CN116284855A - Preparation and application of carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte - Google Patents
Preparation and application of carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte Download PDFInfo
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- CN116284855A CN116284855A CN202310156486.7A CN202310156486A CN116284855A CN 116284855 A CN116284855 A CN 116284855A CN 202310156486 A CN202310156486 A CN 202310156486A CN 116284855 A CN116284855 A CN 116284855A
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- polyvinyl alcohol
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 215
- 239000001913 cellulose Substances 0.000 title claims abstract description 215
- 239000000017 hydrogel Substances 0.000 title claims abstract description 99
- 239000003792 electrolyte Substances 0.000 title claims abstract description 65
- 239000011701 zinc Substances 0.000 title claims abstract description 45
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 37
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 229920002732 Polyanhydride Polymers 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 229920000875 Dissolving pulp Polymers 0.000 claims abstract description 4
- 238000001212 derivatisation Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
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- 229920000742 Cotton Polymers 0.000 claims description 133
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 118
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 118
- 239000000243 solution Substances 0.000 claims description 65
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 49
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 38
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 25
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 25
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 25
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 25
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 23
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 23
- 241001330002 Bambuseae Species 0.000 claims description 23
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 23
- 239000011425 bamboo Substances 0.000 claims description 23
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229960001763 zinc sulfate Drugs 0.000 claims description 18
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 18
- 229920001131 Pulp (paper) Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000003990 capacitor Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- -1 zinc tetrafluoroborate Chemical compound 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- UWHSPZZUAYSGTB-UHFFFAOYSA-N 1,1,3,3-tetraethylurea Chemical compound CCN(CC)C(=O)N(CC)CC UWHSPZZUAYSGTB-UHFFFAOYSA-N 0.000 claims description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008104 plant cellulose Substances 0.000 claims description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 238000010494 dissociation reaction Methods 0.000 claims 1
- 230000005593 dissociations Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000011245 gel electrolyte Substances 0.000 abstract description 34
- 238000013461 design Methods 0.000 abstract description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 38
- 239000002608 ionic liquid Substances 0.000 description 37
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 32
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 31
- 229940014800 succinic anhydride Drugs 0.000 description 31
- 239000000203 mixture Substances 0.000 description 30
- 239000000499 gel Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 19
- 238000003760 magnetic stirring Methods 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- 230000007935 neutral effect Effects 0.000 description 16
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
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- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
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- 150000002500 ions Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- KUBWXQUHENSKGC-UHFFFAOYSA-N 2-chloroacetic acid;ethanol Chemical compound CCO.OC(=O)CCl KUBWXQUHENSKGC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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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
- 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
-
- 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
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
-
- 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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- 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
Abstract
The invention discloses preparation and application of carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte, which comprises the following steps: (1) Dissolving cellulose and high molecular polymer in organic alkali/CO 2 In an organic solvent system, obtaining a product A; (2) Firstly, adding a compound containing a monoanhydride functional group into the product A to carry out derivatization reaction to obtain a product B; (3) Cooling the product B, adding a compound containing polyanhydride functional groups, mixing and stirring uniformly, and pouring into a mould to obtain a product C; (4) Displacing the C product with pure water to neutrality to obtain carboxylated cellulose-based hydrogel; (5) And soaking the carboxylated cellulose-based hydrogel in a zinc-containing electrolyte salt solution to obtain the carboxylated cellulose-based flexible zinc-resistant dendrite hydrogel electrolyte. The invention utilizes organic alkali/organic solvent/CO 2 The system designs a hydrogel electrolyte, solves the problem of zinc dendrite of serious water system ZIHCs and improves the mechanical strength of the gel electrolyte.
Description
Technical Field
The invention belongs to the technical field of zinc ion mixed capacitors, and particularly relates to a preparation method and application of carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte.
Background
Aqueous Zinc Ion Hybrid Capacitors (ZIHCs) integrate the advantages of safety and low investment cost, are expected to be applied to the fields of large-scale power grid energy storage, wearable electronic products and the like, and are considered as one of the most promising energy storage systems. As a hybrid supercapacitor, aqueous ZIHCs is generally composed of a battery-type Zn metal negative electrode, a capacitor-type positive electrode (most widely studied as porous carbon materials), and an aqueous electrolyte. Unlike zinc ion battery cathodes, porous carbon cathodes store charge primarily through Electric Double Layer Capacitance (EDLC) and surface pseudocapacitance. The highly reversible charge storage mechanism of the porous carbon cathode gives ZIHCs an ultra-long lifetime. Zinc anodes store electrical charge by galvanization and dezincification, making ZIHCs have high capacity. And zinc anodes have low redox potentials, aqueous ZIHCs in combination with carbon cathodes can provide a higher voltage window (≡1.6-1.8V) than symmetric C|C supercapacitors (≡1V). Because of this hybrid configuration, ZIHCs can make up for the energy density gap between the supercapacitor and the battery.
However, both metal batteries and capacitors inevitably suffer from dendrite problems due to uneven diffusion and deposition of ions on the metal anode, which makes it difficult to achieve satisfactory safety and service life for a long period of time, which greatly limits the commercial use of ZIHCs. In order to solve these problems, some researchers have proposed a novel ZIHCs gel electrolyte, which is sandwiched between a positive electrode and a negative electrode as a quasi-solid electrolyte, capable of overcoming the above-mentioned problems to some extent. Although various ZIHCs gel electrolytes have been widely studied and applied to ZIHCs at present, the existing ZIHCs gel electrolytes still have the defects of poor flexibility, low mechanical strength, low ionic conductivity, poor electrochemical stability and the like, and are also the main problems of the water system ZIHCs at present.
In recent years, researchers have constructed three-dimensional networks of gel electrolytes using industrial carboxymethylcellulose for use in aqueous ZIHCs. For example, qia et al constructed a gel electrolyte of ZIHCs by adding small amounts of commercial carboxymethylcellulose (4 wt%) to polyvinyl alcohol, and induced Zn by charged functional groups (carboxyl groups) 2+ The prepared carboxymethyl cellulose gel electrolyte has excellent zinc dendrite resistance and electrochemical performance, and can solve the problems to a certain extent. But its mechanical strength and good electrochemical properties. However, the gel electrolyte is largely prepared from non-renewable petroleum-based raw materials (polyvinyl alcohol) and industrial products (carboxymethyl cellulose), and the problem of the increasing exhaustion of fossil energy cannot be fundamentally solved.
The preparation method of the traditional carboxymethyl cellulose raw material comprises the steps of adding 30% -40% of NaOH into an alkali etherification kettle, adding 10ml of absolute ethyl alcohol and a small amount of urea, uniformly stirring, adding 5g of crushed cotton, heating in a constant-temperature water bath kettle at 30-35 ℃ for reaction for 1-2h, dropwise adding a certain amount of chloroacetic acid ethanol solution, reacting at a constant temperature of 40-45 ℃ for 0.5h, and then heating to 70 ℃ for reaction for 1-2h. Then, the crude carboxymethyl cellulose was taken out, neutralized to ph=7 with hydrochloric acid, washed with 80% ethanol solution in a constant temperature water bath at 40-45 ℃ with continuous stirring for 10min at a bath ratio of 1:4, and washed 3 times in total. And (3) centrifugally dealcoholizing the washed product, putting the product into a baking oven at 105 ℃ for drying for 2 hours, and obtaining the odorless and tasteless fibrous small-particle carboxymethyl cellulose after drying. From this, it can be seen that the industrial carboxymethyl cellulose has a complex preparation process, and uses a large amount of strong acid, strong alkali and toxic organic solvents. The cost of the organic solvent is high, and the investment of the organic solvent recovery equipment is high.
Therefore, based on the defects of the electrolyte prepared by the traditional carboxymethyl cellulose, the invention directly takes cellulose as a raw material, and realizes gelation in the carboxylation process, thereby constructing an ion channel with a three-dimensional network structure. The second polymer is skillfully introduced to participate in the gelation process, and the covalent bond and the non-covalent bond participate in the construction of the three-dimensional network of the ion channel, so that the electrical property of the gel electrolyte is improved, the mechanical property of the gel electrolyte is improved, the defect of the traditional electrolyte can be effectively overcome, and the gel electrolyte is very important for popularization of the rechargeable water system ZIHCs.
Disclosure of Invention
The invention aims at solving the dilemma of the development of the prior ZIHCs, and adopts organic alkali/organic solvent/CO from the design modification of aqueous electrolyte 2 The carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte is designed, so that the problem of serious zinc dendrites of water systems ZIHCs is solved, and the service life of the ZIHCs is further prolonged. Meanwhile, the mechanical strength of the gel electrolyte is improved by utilizing covalent bond and non-covalent bond crosslinking.
The technical scheme of the invention is as follows: a method for preparing carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte, comprising the following steps:
(1) Dissolving cellulose in organic base/CO 2 Organic solvent system; wherein the organic alkali in the system has a mass concentration of 0.1-50%, the dissolved cellulose has a mass concentration of 0.1-30%, and the CO is charged 2 The pressure of the solution is 0.1-15MPa, the dissolution temperature is 50-150 ℃ and the dissolution time is 1-24h; then adding high molecular polymer, and continuously stirring and dissolving at 20-50 ℃ to obtain a product A;
(2) Firstly, adding a compound containing a monoanhydride functional group into the product A, and stirring at 20-100 ℃ to carry out derivatization reaction for 1-24 hours to obtain a product B;
(3) Cooling the product B to-20-20 ℃, then adding a compound containing polyanhydride functional groups, mixing and stirring uniformly, pouring into a mould, and reacting for 1-24h at 20-100 ℃ to obtain a product C;
(4) Displacing the C product with pure water for 1-10 times to neutrality to obtain carboxylated cellulose-based hydrogel;
(5) And soaking the carboxylated cellulose-based hydrogel in 0.1-10mol/L zinc-containing electrolyte salt solution for 1-48h to obtain the carboxylated cellulose-based flexible zinc dendrite resisting hydrogel electrolyte.
Preferably, the preparation method of the carboxylated cellulose based flexible zinc dendrite resistant hydrogel electrolyte comprises the step of preparing cellulose, wherein the cellulose is microcrystalline cellulose, alpha-cellulose or any combination of one or more plant cellulose separated from cotton, wood pulp, bamboo pulp and agriculture and forestry lignocellulose waste.
Preferably, the preparation method of the carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte comprises the step of preparing the carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte by using any combination of one or more of dimethyl sulfoxide, N-methylpyrrolidone, tetramethylurea, tetraethylurea, N-dimethyl imidazolidinone, N-dimethylformamide, N-diethylacetamide, pyrrolidone, 2-azacyclic ketone, N-dimethyl propenyl urea or sulfolane.
Preferably, the preparation method of the carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte comprises the steps of:
wherein n=1 or 2; r is independent hydrogen or alkyl with 1-6 carbon atoms; r is R 1 、R 2 、R 3 、R 4 R is R 5 Is independently methyl or ethyl.
Preferably, the method for preparing carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte comprises the following steps of (2) and (b) wherein the molar ratio of the compound containing the monoanhydride functional group to glucose units in the A product is 0.1:1-10:1; the compound containing the monoanhydride functional group comprises the following structural formula:
preferably, the preparation method of the carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte comprises the following steps of (1) and (b) wherein the mass ratio of the high molecular polymer to cellulose in the A product is 0.1:1-10:1; the high molecular polymer is any combination of one or more of polyvinyl alcohol, polyethylene glycol, polyacrylamide, polymethyl methacrylate, polyethyl methacrylate, polyhydroxyethyl methacrylate or polyacrylonitrile.
Preferably, the method for preparing carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte comprises the step (3) wherein the molar ratio of the compound containing the polyanhydride functional group to glucose units in the A product is 0.1:1-10:1; the compound containing the polyanhydride functional group comprises the following structural formula:
preferably, the preparation method of the carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte comprises one or a combination of any more of zinc chloride, zinc sulfate, zinc acetate, zinc nitrate, zinc tetrafluoroborate, zinc trifluoromethane sulfonate, zinc bistrifluoro sulfimide or zinc bistrifluorosulfimide.
A hydrogel electrolyte prepared by the foregoing method.
Use of a hydrogel electrolyte prepared by the method described above in a zinc ion hybrid capacitor.
When the electrolyte is applied, the negative electrode part of the water system ZIHCs directly adopts zinc foil which is stable to water, and is different from the selection of the conventional negative electrode material of the lithium ion or sodium ion mixed capacitor at present. The reason is that lithium metal or sodium metal is very active, and is reacted vigorously when meeting water, so that the safety risk is brought, and the lithium metal or sodium metal can not be directly used as the negative electrode material of the water-based lithium ion or sodium ion hybrid capacitor. In addition, the aqueous ZIHCs gel electrolyte designed by the invention is designed for aqueous ZIHCs and is not suitable for a conventional aqueous lithium ion or sodium ion mixed capacitor.
The beneficial effects of the invention are that
The water system ZIHCs provided by the invention adopts organic alkali/organic solvent/CO 2 The system dissolves cellulose, and the gel electrolyte with good electrochemical property and mechanical property is prepared by directly taking cellulose as a raw material, and in the preparation process of the material, organic alkali not only forms a part of a cellulose dissolution system to play a role in activating and dissolving cellulose, but also serves as a catalyst when a monoanhydride compound reacts with hydroxyl on cellulose, so that the reaction efficiency is greatly improved.
On the basis, the cellulose-based hydrogel network rich in carboxyl is constructed by adding the polyanhydride-containing compound for chemical crosslinking, replacing and soaking zinc salt electrolyte by a solvent, and utilizing chemical crosslinking, physical crosslinking, ionic crosslinking and other modes. On one hand, the addition of the polymer improves the mechanical property and the electrochemical property of the gel electrolyte, and provides possibility for flexible ZIHCs devices; on the other hand, carboxylated cellulose-based gel electrolytes rich in carboxyl groups can be used in Zn 2+ The electric field is homogenized in the deposition and stripping processes, so that the zinc dendrite is inhibited, and the circulation stability of the water system ZIHCs device is improved.
It is noted that when the method of the present invention is carried out, it is necessary to react the cellulose solution with the compound having a monoanhydride functional group according to the steps, to react the hydroxyl active sites on the cellulose, and then to add the compound having a polyanhydride functional group, so that the carboxylated cellulose-based gel can be prepared only in this way.
Drawings
FIG. 1 is a flow chart of the carboxylated cellulose based hydrogel synthesis of the present invention.
FIG. 2 is an optical photograph of the hydrogels prepared in examples 1 and 2 according to the present invention, from which it can be seen that example 2 shrinks significantly after soaking in 2M aqueous zinc sulfate solution compared to before not soaking, demonstrating that Zn 2+ Ionic crosslinking occurs in the gel.
FIG. 3 is a mechanical tensile diagram of the hydrogels of examples 1 and 2 of the present invention, from which it can be seen that example 1 is a hydrogel that has not been soaked in 2M aqueous zinc sulfate solution, and has a tensile strength of 20kPa and an elongation at break of 706%; example 2 was a 2M aqueous zinc sulfate solution having a tensile strength of 220kPa and an elongation at break of 908%. The method shows that the zinc sulfate electrolyte enters and is subjected to ionic crosslinking with the carboxylated cellulose-based hydrogel designed by the invention, so that the strength of the gel can be greatly improved, the toughness of the gel can be improved, and the subsequent assembly ZIHCs and the flexible application of the gel can be completely satisfied.
FIG. 4 shows CV curves (5,10,20, 50, 100 and 200 mVs) of the gel electrolyte of the present invention at different scan rates -1 ). As can be seen from fig. 4, the CV curve shows a symmetric circulation An Fuan characteristic and has good stability in the operating voltage of 0.2-1.8V, but the gel electrolyte of the invention has a change in ion diffusion control transport with an increase in scanning rate, and the CV curve gradually deviates from a rectangle.
FIG. 5 shows that the gel electrolyte of the invention has a charge-discharge current density of 0.25-20.0Ag in the range of 0.2-1.8V -1 The GCD curve of the gel electrolyte of the present invention is approximately symmetrical triangular when it is used, and shows good capacitance characteristics and high charge efficiency, which is typical of the electric double layer behavior. At 0.25, 0.5, 1, 2, 5,10, 15 and 20Ag -1 At current densities of 284.0, 253.4, 227.9, 200.8, 155.0, 116.9, 89.1 and 63.8Fg, respectively -1 。
FIG. 6 shows the zinc test of the gel electrolyte of the present invention at various current densities as the current density increases from 0.1 to 2.0mAcm -2 The polarization voltage remains below 150 mV. A stable zinc deposition behaviour was confirmed.
FIG. 7 shows the gel electrolyte of the present invention at a current density of 1.0mAcm -2 In the case of (2) a Zn symmetric battery test was used, each cycle lasting for 2 hours, revealing the cycling stability of the metallic zinc foil in the gel electrolyte of the invention. In the electrolyte of example 3, the Zn battery was short-circuited rapidly after 172 hours of cycling. In the electrolyte of example 4, the Zn battery was short-circuited rapidly after 67 hours of cycling. Notably, the Zn battery of the hydrogel electrolyte of the present invention is stable over 2000 hours of cycling without shorting or shortingVoltage polarization, which indicates that the hydrogel electrolyte of the present invention has great promise in ZHSCs.
FIG. 8 shows the gel electrolyte assembled soft pack ZIHCs of the present invention at 5Ag -1 Under the current density, the capacities of different bending angles are sequentially bent by 0 degree, 45 degrees, 90 degrees and 180 degrees, and the inserted picture is a soft package ZIHCs bending optical picture, and the capacity still keeps 88% of the initial capacity in the whole process, so that the gel electrolyte has good bending resistance.
FIG. 9 shows that the gel electrolyte assembled soft pack ZIHCs of the present invention can sustain about 1.27V (initial voltage 1.8V) after 260 hours of self-discharge at a self-discharge rate of 2.03mVh -1 The gel electrolyte has excellent self-discharge resistance and can effectively inhibit internal parasitic reaction.
Fig. 10 shows that the gel electrolyte provided by the invention is assembled into a soft package ZIHCs to light an LED lamp, and has good practical application prospect.
FIG. 11 shows that the gel electrolyte provided by the invention is assembled into soft packages ZIHCs, one ZIHCs has a rated voltage of 1.6V, and 2 soft packages ZIHCs are connected in series to supply power for a 3V timer, so that the power can be continuously supplied for more than 15 hours, and the gel electrolyte provided by the invention has a huge practical application prospect.
FIG. 12 shows the gel electrolyte assembly button ZIHCs of the present invention at 5Ag -1 The current density cycled 41000 turns while still maintaining 99.13% capacity and 99.45% coulombic efficiency, the inset shows 10 GCD turns before and 10 GCD turns after cycling. The gel electrolysis of the present invention exhibits ultra-long cycling stability.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Embodiments of the invention
Inventive example 1
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 Reacting for 3h under heating in 50 ℃ oil bath with magnetic stirring to obtain3% by weight of cotton pulp cellulose solution.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
Inventive example 2
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The mixture was reacted for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% cellulose solution as a cotton pulp.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 2M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Example 3 of the invention
(1) 3g of polyvinyl alcohol was dissolved in 57mL of pure water, stirred at 80℃for 3 hours, poured into a mold, and frozen and thawed twice to obtain a polyvinyl alcohol hydrogel.
(2) And (3) soaking the polyvinyl alcohol hydrogel in a 2M zinc sulfate aqueous solution for 24 hours to obtain the polyvinyl alcohol hydrogel electrolyte.
Inventive example 4
(1) Directly soaking commercial glass fiber diaphragm in 2M zinc sulfate to obtain glass fiber diaphragm electrolyte
Inventive example 5
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The mixture was reacted for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% cellulose solution as a cotton pulp.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 1M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Inventive example 6
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 Heating in 50 deg.C oil bathThe reaction was carried out for 3 hours with magnetic stirring to prepare a 3wt% cotton pulp cellulose solution.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 1.5M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Inventive example 7
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The mixture was reacted for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% cellulose solution as a cotton pulp.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 2.5M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Inventive example 8
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The mixture was reacted for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% cellulose solution as a cotton pulp.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 3M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
The hydrogels were soaked with zinc sulfate salts of different concentrations, and the ionic conductivity, mechanical strength and swelling ratio of the gel electrolytes were tested, and the results are shown in table 1.
TABLE 1
Inventive example 9
(1) 1.0g of cotton pulp cellulose and 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in cotton pulp cellulose is 1:1) 29.39gDMSO was charged into the reactor with 1.0MPaCO 2 The mixture was reacted for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% cellulose solution as a cotton pulp.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 2M zinc chloride aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Example 10 of the invention
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The mixture was reacted for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% cellulose solution as a cotton pulp.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 2M zinc triflate aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Inventive example 11
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The mixture was reacted for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% cellulose solution as a cotton pulp.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 2M zinc tetrafluoroborate aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Example 12 of the invention
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The mixture was reacted for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% cellulose solution as a cotton pulp.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 2M zinc nitrate aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Inventive example 13
(1) 1.0g of cotton pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the cotton pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The mixture was reacted for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% cellulose solution as a cotton pulp.
(2) 20g of the 3wt% cotton pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the cotton pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the cotton pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the cotton pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the cotton pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel.
(4) And soaking the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel in a 2M zinc acetate aqueous solution for 24 hours to obtain the carboxylated cotton pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
The hydrogel was soaked with 2M zinc salt of no kind, and the ionic conductivity, mechanical strength and swelling ratio of the gel electrolyte were measured, and the results are shown in table 2.
TABLE 2
Inventive example 14
(1) 1.0g of microcrystalline cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in microcrystalline cellulose: 1:1) and 29.39g of DMSO were charged into a reaction vessel with 1.0MPaCO 2 The reaction was carried out at 50℃under heating in an oil bath for 3 hours with magnetic stirring to prepare a 3% by weight microcrystalline cellulose solution.
(2) 20g of the 3wt% microcrystalline cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the microcrystalline cellulose solution to the microcrystalline cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the microcrystalline cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, cooling is carried out to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the microcrystalline cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould and reacted for 5 hours at 80 ℃ to obtain gel, thus obtaining the microcrystalline cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And replacing the microcrystalline cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated microcrystalline cellulose/polyvinyl alcohol hydrogel.
(4) And immersing the carboxylated microcrystalline cellulose/polyvinyl alcohol hydrogel in a 2M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated microcrystalline cellulose/polyvinyl alcohol hydrogel electrolyte.
Example 15 of the invention
(1) 1.0g of alpha-cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the alpha-cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The reaction was carried out at 50℃under heating in an oil bath for 3 hours with magnetic stirring to prepare a 3% by weight solution of alpha-cellulose.
(2) 20g of 3wt% alpha-cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the alpha-cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the alpha-cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the alpha-cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the alpha-cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the alpha-cellulosic ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated alpha-cellulose/polyvinyl alcohol hydrogel.
(4) And immersing the carboxylated alpha-cellulose/polyvinyl alcohol hydrogel in a 2M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated alpha-cellulose/polyvinyl alcohol hydrogel electrolyte.
Inventive example 16
(1) 1.0g of bamboo pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the bamboo pulp cellulose is 1:1) and 29.39g of DMSO were charged into a reaction vessel with 1.0MPaCO 2 The reaction was carried out at 50℃under heating in an oil bath for 3 hours with magnetic stirring to prepare a 3% by weight solution of cellulose in bamboo pulp.
(2) 20g of the 3wt% bamboo pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the bamboo pulp cellulose glucose unit is 1:1) is added, stirring is carried out at 80 ℃ for 3 hours, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the bamboo pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the mixture, then the mixture is cooled to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the bamboo pulp cellulose glucose unit is 1:1) is added dropwise, and then the mixture is poured into a mould for reacting at 80 ℃ for 5 hours to obtain gel, thus obtaining the bamboo pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And (3) replacing the bamboo pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated bamboo pulp cellulose/polyvinyl alcohol hydrogel.
(4) And immersing the carboxylated bamboo pulp cellulose/polyvinyl alcohol hydrogel in a 2M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated bamboo pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Inventive example 17
(1) 1.0g of wood pulp cellulose, 2.31g of tetramethylguanidine (the ratio of the number of moles of tetramethylguanidine to the number of moles of hydroxyl groups in the wood pulp cellulose is 1:1) and 29.39g of DMSO are charged into a reaction vessel with 1.0MPaCO 2 The mixture was reacted at 50℃for 3 hours under heating in an oil bath with magnetic stirring to prepare a 3% by weight cellulose solution of wood pulp.
(2) 20g of the 3wt% wood pulp cellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the wood pulp cellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the wood pulp cellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, then the temperature is reduced to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the wood pulp cellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould to react for 5 hours at 80 ℃ to obtain gel, thus obtaining the wood pulp cellulose ionic liquid/polyvinyl alcohol organogel.
(3) And replacing the wood pulp cellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated wood pulp cellulose/polyvinyl alcohol hydrogel.
(4) And immersing the carboxylated wood pulp cellulose/polyvinyl alcohol hydrogel in a 2M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated wood pulp cellulose/polyvinyl alcohol hydrogel electrolyte.
Inventive example 18
(1) A reaction vessel was charged with 1.0g of lignocellulose, 2.31g of tetramethylguanidine (molar ratio of tetramethylguanidine to hydroxyl groups in lignocellulose: 1:1), and 29.39g of DMSO with 1.0MPaCO 2 The reaction was carried out for 3 hours at 50℃under heating in an oil bath with magnetic stirring to prepare a 3wt% lignocellulose solution.
(2) 20g of the 3wt% lignocellulose solution is taken in a two-mouth bottle, succinic anhydride (the mol ratio of the succinic anhydride to the lignocellulose glucose unit is 1:1) is added, stirring reaction is carried out for 3 hours at 80 ℃, then polyvinyl alcohol (the mass ratio of the polyvinyl alcohol to the lignocellulose is 1:1) is added, stirring is carried out to completely dissolve the solution, cooling is carried out to 0 ℃ in an ice bath, pyromellitic anhydride (the mol ratio of the pyromellitic anhydride to the lignocellulose glucose unit is 1:1) is dropwise added, and then the mixture is poured into a mould and reacted for 5 hours at 80 ℃ to obtain gel, thus obtaining the lignocellulose ionic liquid/polyvinyl alcohol organogel.
(3) And replacing the lignocellulose ionic liquid/polyvinyl alcohol organogel with pure water to be neutral to obtain carboxylated lignocellulose/polyvinyl alcohol hydrogel.
(4) And immersing the carboxylated lignocellulose/polyvinyl alcohol hydrogel in a 2M zinc sulfate aqueous solution for 24 hours to obtain the carboxylated lignocellulose/polyvinyl alcohol hydrogel electrolyte.
Different kinds of cellulose were prepared to prepare hydrogels, which were soaked with 2M zinc sulfate salt, and the ionic conductivity, mechanical strength and swelling ratio of the gel electrolyte were tested, and the results are shown in Table 3.
TABLE 3 Table 3
Inventive example 19
(1) 2.0g of microcrystalline cellulose, 4.6g of 1, 5-diazabicyclo [4.3.0 g]Charging 0.1MPaCO into a reaction kettle with non-5-alkene and 31.77g N-methyl pyrrolidone 2 The mixture was reacted at 100℃for 12 hours under heating in an oil bath with magnetic stirring to prepare a microcrystalline cellulose solution.
(2) Taking 20g of the microcrystalline cellulose solution, adding maleic anhydride (the molar ratio of the microcrystalline cellulose solution to the microcrystalline cellulose glucose unit is 0.1:1) into a two-mouth bottle, stirring at 20 ℃ for reaction for 24 hours, adding polyethylene glycol (the mass ratio of the polyethylene glycol to the microcrystalline cellulose is 0.1:1), stirring to completely dissolve the microcrystalline cellulose solution, cooling to 0 ℃ in an ice bath, dropwise adding pyromellitic anhydride (the molar ratio of the pyromellitic anhydride to the microcrystalline cellulose glucose unit is 0.1:1), pouring into a mould, and reacting at 20 ℃ for 24 hours to obtain the gel.
(3) The microcrystalline cellulose ionic liquid/polyethylene glycol organogel is replaced by pure water for 2 times, and finally is soaked in 0.1M zinc chloride aqueous solution for 48 hours, so that carboxylated microcrystalline cellulose/polyethylene glycol hydrogel electrolyte is obtained.
Example 20 of the invention
(1) 2.0g of alpha-cellulose, 5.64g of 1, 8-diazabicyclo undec-7-ene and 15.73g of N, N-dimethylformamide are charged into a reaction vessel with 15MPaCO 2 The reaction was carried out for 24 hours at 50℃under heating in an oil bath with magnetic stirring to prepare an alpha-cellulose solution.
(2) Taking 20g of the cellulose solution in a two-mouth bottle, adding phthalic anhydride (the molar ratio of the phthalic anhydride to the alpha-cellulose glucose unit is 5:1), stirring at 60 ℃ for reaction for 12 hours, adding polyacrylamide (the mass ratio of the polyacrylamide to the alpha-cellulose is 5:1), stirring to completely dissolve the cellulose solution, cooling to-15 ℃ in an ice bath, dropwise adding pyromellitic anhydride (the molar ratio of the pyromellitic anhydride to the alpha-cellulose glucose unit is 5:1), pouring into a mould, and reacting at 60 ℃ for 12 hours to obtain the gel, thus obtaining the alpha-cellulosic ionic liquid/polyacrylamide organogel.
(3) The alpha-cellulose ionic liquid/polyacrylamide organogel is replaced by pure water for 5 times, and finally 5M zinc triflate aqueous solution is soaked for 24 hours, so that carboxylated alpha-cellulose/polyacrylamide hydrogel electrolyte is obtained.
Inventive example 21
(1) 1.0g of bamboo pulp cellulose, 2.577g of 1,5, 7-triazabicyclo [4.4.0]The dec-5-alkene, 28.941g2-azabicyclo ketone and 1.0MPaCO are filled into a reaction kettle 2 The reaction was carried out for 1 hour under heating in an oil bath at 150℃with magnetic stirring to prepare a cellulose solution of bamboo pulp.
(2) 20g of the bamboo pulp cellulose solution is taken in a two-mouth bottle, itaconic anhydride (the molar ratio of the itaconic anhydride to the bamboo pulp cellulose glucose unit is 10:1) is added, stirring reaction is carried out for 1h at 100 ℃, polymethyl methacrylate (the mass ratio of polymethyl methacrylate to the bamboo pulp cellulose is 10:1) is added, stirring is carried out for complete dissolution, cooling is carried out under ice bath to 5 ℃, pyromellitic anhydride (the molar ratio of the pyromellitic anhydride to the bamboo pulp cellulose glucose unit is 10:1) is added dropwise, and then the mixture is poured into a mould for reaction for 1h at 100 ℃ to obtain gel. To obtain the bamboo pulp cellulosic ionic liquid/polymethyl methacrylate organogel.
(3) The bamboo pulp cellulose ionic liquid/polymethyl methacrylate organic gel is replaced by pure water for 10 times, and finally 10M zinc tetrafluoroborate aqueous solution is soaked for 1h, so that carboxylated bamboo pulp cellulose/polymethyl methacrylate hydrogel electrolyte is obtained.
While the invention has been described with reference to the preferred embodiments, it should be understood that the invention is not limited to the embodiments described above, but is intended to cover modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A preparation of carboxylated cellulose-based flexible zinc dendrite resistant hydrogel electrolyte, comprising the steps of:
(1) Dissolving cellulose in organic base/CO 2 Organic solvent system; wherein the organic alkali in the system has a mass concentration of 0.1-50%, the dissolved cellulose has a mass concentration of 0.1-30%, and the CO is charged 2 The pressure of the solution is 0.1-15MPa, the dissolution temperature is 50-150 ℃ and the dissolution time is 1-24h; then adding high molecular polymer, and continuing stirring to dissolve the high molecular polymer to obtain a product A;
(2) Firstly, adding a compound containing a monoanhydride functional group into the product A, and stirring at 20-100 ℃ to carry out derivatization reaction for 1-24 hours to obtain a product B;
(3) Cooling the product B to-20-20 ℃, then adding a compound containing polyanhydride functional groups, mixing and stirring uniformly, pouring into a mould, and reacting for 1-24h at 20-100 ℃ to obtain a product C;
(4) Displacing the C product with pure water for 1-10 times to neutrality to obtain carboxylated cellulose-based hydrogel;
(5) And soaking the carboxylated cellulose-based hydrogel in 0.1-10mol/L zinc-containing electrolyte salt solution for 1-48h to obtain the carboxylated cellulose-based flexible zinc dendrite resisting hydrogel electrolyte.
2. The preparation of carboxylated cellulose based flexible zinc dendrite resistant hydrogel electrolyte according to claim 1, characterized in that: the cellulose is microcrystalline cellulose, alpha-cellulose or any combination of one or more plant cellulose separated from cotton, wood pulp, bamboo pulp and agriculture and forestry lignocellulose waste.
3. The preparation of carboxylated cellulose based flexible zinc dendrite resistant hydrogel electrolyte according to claim 1, characterized in that: the organic solvent is one or any combination of a plurality of dimethyl sulfoxide, N-methyl pyrrolidone, tetramethyl urea, tetraethyl urea, N-dimethyl imidazolinone, N-dimethyl formamide, N-diethyl acetamide, pyrrolidone, 2-azahexacyclic ketone, N-dimethyl propenyl urea or sulfolane.
4. The preparation of carboxylated cellulose based flexible zinc dendrite resistant hydrogel electrolyte according to claim 1, wherein the organic base has an acid-base dissociation constant of greater than 20 and has the following structural characteristics:
wherein n=1 or 2; r is independent hydrogen or alkyl with 1-6 carbon atoms; r is R 1 、R 2 、R 3 、R 4 R is R 5 Is independently methyl or ethyl.
5. The preparation of carboxylated cellulose based flexible zinc dendrite resistant hydrogel electrolyte according to claim 1, characterized in that: the molar ratio of the compound containing the monoanhydride functional group in the step (2) to the glucose unit in the A product is 0.1:1-10:1; the compound containing the monoanhydride functional group comprises the following structural formula:
6. the preparation of carboxylated cellulose based flexible zinc dendrite resistant hydrogel electrolyte according to claim 1, characterized in that: the mass ratio of the high molecular polymer to the cellulose in the A product in the step (1) is 0.1:1-10:1; the high molecular polymer is any combination of one or more of polyvinyl alcohol, polyethylene glycol, polyacrylamide, polymethyl methacrylate, polyethyl methacrylate, polyhydroxyethyl methacrylate or polyacrylonitrile.
7. The preparation of carboxylated cellulose based flexible zinc dendrite resistant hydrogel electrolyte according to claim 1, characterized in that: the molar ratio of the compound containing the polyanhydride functional group in the step (3) to glucose units in the A product is 0.1:1-10:1; the compound containing the polyanhydride functional group comprises the following structural formula:
8. the preparation of carboxylated cellulose based flexible zinc dendrite resistant hydrogel electrolyte according to claim 1, characterized in that: the zinc-containing electrolyte salt comprises one or a combination of more than one of zinc chloride, zinc sulfate, zinc acetate, zinc nitrate, zinc tetrafluoroborate, zinc trifluoromethane sulfonate, zinc bistrifluoro sulfimide or zinc bistrifluorosulfimide.
9. A hydrogel electrolyte prepared according to the method of any one of claims 1-8.
10. Use of a hydrogel electrolyte prepared according to the method of any one of claims 1-8 in a zinc ion hybrid capacitor.
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