CN101381429B - Self-supporting lithium ionic cell gel polymer electrolyte, special polymer and preparation method and application thereof - Google Patents
Self-supporting lithium ionic cell gel polymer electrolyte, special polymer and preparation method and application thereof Download PDFInfo
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- CN101381429B CN101381429B CN2008100295695A CN200810029569A CN101381429B CN 101381429 B CN101381429 B CN 101381429B CN 2008100295695 A CN2008100295695 A CN 2008100295695A CN 200810029569 A CN200810029569 A CN 200810029569A CN 101381429 B CN101381429 B CN 101381429B
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Abstract
The invention discloses a self-support lithium ion battery gel polymer electrolyte and a preparation method and application thereof. In the invention, firstly, by the emulsion polymerization of methyl methacrylate, acrylonitrile and vinylacetatemonomer, a terpolymer is obtained; polymer powder is dissolved into N-N dimethylformamide to obtain sticky gel which is coated on a glass plate, the gel is put in a sink to trigger the phase transition, and is further dried to obtain the self-support lithium ion battery gel polymer film; and a film is soaked in the electrolyte so as to obtain the gel polymer electrolyte. The ionic conductivity of the gel polymer electrolyte is as high as 3.48 x 10<-3>S.cm<-1> at the room temperature, the electrochemical stabilization window can reach 5.6V (vs.Li/Li< + >), and the transference number of lithium ions reaches 0.51. The electrolyte and the preparation method and application thereof have the advantages that the material is easily available, and the electrolyte and the preparation method and application thereof are suitably for the industrialized production of lithium ion polymers.
Description
Technical field
The invention belongs to the technical field of gel polymer electrolyte preparation, particularly a kind of is the lithium ion battery gel polymer electrolyte and its production and application of the self-supporting of matrix with polymer poly (methyl methacrylate-vinyl cyanide-vinyl acetate).
Background technology
In the battery that all commercializations can discharge and recharge, lithium ion battery has advantages such as energy density is the highest, operating voltage is high, have extended cycle life, self-discharge is low, uses so it has widely than other discharged and recharged battery.Yet owing to use the liquid electrolyte that contains inflammable organic solvent, lithium ion battery is faced with serious safety issue.This problem can solve by using the solid electrolyte (SPE) that does not contain any solvent molecule.But SPE ionic conductivity at room temperature only is 1 * 10
-5Scm
-1, than probably low three orders of magnitude of business-like liquid electrolyte, this also is not suitable for the use of lithium ion battery.Gel polymer electrolyte (GPE) is to replace SPE to solve a good method of lithium ion safety issue, because it uses polymeric matrix, the liquid organic solvent is converted into gel.Up to now, a variety of polymkeric substance have been reported, as polyvinylidene difluoride (PVDF) (PVDF), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polyoxyethylene (PEO), polyvinyl chloride (PVC) etc. as the GPE matrix.Yet the GPE that is obtained by these matrixes is to use with a kind of monomer polymerization and forms, so lack good over-all properties.For example, the physical strength height, but ionic conductivity is low, and vice versa.
The research lithium ion battery gel polymer electrolyte has received concern both domestic and external, and existing about patent reports such as polyacrylonitrile, polymethylmethacrylates.Application number is that 200410077528.5 Chinese invention patent discloses " a kind of method for preparing gel polymer electrolyte "; Application number is that 200710068639.3 Chinese invention patent application discloses " a kind of porous gel polyelectrolyte thin film and preparation method thereof "; Application number is that 200710068575.7 Chinese invention patent application discloses " a kind of preparation method of polyolefin microporous-film supported gel polymer electrolyte film ".The ionic conductivity of disclosed these three patents (application) has just reached 10
-3Scm
-1, electrochemical stability window is still not ideal, only up to 4.8V (vs.Li/Li
+).
Summary of the invention
In order to overcome the shortcoming and defect of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of lithium ion battery gel attitude polymer dielectric of self-supporting.
Another object of the present invention is to provide the lithium ion battery gel attitude method for preparing polymer electrolytes of above-mentioned self-supporting.
Another purpose of the present invention is to provide the application of lithium ion battery gel attitude polymer dielectric in the preparation polymer Li-ion battery of above-mentioned self-supporting.
A further object of the present invention is to provide a kind of polymkeric substance that is exclusively used in the lithium ion battery gel polymer electrolyte of the above-mentioned self-supporting of preparation.
Purpose of the present invention is achieved through the following technical solutions: the contriver has at first obtained a kind of polymkeric substance that is exclusively used in the lithium ion battery gel polymer electrolyte of preparation self-supporting, and this polymkeric substance has following structural formula:
Wherein w is 10,000～1.5 ten thousand integer.
With this polymkeric substance is main raw material, and the contriver provides a kind of lithium ion battery gel polymer electrolyte of self-supporting, and its preparation method comprises following concrete steps:
(1) at N
2Under the atmosphere protection, with mass percent is that to join mass percent be to dissolve in 60～70% the deionized water for 1～3% emulsifying agent, add mass percent again and be 25～35% monomers methyl methacrylate, vinyl cyanide and vinyl-acetic ester, stir, adding mass percent with constant pressure funnel under 55～65 ℃ is 0.1～0.4% initiator, and the control stirring velocity is reacted; React and obtain white emulsion after 5～7 hours, pouring white emulsion into 1～1.5 times of above-mentioned reaction volume, mass concentration is 2～5% Al
2(SO
4)
3Stirring breakdown of emulsion in the solution, is after 50～70 ℃ of deionizations are washed 2～5 times, to wash 2～5 times with dehydrated alcohol with temperature then again, obtains the polymkeric substance of white, and this polymkeric substance promptly has above-mentioned structural formula; With the white polymer that obtains be placed in the vacuum drying oven 50～70 ℃ dry 24～36 hours down.
(2) under 60～80 ℃, be 5～10% with polymer dissolution mass percent to polymkeric substance in the N-N dimethyl formamide; After the dissolving, the viscous solution that obtains is coated on the clean sheet glass fully, with the fixing thickness of film of the method for two ends subsides hinge with the stainless steel scraper; Together with sheet glass film is immersed in the deionization tank then, obtains the film of white; Film is placed on washes 0.5～1 hour in the flowing water, soaked in the ionized water that puts in 1～2 hour, at last film is placed on vacuum drying oven drying 20～30 hours, prepare the lithium ion battery gel polymer film of self-supporting.
(3) be immersed in the lithium ion battery gel polymer electrolyte that obtains self-supporting in the electrolytic solution after 20～40 minutes after in glove box, this film being cut into appropriate size.
Among the preparation method of the lithium ion battery gel polymer electrolyte of above-mentioned self-supporting:
The mass ratio of the described monomers methyl methacrylate of step (1), monomer vinyl cyanide and monomer vinyl-acetic ester is 4～1: 8～4: 1; Described stirring velocity is controlled at 800～1100r/min; Described emulsifying agent is sodium lauryl sulphate, dodecyl sulphate potassium or ammonium lauryl sulfate; Described initiator is Sodium Persulfate, Potassium Persulphate or ammonium persulphate, adds at twice, and it is slow that rate of addition is wanted.
The thickness of the described film of step (2) is 60 μ m～90 μ m; Described electrolytic solution is by LiPF
6, NSC 11801 (EC), methylcarbonate (DMC) and Methyl ethyl carbonate (EMC) form, EC: DMC wherein: the EMC mass ratio is 1: 1: 1, LiPF
6Volumetric molar concentration get 1mol/L.
The lithium ion battery gel polymer electrolyte of the self-supporting that is obtained by method for preparing may be used on preparing in the polymer Li-ion battery, and concrete application method has two kinds:
A kind of application mode comprises following step: with the lithium ion battery gel polymer electrolyte of self-supporting, positive electrode material and negative material are assembled into lithium-ion button battery together in glove box.This button cell can be used for electronic product such as electronic dictionary, wrist-watch, counter etc.
Another kind of application mode, comprise following step: adopt winding process to be assembled into electric core the lithium ion battery gel polymer electrolyte of self-supporting 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 15～20 hours in 65～75 ℃ 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 5～8 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.
In above-mentioned two kinds of lithium ion batteries, described positive electrode material comprises LiCoO
2, LiMn
2O
4Or LiFePO
4Described negative material comprises synthetic graphite or coke phase carbon microbeads.
Principle of the present invention is as follows: synthetic P of the present invention (MMA-AN-VAc) (poly-(methyl methacrylate-vinyl cyanide-vinyl acetate)) powder is to have made full use of monomer M MA, AN, and the advantage of VAc obtains the superior gelatin polymer of over-all properties at last.Methyl methacrylate (MMA) contains carbonyl in the unit, and the oxygen in the softening agent of carbonyl and carbonates has very strong effect, and fabulous imbibition ability is arranged, simultaneously with advantages such as the good stability at lithium electrode interface and raw material cheaply are easy to get; AN provides good processibility for polymkeric substance, electrochemistry and thermodynamic stability, if use vinyl cyanide (AN) simultaneously, it can also reduce the fragility of polymkeric substance, increases physical strength; And vinyl-acetic ester (VAc) has stronger cohesiveness, and perfect physical strength can be provided, and increases cohesiveness between the positive and negative pole material.Synthesized polymkeric substance with emulsion polymerization: P (MMA-AN-VAc) (poly-(methyl methacrylate-vinyl cyanide-vinyl acetate)), and, prepared the lithium ion battery gel polymer film of self-supporting with phase transfer method based on this polymkeric substance.This film has the fabulous microvoid structure that is cross-linked with each other.This polymeric film is immersed in forms gel polymer electrolyte in the electrolytic solution, after being assembled into battery, electro-chemical test shows that this gel polymer electrolyte has good ion transmission performance and electrochemical stability performance, can be as the ionogen of polymer Li-ion battery.Comparing for the gel polymer electrolyte of matrix with P (MMA-AN), is that the ionogen of matrix has higher ionic conductivity, better mechanical strength, electrochemistry and thermodynamic stability with P (MMA-AN-VAc).
The present invention compared with prior art has following advantage and beneficial effect:
1, ionogen of the present invention ionic conductivity at room temperature is up to 3.48 * 10
-3Scm
-1, lithium ion transference number also reaches 0.51, and is higher by 10.8%～18.5% than the PMMA co-mixing system or the PVdF-HFP system of bibliographical information.
2, electrolyte electrochemical stability window of the present invention is up to 5.6V (vs.Li/Li
+), its electrochemical stability is good.As the P (MMA-AN-VAc) of electrolyte matrix, because the adding of monomer VAc, physical strength is the ionogen height of matrix than with binary polymer P (MMA-AN).
3, the inventive method manufacture craft is simple, and the operating time is short, the production efficiency height, and for suitability for industrialized production provides condition, resulting self-supporting lithium ion battery gel polymer film has splendid absorbency and liquid-maintaining capacity.
4, the used solvent of the present invention is a deionized water, in the process of phase transition, also is to be immersed in to produce precipitation in the deionized water, does not use volatile organic solvent, can not pollute the good and production cost minimizing of environment protecting to environment.
Description of drawings
Fig. 1 is the synthetic route of polymer P (MMA-AN-VAc).
Fig. 2 is the sem photograph (amplifying 20000 times) of the lithium ion battery gel polymer film of self-supporting.
Fig. 3 is differential thermal (DSC) curve of the lithium ion battery gel polymer film of self-supporting.
Fig. 4 is thermogravimetric (TG) curve of the lithium ion battery gel polymer film of self-supporting.
Fig. 5 is the electrochemical stability window of the lithium ion battery gel polymer electrolyte of self-supporting.
Fig. 6 is the ac impedance spectroscopy of the lithium ion battery gel polymer electrolyte of self-supporting under the room temperature.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
(1) monomers methyl methacrylate (MMA) of polymerization use, vinyl cyanide (AN) and vinyl-acetic ester (VAc) are analytical pure.The synthetic route of polymkeric substance as shown in Figure 1.Earlier monomer distillation is removed hydroquinone of polymerization retarder before the experiment.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere protection, with mass percent is that to join mass percent be to dissolve in 65% the deionized water for 1.5% emulsifier sodium lauryl sulfate, add mass percent again and be 33.3% monomer M MA, AN and VAc (MMA, AN and VAc mass ratio are 1: 4: 1), stir, adding mass percent with constant pressure funnel under 55 ℃ is that 0.2% initiator Sodium Persulfate reacts (adding at twice), and stirring velocity is controlled at 1000r/min; React and obtain white emulsion after 6 hours, pour white emulsion into 1 times of above-mentioned reaction volume, mass percent is 3% Al
2(SO
4)
3Stirring breakdown of emulsion in the solution, is after 50 ℃ of deionizations are washed 2 times, to wash 2 times with dehydrated alcohol with temperature then again, with monomer or the emulsifying agent of removing any not complete reaction, obtains the polymkeric substance-P (MMA-AN-VAc) of white powder.The P that obtains (MMA-AN-VAc) powder be placed in the vacuum drying oven 50 ℃ dry 24 hours down.
(2) under 75 ℃, be 7% with polymer P (MMA-AN-VAc) powder dissolution mass percent to P (MMA-AN-VAc) in N-N dimethyl formamide (DMF) of white.Fully after the dissolving, with the stainless steel scraper with the heavy-gravity solution coat that obtains on clean sheet glass, wherein with the method for two ends subsides hinge fixedly the thickness of film be 70 μ m.Together with sheet glass film is immersed in the deionization tank then, after solvent (DMF) and the mutual exchange of non-solvent (water), causes phase transition, obtain the film of white.Film is placed in the flowing water flushing 1 hour, soaked 2 hours in the ionized water that puts in, at last film was placed on vacuum drying oven dry 20 hours, prepare the lithium ion battery gel polymer film of self-supporting.
Can know from the sem photograph (amplifying 20000 times) of the lithium ion battery gel polymer film of Fig. 2 self-supporting, the gelatin polymer film for preparing not only has a large amount of micropores on the surface, and many interconnected micropores also being arranged in lower face, the mean radius in hole is about 0.5 μ m.
From Fig. 3 and Fig. 4 as can be seen, the second-order transition temperature of the gelatin polymer film of preparation is lower, is 48.6 ℃.This film has good thermostability in 310 ℃ of scopes.So prepared gelatin polymer film can be applied to lithium ion battery safely.
(3) in glove box (Mikrouna Super 12201750), the lithium ion battery gel polymer film of self-supporting is immersed in (1mol/L LiPF in the electrolytic solution
6+ EC+DMC+EMC, EC: DMC: the EMC mass ratio is 1: 1: 1), obtain the lithium ion battery gel polymer electrolyte of self-supporting after 30 minutes.
In contrast, reference 1 and 2 (1, M.M.Rao, J.S.Liu, W.S.Li, Y.Liang, D.Y.Zhou, J.Membr.Sci.doi:10.1016/j.memsci.2008.06.004.2, D.Y.Zhou, G.Z.Wang, W.S.Li, G.L.Li, C.L.Tan, M.M.Rao, Y.H.Liao, J.Power Sources doi:10.1016/j.jpowsour.2008.05.027.) method to have prepared with P (MMA-AN) be the gel polymer electrolyte of matrix.
The ionic conductivity ac impedance measurement of gel polymer electrolyte:
The lithium ion battery gel polymer electrolyte of the self-supporting that embodiment 1 is obtained is placed between two stainless steels (SS) electrode, carries out the alternating-current impedance test.Shown in Figure 5, linear intersection point with real axis is the resistance of gel polymer electrolyte, (wherein L represents the thickness of gel polymer electrolyte can to obtain the ionic conductivity of gel polymer electrolyte: σ=L/AR thus, A is the contact area of stainless steel plate and film, and R is the resistance of polymer dielectric).Calculate ionic conductivity σ=3.48 * 10 of gel polymer electrolyte under the room temperature
-3Scm
-1, likening to what contrast is the ionic conductivity height of the gel polymer electrolyte of matrix with P (MMA-AN).
The electrochemical stability window test:
The lithium ion battery gel polymer electrolyte and the metallic lithium of the self-supporting that embodiment 1 is obtained are assembled into button cell, and its structure is Li/ gel polymer electrolyte/Li, carry out the electrochemical stability window test.It is an electrochemical stability window of determining gel polymer electrolyte with linear sweep voltammetry.The linear time base sweep volt-ampere curve of the gel polymer electrolyte for preparing as shown in Figure 6, compare with the electrochemical stability window 4.6V that with P (MMA-AN) is the gel polymer electrolyte of matrix as can be known, gel polymer electrolyte of the present invention has higher electrochemical stability window, is 5.6V (vs.Li/Li
+).
Embodiment 2
(1) presses embodiment 1 pre-treatment monomer M MA, AN and VAc.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere protection, with mass percent is that to join mass percent be to dissolve in 61.6% the deionized water for 3% emulsifying agent dodecyl sulphate potassium, add mass percent again and be 35% monomer M MA, AN and VAc (MMA, AN and VAc mass ratio are 2: 8: 1), stir, adding mass percent with constant pressure funnel under 60 ℃ is that 0.4% initiator potassium persulfate is reacted (adding at twice), and stirring velocity is controlled at 800r/min; React and obtain white emulsion after 7 hours, pour white emulsion into 1 times of above-mentioned reaction volume, mass concentration is 3.5% Al
2(SO
4)
3Stirring breakdown of emulsion in the solution, is after 60 ℃ of deionizations are washed 3 times, to wash 3 times with dehydrated alcohol, with monomer or the emulsifying agent of removing any not complete reaction with temperature then again.With white polymer P (MMA-AN-VAc) powder that obtains be placed in the vacuum drying oven 60 ℃ dry 28 hours down.
(2) under 60 ℃, with polymer P (MMA-AN-VAc) powder dissolution of white in N-N dimethyl formamide (DMF) to P (MMA-AN-VAc) mass percent be 8%; The method of pasting hinge with the two ends fixedly thickness of film is 60 μ m.All the other are with embodiment 1 step (2).
(3) in glove box, micropore shape film is immersed in (1mol/L LiPF in the electrolytic solution
6+ EC+DMC+EMC, EC: DMC: the EMC mass ratio is 1: 1: 1), obtain the lithium ion battery gel polymer electrolyte of self-supporting after 20 minutes.
Embodiment 3
(1) presses embodiment 1 pre-treatment monomer M MA, AN and VAc.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere protection, with mass percent is that to join mass percent be to dissolve in 68.65% the deionized water for 1% emulsifying agent ammonium lauryl sulfate, add mass percent again and be 30% monomer M MA, AN and VAc (MMA, AN and VAc mass ratio are 4: 8: 1), stir, adding mass percent with constant pressure funnel under 60 ℃ is that 0.35% initiator ammonium persulfate reacts (adding at twice), and stirring velocity is controlled at 800r/min; React and obtain white emulsion after 6.5 hours, pour white emulsion into 1.5 times of above-mentioned reaction volumes, mass concentration is 3.5% Al
2(SO
4)
3Stirring breakdown of emulsion in the solution, is after 60 ℃ of deionizations are washed 4 times, to wash 4 times with dehydrated alcohol, with monomer or the emulsifying agent of removing any not complete reaction with temperature then again.With white polymer P (MMA-AN-VAc) powder that obtains be placed in the vacuum drying oven 65 ℃ dry 30 hours down.
(2) under 60 ℃, with polymer P (MMA-AN-VAc) powder dissolution of white in mass percent is 6% N-N dimethyl formamide (DMF); The method of pasting hinge with the two ends fixedly thickness of film is 90 μ m, and all the other are with embodiment 1 step (2).
(3) handle by embodiment 1 corresponding steps.
Embodiment 4
(1) presses embodiment 1 pre-treatment monomer M MA, AN and VAc.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere protection, with mass percent is that to join mass percent be to dissolve in 70% the deionized water for 2% emulsifier sodium lauryl sulfate, add mass percent again and be 27.7% monomer M MA, AN and VAc (MMA, AN and VAc mass ratio are 2: 4: 1), stir, adding mass percent with constant pressure funnel under 65 ℃ is that 0.3% initiator Sodium Persulfate reacts (adding at twice), and stirring velocity is controlled at 900r/min; React and obtain white emulsion after 5.5 hours, pour white emulsion into 1.2 times of above-mentioned reaction volumes, mass concentration is 3.5% Al
2(SO
4)
3Stirring breakdown of emulsion in the solution, is after 70 ℃ of deionizations are washed 5 times, to wash 5 times with dehydrated alcohol, with monomer or the emulsifying agent of removing any not complete reaction with temperature then again.With white polymer P (MMA-AN-VAc) powder that obtains be placed in the vacuum drying oven 70 ℃ dry 30 hours down.
(2) under 80 ℃, be 9% with polymer P (MMA-AN-VAc) powder dissolution mass percent to P (MMA-AN-VAc) in N-N dimethyl formamide (DMF) of white.All the other are with embodiment 1 step (2).
(3) handle by embodiment 1 corresponding steps.
(1) presses embodiment 1 pre-treatment monomer M MA, AN and VAc.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere protection, with mass percent is that to join mass percent be to dissolve in 65.35% the deionized water for 2.5% emulsifier sodium lauryl sulfate, add mass percent again and be 32% monomer M MA, AN and VAc (MMA, AN and VAc mass ratio are 2: 4: 1), stir, adding mass percent with constant pressure funnel under 60 ℃ is that 0.15% initiator Sodium Persulfate reacts (adding at twice), and stirring velocity is controlled at 1100r/min; React and obtain white emulsion after 7 hours, pour white emulsion into 1.5 times of above-mentioned reaction volumes, mass percent is 4.5% Al
2(SO
4)
3Stirring breakdown of emulsion in the solution, is after 60 ℃ of deionizations are washed 4 times, to wash 4 times with dehydrated alcohol, with monomer or the emulsifying agent of removing any not complete reaction with temperature then again.With white polymer P (MMA-AN-VAc) powder that obtains be placed in the vacuum drying oven 65 ℃ dry 36 hours down.
(2) under 80 ℃, with polymer P (MMA-AN-VAc) powder dissolution of white in N-N dimethyl formamide (DMF) to P (MMA-AN-VAc) mass percent be 10%.All the other are with embodiment 1 step (2).
(3) handle by embodiment 1 corresponding steps.
Embodiment 6
(1) presses embodiment 1 pre-treatment monomer M MA, AN and VAc.The aggregation test concrete grammar is as follows: at N
2Under the atmosphere protection, with mass percent is that to join mass percent be to dissolve in 62.75% the deionized water for 3% emulsifier sodium lauryl sulfate, add mass percent again and be 34% monomer M MA, AN and VAc (MMA, AN and VAc mass ratio are 2: 4: 1), stir, adding mass percent with constant pressure funnel under 62 ℃ is that 0.25% initiator Sodium Persulfate reacts (adding at twice), and stirring velocity is controlled at 1000r/min; React and obtain white emulsion after 5 hours, pour white emulsion into 1.25 times of above-mentioned reaction volumes, mass percent is 5% Al
2(SO
4)
3Stirring breakdown of emulsion in the solution, is after 70 ℃ of deionizations are washed 3 times, to wash 3 times with dehydrated alcohol, with monomer or the emulsifying agent of removing any not complete reaction with temperature then again.With polymer P (MMA-AN-VAc) powder of the white that obtains be placed in the vacuum drying oven 65 ℃ dry 33 hours down.
(2) under 78 ℃, with polymer P (MMA-AN-VAc) powder dissolution of white in N-N dimethyl formamide (DMF) to P (MMA-AN-VAc) mass percent be 7.5%.All the other are with embodiment 1 step (2).
(3) handle by embodiment 1 corresponding steps.
Application Example 1
The lithium ion battery gel polymer electrolyte of synthetic self-supporting among the embodiment 1 is pressed positive electrode material (LiCoO successively
2, LiMn
2O
4Or LiFePO
4), gel polymer electrolyte, negative material (synthetic graphite or MCMB (coke phase carbon microbeads)) be assembled into button cell in glove box.This battery can be used for daily electronic product such as electronic dictionary, wrist-watch, counter etc.
Application Example 2
Synthetic gel polymer electrolyte among the embodiment 1 is pressed positive electrode material (LiCoO successively
2, LiMn
2O
4Or LiFePO
4), gel polymer electrolyte and negative material (synthetic graphite or MCMB (coke phase carbon microbeads)) adopt winding process to be assembled into electric core.Positive pole is drawn with aluminium pole ears spot welding, and negative pole is drawn with the spot welding of nickel lug.Electric core is taken out after dry 18 hours in 65 ℃ 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 LiPF6+EC+DMC+EMC, EC: DMC: the 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 6 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.
Above-mentioned embodiment is the preferred embodiments of the present invention; can not limit claim of the present invention; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. the preparation method of the lithium ion battery gel polymer electrolyte of a self-supporting is characterized in that: may further comprise the steps:
(1) at N
2Under the atmosphere protection, with mass percent is that to join mass percent be to dissolve in 60～70% the deionized water for 1～3% emulsifying agent, add mass percent again and be 25～35% monomers methyl methacrylate, vinyl cyanide and vinyl-acetic ester, stir, adding mass percent with constant pressure funnel under 55～65 ℃ is that 0.1～0.4% initiator reacts; React and obtain white emulsion after 5～7 hours, pouring white emulsion into 1～1.5 times of white emulsion volume, mass concentration is 2～5% Al
2(SO
4)
3Stirring breakdown of emulsion in the solution, is after 50～70 ℃ of deionizations are washed 2～5 times, to wash 2～5 times with dehydrated alcohol with temperature then again, obtains the polymkeric substance of white; With the white polymer that obtains be placed in the vacuum drying oven 50～70 ℃ dry 24～36 hours down; The polymkeric substance of described white has following structural formula:
Wherein w is 10,000～1.5 ten thousand integer;
(2) under 60～80 ℃, be 5～10% with polymer dissolution mass percent to polymkeric substance in the N-N dimethyl formamide; After the dissolving, the viscous solution that obtains is coated on the clean sheet glass, fixedly the thickness of film fully; Together with sheet glass film is immersed in the deionization tank then, obtains the film of white; Film is placed on washes 0.5～1 hour in the flowing water, soaked in the ionized water that puts in 1～2 hour, at last film is placed on vacuum drying oven drying 20～30 hours, prepare the lithium ion battery gel polymer film of self-supporting;
(3) in glove box, the lithium ion battery gel polymer film of self-supporting is immersed in the lithium ion battery gel polymer electrolyte that obtains self-supporting in the electrolytic solution after 20～40 minutes.
2. the preparation method of the lithium ion battery gel polymer electrolyte of self-supporting according to claim 1, it is characterized in that: the mass ratio of the described monomers methyl methacrylate of step (1), monomer vinyl cyanide and monomer vinyl-acetic ester is 1～4: 4～8: 1; Described stirring velocity is controlled at 800～1100r/min; Described emulsifying agent is sodium lauryl sulphate, dodecyl sulphate potassium or ammonium lauryl sulfate; Described initiator is Sodium Persulfate, Potassium Persulphate or ammonium persulphate, adds at twice; The described Al of step (1)
2(SO
4)
3The volume of solution is that 1～1.5 times of white emulsion volume, mass concentration are 2～5%.
3. the preparation method of the lithium ion battery gel polymer electrolyte of self-supporting according to claim 1, it is characterized in that: the thickness of the described film of step (2) is 60 μ m～90 μ m; Described electrolytic solution is by LiPF
6, NSC 11801, methylcarbonate and Methyl ethyl carbonate form, solvent NSC 11801 wherein: methylcarbonate: the mass ratio of Methyl ethyl carbonate is 1: 1: 1, LiPF
6Volumetric molar concentration get 1mol/L.
4. lithium ion battery gel polymer electrolyte according to the self-supporting of each described method preparation of claim 1～3.
5. the application of the lithium ion battery gel polymer electrolyte of self-supporting according to claim 4 in the preparation polymer Li-ion battery.
6. the application of the lithium ion battery gel polymer electrolyte of self-supporting according to claim 5 in the preparation polymer Li-ion battery is characterized in that: gel polymer electrolyte is assembled into button cell by positive electrode material, gel polymer electrolyte, negative material successively in glove box.
7. the lithium ion battery gel polymer electrolyte of self-supporting according to claim 5 is characterized in that in the application of preparation in the polymer Li-ion battery: gel polymer electrolyte and positive electrode material and negative material employing winding process are assembled into electric core; Positive pole is drawn with aluminium pole ears spot welding, and negative pole is drawn with the spot welding of nickel lug, then electric core is taken out after dry 15～20 hours in 65～75 ℃ 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 5～8 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.
8. according to the application of lithium ion battery gel polymer electrolyte in the preparation polymer Li-ion battery of claim 6 or 7 described self-supportings, it is characterized in that: described positive electrode material comprises LiCoO
2, LiMn
2O
4Or LiFePO
4Described negative material comprises synthetic graphite or coke phase carbon microbeads.
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| CN104241685A (en) * | 2014-09-22 | 2014-12-24 | 张家港市国泰华荣化工新材料有限公司 | Anti-overcharging lithium ion battery electrolyte |
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| CN102694203B (en) * | 2012-05-29 | 2014-11-05 | 深圳华粤宝电池有限公司 | Preparation method of gel polymer electrolyte |
| CN103923333A (en) * | 2013-01-14 | 2014-07-16 | 海洋王照明科技股份有限公司 | Polyacrylonitrile gel thin film and preparation method thereof, corresponding electrolyte and preparation method thereof, and lithium ion battery |
| CN103840207B (en) * | 2014-03-12 | 2016-09-14 | 中国海诚工程科技股份有限公司 | A kind of resistant to elevated temperatures lithium ion battery gel polymer electrolyte and preparation method thereof |
| CN109400786B (en) * | 2017-08-16 | 2020-12-29 | 东莞东阳光科研发有限公司 | High-molecular polymer, preparation method thereof and electrolyte containing high-molecular polymer |
| CN109485882B (en) * | 2018-10-08 | 2023-09-01 | 长春理工大学 | Preparation method of self-supporting film |
| CN112194807A (en) * | 2019-07-08 | 2021-01-08 | 长春理工大学 | Method for preparing latex film based on demulsification induced curing technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104241685A (en) * | 2014-09-22 | 2014-12-24 | 张家港市国泰华荣化工新材料有限公司 | Anti-overcharging lithium ion battery electrolyte |
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