CN110299557A - Water soluble polymer gel polymer electrolyte and the preparation method and application thereof - Google Patents
Water soluble polymer gel polymer electrolyte and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110299557A CN110299557A CN201910374116.4A CN201910374116A CN110299557A CN 110299557 A CN110299557 A CN 110299557A CN 201910374116 A CN201910374116 A CN 201910374116A CN 110299557 A CN110299557 A CN 110299557A
- Authority
- CN
- China
- Prior art keywords
- polymer electrolyte
- gel polymer
- water soluble
- electrolyte
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 54
- 229920003169 water-soluble polymer Polymers 0.000 title claims description 29
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 29
- 229920006254 polymer film Polymers 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 7
- 239000011149 active material Substances 0.000 claims abstract description 6
- 239000000499 gel Substances 0.000 claims description 48
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229920000609 methyl cellulose Polymers 0.000 claims description 17
- 239000001923 methylcellulose Substances 0.000 claims description 17
- 235000010981 methylcellulose Nutrition 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000011256 inorganic filler Substances 0.000 claims description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 13
- 229920002521 macromolecule Polymers 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000010416 ion conductor Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 150000004676 glycans Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229920001282 polysaccharide Polymers 0.000 claims description 6
- 239000005017 polysaccharide Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 229920001817 Agar Polymers 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims description 5
- 239000008272 agar Substances 0.000 claims description 5
- 235000010419 agar Nutrition 0.000 claims description 5
- 238000004146 energy storage Methods 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 claims description 4
- NOEXTUJBYPORTG-UHFFFAOYSA-L [Ti+4].C([O-])([O-])=O.[Li+] Chemical compound [Ti+4].C([O-])([O-])=O.[Li+] NOEXTUJBYPORTG-UHFFFAOYSA-L 0.000 claims description 4
- 239000005486 organic electrolyte Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229930188620 butyrolactone Natural products 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 239000012528 membrane Substances 0.000 description 14
- 229910001290 LiPF6 Inorganic materials 0.000 description 9
- -1 hexafluoro phosphorus Chemical compound 0.000 description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005213 imbibition Methods 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 230000008602 contraction Effects 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 108010025899 gelatin film Proteins 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 2
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- PWGVOCGNHYMDLS-UHFFFAOYSA-N 3-(2-methoxyethoxy)propan-1-amine Chemical compound COCCOCCCN PWGVOCGNHYMDLS-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- MUETXHPIRUFIOK-UHFFFAOYSA-N B([O-])([O-])[O-].[K+].C(C(=O)O)(=O)O.[K+].[K+] Chemical class B([O-])([O-])[O-].[K+].C(C(=O)O)(=O)O.[K+].[K+] MUETXHPIRUFIOK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910020261 KBF4 Inorganic materials 0.000 description 1
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910020892 NaBOB Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- DFGMFVYRMVYRRA-UHFFFAOYSA-N [O].CC Chemical compound [O].CC DFGMFVYRMVYRRA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) 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
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910001541 potassium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 1
- 239000011555 saturated liquid Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001542 sodium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LZOZLBFZGFLFBV-UHFFFAOYSA-N sulfene Chemical compound C=S(=O)=O LZOZLBFZGFLFBV-UHFFFAOYSA-N 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to high molecular materials and field of batteries, and in particular to water-soluble high-molecular material gel polymer electrolyte and its preparation, while further including application of this gel polymer electrolyte in primary or making active materials for use in secondary electrochemical energy-storage system.The gel polymer electrolyte is made of polymer film and liquid electrolyte.The present invention relates to a kind of method for preparing gel polymer electrolyte, this method preparation process is simple, low in cost, preparation process environmental protection.Prepared gel polymer electrolyte conductivity height, electrochemical window mouth width, lithium ion transference number are high and good with electrode material compatibility, can effectively inhibit the growth of metallic dendrite, be obviously improved the cyclical stability and high rate performance of battery and capacitor.The gel polymer electrolyte can be used in the primary or making active materials for use in secondary electrochemical energy-storage system of high-energy density, large capacity, high security.
Description
Technical field
The present invention relates to electrochemical energy storage technical fields, and in particular to a kind of water soluble polymer gel polymer electrolyte
And the preparation method and application thereof.
Background technique
Lithium ion battery is current important electrochemical energy storage device, has energy density height, environmental-friendly, memoryless effect
The advantages that answering has produced profound influence to the modern life since commercialization, it has also become 3C Product, electric car (EV) and small-sized
The first choice energy storage device such as smart grid.However, lithium ion battery is limited by self-condition instantly, it need to be largely using organic liquid electricity
Solve liquid.Organic liquid electrolyte easily burns in the case where battery abuse, over-heat inside or micro-short circuit, causes cell safety thing
Therefore.For the safety for improving battery, solid electrolyte becomes researcher's focus of attention.Solid electrolyte can be divided into inorganic fast
Ion conductor and gel polymer electrolyte (gel polymer electrolytes, GPEs), the former is due to compatible with electrode
Property is poor, generates biggish interface resistance, therefore gel polymer electrolyte is considered as more appropriate solid electrolyte system.
Gel is the polymer network system being swollen, and special network structure has the dispersion conductibility of liquid simultaneously and consolidates
The cohesiveness of body, low with electrode reaction, compatibility is good, avoid that liquid electrolyte is inflammable and explosive and inorganic fast ionic conductor with
The disadvantages of electrode poor compatibility.In addition, gel polymer electrolyte have with traditional comparable conductivity of organic liquid electrolyte,
And thermal stability is good, electrochemical window mouth width, it has also become the research hotspot of solid electrolyte.Gel polymer electrolyte at this stage
A large amount of organic solvents are expended in preparation process, cause serious environmental pollution, while preparation process is complicated, with high costs, therefore,
It is necessary to develop the polymer electrolyte system that water-soluble polymer is raw material.
Water soluble polymer, such as polysaccharide (methylcellulose (MC), sodium carboxymethylcellulose (CMC-Na), chitosan, shallow lake
Powder, sodium alginate, agar etc.), polyvalent alcohol (polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene oxide (PEO) etc.),
Polymer salt (poly- (methyl) acrylates, poly salt, polysulfonate etc.) and other water-soluble polymer (polyacrylamides
(PAM), aqueous polyurethane, polyvinylpyrrolidone (PVP) etc.) etc..Preparation process is simple, and cost is relatively low, is widely used in eating
All conglomeraties such as product, medical treatment, clothes, beauty, building, electric, office equipment, aerospace.
Vacuum freeze-drying method (freeze-drying) be using ice crystal distillation principle, low temperature (- 10 DEG C~-70 DEG C),
Under the conditions of low pressure (1.3~20Pa), the sample to have freezed is directly distilled by ice and makes a kind of side of sample drying for steam
Method.Different from common heating drying means, the water in material is the direct lyophilization in the form of solid ice, and material keeps original
The shape of ice shelf, therefore gained sample volume is constant, it is loose porous.The polymeric membrane porosity prepared by this kind of method
Height, imbibition rate are high.In addition, reticular structure can effectively prevent the nonuniform deposition of lithium metal during circulating battery, to metal branch
Crystals growth has good inhibiting effect, and preferable application prospect is shown in lithium metal secondary cell.
Summary of the invention
It is an object of the invention to prepare a kind of gel polymer electrolyte, preparation process using freeze-drying and pressure sintering
Simply, environmental-friendly and low in cost.The gel polymer electrolyte of preparation has conductivity height, satisfactory mechanical property, ion
The features such as transport number is big, electrochemical window mouth width, can be substantially improved the cyclical stability and high rate performance of electrochemical energy storage system.
The present invention also aims to the gel polymer electrolyte of preparation and the electrode material of electrochemical energy storage system are glutinous
Attached power is strong, can effectively avoid micro-short circuit, overcome existing electrolyte it is inflammable, it is explosive etc. caused by safety problem.
To reach above-mentioned purpose, inventive solution is as follows:
A kind of water soluble polymer gel polymer electrolyte, it is characterised in that: the water soluble polymer gel polymerisation
The raw material of object electrolyte includes the mixture of macromolecule or the macromolecule and inorganic filler；The macromolecule includes but is not limited to
Polysaccharide, polyvalent alcohol, one of polymer salt and other water-soluble polymers or a variety of；The inorganic filler includes but not
It is limited to one of silica, aluminium oxide, zirconium oxide, titanium oxide, inorganic fast ionic conductor or a variety of.
The polysaccharide includes but is not limited to methylcellulose (MC), sodium carboxymethylcellulose (CMC-Na), chitosan, shallow lake
One of powder, sodium alginate, agar are a variety of；The polyvalent alcohol includes but is not limited to polyvinyl alcohol (PVA), polyethylene glycol
(PEG), one of polyethylene oxide (PEO) or a variety of；The polymer salt includes but is not limited to poly-methyl acrylate, gathers
One of maleate, polysulfonate are a variety of；Other water-soluble polymers include but is not limited to polyacrylamide (PAM),
One of aqueous polyurethane, polyvinylpyrrolidone (PVP) are a variety of；The inorganic filler include but is not limited to silica,
One of aluminium oxide, zirconium oxide, titanium oxide, inorganic fast ionic conductor are a variety of；Inorganic fast ionic conductor includes but is not limited to
One of lithium lanthanum zirconium oxygen, titanium carbonate lithium, lanthanium titanate lithium, lithium aluminosilicate are a variety of.
A method of preparing the water soluble polymer gel polymer electrolyte, it is characterised in that: first by high score
Son or the macromolecule and inorganic filler mixture are soluble in water with certain proportion, and then the method by freeze-drying obtains three-dimensional
The polymer film of reticular structure obtains gel polymer electrolyte for liquid organic electrolyte is immersed in after its roll-in for a period of time
Matter.
The freeze-drying and heating nipping process uses commercially available freeze drier and roll squeezer respectively.
A kind of water soluble polymer method for preparing gel polymer electrolyte, it is characterised in that: the following steps are included:
(1) by the high molecular material or the mixture and water of the macromolecule and inorganic filler with 1/1~1/100 (w/
W) ratio mixes, and stirring and dissolving obtains uniform mixture at 20 DEG C~80 DEG C, and is cooled to room temperature；
(2) liquid mixture of different proportion is freeze-dried using freeze drier, drying temperature be -60 DEG C~
0 DEG C, obtain mesh structural porous polymer film；
(3) by above-mentioned polymer film by roll squeezer, roll temperature is 25 DEG C~150 DEG C, roll-in 1~100 time, is closed
The polymer film of suitable thickness；
(4) above-mentioned polymer film is placed in a vacuum drying oven, is dried in vacuo at room temperature~120 DEG C, remove trace water；
(5) in the environment of anhydrous and oxygen-free by the polymer film of above-mentioned drying be immersed in 1min in liquid organic electrolyte~
48h obtains gel polymer electrolyte.
Suitable polymer film described in step (3) with a thickness of 10 μm~100 μm.
Anhydrous and oxygen-free environment described in step (5) refers to the glove box that water oxygen content is both less than 0.1ppm, atmosphere is argon gas.
Liquid electrolyte described in step (5) be organic solvent or ionic liquid and LITHIUM BATTERY electrolyte lithium salt, sodium salt,
The solution of sylvite.Concentration is in 0.5mol L-1~2mol L-1Between.
The organic solvent include but is not limited to ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate,
One of γ~butyrolactone, vinylene carbonate, dimethyl carbonate are a variety of.
A kind of application of water soluble polymer gel polymer electrolyte in primary or making active materials for use in secondary electrochemical energy-storage system.
The water soluble polymer includes but is not limited to polysaccharide (methylcellulose (MC), sodium carboxymethylcellulose (CMC-
Na), chitosan, starch, sodium alginate, agar etc.), polyvalent alcohol (polyvinyl alcohol (PVA), polyethylene glycol (PEG), polycyclic oxygen
Ethane (PEO) etc.), polymer salt (poly- (methyl) acrylates, poly salt, polysulfonate etc.) and other water-soluble polymerics
One of object (polyacrylamide (PAM), aqueous polyurethane, polyvinylpyrrolidone (PVP) etc.) is a variety of.What is be related to is inorganic
Filler include but is not limited to silica, aluminium oxide, zirconium oxide, titanium oxide, inorganic fast ionic conductor (lithium lanthanum zirconium oxygen, titanium carbonate lithium,
Lanthanium titanate lithium, lithium aluminosilicate etc.) it is one or more.
Above-mentioned organic solvent include but is not limited to ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate,
One or more of γ~butyrolactone, vinylene carbonate, dimethyl carbonate；Electrolyte lithium salt includes but is not limited to hexafluoro phosphorus
Sour lithium (LiPF6), LiBF4 (LiBF4), two (trimethyl fluoride sulfonyl) imine lithium (LiN (CF3SO2)2), double fluoroform sulphurs
Imide li (LiTFSI), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), trifluoromethyl sulfonic acid lithium (LiCF3SO3)、
Di-oxalate lithium borate (LiBOB)；Sodium salt includes but is not limited to sodium perchlorate (NaClO4), lithium hexafluoro phosphate (NaPF6), double oxalic acid
Boratex (NaBOB), sodium tetrafluoroborate (NaBF4), hexafluoroarsenate sodium (NaAsF6), double trifluoromethanesulfonimide sodium
(NaTFSI), two (trimethyl fluoride sulfonyl) imines sodium (NaN (CF3SO2)2)；Sylvite includes but is not limited to potassium hyperchlorate (KClO4)、
Potassium Hexafluorophosphate (KPF6), double oxalic acid potassium borates (KBOB), potassium tetrafluoroborate (KBF4), potassium hexafluoroarsenate (KAsF6), double trifluoros
Sulfonyl methane imines potassium (KTFSI), two (trimethyl fluoride sulfonyl) imines potassium (KN (CF3SO2)2)。
The present invention uses water as solvent, and it is dirty using organic solvent bring environment to avoid conventional polymer electrolyte
Dye, and macromolecule raw material is from a wealth of sources, and preparation process is simple, low in cost.Prepared gel polymer electrolyte and electricity
There is good adhesiveness in pole, can effectively inhibit the growth of metallic dendrite, prevents micro-short circuit, while having transference number of ions high, electric
The advantages that chemical window is wide, conductivity is high is conducive to the promotion of energy-storage system long circulating and high rate performance, the gel of the method
Polymer dielectric product can be widely applied to the electricity such as lithium ion battery, sodium-ion battery, kalium ion battery or supercapacitor
In in chemical energy storage device.
The invention belongs to high molecular materials and field of batteries, and in particular to water-soluble high-molecular material gel polymer electrolyte
Matter and its preparation, while further including application of this gel polymer electrolyte in primary or making active materials for use in secondary electrochemical energy-storage system.
The gel polymer electrolyte is made of polymer film and liquid electrolyte.The raw material for preparing such polymer film is
Water soluble polymer (or compound of water soluble polymer and inorganic filler), the macromolecule being related to includes but is not limited to polysaccharide
(methylcellulose (MC), sodium carboxymethylcellulose (CMC-Na), chitosan, starch, sodium alginate, agar etc.), polyvalent alcohol
(poly- (methyl) acrylates gathers for (polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene oxide (PEO) etc.), polymer salt
Maleate, polysulfonate etc.) and other water-soluble high-molecular material (polyacrylamides (PAM), aqueous polyurethane, polyethylene
Pyrrolidones (PVP)) one of or it is a variety of.The inorganic filler being related to include but is not limited to silica, aluminium oxide, zirconium oxide,
Titanium oxide, inorganic fast ionic conductor (lithium lanthanum zirconium oxygen, titanium carbonate lithium, lanthanium titanate lithium, lithium aluminosilicate etc.) it is one or more.This hair
Bright to be related to a kind of method for preparing gel polymer electrolyte, this method preparation process is simple, low in cost, preparation process ring
It protects.Prepared gel polymer electrolyte conductivity height, electrochemical window mouth width, lithium ion transference number are high, and and electrode material
Compatibility is good, can effectively inhibit the growth of metallic dendrite, is obviously improved the cyclical stability of battery and capacitor and forthright again
Energy.The gel polymer electrolyte can be used for the primary or making active materials for use in secondary electrochemical energy storage system of high-energy density, large capacity, high security
In system.
Detailed description of the invention
Fig. 1 a is polymer film of the embodiment of the present invention (MC-membrane) surface scan electron microscope.
Fig. 1 b is polymer film of the embodiment of the present invention (MC-membrane) cross-sectional scans electron microscope.
Fig. 2 a be Celgard 2730 used in polymer film of the embodiment of the present invention (MC-membrane) and comparative example 1 every
The TG of film schemes.
Fig. 2 b be Celgard 2730 used in polymer film of the embodiment of the present invention (MC-membrane) and comparative example 1 every
The DSC of film schemes.
Fig. 3 a be Celgard 2730 used in polymer film of the embodiment of the present invention (MC-membrane) and comparative example 1 every
The thermal contraction test figure of film compares the variation photo of (25 DEG C) of room temperature heat preservations two hours.
Fig. 3 b be Celgard 2730 used in polymer film of the embodiment of the present invention (MC-membrane) and comparative example 1 every
The thermal contraction test figure of film compares the variation photo of 120 DEG C of heat preservations two hours.
Fig. 3 c be Celgard 2730 used in polymer film of the embodiment of the present invention (MC-membrane) and comparative example 1 every
The thermal contraction test figure of film compares the variation photo of 150 DEG C of heat preservations two hours.
Fig. 4 a is 1 gained 1molL of gel polymer electrolyte of the embodiment of the present invention (MC-GPE) and comparative example-1LiPF6Electricity
Solve the TG figure of 2730 diaphragm of Celgard of liquid saturation.
Fig. 4 b is 1 gained 1molL of gel polymer electrolyte of the embodiment of the present invention (MC-GPE) and comparative example-1LiPF6Electricity
Solve the DSC figure of 2730 diaphragm of Celgard of liquid saturation.
Fig. 5 is 1 gained 1molL of 1 gel polymer electrolyte of the embodiment of the present invention (MC-GPE) and comparative example-1LiPF6Electricity
Solve the cyclic voltammetry curve of 2730 diaphragm of Celgard of liquid saturation.
Fig. 6 is 1 gained 1molL of gel polymer electrolyte of the embodiment of the present invention (MC-GPE) and comparative example-1LiPF6Electrolysis
The cycle performance figure (Li/LFP battery, 1C multiplying power) of 2730 diaphragm of Celgard of liquid saturation.
Fig. 7 is 1 gained 1mol L of gel polymer electrolyte of the embodiment of the present invention (MC-GPE) and comparative example-1LiPF6Electricity
Solve the high rate performance (Li/LFP battery) of 2730 diaphragm of Celgard of liquid saturation.
Fig. 8 a is the surface SEM of Li/LFP battery lithium anode before 1C circulation 200 weeks of the embodiment of the present invention 1
Figure.
Fig. 8 b is the Li/LFP battery of the embodiment of the present invention 1 after 1C circulation 200 weeks, and it is poly- to observe gel by SEM
Rejection ability figure of the polymer electrolyte (MC-GPE) to Li dendrite.
Fig. 8 c is the Li/LFP battery of comparative example of the present invention after 1C circulation 200 weeks, observes Celgard by SEM
Rejection ability figure of 2730 diaphragms to Li dendrite.
Specific embodiment
Invention is described further with reference to the accompanying drawing.
Such as Fig. 1 to Fig. 8, embodiment 1
(1) mixing that methylcellulose (MC) and water are pressed to 1/400 (w/w) is stirred 6 hours at normal temperature and is clarified
Uniform aqueous solution.
(2) aqueous solution is poured into freeze drier container for storing, -60 DEG C of condenser temperature, is carried out under vacuum degree 10Pa cold
It is lyophilized dry.
(3) dried product roll-in 30 times, is obtained into the polymer film of 35 μ m-thicks by 80 DEG C of heating roll-ins.
(4) after polymer film obtained being cut into appropriate size, be placed in a vacuum drying oven, 80 DEG C of dryings 24 hours with
Trace water is removed, room temperature is cooled under vacuum state, is transferred into glove box and saves.It is immersed in 1molL-1LiPF6Electrolysis
In liquid (be purchased from Zhangjiagang Cathay Huarong new material Co., Ltd) 12 hours to get methyl cellulose gel polymer dielectric
(MC-GPE)。
Embodiment 2
(1) by sodium carboxymethylcellulose (CMC), lithium lanthanum zirconium oxygen solid electrolyte and water according to the ratio of 1/1/200 (w/w/w)
Example mixing, 6 hours of stirring obtain scattered aqueous solution at normal temperature.
(2) aqueous solution is poured into freeze drier container for storing, -60 DEG C of condenser temperature, is carried out under vacuum degree 10Pa cold
It is lyophilized dry.
(3) dried product roll-in 50 times, is obtained into 35 μm of polymer film by 80 DEG C of heating roll-ins.
(4) after dielectric film obtained being cut into appropriate size, be placed in a vacuum drying oven, 80 DEG C of dryings 24 hours with
Trace water is removed, room temperature is cooled under vacuum state and is transferred into glove box and save.It is immersed in 1molL-1LiPF6Electrolyte
In (be purchased from Zhangjiagang Cathay Huarong new material Co., Ltd) 12 hours up to carboxy methylcellulose gel polymer dielectric
(CMC-GPE)。
Embodiment 3
(1) polyvinyl alcohol (PVA) and polyethylene oxide (PEO) are mixed with water according to the ratio of 1/1/100 (w/w/w),
6 hours of stirring obtain clarifying uniform solution at normal temperature.
(2) aqueous solution is poured into freeze drier container for storing, -60 DEG C of condenser temperature, is carried out under vacuum degree 10Pa cold
It is lyophilized dry.
(3) dried product roll-in 30 times, roll-in 50 times, is obtained into 20 μm of polymer by 60 DEG C of heating roll-ins
Film.
(4) after dielectric film obtained being cut into appropriate size, be placed in a vacuum drying oven, 80 DEG C of dryings 24 hours with
Trace water is removed, room temperature is cooled under vacuum state and is transferred into glove box and save.It is immersed in 1molL-1LiTFSI electrolysis
In liquid (be purchased from Zhangjiagang Cathay Huarong new material Co., Ltd) 12 hours up to polyvinyl alcohol-according to ethylene oxide gelatin polymer
Electrolyte (PVA-PEO-GPE).
(5) for active carbon as cathode, cobaltosic oxide is anode and polyvinyl alcohol-according to ethylene oxide gel polymer electrolyte
Matter is assembled into supercapacitor.
Comparative example 1
It is cut into size appropriate using commercial lithium ion battery separator (polyethylene diagrams) (Celgard 2730), so
80 DEG C of 24 hours of vacuum oven are placed on, goes in glove box and saves after cooling under vacuum.Needed before electro-chemical test by
It is immersed in 1molL-1LiPF612 hours in electrolyte (being purchased from Zhangjiagang Cathay Huarong new material Co., Ltd).
In the methyl cellulose gel polymer film (MC-membrane) and comparative example obtained to above-mentioned 1 method of example
2730 diaphragm of Celgard has carried out infrared spectroscopy, scanning electron microscope microscope, TG-DSC, imbibition rate, porosity and thermal contraction table
Sign；To 2730 diaphragm of Celgard of methyl cellulose gel polymer dielectric (MC-GPE) and absorption saturated liquid electrolyte
TG-DSC, conductivity, lithium ion transference number, CV and charge-discharge test are carried out.
Prepared dielectric film (MC-membrane) is first immersed in by the calculating of porosity with 2730 diaphragm of Celgard
In n-butanol after 4 hours, formula (2) is obtained:
Wherein, p is porosity, W0And WtIt respectively represents raw sample and is saturated with the quality of film before and after n-butanol.ρ and V difference
It is the density of n-butanol and the apparent volume of film.1 method of embodiment obtain polymer film (MC-membrane) porosity be
52.5%, the porosity of Celgard2730 diaphragm is 37.8% in comparative example.Prepared polymeric membrane (MC-membrane)
With the imbibition rate of 2730 diaphragm of Celgard by the way that two kinds of samples are immersed in electrolyte 12 hours after, calculated according to formula (1)
It obtains:
η=(Wt–W0)/W0× 100% (2)
Wherein, W0And WtRespectively represent former dry film and the quality for being saturated with electrolyte caudacoria.The polymerization that 1 method of embodiment obtains
Object film (MC-membrane) imbibition rate is 148.2%, and the imbibition rate of Celgard2730 diaphragm is 90.5% in comparative example.
The calculating of conductivity is obtained according to formula (3):
σ=l/ (RbA)(S cm-1) (3)
Wherein, σ is conductivity, and l is the thickness of film, RbIt is the resistance of film and the area of electrode respectively with A.1 side of embodiment
The room-temperature conductivity that method obtains methyl cellulose gel film (MC-GPE) is 0.7mS cm-1, in comparative example Celgard 2730 every
The conductivity of film is 0.43mS cm-1。
Lithium ion transference number is calculated by formula (4):
tLi +=ISS/I0 (4)
Wherein, I0And ISSIt is the initial state current value and steady-state current value obtained by timing discharge method respectively.Embodiment 1
The lithium ion transference number that method obtains methyl cellulose gel film (MC-GPE) is 0.48,2730 diaphragm of Celgard in comparative example
Lithium ion transference number be 0.27.
From the point of view of the comparison of embodiment and comparative example, the gel based on cellulose made from simple freeze-drying method is poly-
Polymer electrolyte has good thermal stability, cheap, under high temperature the features such as high security, and has with battery electrode
Preferable adhesiveness can effectively prevent the micro-short circuit of battery.Compared to traditional commerce diaphragm, gel polymerisation prepared by embodiment
Object electrolyte has higher conductivity, lithium ion transference number and electrochemical properties, to high-power, high-energy density electric car
And the development of large-scale energy storage device is of great significance.
Claims (10)
1. a kind of water soluble polymer gel polymer electrolyte, it is characterised in that: the water soluble polymer gelatin polymer
Electrolyte raw material includes the mixture of macromolecule or the macromolecule and inorganic filler；The macromolecule includes but is not limited to more
Sugar, polyvalent alcohol, one of polymer salt and other water-soluble polymers or a variety of；The inorganic filler includes but unlimited
In one of silica, aluminium oxide, zirconium oxide, titanium oxide, inorganic fast ionic conductor or a variety of.
2. water soluble polymer gel polymer electrolyte according to claim 1, it is characterised in that: the polysaccharide includes
But it is not limited to methylcellulose (MC), sodium carboxymethylcellulose (CMC-Na), chitosan, starch, sodium alginate, one in agar
Kind is a variety of；The polyvalent alcohol includes but is not limited to polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene oxide (PEO)
One of or it is a variety of；The polymer salt includes but is not limited to poly-methyl acrylate, poly salt, in polysulfonate
It is one or more；Other water-soluble polymers include but is not limited to polyacrylamide (PAM), aqueous polyurethane, polyvinyl pyrrole
One of alkanone (PVP) is a variety of；The inorganic filler include but is not limited to silica, aluminium oxide, zirconium oxide, titanium oxide,
One of inorganic fast ionic conductor is a variety of；Inorganic fast ionic conductor includes but is not limited to lithium lanthanum zirconium oxygen, titanium carbonate lithium, metatitanic acid
One of lanthanum lithium, lithium aluminosilicate are a variety of.
3. a kind of prepare water soluble polymer method for preparing gel polymer electrolyte of any of claims 1 or 2, feature
It is: it is first that macromolecule or the macromolecule and inorganic filler mixture is soluble in water with certain proportion, then by freeze-drying
Method obtain the polymer film of tridimensional network, obtained liquid organic electrolyte is immersed in after its roll-in for a period of time
Gel polymer electrolyte.
4. a kind of water soluble polymer method for preparing gel polymer electrolyte according to claim 3, feature exist
In: the freeze-drying and heating nipping process uses commercially available freeze drier and roll squeezer respectively.
5. a kind of water soluble polymer method for preparing gel polymer electrolyte according to claim 3, feature exist
In: the following steps are included:
(1) by the high molecular material or the mixture and water of the macromolecule and inorganic filler with 1/1~1/100 (w/w) ratio
Example mixing, stirring and dissolving obtains uniform mixture at 20 DEG C~80 DEG C, and is cooled to room temperature；
(2) liquid mixture of different proportion being freeze-dried using freeze drier, drying temperature is -60 DEG C~0 DEG C,
Obtain mesh structural porous polymer film；
(3) by above-mentioned polymer film by roll squeezer, roll temperature is 25 DEG C~150 DEG C, roll-in 1~100 time, obtains suitable thickness
The polymer film of degree；
(4) above-mentioned polymer film is placed in a vacuum drying oven, is dried in vacuo at room temperature~120 DEG C, remove trace water；
(5) polymer film of above-mentioned drying is immersed in 1min~48h in liquid organic electrolyte in the environment of anhydrous and oxygen-free,
Obtain gel polymer electrolyte.
6. a kind of water soluble polymer method for preparing gel polymer electrolyte according to claim 5, feature exist
The suitable polymer film described in step (3) with a thickness of 10 μm~100 μm.
7. a kind of water soluble polymer method for preparing gel polymer electrolyte according to claim 5, feature exist
The anhydrous and oxygen-free environment described in step (5) refers to the glove box that water oxygen content is both less than 0.1ppm, atmosphere is argon gas.
8. a kind of water soluble polymer method for preparing gel polymer electrolyte according to claim 5, feature exist
The liquid electrolyte described in step (5) is organic solvent or ionic liquid and LITHIUM BATTERY electrolyte lithium salt, sodium salt, sylvite
Solution.Concentration is in 0.5mol L-1~2mol L-1Between.
9. a kind of water soluble polymer method for preparing gel polymer electrolyte according to claim 8, organic solvent
Including but not limited to ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate, γ~butyrolactone, vinylene carbonate
One of ester, dimethyl carbonate are a variety of.
10. a kind of water soluble polymer gel polymer electrolyte such as claimed in claims 1-2 is in primary or making active materials for use in secondary electrochemical
Application in energy-storage system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910374116.4A CN110299557A (en) | 2019-05-07 | 2019-05-07 | Water soluble polymer gel polymer electrolyte and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910374116.4A CN110299557A (en) | 2019-05-07 | 2019-05-07 | Water soluble polymer gel polymer electrolyte and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110299557A true CN110299557A (en) | 2019-10-01 |
Family
ID=68026590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910374116.4A Pending CN110299557A (en) | 2019-05-07 | 2019-05-07 | Water soluble polymer gel polymer electrolyte and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110299557A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019159A (en) * | 2019-12-22 | 2020-04-17 | 复旦大学 | Low-temperature hydrogel electrolyte and preparation method thereof |
| CN111834668A (en) * | 2020-06-30 | 2020-10-27 | 华中科技大学 | γ-LiAlO2With gamma-Al2O3Composite nanosheet and application in preparation of alkali metal ion electrolyte |
| CN112072171A (en) * | 2020-08-13 | 2020-12-11 | 华南理工大学 | Chitosan polyion liquid blended PEO-based solid electrolyte and preparation method and application thereof |
| CN112466674A (en) * | 2020-10-29 | 2021-03-09 | 电子科技大学 | Preparation method of high-temperature gel polymer electrolyte lithium ion capacitor |
| CN112510255A (en) * | 2020-12-23 | 2021-03-16 | 长春工业大学 | Gel electrolyte of zinc-based battery and preparation and application thereof |
| WO2021082074A1 (en) * | 2019-11-01 | 2021-05-06 | 中国科学院金属研究所 | Polymer electrolyte film and preparation method therefor, and application in all-solid-state lithium battery |
| CN112786961A (en) * | 2021-03-23 | 2021-05-11 | 上海电气集团股份有限公司 | Biomass-based gel electrolyte, lithium ion battery, preparation method and application |
| CN112851198A (en) * | 2021-03-16 | 2021-05-28 | 韩新民 | Preparation method of ceramsite brick |
| CN113346129A (en) * | 2020-03-03 | 2021-09-03 | 天津理工大学 | Composite solid electrolyte and preparation method and application thereof |
| CN113363574A (en) * | 2021-06-21 | 2021-09-07 | 广东工业大学 | Polymer electrolyte and preparation method thereof |
| CN113506951A (en) * | 2021-07-01 | 2021-10-15 | 丹阳欣信新材料科技有限公司 | Cellulose-based composite diaphragm for metal secondary battery and preparation method thereof |
| CN113506910A (en) * | 2021-07-01 | 2021-10-15 | 丹阳欣信新材料科技有限公司 | Sodium ion composite solid electrolyte and preparation method thereof |
| CN113972408A (en) * | 2021-10-28 | 2022-01-25 | 长春工业大学 | Zinc-based battery gel polymer electrolyte and preparation and application thereof |
| CN114026739A (en) * | 2019-12-13 | 2022-02-08 | 株式会社Lg新能源 | Solid-liquid mixed electrolyte membrane, method for manufacturing the same, and lithium secondary battery including the same |
| CN114106378A (en) * | 2021-11-24 | 2022-03-01 | 南京工业大学 | Preparation method of natural cellulose-based polymer electrolyte |
| CN114497748A (en) * | 2022-01-07 | 2022-05-13 | 上海工程技术大学 | Cellulose self-repairing gel electrolyte material and preparation method and application thereof |
| EP4078716A4 (en) * | 2019-12-20 | 2024-03-20 | Enevate Corp | Energy storage devices with polymer electrolytes and fillers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888014A (en) * | 2011-07-20 | 2013-01-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Porous composite polymer electrolyte and its preparation method and use |
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| CN106654365A (en) * | 2013-01-23 | 2017-05-10 | 浙江地坤键新能源科技有限公司 | Solid polymer electrolyte-based composite gel polymer electrolyte and preparation method and application thereof |
| CN109037769A (en) * | 2018-07-23 | 2018-12-18 | 珠海光宇电池有限公司 | A kind of compound carbonic acid cross-linked structure method for preparing gel polymer electrolyte |
-
2019
- 2019-05-07 CN CN201910374116.4A patent/CN110299557A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888014A (en) * | 2011-07-20 | 2013-01-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Porous composite polymer electrolyte and its preparation method and use |
| CN106654365A (en) * | 2013-01-23 | 2017-05-10 | 浙江地坤键新能源科技有限公司 | Solid polymer electrolyte-based composite gel polymer electrolyte and preparation method and application thereof |
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| CN109037769A (en) * | 2018-07-23 | 2018-12-18 | 珠海光宇电池有限公司 | A kind of compound carbonic acid cross-linked structure method for preparing gel polymer electrolyte |
Non-Patent Citations (1)
| Title |
|---|
| 张大为: "《海洋食品加工应用技术》", 31 December 2018 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021082074A1 (en) * | 2019-11-01 | 2021-05-06 | 中国科学院金属研究所 | Polymer electrolyte film and preparation method therefor, and application in all-solid-state lithium battery |
| CN114026739A (en) * | 2019-12-13 | 2022-02-08 | 株式会社Lg新能源 | Solid-liquid mixed electrolyte membrane, method for manufacturing the same, and lithium secondary battery including the same |
| EP4078716A4 (en) * | 2019-12-20 | 2024-03-20 | Enevate Corp | Energy storage devices with polymer electrolytes and fillers |
| CN111019159A (en) * | 2019-12-22 | 2020-04-17 | 复旦大学 | Low-temperature hydrogel electrolyte and preparation method thereof |
| CN113346129A (en) * | 2020-03-03 | 2021-09-03 | 天津理工大学 | Composite solid electrolyte and preparation method and application thereof |
| CN111834668A (en) * | 2020-06-30 | 2020-10-27 | 华中科技大学 | γ-LiAlO2With gamma-Al2O3Composite nanosheet and application in preparation of alkali metal ion electrolyte |
| CN112072171B (en) * | 2020-08-13 | 2021-12-21 | 华南理工大学 | Chitosan polyion liquid blended PEO-based solid electrolyte and preparation method and application thereof |
| CN112072171A (en) * | 2020-08-13 | 2020-12-11 | 华南理工大学 | Chitosan polyion liquid blended PEO-based solid electrolyte and preparation method and application thereof |
| CN112466674B (en) * | 2020-10-29 | 2022-03-15 | 电子科技大学 | Preparation method of high-temperature gel polymer electrolyte lithium ion capacitor |
| CN112466674A (en) * | 2020-10-29 | 2021-03-09 | 电子科技大学 | Preparation method of high-temperature gel polymer electrolyte lithium ion capacitor |
| CN112510255A (en) * | 2020-12-23 | 2021-03-16 | 长春工业大学 | Gel electrolyte of zinc-based battery and preparation and application thereof |
| CN112851198B (en) * | 2021-03-16 | 2021-08-17 | 韩新民 | Preparation method of ceramsite brick |
| CN112851198A (en) * | 2021-03-16 | 2021-05-28 | 韩新民 | Preparation method of ceramsite brick |
| CN112786961A (en) * | 2021-03-23 | 2021-05-11 | 上海电气集团股份有限公司 | Biomass-based gel electrolyte, lithium ion battery, preparation method and application |
| CN113363574A (en) * | 2021-06-21 | 2021-09-07 | 广东工业大学 | Polymer electrolyte and preparation method thereof |
| CN113506910A (en) * | 2021-07-01 | 2021-10-15 | 丹阳欣信新材料科技有限公司 | Sodium ion composite solid electrolyte and preparation method thereof |
| CN113506951A (en) * | 2021-07-01 | 2021-10-15 | 丹阳欣信新材料科技有限公司 | Cellulose-based composite diaphragm for metal secondary battery and preparation method thereof |
| CN113972408A (en) * | 2021-10-28 | 2022-01-25 | 长春工业大学 | Zinc-based battery gel polymer electrolyte and preparation and application thereof |
| CN113972408B (en) * | 2021-10-28 | 2024-04-12 | 长春工业大学 | Zinc-based battery gel polymer electrolyte and preparation and application thereof |
| CN114106378A (en) * | 2021-11-24 | 2022-03-01 | 南京工业大学 | Preparation method of natural cellulose-based polymer electrolyte |
| CN114497748A (en) * | 2022-01-07 | 2022-05-13 | 上海工程技术大学 | Cellulose self-repairing gel electrolyte material and preparation method and application thereof |
| CN114497748B (en) * | 2022-01-07 | 2023-08-29 | 上海工程技术大学 | Cellulose self-repairing gel electrolyte material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110299557A (en) | Water soluble polymer gel polymer electrolyte and the preparation method and application thereof | |
| US11843109B2 (en) | Method of preparing and application of carbon-selenium composites | |
| Li et al. | A dense cellulose-based membrane as a renewable host for gel polymer electrolyte of lithium ion batteries | |
| CN102244292A (en) | Lithium ion battery ionic liquid based gel polymer electrolyte as well as preparation and applications thereof | |
| CN106299471A (en) | A kind of hybrid solid-state polymer dielectric and preparation method and application | |
| CN102199846A (en) | Porous polymer electrolyte supporting membrane material, preparation method thereof and application thereof | |
| CN111313083B (en) | Composite solid electrolyte film and preparation and application thereof | |
| CN103441300A (en) | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof | |
| CN103022557B (en) | Based on the lithium ion battery gel polymer electrolyte and preparation method thereof of nonwoven fabrics | |
| CN111009686A (en) | All-solid-state polymer electrolyte containing high-concentration lithium salt and preparation method thereof | |
| CN110190284B (en) | Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof | |
| CN104183820B (en) | A kind of lithium-sulphur cell positive electrode membrane material | |
| CN110459723A (en) | Battery diaphragm and preparation method thereof and battery with the battery diaphragm | |
| CN111952670A (en) | Lithium ion battery with wide working temperature range | |
| CN103268955B (en) | A kind of composite gel polymer electrolyte and preparation method and application | |
| CN110808411B (en) | Electrolyte and lithium ion battery | |
| CN114256560A (en) | Cellulose inorganic composite membrane, high-temperature-resistant battery diaphragm, and preparation method and application thereof | |
| CN112002562B (en) | Preparation of self-healing hydrogel electrolyte with ion channel and application of self-healing hydrogel electrolyte in all-solid-state supercapacitor | |
| CN105826598A (en) | PVDF-P(VC-VAc)-based blended gel polymer electrolyte and preparation method and application thereof | |
| CN110994016B (en) | Polymer solid electrolyte and preparation method and application thereof | |
| CN112448027B (en) | Blended gel polymer electrolyte and preparation method and application thereof | |
| CN116895842A (en) | Lithium ion battery and application thereof | |
| CN116565308A (en) | Solid electrolyte membrane and preparation method and application thereof | |
| CN110970654B (en) | Composite gel polymer electrolyte for lithium ion battery and preparation and application thereof | |
| CN115775917A (en) | Preparation method of gel electrolyte applied to secondary sodium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191001 |
|
| RJ01 | Rejection of invention patent application after publication |