CN106832135A - A kind of modified poly ethylene alcohol copolymer and its preparation and gel polymer electrolyte - Google Patents
A kind of modified poly ethylene alcohol copolymer and its preparation and gel polymer electrolyte Download PDFInfo
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- CN106832135A CN106832135A CN201710113130.XA CN201710113130A CN106832135A CN 106832135 A CN106832135 A CN 106832135A CN 201710113130 A CN201710113130 A CN 201710113130A CN 106832135 A CN106832135 A CN 106832135A
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- alcohol copolymer
- modified poly
- poly ethylene
- gel polymer
- ethylene alcohol
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- -1 poly ethylene Polymers 0.000 title claims abstract description 61
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 52
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 52
- 229920001577 copolymer Polymers 0.000 title claims abstract description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000005518 polymer electrolyte Substances 0.000 title abstract description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 67
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 66
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 66
- 229920000642 polymer Polymers 0.000 claims abstract description 53
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910021538 borax Inorganic materials 0.000 claims abstract description 12
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 12
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 11
- 230000008961 swelling Effects 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 45
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 36
- 230000007935 neutral effect Effects 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical group CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000001186 cumulative effect Effects 0.000 claims description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical class C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 70
- 230000000052 comparative effect Effects 0.000 description 12
- 108010010803 Gelatin Proteins 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 2
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical class C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Electrochemistry (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention particularly discloses a kind of modified poly ethylene alcohol copolymer and preparation method thereof, and the gel polymer electrolyte containing the modified poly ethylene alcohol copolymer.The preparation method of the modified poly ethylene alcohol copolymer includes：Weigh polyvinylalcohol solids, add water swelling, it is placed in after rising temperature for dissolving in 40~45 DEG C of water-baths and is heated, logical argon gas, is subsequently adding N vinyl pyrrolidones and function monomer, after stirring, add acid cerium ion solution, 3~5h of reaction, is obtained modified poly ethylene alcohol copolymer, and the modified poly ethylene alcohol copolymer possesses excellent electrolyte resistance.Using modified poly ethylene alcohol copolymer of the present invention as matrix material, with glutaraldehyde or borax as crosslinking agent, and add appropriate electrolyte (LiCl or LiOH), preparing has ideal machine performance, the neutrality of capacitive property, base gel polymer dielectric, and water content in gel is adjustable, the applications well in flexible solid-state supercapacitor is met.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of modified poly ethylene alcohol copolymer and its preparation side
Method, and the gel polymer electrolyte containing the modified poly ethylene alcohol copolymer.
Background technology
Gel polymer electrolyte as assembling a kind of necessary functional material of flexible solid-state supercapacitor, not only directly
Its capacitance, high rate performance, high temperature performance etc. are influenceed, and the phenomenon of leakage can be avoided, safe and convenient to use, being especially suitable for should
For in flexible electronic and energy storage device field.
Currently, be used for flexible solid-state supercapacitor assembling gel polymer electrolyte generally by：Gelatin polymer
(matrix material), organic/aqueous solvent (plasticizer) and the part of electrolyte three constitute.Matrix material Typical Representative has：Polyacrylic acid
(PAA or PAAK), PEO (PEO), polyvinylidene fluoride (PVdF), polymethyl methacrylate (PMMA), polyethylene
Blend (PAN-B-PEG) of alcohol (PVA), polyacrylonitrile (PAN) and polyethylene glycol and polyacrylonitrile etc..And PVA is because with easy
Into gelation, easy film forming, film good mechanical performance, and the characteristic such as nontoxic, cheap and good chemical stability has been solidifying
The object that xanthan polymer electrolyte research field is widely paid close attention to.
PVA by Haehnel and Herrmann taken the lead in nineteen twenty-four report because it have it is biodegradable, nontoxic, honest and clean
The feature such as valency and good chemical stability, has turned into one of wide variety of polymer at present.Again because in PVA molecular structures
Containing a large amount of-OH, it can be with H2O combines a certain amount of water by hydrogen bond action；In acid condition, part-OH and some aldehyde-
CHO reactions form the water-insoluble gelatinous polymer with chemical crosslinking structure to form acetal or hemiacetal, with allusion quotation
The physical gel of type is compared, and this chemical type gel polymer electrolyte (PVA based aquagels) has good mechanical performance
With certain ionic conductivity；Also using the wherein activity of-OH, functional form modified PVA is prepared.Just because of this, it is solid in flexibility
State ultracapacitor research field, the research report on PVA base gel polymer electrolytes is relatively more at present, and it covers
：PVA/H based on polyacid2SO4/H2O、PVA/H3PO4/H2O and PVA/H3PO4The proton type such as/silico-tungstic acid gelatin polymer electricity
Xie Zhi, the PVA/LiCl/H based on neutral salt2O and PVA/LiClO4/H2The type lithium ion gel polymer electrolyte such as O, and
PVA/LiCl/H2The polytypes such as O base gel polymer dielectrics.For example：Wang et al. utilizes RuO2/TiO2It is nano combined
Material is electrode, PVA/H3PO4/H2O gel electrolytes assemble pseudocapacitors, and its maximum capacitor may be up to 1263F G-1；Recently,
Some the research reports on neutral gel polymer dielectric, such as PVA/LiCl/H2O, by controlling gel polymer electrolyte
The water content of matter, can effectively suppress VOxWith the chemolysis of VN electrode materials and the irreversible electrochemical oxidation of electrode
Reaction, effectively improves the cyclical stability of ultracapacitor, that is, its electric capacity retention rate is still greater than 85% after circulating 5000 times；
Choudhury et al. have studied by build acid, alkaline of poly- (vinyl alcohol) and poly- (acrylic acid) blend (PVA+PAA) or in
Property gel polymer electrolyte (BHES), as a result shows：The ionic conductivity of acid BHES increases with the ratio of PAA in blend
Reduce greatly；And alkalescence and neutral BHES show reverse effect, its corresponding stability and mechanical performance are poor；To the greatest extent
PVA/H of the pipe based on polyacid2SO4/H2O、PVA/H3PO4/H2O and PVA/H3PO4The proton type such as/silico-tungstic acid gelatin polymer electricity
Solution matter has a mechanical performance of relative ideal, but it has poor process control and a low defect of ionic conductivity, and neutral,
Alkaline PVA bases gel polymer electrolyte seldom, and generally existing bad mechanical property problem, it is difficult to meet in flexible capacitor
The application demands such as part assembling.Therefore, the mechanical performance for improving gel polymer electrolyte is neutral or alkalescence PVA base gel polymerisations
Thing electrolyte is widely used in one of key technology of flexible super capacitor.
In addition, the electrolyte resistance of the PVA base gelatin polymer aqueous solution is poor, easily flocculation is not suitable for preparing aqueous
Measure regulatable water system gel polymer electrolyte.
To sum up, it is necessary to research is modified to PVA, and develops corresponding neutral or alkalescence PVA base gel polymerisations
Thing electrolyte, realizes that the research in gel polymer electrolyte field breaks through.
The content of the invention
In order to solve problems of the prior art (electrolyte resistance of such as PVA bases gelatin polymer aqueous solution is poor,
Bad mechanical property of neutral or alkalescence PVA base gel polymer electrolytes etc.), first purpose of the invention is to provide a kind of
The preparation method of modified poly ethylene alcohol copolymer and the modified poly ethylene alcohol copolymer obtained by the method, using cheap and normal
Based on polyvinyl alcohol, by grafting, copolymerization and modification, the excellent modified poly ethylene alcohol copolymer of electrolyte resistance is prepared.
The preparation method of the modified poly ethylene alcohol copolymer that the present invention is provided, specifically includes following steps：
The dissolving of S1, polyvinyl alcohol：Weigh polyvinylalcohol solids 10g to be placed in there-necked flask, 50mL water is added, at 60 DEG C
Under heating water bath, swelling 0.5h is stirred, it is another in swelling process to add water, make cumulative volume be 60mL；Then 95 DEG C are warming up to, are protected
95 DEG C of stirrings are held up to polyvinylalcohol solids are completely dissolved, natural cooling is obtained poly-vinyl alcohol solution, standby；
The graft modification of S2, polyvinyl alcohol：8~the 12g of poly-vinyl alcohol solution is weighed, is fitted into there-necked flask, and will
It is placed in 40~45 DEG C of water-baths and heats；Then toward logical argon gas in there-necked flask, NVP is added after 4~6min
0.4~1mL of 7~14mL and function monomer, after stirring, adds acid cerium ion solution；Keep bath temperature be 40~
45 DEG C, persistently lead to argon gas, stirring, 3~5h of coreaction is obtained modified poly ethylene alcohol copolymer.
Preferably, described function monomer is 2-hydroxyethyl methacry-late or GMA.
Preferably, described acid cerium ion solution passes through to add 0.04~0.08g ceric sulfates and 0.1 toward 20mL water
~0.4mL concentrated nitric acids, stir prepared.
The modified poly ethylene alcohol copolymer as obtained in the preparation method of above-mentioned modified poly ethylene alcohol copolymer, it possesses excellent
Electrolyte resistance, be suitable for prepare the regulatable water system gel polymer electrolyte of water content；As matrix material, energy
Enough effectively improve the mechanical performance and capacitive property of gel polymer electrolyte.
Another object of the present invention is to provide the neutral gel electrostrictive polymer containing the modified poly ethylene alcohol copolymer
Xie Zhi, the neutral gel polymer dielectric is specifically obtained by following methods：The modified poly ethylene alcohol copolymer 5mL is taken to be placed in
In beaker, LiCl aqueous solution 4mL are added, stirred, add 0.1~0.4mL of glutaraldehyde water solution, poured into after stirring
In culture dish, sealing preserve solidifies at room temperature, and neutral gel polymer dielectric is obtained.
Preferably, the concentration of the LiCl aqueous solution is 1~4mol/L.
Preferably, the concentration of the glutaraldehyde water solution is 0.5~3%wt.
A further object of the present invention is to provide the base gel electrostrictive polymer containing the modified poly ethylene alcohol copolymer
Xie Zhi, the base gel polymer dielectric is specifically obtained by following methods：The modified poly ethylene alcohol copolymer 5mL is taken to be placed in
In beaker, LiOH aqueous solution 4mL are added, stirred, add 0.1~0.2mL of borax solution, poured into after stirring
In culture dish, sealing preserve solidifies at room temperature, and base gel polymer dielectric is obtained.
Preferably, the concentration of the LiOH aqueous solution is 0.5~2mol/L.
Preferably, the concentration of the borax solution is 2~5%wt.
In the inventive solutions, using " oxidationreduction " free radical polymerization initiation based on ceric sulfate
System, by graft copolymerization strategy, is carried out under certain condition using specific NVP monomer (NVP) and PVA
Copolyreaction, prepares modified poly ethylene alcohol copolymer (PVA-M-NVP), and strictly controls the consumption of each raw material, such as PVA and
The mass ratio of NVP, the mass ratio of NVP and function monomer so that the electrical conductivity of corresponding gel polymer electrolyte it is accessible or
Reach 10-3S/cm (25 DEG C) preferable rank.With modified poly ethylene alcohol copolymer of the invention as matrix material, with glutaraldehyde or boron
Sand is crosslinking agent, and adds appropriate electrolyte (LiCl or LiOH), and preparing has ideal machine performance, the neutrality of capacitive property
Gel polymer electrolyte (modified PVA/LiCl/H2) and base gel polymer dielectric (modified PVA/LiOH/H O2O), and
And by adjusting the concentration of electrolyte the water content in gel can be made adjustable in the range of 50~90%, meet super in flexible solid
Applications well in level capacitor.
Therefore, compared with prior art, advantage of the invention is that：
(1) the invention provides a kind of new modified poly ethylene alcohol copolymer, by polyvinyl alcohol and N- vinyl pyrroles
Alkanone graft copolymerization under certain condition is obtained, and it possesses excellent electrolyte resistance, and being suitable for preparation water content can
The water system gel polymer electrolyte of regulation and control；As matrix material, the mechanicalness of gel polymer electrolyte can be effectively improved
Energy and capacitive property；In addition, the preparation method of modified poly ethylene alcohol copolymer of the present invention is simple, process stabilizing, condition is controllable, can
Popularization and application.
(2) the invention provides two kinds of new gel polymer electrolytes, respectively neutral gel polymer dielectric (changes
Property PVA/LiCl/H2) and base gel polymer dielectric (modified PVA/LiOH/H O2O), both gel polymer electrolytes
The water content being provided with good mechanical performance and capacitive property, and gel is adjustable in the range of 50~90%, meets
Applications well in flexible solid-state supercapacitor, and enrich the neutral, species of base gel polymer dielectric.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the polyvinyl alcohol of model PVA-1799
Fig. 2 is the infrared spectrogram of the modified poly ethylene alcohol copolymer (PVA-M-NVP) of embodiment 3
Fig. 3 is the scanning electron microscope (SEM) photograph of the neutral gel polymer dielectric of embodiment 4
Fig. 4 is the scanning electron microscope (SEM) photograph of the base gel polymer dielectric of embodiment 7
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but specific embodiment does not do to the present invention
Any restriction, protection scope of the present invention should be defined by claim.
In embodiment 1~3, using the polyvinyl alcohol of model PVA-1799 as reaction raw materials.
Embodiment 1, modified poly ethylene alcohol copolymer of the present invention and its preparation
The dissolving of S1, polyvinyl alcohol：Weigh polyvinylalcohol solids 10g to be placed in there-necked flask, 50mL water is added, at 60 DEG C
Under heating water bath, swelling 0.5h is stirred, it is another in swelling process to add water, make cumulative volume be 60mL；Then 95 DEG C are warming up to, are protected
95 DEG C of stirrings are held up to polyvinylalcohol solids are completely dissolved, natural cooling is obtained poly-vinyl alcohol solution, standby；
The graft modification of S2, polyvinyl alcohol：The poly-vinyl alcohol solution 8g is weighed, is fitted into there-necked flask, and put
Heated in 40~45 DEG C of water-baths；Then toward logical argon gas in there-necked flask, NVP 7mL is added after 4~6min
With 2-hydroxyethyl methacry-late 0.4mL, after stirring, acid cerium ion solution is added；Keep bath temperature be 40~
45 DEG C, persistently lead to argon gas, stirring, coreaction 4h is obtained modified poly ethylene alcohol copolymer.
The preparation of described acid cerium ion solution：0.04g ceric sulfates and 0.1mL concentrated nitric acids are added toward 20mL water,
Stir prepared.
Embodiment 2, modified poly ethylene alcohol copolymer of the present invention and its preparation
The dissolving of S1, polyvinyl alcohol：Weigh polyvinylalcohol solids 10g to be placed in there-necked flask, 50mL water is added, at 60 DEG C
Under heating water bath, swelling 0.5h is stirred, it is another in swelling process to add water, make cumulative volume be 60mL；Then 95 DEG C are warming up to, are protected
95 DEG C of stirrings are held up to polyvinylalcohol solids are completely dissolved, natural cooling is obtained poly-vinyl alcohol solution, standby；
The graft modification of S2, polyvinyl alcohol：The poly-vinyl alcohol solution 12g is weighed, is fitted into there-necked flask, and put
Heated in 40~45 DEG C of water-baths；Then toward logical argon gas in there-necked flask, NVP 14mL is added after 4~6min
With GMA 1mL, after stirring, acid cerium ion solution is added；Keep bath temperature be 40~
45 DEG C, persistently lead to argon gas, stirring, coreaction 4h is obtained modified poly ethylene alcohol copolymer.
The preparation of described acid cerium ion solution：0.08g ceric sulfates and 0.4mL concentrated nitric acids are added toward 20mL water,
Stir prepared.
Embodiment 3, modified poly ethylene alcohol copolymer of the present invention and its preparation
The dissolving of S1, polyvinyl alcohol：Weigh polyvinylalcohol solids 10g to be placed in there-necked flask, 50mL water is added, at 60 DEG C
Under heating water bath, swelling 0.5h is stirred, it is another in swelling process to add water, make cumulative volume be 60mL；Then 95 DEG C are warming up to, are protected
95 DEG C of stirrings are held up to polyvinylalcohol solids are completely dissolved, natural cooling is obtained poly-vinyl alcohol solution, standby；
The graft modification of S2, polyvinyl alcohol：The poly-vinyl alcohol solution 10g is weighed, is fitted into there-necked flask, and put
Heated in 40~45 DEG C of water-baths；Then toward logical argon gas in there-necked flask, NVP 12mL is added after 4~6min
With 2-hydroxyethyl methacry-late 0.7mL, after stirring, acid cerium ion solution is added；Keep bath temperature be 40~
45 DEG C, persistently lead to argon gas, stirring, coreaction 4h is obtained modified poly ethylene alcohol copolymer.
The preparation of described acid cerium ion solution：0.06g ceric sulfates and 0.2mL concentrated nitric acids are added toward 20mL water,
Stir prepared.
Embodiment 4, neutral gel polymer dielectric of the present invention
The present embodiment neutral gel polymer dielectric is obtained by following methods：Modified poly ethylene obtained in Example 2
Alcohol copolymer 5mL is placed in beaker, adds LiCl aqueous solution 4mL, is stirred, and adds glutaraldehyde water solution 0.2mL, is stirred
Poured into culture dish after uniform, sealing preserve solidifies at room temperature, neutral gel polymer dielectric is obtained.
The concentration of the LiCl aqueous solution is 2mol/L；The concentration of the glutaraldehyde water solution is 0.5%wt.
Embodiment 5, neutral gel polymer dielectric of the present invention
The present embodiment neutral gel polymer dielectric is obtained by following methods：Modified poly ethylene obtained in Example 3
Alcohol copolymer 5mL is placed in beaker, adds LiCl aqueous solution 4mL, is stirred, and adds glutaraldehyde water solution 0.4mL, is stirred
Poured into culture dish after uniform, sealing preserve solidifies at room temperature, neutral gel polymer dielectric is obtained.
The concentration of the LiCl aqueous solution is 4mol/L；The concentration of the glutaraldehyde water solution is 3%wt.
Embodiment 6, neutral gel polymer dielectric of the present invention
The present embodiment neutral gel polymer dielectric is obtained by following methods：Modified poly ethylene obtained in Example 3
Alcohol copolymer 5mL is placed in beaker, adds LiCl aqueous solution 4mL, is stirred, and adds glutaraldehyde water solution 0.3mL, is stirred
Poured into culture dish after uniform, sealing preserve solidifies at room temperature, neutral gel polymer dielectric is obtained.
The concentration of the LiCl aqueous solution is 2mol/L；The concentration of the glutaraldehyde water solution is 1%wt.
Embodiment 7, base gel polymer dielectric of the present invention
The present embodiment base gel polymer dielectric is obtained by following methods：Modified poly ethylene obtained in Example 2
Alcohol copolymer 5mL is placed in beaker, adds LiOH aqueous solution 4mL, is stirred, and adds borax solution 0.1mL, stirring
Poured into culture dish after uniform, sealing preserve solidifies at room temperature, base gel polymer dielectric is obtained.
The concentration of the LiOH aqueous solution is 0.5mol/L；The concentration of the borax solution is 2%wt.
Embodiment 8, base gel polymer dielectric of the present invention
The present embodiment base gel polymer dielectric is obtained by following methods：Modified poly ethylene obtained in Example 3
Alcohol copolymer 5mL is placed in beaker, adds LiOH aqueous solution 4mL, is stirred, and adds borax solution 0.2mL, stirring
Poured into culture dish after uniform, sealing preserve solidifies at room temperature, base gel polymer dielectric is obtained.
The concentration of the LiOH aqueous solution is 2mol/L；The concentration of the borax solution is 5%wt.
Embodiment 9, base gel polymer dielectric of the present invention
The present embodiment base gel polymer dielectric is obtained by following methods：Modified poly ethylene obtained in Example 3
Alcohol copolymer 5mL is placed in beaker, adds LiOH aqueous solution 4mL, is stirred, and adds borax solution 0.2mL, stirring
Poured into culture dish after uniform, sealing preserve solidifies at room temperature, base gel polymer dielectric is obtained.
The concentration of the LiOH aqueous solution is 1mol/L；The concentration of the borax solution is 4%wt.
Test example one, infrared analysis
What Fig. 1 was represented is the infrared spectrogram of the polyvinyl alcohol of model PVA-1799
What Fig. 2 was represented is the infrared spectrogram of the modified poly ethylene alcohol copolymer (PVA-M-NVP) of embodiment 3
By Fourier transform infrared spectroscopy (FT-IR) to modified poly ethylene alcohol copolymer (PVA-M- obtained in embodiment 3
NVP) it is analyzed, is compareed with the FT-IR test results (see Fig. 1) of raw material PVA-1799,3400cm in Fig. 2-1、1650cm-1Place
The peak shape or peak intensity at peak increase, because caused by PVA is by graft copolymerization introducing NVP chain links, 1290cm-1There is absworption peak
Go out to show that NVP monomers successfully participate in graft copolymerization.
Test example two, electron-microscope scanning is analyzed
What Fig. 3 was represented is the scanning electron microscope (SEM) photograph of the neutral gel polymer dielectric of embodiment 4
What Fig. 4 was represented is the scanning electron microscope (SEM) photograph of the base gel polymer dielectric of embodiment 7
Fig. 3 and Fig. 4 show：Electrolyte is dispersed in system, and when added in system different electrolyte (LiCl or
LiOH), had no significant effect for the structure inside gel, illustrate that modified poly ethylene alcohol copolymer of the present invention possesses excellent resistance to electricity
Solution matter performance.
Test example three, elongation at break and ionic conductivity are analyzed
Comparative example 1：Compared with Example 3, the difference of this comparative example is：In step S2, NVP
Addition increases to 18mL by 12mL.In addition, gel polymer electrolyte is obtained further according to the method for embodiment 6.
Comparative example 2：Compared with Example 3, the difference of this comparative example is：In step S2,2-hydroxyethyl methacry-late
Addition 2mL is increased to by 0.7mL.In addition, gel polymer electrolyte is obtained further according to the method for embodiment 6.
Comparative example 3：Compared with Example 6, the difference of this comparative example is：The concentration of the glutaraldehyde water solution is by 1%
Wt is improved to 5%wt.
Comparative example 4：Compared with Example 9, the difference of this comparative example is：The concentration of the borax solution is by 4%wt
Improve to 7%wt.
Comparative example 5：Compared with Example 9, the difference of this comparative example is：The concentration of the LiOH aqueous solution is by 1mol/L
Improve to 4mol/L.
Gel polymer electrolyte to embodiment 4~9 and comparative example 1~5 carries out elongation at break and ionic conductivity
Analysis, as a result see the table below 1.
The test result of each gel polymer electrolyte of table 1
From upper table 1：
(1) neutral gel polymer dielectric of the present invention and base gel polymer dielectric have ideal machine performance and
Capacitive property, is mainly reflected in that elongation at break is moderate, and ionic conductivity is close to or up 10-3S/cm (25 DEG C) preferable rank,
And water content in gel is adjustable in the range of 50~90%, the applications well in flexible solid-state supercapacitor is met.
(2) preparation parameter of the modified poly ethylene alcohol copolymer of the present invention of comparative example 1~5 pair or gel polymer electrolyte enters
Gone adjustment, as a result elongation at break occur it is different degrees of is raised and lowered, and ionic conductivity has different degrees of drop
It is low, show as combination property variation.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Shield scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of modified poly ethylene alcohol copolymer, it is characterised in that comprise the following steps：
The dissolving of S1, polyvinyl alcohol：Weigh polyvinylalcohol solids 10g to be placed in there-necked flask, 50mL water is added, in 60 DEG C of water-baths
Under heating, swelling 0.5h is stirred, it is another in swelling process to add water, make cumulative volume be 60mL；Then 95 DEG C are warming up to, 95 are kept
DEG C stirring until polyvinylalcohol solids be completely dissolved, natural cooling, be obtained poly-vinyl alcohol solution, it is standby；
The graft modification of S2, polyvinyl alcohol：8~the 12g of poly-vinyl alcohol solution is weighed, is fitted into there-necked flask, and put
Heated in 40~45 DEG C of water-baths；Then toward argon gas is led in there-necked flask, added after 4~6min NVP 7~
0.4~1mL of 14mL and function monomer, after stirring, adds acid cerium ion solution；It is 40~45 to keep bath temperature
DEG C, persistently leading to argon gas, stirring, 3~5h of coreaction is obtained modified poly ethylene alcohol copolymer.
2. the preparation method of modified poly ethylene alcohol copolymer as claimed in claim 1, it is characterised in that described function monomer
It is 2-hydroxyethyl methacry-late or GMA.
3. the preparation method of modified poly ethylene alcohol copolymer as claimed in claim 1, it is characterised in that described acid cerium from
Sub- solution passes through to add 0.04~0.08g ceric sulfates and 0.1~0.4mL concentrated nitric acids toward 20mL water, stirs prepared.
4. the modified polyvinylalcohol as obtained in the preparation method of claims 1 to 3 any modified poly ethylene alcohol copolymer is total to
Polymers.
5. a kind of neutral gel polymer dielectric containing modified poly ethylene alcohol copolymer as claimed in claim 4, its feature
It is to be obtained by following methods：Take modified poly ethylene alcohol copolymer 5mL as claimed in claim 4 to be placed in beaker, add
LiCl aqueous solution 4mL, stir, and add 0.1~0.4mL of glutaraldehyde water solution, are poured into culture dish after stirring, close
Envelope is preserved, and is solidified at room temperature, and neutral gel polymer dielectric is obtained.
6. neutral gel polymer dielectric as claimed in claim 5, it is characterised in that the concentration of the LiCl aqueous solution is
1~4mol/L.
7. neutral gel polymer dielectric as claimed in claim 5, it is characterised in that the concentration of the glutaraldehyde water solution
It is 0.5~3%wt.
8. a kind of base gel polymer dielectric containing modified poly ethylene alcohol copolymer as claimed in claim 4, its feature
It is to be obtained by following methods：Take modified poly ethylene alcohol copolymer 5mL as claimed in claim 4 to be placed in beaker, add
LiOH aqueous solution 4mL, stir, and add 0.1~0.2mL of borax solution, are poured into culture dish after stirring, sealing
Preserve, solidify at room temperature, base gel polymer dielectric is obtained.
9. base gel polymer dielectric as claimed in claim 8, it is characterised in that the concentration of the LiOH aqueous solution is
0.5~2mol/L.
10. base gel polymer dielectric as claimed in claim 8, it is characterised in that the concentration of the borax solution
It is 2~5%wt.
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| CN112646209A (en) * | 2019-10-11 | 2021-04-13 | 天津大学 | Double-network physical crosslinking ionic gel electrolyte system based on polyvinyl alcohol-poloxamer and preparation method thereof |
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| CN110776703A (en) * | 2018-07-30 | 2020-02-11 | 天津大学 | Blend with self-repairing performance, blend film, preparation method and application thereof |
| CN109503769A (en) * | 2018-12-10 | 2019-03-22 | 郑州奥恒印刷技术有限公司 | The preparation method of polyvinyl alcohol graft copolymerized copolymer |
| CN109503769B (en) * | 2018-12-10 | 2020-12-08 | 郑州奥恒印刷技术有限公司 | Preparation method of polyvinyl alcohol graft copolymer |
| CN112646209A (en) * | 2019-10-11 | 2021-04-13 | 天津大学 | Double-network physical crosslinking ionic gel electrolyte system based on polyvinyl alcohol-poloxamer and preparation method thereof |
| CN112646209B (en) * | 2019-10-11 | 2021-11-23 | 天津大学 | Double-network physical crosslinking ionic gel electrolyte system based on polyvinyl alcohol-poloxamer and preparation method thereof |
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| CN112563660B (en) * | 2020-12-07 | 2022-05-27 | 界首市天鸿新材料股份有限公司 | Method for preparing diaphragm for solid electrolyte lithium battery |
| CN116218011A (en) * | 2023-03-01 | 2023-06-06 | 哈尔滨工业大学 | Gel material with high adhesion bacteriostasis and conductivity stability and preparation method and application thereof |
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