 1.5% emulsifier sodium lauryl sulfate joins in 68.2% deionized water and dissolves, add 30% monomer M MA and VAc (MMA and VAc mass ratio are 9:1) and 0.1% linking agent diallyl phthalate again, stir, the initiator Sodium Persulfate of adding 0.2% reacts under 65 ℃; React and obtain white emulsion after 8 hours, emulsion is poured into 3% Al
2(SO
4)
3Stir breakdown of emulsion in the solution, by 3 times washing, use ethanol successively: deionized water is the solvent of 1:1 (mass ratio), acetone: after deionized water is the unreacted monomer of solvent flush away of 1:1 (mass ratio), and 60 ℃ of following N
2Purge and obtained white PMMA-VAc powder in 36 hours.
(2) with 4% PMMA-VAc powder dissolution in 46% N, in-N the dimethyl formamide (DMF), and add 50% softening agent diethyl carbonate (DEC) and obtain the heavy-gravity gel;
(3) polyalkene diaphragm is dipped in taking-up after 10 minutes in the gel, drying is 8 hours in 70 ℃ of air dry ovens, promptly obtains the two-sided polymeric film (as shown in Figure 1 and Figure 2) that contains polymkeric substance.Polymeric film is immersed in battery liquid-filling 40 minutes, promptly obtains gel state lithium ion battery polymer electrolyte.
The application of gel state lithium ion battery polymer electrolyte of the present invention in the preparation polymer Li-ion battery, the preparation method of polymer Li-ion battery is as follows:
Method 1: synthetic polymeric film in the step (3) is pressed positive electrode material (LiCoO successively
2, LiMn
2O
4Or LiFePO
4), polymeric film and negative material (synthetic graphite or MCMB (coke phase carbon microbeads)) adopt winding process to be assembled into electric core, electric core is taken out after dry 30 hours in 70 ℃ of vacuum drying ovens, in glove box, electric core is placed 2032 button cells again, inject electrolytic solution (1mol/L LiPF
6+ EC+DMC+EMC, EC:DMC:EMC mass ratio are 1:1:1) sealing after leave standstill changed in 8 hours be used for the test.
Method 2: positive pole is drawn with aluminium pole ears spot welding, and negative pole is drawn with the spot welding of nickel lug, and all the other electric cores prepare the same.Electric core is taken out after dry 20 hours in 80 ℃ of vacuum drying ovens, the electric core of drying is placed the aluminum plastic film bag, in glove box, inject electrolytic solution (1mol/L LiPF
6+ EC+DMC+EMC, the EC:DMC:EMC mass ratio is 1:1:1) after seal in advance, seal with vacuum sealer then, reserve vesicula when sealing in the bag, leave standstill after 8 hours and change into, after the end to be changed, seal once more after a small amount of gas that changes into generation enters air bag, obtain the Soft Roll polymer Li-ion battery, be used for testing.
Wherein the positive and negative electrode manufacture craft is as follows: with anodal LiCoO
2, LiMn
2O
4Or LiFePO
4, acetylene black, PVDF, N-Methyl pyrrolidone (NMP) presses mass ratio 92.0:3.5:4.5:70.0 mixing, double spread on the aluminium foil of 15 μ m; Negative plate: carbon material, acetylene black, PVDF, NMP are pressed mass ratio 90.0:3.0:7.0:60.0 mixing, double spread on the Copper Foil of 10 μ m, with coated electrode 120 ℃ of vacuum-dryings, remove NMP, be cut into 100～130mm * 10～13mm positive plate and 100～130mm * 10～13mm negative plate after the roll-in.
The mensuration of the absorbent of polymeric film:
The microporous polymer membranes (W that has weighed
1), in ternary solution (EC+DMC+EMC, EC:DMC:EMC mass ratio are 1:1:1), soak after 10～50 minutes and take out, blot its surperficial electrolytic solution gently with filter paper, take by weighing its quality (W
2), promptly get the polymeric film dry film and be: [(W the pick up of electrolytic solution
2-W
1)/W
1] * 100%.The experiment record polymeric film pick up up to more than 1000%, be higher than far away other bibliographical informations (1, Song, M.K; Kim, Y.T; Cho, J.Y; Cho, B.W; Popov, P.N; Rhee, H.W.J Power Sources.2004,125,10.2, Jeong, Y.B; Kin, D.W.J PowerSources.2004,128,256.3, Liang, H.Y; Qiu, X.P; Zhang, S.C; Zhu, W.T; Chen, L.Q.J Appl Electrochemistry.2004,34,1211.) the result.
The ionic conductivity ac impedance measurement of polymeric film:
The gelatin polymer film (GPE) that polyolefin porous membrane is supported is clipped between two stainless steels (SS) electrode, carries out the alternating-current impedance test.Linear intersection point with real axis is the resistance of polymer dielectric, can obtain thus polymer dielectric ionic conductivity: σ=L/A*R (wherein L represents the thickness of polymer dielectric, and A is an electrode area, and R is the resistance of polymer dielectric).Calculate ionic conductivity σ=1.85 * 10 of polymeric film under the room temperature
-3S * cm
-1, practical requirement.As shown in Figure 3, be the alternating-current impedance figure of polymer dielectric at 25 ℃.
As can be seen from Figure 4, the polymeric film of preparation has good thermostability in 380 ℃ of scopes.This shows that the polymeric film of preparation can be applied to lithium ion battery safely.
As can be seen from Figure 5, the adding one of linking agent has improved the pick up of polymeric film greatly, has also improved the imbibition conservation rate of polymeric film simultaneously.
Fig. 6 charges the curve of different current discharges for 2032 button cells that are wound into polymer dielectric with 5mA.As can be seen from Figure 6, this polymer battery has good multiplying power discharging property.
Embodiment 2
The synthetic method of gel state lithium ion battery polymer electrolyte:
(1) presses embodiment 1 pre-treatment monomer M MA and VAc.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere, with mass percent is that 2% emulsifier sodium lauryl sulfate joins in 72.7% deionized water and dissolves, add 25% monomer M MA and VAc (MMA and VAc mass ratio are 7:3) and 0.2% linking agent diallyl phthalate again, stir, the initiator Sodium Persulfate of adding 0.1% reacts under 60 ℃; React and obtain white emulsion after 6 hours, emulsion is poured into 2% Al
2(SO
4)
3Stir breakdown of emulsion in the solution, by 3 times washing, ethanol: deionized water is the solvent of 1:1, acetone: deionized water is after the solvent of 1:1 is washed, 60 ℃ of following N
2Purge and obtained white PMMA-VAc powder in 30 hours.
(2) with 4% PMMA-VAc powder dissolution in 50% DMF solution, and add 46% softening agent DEC and obtain the heavy-gravity gel.
(3) polyalkene diaphragm is dipped in taking-up after 5 minutes in the gel, drying is 12 hours in 60 ℃ of air dry ovens, promptly obtains the two-sided polymeric film that contains polymkeric substance.Polymeric film is immersed in electrolytic solution 15 minutes, promptly obtains gel state lithium ion battery polymer electrolyte.
Embodiment 3
The synthetic method of gel state lithium ion battery polymer electrolyte:
(1) presses embodiment 1 pre-treatment monomer M MA and VAc.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere, with mass percent is that 3% emulsifier sodium lauryl sulfate joins in 61.2% deionized water and dissolves, add 35% monomer M MA and VAc (MMA and VAc mass ratio are 5:5) and 0.4% linking agent diallyl phthalate again, stir, add initiator 0.4% Sodium Persulfate down at 75 ℃ and react; React and obtain white emulsion after 10 hours, emulsion is poured into 5% Al
2(SO
4)
3Stir breakdown of emulsion in the solution, by 4 times washing, ethanol: deionized water is the solvent of 1:1, acetone: deionized water is after the solvent of 1:1 is washed, 75 ℃ of following N
2Purge and obtained white PMMA-VAc powder in 24 hours.
(2) with 2% PMMA-VAc powder and the 2%PVP-VA64 multipolymer of vinyl-acetic ester (VAc) (the N-V-Pyrol RC (NVP) with) blend, be dissolved among 46% the NMP (N-Methyl pyrrolidone), and add 50% softening agent DEC and obtain the heavy-gravity gel.
(3) the polyolefine non-woven fabrics is dipped in taking-up after 20 minutes in the gel, drying is 8 hours in 70 ℃ of air dry ovens, promptly obtains the two-sided polymeric film that contains polymkeric substance.Polymeric film is immersed in electrolytic solution 45 minutes, promptly obtains gel state lithium ion battery polymer electrolyte.
Embodiment 4
(1) presses embodiment 1 pre-treatment monomer M MA and VAc.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere, with mass percent is that 1% emulsifier sodium lauryl sulfate joins in 68.6% deionized water and dissolves, add 30% monomer M MA and VAc (MMA and VAc mass ratio are 8:2) and 0.2% linking agent diallyl phthalate again, stir, the initiator Sodium Persulfate of adding 0.2% reacts under 60 ℃; React and obtain white emulsion after 6 hours, emulsion is poured into 2% Al
2(SO
4)
3Stir breakdown of emulsion in the solution, by 5 times washing, ethanol: deionized water is the solvent of 1:1, acetone: deionized water is after the solvent of 1:1 is washed, 80 ℃ of following N
2Purge and obtained white PMMA-VAc powder in 30 hours.
(2) with the PMMA-VAc powder of mass percent 3% and 1% PVDF (poly(vinylidene fluoride)) blend, and they are dissolved in acetone (mass percent the is 40%) solvent, and to add mass percent be that 55% softening agent diethyl carbonate (DEC) obtains the heavy-gravity gel.
(3) polyalkene diaphragm is dipped in taking-up after 30 minutes in the gel, vacuum-drying is 6 hours in 80 ℃ of vacuum drying ovens, promptly obtains the two-sided polymeric film that contains polymkeric substance.Polymeric film is immersed in electrolytic solution 30 minutes, promptly obtains gel state lithium ion battery polymer electrolyte.
Embodiment 5
(1) presses embodiment 1 pre-treatment monomer M MA and VAc.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere, with mass percent is that 2% emulsifier sodium lauryl sulfate joins in 62.3% deionized water and dissolves, add 35% monomer M MA and Vac (MMA and VAc mass ratio are 5:5) and 0.3% linking agent diallyl phthalate again, stir, add initiator 0.4% Sodium Persulfate down at 75 ℃ and react; React and obtain white emulsion after 8 hours, emulsion is poured into 3% Al
2(SO
4)
3Stir breakdown of emulsion in the solution, by 2 times washing, ethanol: deionized water is the solvent of 1:1, acetone: deionized water is after the solvent of 1:1 is washed, 75 ℃ of following N
2Purge and obtained white PMMA-VAc powder in 24 hours.
(2) with the PMMA-VAc powder of mass percent 2% and 1.5% PTFE (tetrafluoroethylene) blend, and they are dissolved in NMP (mass percent the is 43.5%) solvent, and to add mass percent be that 53% softening agent diethyl carbonate (DEC) obtains the heavy-gravity gel.
(3) the polyolefine non-woven fabrics is dipped in taking-up after 20 minutes in the gel, drying is 6 hours in 80 ℃ of air dry ovens, promptly obtains the two-sided polymeric film that contains polymkeric substance.Polymeric film is immersed in electrolytic solution 50 minutes, promptly obtains gel state lithium ion battery polymer electrolyte.
Above-mentioned embodiment is the preferred embodiments of the present invention; can not limit claim of the present invention; other any change or other equivalent substitute mode that does not deviate from technical scheme of the present invention and made is included within protection scope of the present invention.
Claims (6)
1, a kind of preparation method of gel state lithium ion battery polymer electrolyte is characterized in that comprising the steps:
(1) at N
2Under the atmosphere, with mass percent is that to join mass percent be to dissolve in 61.2～72.7% the deionized water for 1～3% emulsifier sodium lauryl sulfate, add mass percent again and be 25～35% monomers methyl methacrylate and vinyl-acetic ester and mass percent and be 0.1～0.4% linking agent diallyl phthalate, stir, adding down mass percents at 60～75 ℃ is that 0.1～0.4% initiator Sodium Persulfate reacts; React and obtain white emulsion after 6～10 hours, pouring white emulsion into mass percent is 2～5% Al
2(SO
4)
3Stir breakdown of emulsion in the solution, wash 2～5 times then after, use ethanol successively: the deionized water quality is than being the solution of 1:1, acetone: the deionized water quality is than for behind the unreacted monomer of solution flush away of 1:1,60～80 ℃ of following N
2Purged 24～36 hours, and obtained the polymethylmethacrylate-vinyl-acetic ester powder of white;
(2) copolymer blended with the N-V-Pyrol RC of the polymethylmethacrylate-vinyl-acetic ester powder of mass percent 1～3% and 1～2% and vinyl-acetic ester, and they are dissolved in mass percent is in 40～46% the acetone or N-Methyl pyrrolidone solvent, adds mass percent then and is 50～55% softening agent diethyl carbonate and obtain the heavy-gravity gel;
(3) polyalkene diaphragm or polyolefine non-woven fabrics are dipped in taking-up after 5～20 minutes in the gel, drying is 6～12 hours in 60～80 ℃ of air dry ovens, promptly obtain the two-sided polymeric film that contains polymkeric substance, polymeric film is immersed in the electrolytic solution 10～50 minutes, promptly obtains gel state lithium ion battery polymer electrolyte;
Described electrolytic solution is LiPF
6+ EC+DMC+EMC.
2, the preparation method of a kind of gel state lithium ion battery polymer electrolyte according to claim 1 is characterized in that: methyl methacrylate and vinyl-acetic ester mass ratio are 9:1～5:5 in the described step (1).
3, a kind of gel state lithium ion battery polymer electrolyte, it is to be prepared from by the described preparation method of claim 1.
4, the application of a kind of gel state lithium ion battery polymer electrolyte according to claim 3 in the preparation polymer Li-ion battery.
5, application according to claim 4, it is characterized in that: adopt winding process to be assembled into electric core polymeric film and positive electrode material and negative material, then electric core is taken out after dry 20～30 hours in 70～80 ℃ of vacuum drying ovens, again electric core is placed battery, inject to leave standstill after the electrolytic solution sealing and changed in 8 hours, obtain polymer Li-ion battery.
6, application according to claim 4, it is characterized in that: adopt winding process to be assembled into electric core polymeric film and positive electrode material and negative material, positive pole is drawn with aluminium pole ears spot welding, negative pole is drawn with the spot welding of nickel lug, then electric core is taken out after dry 20～30 hours in 70～80 ℃ of vacuum drying ovens, the electric core of oven dry is placed the aluminum plastic film bag, seal in advance after in glove box, injecting electrolytic solution, seal with vacuum sealer then, reserve vesicula when sealing in the bag, leave standstill after 8 hours and change into, after the end to be changed, seal once more after the gas that changes into generation enters air bag, obtain the Soft Roll polymer Li-ion battery.
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| CN101872875A (en) * | 2010-05-27 | 2010-10-27 | 西北工业大学 | Assembly process of polyolefin gel polymer electrolyte lithium-ion battery |
| CN103022557B (en) * | 2012-12-25 | 2015-10-28 | 复旦大学 | Based on the lithium ion battery gel polymer electrolyte and preparation method thereof of nonwoven fabrics |
| CN104140502B (en) * | 2013-11-14 | 2016-12-07 | 上海泛能新材料科技有限公司 | A kind of lithium ion battery separator binding agent, preparation method and use the barrier film of this binding agent |
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| CN110112009B (en) * | 2019-05-31 | 2021-06-01 | 广州大学 | Capacitor composite electrolyte and preparation method and application thereof |
| CN114976229B (en) * | 2022-05-25 | 2024-04-19 | 济南大学 | Method for preparing tetrafluoroethylene-based polymer electrolyte for lithium battery |
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| CN1986585A (en) | 2007-06-27 |
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