CN101130587A - Acetic acid vinyl ester-acrylic ester copolymer basis solid polymer electrolyte and film - Google Patents

Acetic acid vinyl ester-acrylic ester copolymer basis solid polymer electrolyte and film Download PDF

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CN101130587A
CN101130587A CNA2007100925271A CN200710092527A CN101130587A CN 101130587 A CN101130587 A CN 101130587A CN A2007100925271 A CNA2007100925271 A CN A2007100925271A CN 200710092527 A CN200710092527 A CN 200710092527A CN 101130587 A CN101130587 A CN 101130587A
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polymer
matrix
acetic acid
acrylic ester
acid vinyl
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CN101130587B (en
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傅相锴
杨道均
龚永锋
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CHONGQING YIPAIYIN CHEMICAL INDUSTRY PRODUCTS Co Ltd
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CHONGQING YIPAIYIN CHEMICAL INDUSTRY PRODUCTS Co Ltd
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Abstract

The invention discloses a solid polymer electrolyte with same structure and different composite and electrolytic film, which is characterized by the following: setting the electrolytic polymer base as random copolymer of vinyl acetate VAc with feeding mole ratio at 8. 5 : 1. 5-1. 5 : 8. 5 and acrylic ester MA, MMA, EA, BA and so on; and setting as vinyl acetate-acrylic ester polymer and second polymer; setting polymer blending base as PMMA, PVdF and so on; adopting semi-continuous seed emulsion polymeric method synthesis; mixing and stirring synthetic vinyl acetate-acrylic ester random copolymer base, second polymer and Li salt under the function of the solvent evenly; getting mixed solution; casting into die; pressing; fetching film; drying; getting the product. This invention possesses better mechanical force property, hot stability and higher light transmittance ratio, which can be used to twice Li battery.

Description

Acetic acid vinyl ester-acrylic ester copolymer basis solid polymer dielectric and film
Technical field
The present invention relates to a kind of polymer electrolyte, be specifically related to a kind of with vinyl acetate and acrylate, as: methyl acrylate MA, methyl methacrylate MMA, ethyl propenoate EA, butyl acrylate BA etc. are comonomer synthetic random copolymers and multipolymer and second kind of polymkeric substance, as the blend of PMMA, PVdF etc. the solid polymer electrolyte as polymeric matrix.The solid polymer electrolyte that the present invention makes uses with the form of polymer dielectric film usually.Vinyl acetate-acrylate multipolymer, second kind of polymkeric substance, lithium salts and solvent are stirred, and the curtain coating casting film can obtain solid polymer dielectric film again.The solid polymer electrolyte that the present invention makes has ionic conductivity height, good film-forming property, characteristics such as transmittance height, mechanical property are good, at lithium-ion secondary cell, aspects such as electrochromic device and dexterous light modulation window are expected to replace traditional liquid electrolyte, are with a wide range of applications.
Background technology
Polymer solid electrolyte (Solid polymer electrolyte) is called ionophore polymkeric substance (Ion-conductingpolymer) again, is a kind of novel solid electrolyte that develops rapidly from the seventies in 20th century.Because have light weight, visco-elasticity is good, easily distinct advantages such as film forming, Heat stability is good and lithium ion conductivity height have in electrochemical devices such as lithium-ion secondary cell, ultra-capacitor, ionization sensor, full-solid electrochromic device, the energy-conservation smart windows of electrochromism, electrochromic display device widely and use.Reported first such as Wright in 1973 polyoxyethylene (PEO)/an alkali metal salt complex compound have ionic conductivity.Armand in 1979 etc. have reported that PEO/ an alkali metal salt complex compound ionic conductivity in the time of 40-60 ℃ reaches 10 -5S/cm, and have film-forming properties preferably, can be used as the ionogen of lithium ion battery.After this, all started the research boom of copolymer solid electrolyte in global scope.In decades, people's research is carried out modification by means such as polymer modification, different monomers copolymerization, different polymer blending, crosslinked polymers to all kinds of polymeric matrixs, improve the polymer dielectric specific conductivity with the state of aggregation regularity that destroys the polymkeric substance chain link, existing many reports and patent application.Research at present polymer dielectric matrix the most widely mainly contains PEO, PAN, PMMA and PVdF etc.But all good polymer electrolyte film reports of electrical property and mechanical property and few so far.It is the polymer dielectric of matrix with the blend of polyvinyl acetate (PVA) (PVAc) and other polymkeric substance that bibliographical information has been arranged, as PVAc/PMMA blend (Baskaran R, Selvasekarapandian S, Kuwata N, Kawamura J, Hattori T.[J] .Solid State Ionics, 2006,177:2679-2682), PVAc/PVdF blend (Baskaran R, Selvasekarapandian S, Kuwata N, Kawamur J, Hattori T.[J] .Materials Chemistry and Physics, 2006,98:55-61), PVAc/PEO blend (Animitsa I E, Kruglyashov A L, Bushkova O V, Zhukovsky V M.[J] .Solid StateIonics, 1998,106:321-327) and PVAc/P (VdF-co-HFP) blend (Nam-Soon Choi, Young-Gi Lee, Jung-Ki Park, Jang-Myoun Ko.[J] .ElectrochimicaActa, 2001,46:1581-1586) etc., they all have higher ionic conductivity and mechanical property preferably.But with vinyl acetate between to for plastic base ester and acrylate, as: MA, EA, BA etc. for comonomer synthetic random copolymers and multipolymer and second kind of other polymkeric substance (as PMMA, PVdF etc.) blend be matrix solid polymer electrolyte also do not appear in the newspapers, do not have patent application yet.Recently, though bibliographical information is arranged with the multipolymer of the derivative-methyl methacrylate MMA of 9: 1 mole ratio of acrylic acid esters and vinyl acetate matrix as solid polymer electrolyte, (Lu Lei, Zuo Xiaoxi, Li Weishan, Liu Jiansheng etc., [J]. chemical journal, 2007,65 (6): 475-480), still, because the vinyl acetate content in the multipolymer is too low, can not play the mutual promoting action between each component of multipolymer.And be that the solid polymer electrolyte of matrix had not been seen bibliographical information and patent application yet with the blend of the multipolymer of methyl methacrylate beyond this mol ratio and vinyl acetate and multipolymer and second kind of polymkeric substance.
Summary of the invention
For character such as the ionic conductivity that further improves polymer dielectric in the prior art and mechanical properties, the present invention proposes a kind of novel solid polymer ionogen, the solid polymer dielectric film that adopts a step casting film-forming is provided simultaneously.
The solid polymer electrolyte that the present invention proposes, its polymeric matrix adopts the binary random copolymer of semi-continuous seed emulsion polymerization method preparation by vinyl acetate between to for plastic base ester VAc and acrylate (being selected from methyl acrylate MA, methyl methacrylate MMA, ethyl propenoate EA or butyl acrylate BA) as comonomer, promptly is P (VAc-MA), P (VAc-MMA), P (VAc-EA), P (VAc-BA), P (VAc-MA)/PMMA, P (VAc-MA)/PVdF, P (VAc-MMA)/PVdF etc.Wherein, P (VAc-MA), P (VAc-EA), P (VAc-BA) are to be monomer with vinyl acetate (VAc) and methyl acrylate (MA) or ethyl propenoate (EA) or butyl acrylate (BA), adopt the random copolymers of semi-continuous seed emulsion polymerization method preparation.P (VAc-MMA) matrix is to be monomer with vinyl acetate (VAc) and methyl methacrylate (MMA), adopts the random copolymers of semi-continuous seed emulsion polymerization method preparation.Described polymeric matrix P (VAc-MA), P (VAc-MMA), P (VAc-EA), P (VAc-BA) are binary random copolymer, and its structure is the statistic copolymer of VAc and MA, MMA, EA, BA.The molar ratio of VAc and MA, MMA, EA, BA is 8.5: 1.5～1.5: 8.5, and most preferred mol ratio is for being 1: 1.
The polymeric matrix polymer blending matrix that also can be above-mentioned acetic acid vinyl ester-acrylic ester copolymer form with second kind of polymer P MMA or PVdF blend, as polymeric matrix P (VAc-MA)/PMMA, P (VAc-MA)/PVdF is with copolymer p (VAc-MA) and second kind of polymkeric substance, forms polymeric matrix as the blend of PMMA, PVdF.Polymeric matrix P (VAc-MMA)/PVdF forms polymeric matrix with copolymer p (VAc-MMA) and the blend of second kind of polymer P VdF.The content of second kind of polymer P MMA or PVdF is m (PMMA)/(copolymer)=0.01～1.5 among polymer blend matrix P (VAc-MA)/PMMA, P (VAc-MA)/PVdF, P (VAc-MMA)/PVdF, m (PVdF)/(copolymer)=0～1.5, promptly, PMMA or PVdF quality/acetic acid vinyl ester-acrylic ester copolymer quality=0.01～1.5, most preferred ratio is 0.5.
Above-mentioned solid polymer electrolyte is a solvent with tetrahydrofuran (THF) (THF), mixes in above-mentioned polymeric matrix P (VAc-MA), P (VAc-MMA), P (VAc-EA), P (VAc-BA), P (VAc-MA)/PMMA, P (VAc-MA)/PVdF, P (VAc-MMA)/PVdF and is dissolved into LiClO 4, can be prepared into polymer dielectric film.LiClO in the polymer dielectric 4Consumption be m (LiClO 4)/m (copolymer)=1～50%, that is, and LiClO 4Quality is 1～50% of the polymer blending substrate quality formed of acetic acid vinyl ester-acrylic ester random copolymers matrix or itself and second kind of polymer blending, and most preferred mass ratio is 5～40%.
The semi-continuous seed emulsion polymerization method of the employing of synthetic random copolymers polymeric matrix of the present invention is: add initiator in containing the aqueous solution of emulsifying agent, logical nitrogen stirs, the mixed solution that adds 4-10% vinyl acetate between to for plastic base ester and acrylate monomer causes copolymerization as seed, the reaction certain hour, polymerization is complete substantially to treat seed, slowly drip remaining 96-90% monomer mixed solution again, stirring reaction finishes until reaction, and breakdown of emulsion suction filtration, washing, drying, purifying are promptly finished.
Binary random copolymer P (VAc-EA), P (VAc-BA) polymeric matrix synthetic method are similar to above-mentioned random copolymers.
In the polymeric matrix building-up process of the present invention, used initiator is ammonium persulphate ((NH 4) 2S 2O 8) or Potassium Persulphate (K 2S 2O 8), initiator system of ammonium persulfate ((NH 4) 2S 2O 8); Used emulsifying agent is sodium lauryl sulphate or Sodium dodecylbenzene sulfonate, preferably sodium dodecyl sulfate.
Solid polymer dielectric film preparation method disclosed by the invention is as follows:
At first, with random copolymers matrix or itself and second kind of polymer blending matrix and mixing and stirring such as lithium salts, solvent that polymer blending is formed;
Then, mixing solutions watered in the mould that polytetrafluoroethylmaterial material makes suppress, take out film 50～100 ℃ of dryings in vacuum drying oven after the solvent evaporates, preferred drying temperature is 60 ℃, can obtain solid polymer dielectric film.
In the polymer dielectric of the present invention, described lithium salts is LiClO 4Or LiCF 3SO 3, the lithium salts consumption accounts for 1～50% of polymeric matrix total amount, and preferred lithium salts consumption is 5～40%.Because LiClO 4Compare LiCF 3SO 3Low price, and performance is identical, therefore preferably uses LiClO 4The used solvent of preparation polymer dielectric can be tetrahydrofuran (THF) (THF), N-Methyl pyrrolidone (NMP) etc., preferred tetrahydrofuran (THF).Solvent load is 100～800% of a polymeric matrix quality, and preferred consumption is 200～400%.
The solid polymer dielectric film of the present invention's preparation has been obtained following effect: (1) under the condition of not adding softening agent, polymer dielectric has higher ionic conductivity, can reach 10 -3The S/cm order of magnitude; (2) VAc participates in and acrylate, as: MA, MMA, EA, BA copolymerization, resulting multipolymer can be further and second kind of polymer blending, two kinds of measures all make single homopolymer crystalline state change, significantly increased amorphous phase region, reduce the energy barrier of sub-chain motion, improved mechanical property and thermostabilitys such as tensile strength.(3) solid polymer dielectric film of the present invention's preparation has very high visible light permeability.(4) filming technology adopts the automatic curtain coating of step casting, and technology is simple, and cost is low.
Its electrical property of novel solid polymer ionogen and mechanical mechanics property that the present invention proposes are all good, can be applied in the electrochemical devices such as serondary lithium battery, ultra-capacitor, ionization sensor, full-solid electrochromic device, the energy-conservation smart windows of electrochromism, electrochromic display device.
Embodiment
Below in conjunction with specific embodiment enforcement of the present invention is described further:
Embodiment one:
Be to join in the there-necked flask of 250ml after 1% the sodium lauryl sulphate with 80g deionized water dissolving massfraction, magnetic agitation also slowly is warmed up to 70 ℃, constant temperature; Add with 0.4% (wt%) ammonium persulphate of 20g deionized water dissolving and the mixing solutions of 0.4% (wt%) sodium bicarbonate.Logical nitrogen stirs 20min, adds massfraction and be 8% monomer VAc and the mixed solution (mol ratio is 1: 1) of MA; Behind the reaction 30min, polymerization is complete substantially for seed, slowly drips the residual monomers mixed solution again, and the control rate of addition is 0.4ml/min, and 2.5h dropwises.React 1h after being added dropwise to complete again, stopped reaction is cooled to room temperature.Entire reaction is all carried out under nitrogen protection.With suction filtration behind the potassium aluminium sulfate breakdown of emulsion of 0.01mol/L, with deionized water wash for several times, and be dried to constant weight.Again with tetrahydrofuran (THF) dissolving, elimination insolubles (gel) revolves and boils off solvent, vacuum-drying.Promptly obtain the monomer molar feed ratio and be 1: 1 white powder copolymer p (VAc-MA).
The above-mentioned random copolymers of getting certain mass respectively is dissolved in the solvents tetrahydrofurane of 10mL and stirs under 40 ℃ in the exsiccant there-necked flask, adds the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 1.9～30 * 10 after 60 ℃ of following vacuum-dryings -5Scm -1Following table is Different L iClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 2.258 1.506 0.892 1.056 1.262 1.518 0.8 1.314
PMMA quality (g) 0 0 0 0 0 0 0 0
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.1129 0.1506 0.1338 0.2112 0.3155 0.4554 0.28 0.5256
Specific conductivity * 10 -5(S/cm) 1.9764 3.7072 8.1125 12.230 19.864 29.422 13.049 5.3347
Embodiment two:
Get the PMMA of 1: 1 P of monomer molar feed ratio (VAc-MA) random copolymers, certain mass, make m (PMMA)/m (copolymer)=0.5, in the exsiccant there-necked flask, be dissolved in the solvents tetrahydrofurane of 10mL, stir under 40 ℃, add the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.98～12 * 10 after 60 ℃ of following vacuum-dryings -4Scm -1Following table is Different L iClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 1.232 2.008 1.204 1.132 0.9308 1.5168 1.62 1.144
PMMA quality (g) 0.616 1.004 0.602 0.566 0.4654 0.7584 0.81 0.572
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.0924 0.3012 0.2709 0.3396 0.3491 0.6826 0.8505 0.6864
Specific conductivity * 10 -4(S/cm) 0.9815 2.3876 5.6625 8.1605 11.684 8.0328 6.0328 3.5292
Embodiment three:
Get the PMMA of 1: 1 P of monomer molar feed ratio (VAc-MA) random copolymers, certain mass, make m (PMMA)/m (copolymer)=1.0, in the exsiccant there-necked flask, be dissolved in the solvents tetrahydrofurane of 10mL and stir under 40 ℃, add the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.4～6.5 * 10 after 60 ℃ of following vacuum-dryings -4Scm -1Following table is Different L iClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 0.994 1.0144 1.722 1.147 0.854 1.604 1.19 1.534
PMMA quality (g) 0.994 1.0144 1.722 1.147 0.854 1.604 1.19 1.534
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.0994 0.2029 0.5166 0.4588 0.4270 0.9624 0.8330 1.2272
Specific conductivity * 10 -4(S/cm) 0.4855 0.8087 1.8778 2.8439 6.4013 4.9289 2.6860 1.0448
Embodiment four:
Get the PMMA of 1: 1 P of monomer molar feed ratio (VAc-MA) random copolymers, certain mass, make m (PMMA)/m (copolymer)=1.5, in the exsiccant there-necked flask, be dissolved in the solvents tetrahydrofurane of 10mL and stir under 40 ℃, add the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.1～13 * 10 after 60 ℃ of following vacuum-dryings -4Scm -1Following table is Different L iClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 0.758 1.014 0.786 0.963 0.875 0.994 0.952 0.865
PMMA quality (g) 1.137 1.521 1.179 1.444 1.3125 1.491 1.428 1.2975
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.09475 0.2535 0.2948 0.4815 0.5469 0.7455 0.833 0.865
Specific conductivity * 10 -5(S/cm) 0.05097 0.09707 2.1125 4.2230 11.490 16.367 17.3049 0.07335
Embodiment five:
Get monomer VAc38.74g and monomer M MA11.26g mixes in beaker.With joining in the there-necked flask of 250ml behind the 80g deionized water dissolving 0.50g emulsifier sodium lauryl sulfate, magnetic agitation also slowly is warmed up to 70 ℃, constant temperature; Add 0.17g initiator ammonium persulfate ((NH with the 20g deionized water dissolving 4) 2S 2O 8) and 0.17g buffer reagent sodium bicarbonate (NaHCO 3) mixing solutions.Logical nitrogen stirs 20min, adds the mixed solution of 4.0g monomer VAc and MMA; Behind the reaction 30min, polymerization is complete substantially for seed, slowly drips remaining 46g monomer mixed solution again, and 3.5h dropwises.React 1h after being added dropwise to complete again, stopped reaction is cooled to room temperature.Entire reaction is all carried out under nitrogen protection.Emulsion splitter potassium aluminium sulfate (KAI (SO with 0.01mol/L 4) 2) suction filtration behind the breakdown of emulsion, with deionized water wash for several times, and be dried to constant weight.Use solvents tetrahydrofurane (THF) dissolving again, elimination insolubles (gel) revolves and boils off solvent, vacuum-drying.Promptly obtained monomeric charge than VAc: MMA=8: the random copolymers P (VAc-MMA) under 2 (mol).
Getting above-mentioned random copolymers certain mass (1.0g～1.5g) in the exsiccant there-necked flask, is dissolved in the solvents tetrahydrofurane of 10mL and stirs under 40 ℃, add the EC softening agent of following table amount and the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 1.4～3.7 * 10 after 60 ℃ of following vacuum-dryings -3Scm -1(containing EC) and 0.1～13 * 10 -4Scm -1(not conforming to EC).Following table is Different L iClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 1.0056 0.7682 0.6474 0.8848 0.8804 0.9901 0.9927 0.9193
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.0529 0.0854 0.1143 0.2212 0.2201 0.279 0.3474 0.3677
Specific conductivity * 10 -4(S/cm) 0.11382 2.9963 5.7098 11.31 12.738 9.5741 5.9228 2.1991
Copolymer quality (g) 1.3741 1.4088 1.2895 1.2397 1.4103 1.0495 1.098 1.039
LiClO 4Quality (g) 0.3435 0.3522 0.3224 0.3099 0.3526 0.2624 0.2746 0.26
EC/ multipolymer (wt%) 0.2 0.4 0.6 0.8 1 1.5 2 2.5
EC quality (g) 0.2748 0.5635 0.7737 0.9918 1.4103 1.5742 2.1964 2.6
Specific conductivity * 10 -3(S/cm) 1.401 1.626 1.844 2.211 2.7388 3.5685 3.6517 3.6658
Embodiment six:
Get monomer VAc36.71g and monomer M MA18.29g mixes in beaker.With joining in the there-necked flask of 250ml behind the 80g deionized water dissolving 0.50g emulsifier sodium lauryl sulfate, magnetic agitation also slowly is warmed up to 70 ℃, constant temperature; Add 0.17g initiator ammonium persulfate ((NH with the 20g deionized water dissolving 4) 2S 2O 8) and 0.17g buffer reagent sodium bicarbonate (NaHCO 3) mixing solutions.Logical nitrogen stirs 20min, adds the mixed solution of 4.0g monomer VAc and MMA; Behind the reaction 30min, polymerization is complete substantially for seed, slowly drips the residual monomers mixed solution again, and 3.5h dropwises.React 1h after being added dropwise to complete again, stopped reaction is cooled to room temperature.Entire reaction is all carried out under nitrogen protection.Emulsion splitter potassium aluminium sulfate (KAI (SO with 0.01mol/L 4) 2) suction filtration behind the breakdown of emulsion, with deionized water wash for several times, and be dried to constant weight.Use solvents tetrahydrofurane (THF) dissolving again, elimination insolubles (gel) revolves and boils off solvent, vacuum-drying.Promptly obtained monomeric charge than VAc: MMA=7: the random copolymers P (VAc-MMA) under 3 (mol).
Getting above-mentioned random copolymers certain mass (1.0g～1.5g) in the exsiccant there-necked flask, is dissolved in the solvents tetrahydrofurane of 10mL and stirs under 40 ℃, add the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.04～9 * 10 after 60 ℃ of following vacuum-dryings -4Scm -1Following table is different mass LiClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 1.5 1.05 1.322 1.022 1.24 1.37 1.266 1.316
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.075 0.105 0.1983 0.2044 0.31 0.411 0.4431 0.5264
Specific conductivity * 10 -4(S/cm) 0.041748 1.2777 3.6743 6.6631 7.699 8.3269 4.9441 0.9995
Embodiment seven:
Similar to embodiment six, get monomer VAc30.98g, MMA24.02g, use 80g deionized water, 0.50g emulsifier sodium lauryl sulfate, 70 ℃ of constant temperature; Add 0.17g initiator ammonium persulfate ((NH with the 20g deionized water dissolving 4) 2S 2O 8) and 0.17g buffer reagent sodium bicarbonate (NaHCO 3) mixing solutions.Logical nitrogen stirs 20min, adds the mixed solution of 4.0g monomer VAc and MMA; Behind the reaction 30min, slowly drip the residual monomers mixed solution again, 3.5h dropwises.React 1h after being added dropwise to complete again, stopped reaction is cooled to room temperature.Entire reaction is all carried out under nitrogen protection.Emulsion splitter potassium aluminium sulfate (KAI (SO with 0.01mol/L 4) 2) suction filtration behind the breakdown of emulsion, washing is dried to constant weight.Use solvents tetrahydrofurane (THF) dissolving again, filtration, drying.Promptly obtained monomeric charge than VAc: MMA=6: the random copolymers P (VAc-MMA) under 4 (mol).
Get above-mentioned random copolymers certain mass 1.5g in the exsiccant there-necked flask, be dissolved in the solvents tetrahydrofurane of 10mL and stir under 40 ℃, add the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.01～6 * 10 after 60 ℃ of following vacuum-dryings -4Scm -1Following table is different mass LiClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.075 0.15 0.225 0.3 0.375 0.45 0.525 0.6
Specific conductivity * 10 -4(S/cm) 0.016438 0.8839 1.4633 2.9804 3.4506 5.7288 3.2284 0.6128
Embodiment eight:
Similar to embodiment six, get monomer VAc25.43g and MMA29.57g, 80g deionized water, 0.50g emulsifying agent dodecyl sulphate, 70 ℃ of constant temperature; Add 0.17g initiator ammonium persulfate ((NH with the 20g deionized water dissolving 4) 2S 2O 8) and 0.17g buffer reagent sodium bicarbonate (NaHCO 3) mixing solutions.Logical nitrogen stirs 20min, adds the mixed solution of 4.0g monomer VAc and MMA; Behind the reaction 30min, polymerization is complete substantially for seed, slowly drips the residual monomers mixed solution again, and 3.5h dropwises, and reacts 1h again.Breakdown of emulsion, suction filtration, washing, drying.Use solvents tetrahydrofurane (THF) dissolving again, filtration, drying.Promptly obtained monomeric charge than VAc: MMA=5: the random copolymers P (VAc-MMA) under 5 (mol).
Getting above-mentioned random copolymers certain mass (1.2g～1.8g) in the exsiccant there-necked flask, is dissolved in the solvents tetrahydrofurane of 10mL and stirs under 40 ℃, add the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.09～45 * 10 after 60 ℃ of following vacuum-dryings -5Scm -1Following table is different mass LiClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 1.2834 1.498 1.4112 1.6668 1.3824 1.4528 1.5156 1.7672
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.06417 0.1498 0.21168 0.3334 0.3456 0.4358 0.5305 0.7069
Specific conductivity * 10 -5(S/cm) 0.090589 5.6291 6.586 12.025 28.29 40.994 9.9565 1.206
Embodiment nine:
(monomeric charge of 1.0g～1.5g) is than VAc: MMA=7: the P of 3 (mol) (VAc-MMA) random copolymers to get certain mass, in the exsiccant there-necked flask, be dissolved in the solvent N-Methyl pyrrolidone (NMP) of 10mL, stir under 40 ℃, add the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.04～9 * 10 after 60 ℃ of following vacuum-dryings -4Scm -1Following table is different mass LiClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.075 0.15 0.225 0.3 0.375 0.45 0.525 0.6
Specific conductivity * 10 -4(S/cm) 0.1210 0.9843 1.9633 2.1504 3.5806 5.7288 3.2284 0.6128
Embodiment ten:
By embodiment five preparation feed ratio is VAc: MMA=8: the copolymer p of 2 (mol) (VAc-MMA).The copolymer p (VAc-MMA) that takes by weighing certain mass (1.0g), PVdF (0.5g) is dissolved in the solvent N-Methyl pyrrolidone (NMP) of 10mL, stirs under 40 ℃, adds the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.20～15 * 10 after 60 ℃ of following vacuum-dryings -4Scm -1Following table is different mass LiClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
PVdF quality (g) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.075 0.15 0.225 0.3 0.375 0.45 0.525 0.6
Specific conductivity * 10 -4(S/cm) 0.2246 3.8812 7.6316 12.410 14.576 11.325 8.326 5.732
Embodiment 11:
Getting monomer VAc17.22g and BA25.63g mixes in beaker.With joining in the there-necked flask of 250ml behind the 80g deionized water dissolving 1.0g emulsifier sodium lauryl sulfate, magnetic agitation also slowly is warmed up to 70 ℃, constant temperature; Add 0.25g initiator ammonium persulfate ((NH with the 20g deionized water dissolving 4) 2S 2O 8) and 0.25g buffer reagent sodium bicarbonate (NaHCO 3) mixing solutions.Logical nitrogen stirs 20min, adds the mixed solution of 4.0g monomer VAc and MMA; Behind the reaction 30min, polymerization is complete substantially for seed, slowly drips the residual monomers mixed solution again, and 2h dropwises.React 1h after being added dropwise to complete again, stopped reaction is cooled to room temperature.Entire reaction is all carried out under nitrogen protection.Emulsion splitter potassium aluminium sulfate (KAI (SO with 0.01mol/L 4) 2) suction filtration behind the breakdown of emulsion, with deionized water wash for several times, and be dried to constant weight.Use solvents tetrahydrofurane (THF) dissolving again, elimination insolubles (gel) revolves and boils off solvent, vacuum-drying.Promptly obtained the random copolymers P (VAc-BA) of monomeric charge than VAc: BA=1: 1 (mol).
Get above-mentioned random copolymers certain mass (1.5g) in the exsiccant flask, be dissolved in the solvents tetrahydrofurane of 10mL and stir under 40 ℃, add the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.03～5.5 * 10 after 60 ℃ of following vacuum-dryings -4Scm -1Following table is different mass LiClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.075 0.15 0.225 0.3 0.375 0.45 0.525 0.6
Specific conductivity * 10 -4(S/ cm) 0.03521 0.09843 0.6658 1.004 5.4206 3.6523 0.9264 0.1283
Embodiment 12:
Get monomer 0.2mol VAc and 0.2mol EA mixes in beaker.With joining in the there-necked flask of 250ml behind the 80g deionized water dissolving 0.8g emulsifier sodium lauryl sulfate, magnetic agitation also slowly is warmed up to 70 ℃, constant temperature; Add 0.4g initiator ammonium persulfate ((NH with the 20g deionized water dissolving 4) 2S 2O 8) and the mixing solutions of 0.4g buffer reagent trisodium phosphate.Logical nitrogen stirs 20min, adds the mixed solution of 4.0g monomer VAc and EA; Behind the reaction 30min, polymerization is complete substantially for seed, slowly drips the residual monomers mixed solution again, and 2h dropwises.React 1h after being added dropwise to complete again, stopped reaction is cooled to room temperature.Entire reaction is all carried out under nitrogen protection.Emulsion splitter potassium aluminium sulfate (KAl (SO with 0.01mol/L 4) 2) suction filtration behind the breakdown of emulsion, with deionized water wash for several times, and be dried to constant weight.Use solvents tetrahydrofurane (THF) dissolving again, elimination insolubles (gel) revolves and boils off solvent, vacuum-drying.Promptly obtained monomeric charge than VAc: EA=1: the random copolymers P (VAc-EA) under 1 (mol).
Get above-mentioned random copolymers certain mass (1.5g) in the exsiccant flask, be dissolved in the solvents tetrahydrofurane of 10mL and stir under 40 ℃, add the LiClO of following table amount 4Or LiCF 3SO 3Slow solvent evaporated in the environment dry, that ventilation effect is good, the electrolytical conductivity at room temperature of resulting polymers is 0.02～6 * 10 after 60 ℃ of following vacuum-dryings -4Scm -1Following table is different mass LiClO 4The conductivity at room temperature data of polymer dielectric under the content.Specific conductivity unit is Scm -1
Copolymer quality (g) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
LiClO 4/ multipolymer (wt%) 5 10 15 20 25 30 35 40
LiClO 4Quality (g) 0.075 0.15 0.225 0.3 0.375 0.45 0.525 0.6
Specific conductivity * 10 -4(S/ cm) 0.02761 0.09984 0.3217 1.2356 5.4569 1.0236 0.3587 0.07318

Claims (8)

1. one kind is the solid polymer electrolyte of matrix with the acetic acid vinyl ester-acrylic ester copolymer, the polymeric matrix that it is characterized in that solid polymer electrolyte is the binary random copolymer that adopts the semi-continuous seed emulsion polymerization method to prepare as comonomer by vinyl acetate between to for plastic base ester VAc and acrylate, and vinyl acetate between to for plastic base ester and acrylate carry out copolymerization according to 8.5: 1.5～1.5: 8.5 mol ratios.
2. according to claim 1 is the solid polymer electrolyte of matrix with the acetic acid vinyl ester-acrylic ester copolymer, it is characterized in that: described acrylate is selected from methyl acrylate MA, methyl methacrylate MMA, ethyl propenoate EA or butyl acrylate BA.
3. according to claim 1 and 2 is the solid polymer electrolyte of matrix with the acetic acid vinyl ester-acrylic ester copolymer, it is characterized in that: described semi-continuous seed emulsion polymerization method is to add initiator in containing the aqueous solution of emulsifying agent, logical nitrogen stirs, the monomer mixed solution that adds vinyl acetate between to for plastic base ester and acrylate monomer mixed solution total amount 4-10% earlier causes copolymerization as seed, reaction, polymerization is complete substantially to treat seed, slowly drip remaining 96-90% monomer mixed solution again, stirring reaction finishes until reaction, the breakdown of emulsion suction filtration, washing, dry, purifying is promptly finished; Used initiator is ammonium persulphate (NH 4) 2S 2O 8Or Potassium Persulphate K 2S 2O 8; Used emulsifying agent is sodium lauryl sulphate or Sodium dodecylbenzene sulfonate.
4. according to claim 1 is the solid polymer electrolyte of matrix with the acetic acid vinyl ester-acrylic ester copolymer, it is characterized in that: the polymeric matrix of the solid polymer electrolyte polymer blending matrix that to be acetic acid vinyl ester-acrylic ester copolymer form with second kind of polymer P MMA or PVdF blend; The content of second kind of polymer P MMA or PVdF is PMMA or PVdF quality/acetic acid vinyl ester-acrylic ester copolymer quality=0.01～1.5 in the polymer blending matrix.
5. according to claim 4 is the solid polymer electrolyte of matrix with the acetic acid vinyl ester-acrylic ester copolymer, it is characterized in that: the content of second kind of polymer P MMA or PVdF is PMMA or PVdF quality/acetic acid vinyl ester-acrylic ester copolymer quality=0.5 in the polymer blending matrix.
6. adopt claim 1,4 or 5 described be the polymer dielectric film that the solid polymer electrolyte of matrix is made with the acetic acid vinyl ester-acrylic ester copolymer, it is characterized in that: described solid polymer dielectric film is that polymer blending matrix and lithium salts mixing and stirring under solvent action that synthetic acetic acid vinyl ester-acrylic ester random copolymers matrix or itself and second kind of polymer blending are formed are obtained mixing solutions, mixing solutions is cast in the mould that polytetrafluoroethylmaterial material makes suppresses, after treating solvent evaporates, take out film, vacuum-drying promptly obtains solid polymer dielectric film.
7. polymer dielectric film according to claim 6 is characterized in that: described lithium salts is LiClO 4Or LiCF 3SO 3, consumption is 1～50% of the polymer blending substrate quality formed of acetic acid vinyl ester-acrylic ester random copolymers matrix or itself and second kind of polymer blending; Solvent is tetrahydrofuran THF or N-Methyl pyrrolidone NMP, and consumption is 100～800% of the polymer blending substrate quality formed for acetic acid vinyl ester-acrylic ester random copolymers matrix or itself and second kind of polymer blending.
8. polymer dielectric film according to claim 6 is characterized in that: described lithium salts is LiClO 4Consumption is for being 5～40% of the polymer blending substrate quality of acetic acid vinyl ester-acrylic ester random copolymers matrix or itself and second kind of polymer blending composition, solvent is a tetrahydrofuran (THF), and consumption is 200～400% of the polymer blending substrate quality formed for acetic acid vinyl ester-acrylic ester random copolymers matrix or itself and second kind of polymer blending.
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