CN112898596A - Hydrogel electrolyte and super capacitor thereof - Google Patents
Hydrogel electrolyte and super capacitor thereof Download PDFInfo
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- CN112898596A CN112898596A CN202110082991.2A CN202110082991A CN112898596A CN 112898596 A CN112898596 A CN 112898596A CN 202110082991 A CN202110082991 A CN 202110082991A CN 112898596 A CN112898596 A CN 112898596A
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- zinc
- hydrogel electrolyte
- chloride
- electrolyte
- hydrogel
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 59
- 239000000017 hydrogel Substances 0.000 title claims abstract description 55
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003751 zinc Chemical class 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 18
- 230000000379 polymerizing effect Effects 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 11
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000661 sodium alginate Substances 0.000 claims description 10
- 235000010413 sodium alginate Nutrition 0.000 claims description 10
- 229940005550 sodium alginate Drugs 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011592 zinc chloride Substances 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- -1 3-sulfopropyl tetradecyl Chemical group 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 229960003237 betaine Drugs 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229920002101 Chitin Polymers 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 4
- UBLOJEHIINPTTG-UHFFFAOYSA-J disodium;zinc;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Zn+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UBLOJEHIINPTTG-UHFFFAOYSA-J 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 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
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- WPZSJJJTNREFSV-UHFFFAOYSA-N [Zn].[O-][N+]1=CC=CC=C1S Chemical compound [Zn].[O-][N+]1=CC=CC=C1S WPZSJJJTNREFSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000011245 gel electrolyte Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- QEORIOGPVTWFMH-UHFFFAOYSA-N zinc;bis(trifluoromethylsulfonyl)azanide Chemical compound [Zn+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QEORIOGPVTWFMH-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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Dispersion Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a hydrogel electrolyte and a supercapacitor thereof, wherein the hydrogel electrolyte polymerizes a polymeric monomer containing the polymeric monomer, a high molecular polymer and the polymeric monomer in water to form a hydrogel electrolyte polymer precursor under the action of an initiator, and then the hydrogel electrolyte polymer precursor is soaked in an aqueous solution containing inorganic salt and zinc salt for crosslinking the high molecular polymer; the super capacitor has excellent mechanical strength and flexibility, a diaphragm does not need to be added when the super capacitor is assembled, the manufacturing process is simplified, the voltage application range of the capacitor is widened, and the super capacitor has practical application value.
Description
Technical Field
The invention relates to the field of energy storage, in particular to a hydrogel electrolyte and a super capacitor prepared from the hydrogel electrolyte.
Background
In recent years, the personalized demand of people for electronic products has driven the emergence and development of flexible electronic technology, which changes our thinking way and life way to some extent and is regarded as one of the most competitive and development promising technologies in the 21 st century. With the development and progress of flexible electronic technology, related flexible electronic products have appeared in the fields of flexible display, implantable medical treatment, portability, wearable and the like, and common traditional electronic products are different, and the flexible electronic products have various novel characteristics such as flexibility, folding, flexibility, shape deformation and the like. Therefore, an energy supply system for flexible electronic products, namely a flexible energy storage device, is produced. The flexible super capacitor is used as an important component of a flexible energy storage device, has a series of advantages of high charging and discharging speed, high power density, long cycle life and the like, and can ensure continuous and stable energy output under the condition of mechanical deformation, so that the flexible super capacitor can be embedded into an object which is dynamically deformed and has any shape to be used as a flexible power supply, which cannot be realized by a traditional power supply.
The electrostatic discharge of zinc ions in the electrolyte of the zinc ion hybrid supercapacitor has the advantages of safety, environmental protection, low cost and the like, and is a promising wearable device. The zinc anode has higher theoretical capacity (823mAh g)-1) And a lower redox potential (-0.76V relative to a standard hydrogen electrode). The zinc ion hybrid supercapacitor combines the advantages of both supercapacitors and batteries, and has become an area of research of great interest in recent years due to its high energy and power densities.
However, the existing energy storage materials generally adopt gel electrolytes, the gel electrolytes comprise hydrogel electrolytes and organic gel electrolytes, and the organic gel electrolytes have the advantages of high energy density, but poor flexibility, toxicity and hidden danger; hydrogel electrolytes solve the toxicity problem, but suffer from poor flexibility and low energy density, and are not suitable for use in cold environments. Therefore, there is a need to improve hydrogel properties to meet practical applications.
Disclosure of Invention
In view of the above, one of the objectives of the present invention is to provide a hydrogel electrolyte, which is prepared by soaking a polymer in an aqueous solution containing inorganic salts and zinc salts of a cross-linked high molecular polymer, and has the characteristics of flexibility, folding and wide voltage window; the invention also aims to provide the super capacitor, which does not need to add a diaphragm, simplifies the manufacturing process and has high energy density.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a hydrogel electrolyte prepared by the method of: under the action of an initiator, polymerizing a polymerizing monomer containing a polymerizing monomer, a high molecular polymer and water to form a hydrogel electrolyte polymer precursor, and then soaking the hydrogel electrolyte polymer precursor in an aqueous solution containing inorganic salt and zinc salt for crosslinking the high molecular polymer.
In the invention, the mass of the zinc salt in the aqueous solution is larger than that of the solvent water.
In the invention, the polymerization monomer is at least one of N, N-dimethylacrylamide, acrylamide, 3-sulfopropyl tetradecyl dimethyl betaine, 3-sulfopropyl hexadecyl dimethyl betaine, acrylic acid and 2-acrylamido-2-methyl-1-propane sulfonic acid; the high molecular polymer is one of carboxymethyl cellulose, cellulose acetate butyrate, cellulose powder, chitin and sodium alginate; the inorganic salt for crosslinking the high molecular polymer is one of zinc chloride, calcium chloride, aluminum chloride, cerium nitrate, magnesium chloride, copper chloride and silver chloride; the zinc salt is one of zinc chloride, zinc sulfate, zinc tetrafluoroborate, 2-mercaptopyridine-N-oxide zinc salt, zinc trifluoromethanesulfonate, disodium zinc ethylenediamine tetraacetate, zinc acetylacetonate and bis (trifluoromethylsulfonyl) imide zinc; the initiator is ammonium persulfate.
In the invention, the mass ratio of the polymerized monomer to the high molecular polymer to the water is 30:1:100-30:3:200 of a carrier; more preferably, the mass ratio of the polymerized monomer, the high molecular polymer and the water is 30: 1.5: 150.
in the invention, the concentration of inorganic salt in the aqueous solution is 0.1-1M; the concentration of the zinc salt is 7.5-12M; more preferably, the aqueous solution has an inorganic salt concentration of 0.1M and a zinc salt concentration of 10M.
In the invention, the mass ratio is 4: 30: 6000: 30: 300 respectively taking N, N-dimethylacrylamide, ammonium persulfate, acrylamide, deionized water and sodium alginate, stirring and dissolving, and heating and polymerizing in an oven; and soaking the polymerized hydrogel electrolyte precursor in a mixed solution of 10M zinc chloride and 0.1M calcium chloride for 1 hour to obtain the hydrogel electrolyte.
2. The electrolyte of the super capacitor is the prepared hydrogel electrolyte.
In the invention, the cathode of the super capacitor is a zinc sheet, the anode takes titanium foil as an anode current collector, and the current collector is coated with active substances: conductive carbon black: the mass ratio of the adhesive polyvinylidene fluoride is 8: 1:1, substance (b).
In the invention, the active substance is activated carbon.
In the invention, the positive electrode is prepared by the following method: the positive electrode was prepared by mixing 80 wt% of activated carbon, 10 wt% of carbon black and 10 wt% of polyvinylidene fluoride in an N-methylpyrrolidone solvent, and then coating the mixture on a titanium foil, followed by drying in a constant temperature oven at 80 ℃.
The invention has the beneficial effects that: the invention discloses a hydrogel electrolyte, which adopts water as a solvent, has good safety and no toxicity, obtains excellent mechanical strength and flexibility by soaking a polymer in an aqueous solution containing inorganic salt and zinc salt of a cross-linked high-molecular polymer, and can widen the voltage application range of a capacitor; when the electrolyte is used for assembling the super capacitor, no diaphragm is required to be added, so that the manufacturing process is simplified; and the raw materials and the structure for preparing the super capacitor device are simple, the rechargeable capacitor which is low in cost and can be widely used can be realized at extremely low manufacturing cost, and the requirement of large-scale energy storage is met.
Solves the problems of poor flexibility, hidden danger, toxicity and extremely low energy density of the prior energy storage material. Meanwhile, the super capacitor can be charged and discharged in a voltage range of 0-2.1V, has a wide and stable voltage window, and is connected with a clock at-75 ℃ to find that the prepared super capacitor is not frozen at low temperature and continues to work.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a schematic diagram of calcium ion crosslinked sodium alginate;
FIG. 2 is a CV curve of a super capacitor with a voltage window of 0-2.1V;
FIG. 3 is a charging and discharging curve of the super capacitor, and the voltage window is 0-2.1V.
FIG. 4 shows the result of the supercapacitor communicating with the timepiece at a bend angle;
FIG. 5 shows the result of the supercapacitor communicating with the timepiece at a bend angle;
fig. 6 shows the result of the connection of the clock immediately after the supercapacitor was removed in the-75 ℃ freezer.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1 preparation of hydrogel electrolyte
A process for preparing the hydrogel electrolyte includes such steps as respectively preparing the monomer for polymerizing gel electrolyte, trigger, high-molecular polymer and water, stirring, heating to trigger polymerizing temp for full polymerization to obtain the precursor of gel electrolyte polymer, immersing the precursor of gel electrolyte polymer in the aqueous solution of inorganic salt and zinc salt containing cross-linked high-molecular polymer, which contains zinc salt whose mass is greater than that of solvent water, and high-concentration zinc ions to form water-in-salt electrolyte.
In the present invention, the gel electrolyte polymerization monomer is preferably at least one of acrylamide, 3-sulfopropyltetradecyldimethyl betaine, 3-sulfopropylhexadecyldimethylbetaine, acrylic acid, and 2-acrylamido-2-methyl-1-propanesulfonic acid.
The high molecular polymer is preferably one of carboxymethyl cellulose, cellulose acetate butyrate, cellulose powder, chitin and sodium alginate.
The inorganic salt of the crosslinked high molecular polymer is preferably one of zinc chloride, calcium chloride, aluminum chloride, cerium nitrate, magnesium chloride, copper chloride, and silver chloride.
The zinc salt in the soaking solution is preferably one of zinc chloride, zinc sulfate, zinc tetrafluoroborate, zinc 2-mercaptopyridine-N-oxide, zinc trifluoromethanesulfonate, disodium zinc ethylenediaminetetraacetate, zinc acetylacetonate and zinc bis (trifluoromethylsulfonyl) imide.
Taking calcium chloride cross-linked sodium alginate as an example, the schematic diagram after cross-linking is shown in figure 1. The mechanical property of the hydrogel electrolyte can be improved through crosslinking.
Scheme 1: the preparation method of the hydrogel electrolyte comprises the following specific steps: respectively taking 4mg of N, N-dimethylacrylamide, 30mg of ammonium persulfate, 6g of acrylamide, 30ml of deionized water and 0.3g of sodium alginate, stirring for dissolving, and then heating and polymerizing in an oven for 40 minutes; and soaking the polymerized hydrogel electrolyte precursor in a mixed solution of 10M zinc chloride and 0.1M calcium chloride for 1 hour to obtain the hydrogel electrolyte.
Scheme 2: the preparation method of the hydrogel electrolyte comprises the following specific steps: respectively taking 4mg of N, N-dimethylacrylamide, 30mg of ammonium persulfate, 6g of 3-sulfopropyltetradecyldimethyl betaine, 30ml of deionized water and 0.3g of cellulose acetate butyrate, stirring and dissolving, and then heating and polymerizing in an oven for 60 minutes; and soaking the polymerized hydrogel electrolyte precursor in a mixed solution of 10M zinc tetrafluoroborate and 0.1M aluminum chloride for 1 hour to obtain the hydrogel electrolyte.
Scheme 3: the preparation method of the hydrogel electrolyte comprises the following specific steps: the preparation method of the gel electrolyte comprises the steps of stirring and dissolving 4mg of N, N-dimethylacrylamide, 30mg of ammonium persulfate, 6g of acrylamide, 30ml of deionized water and 0.3g of carboxymethyl cellulose, and then heating and polymerizing in an oven for 90 minutes; and soaking the polymerized hydrogel electrolyte in a mixed solution of 10M of bis (trifluoromethylsulfonyl) imide zinc and 0.1M of cerium nitrate for 1 hour to obtain the hydrogel electrolyte.
Scheme 4: the preparation method of the hydrogel electrolyte comprises the following specific steps: 4mg of N, N-dimethylacrylamide, 30mg of ammonium persulfate, 6g of acrylic acid, 30ml of deionized water and 0.3g of carboxymethyl cellulose, stirring and dissolving, and then heating and polymerizing in an oven for 120 minutes; and soaking the polymerized hydrogel electrolyte in a mixed solution of 10M 2-mercaptopyridine-N-oxide zinc salt and 0.1M magnesium chloride for 1 hour to obtain the hydrogel electrolyte.
Scheme 5: the preparation method of the hydrogel electrolyte comprises the following specific steps: 4mg of N, N-dimethylacrylamide, 30mg of ammonium persulfate, 6g of 2-acrylamido-2-methyl-1-propanesulfonic acid, 30ml of deionized water and 0.3g of chitin are stirred and dissolved, and then heated and polymerized in an oven for 150 minutes; and soaking the polymerized hydrogel electrolyte in a mixed solution of 10M zinc sulfate and 0.1M magnesium chloride for 1 hour to obtain the hydrogel electrolyte.
Scheme 6: the preparation method of the hydrogel electrolyte comprises the following specific steps: 4mg of N, N-dimethylacrylamide, 30mg of ammonium persulfate, 6g of acrylamide, 30ml of deionized water and 0.3g of sodium alginate, stirring and dissolving, and then heating and polymerizing in an oven for 180 minutes; and soaking the polymerized hydrogel electrolyte in a mixed solution of 10M zinc trifluoromethanesulfonate and 0.1M silver chloride for 1 hour to obtain the hydrogel electrolyte.
Scheme 7: the preparation method of the hydrogel electrolyte comprises the following specific steps: 4mg of N, N-dimethylacrylamide, 30mg of ammonium persulfate, 6g of acrylamide, 30ml of deionized water and 0.3g of sodium alginate, stirring and dissolving, and then heating and polymerizing in an oven for 210 minutes; and soaking the polymerized hydrogel electrolyte in a mixed solution of 10M disodium-zinc ethylenediamine tetraacetate and 0.1M calcium chloride for 1 hour to obtain the hydrogel electrolyte.
Example 2 Flexible supercapacitor
The flexible super capacitor comprises an upper part, a middle part and a lower part, wherein the upper part is a zinc sheet as a negative electrode, the middle part is gel electrolyte, the lower part is a titanium foil as a positive current collector, and active substances are coated on the titanium foil current collector: conductive carbon black: the mass ratio of the adhesive polyvinylidene fluoride is 8: 1:1, wherein the active substance is activated carbon.
Preferably, the negative electrode is a zinc sheet with the length of 2cm and the width of 3 cm. The positive electrode was prepared by mixing 80 wt% of activated carbon, 10 wt% of carbon black, and 10 wt% of polyvinylidene fluoride in NMP solvent, then coating the mixture on a titanium foil, and drying in a constant temperature oven at 80 ℃.
The electrochemical performance measurement adopts CHI760E electrochemical workstation of Shanghai Hua company to perform CV curve test, the reference electrode and the counter electrode are connected with a zinc sheet, the positive current collector of the working electrode is connected with a zinc sheet, and the electrochemical test is performed at the scanning speed of 5mV/s-100mV/s to obtain a CV curve graph, and the result is shown in figure 2. The result shows that the CV curve of the super capacitor is symmetrical, has no obvious polarization phenomenon and has stable electrochemical performance at 0-2.1V.
The battery performance test adopts a CT2001A type battery tester of Wuhan blue electric company, and the capacity test of the battery is carried out under the current corresponding to 1A/-5A/g of the positive active material, and the result is shown in figure 3. The result shows that the specific capacity is high, and the specific capacity is about 130mAh/g at 1A/g, so that the method has practical value.
Fig. 4 and 5 show that the super capacitor manufactured by the invention is communicated with a clock under different bending angles and shows numbers. The result shows that the zinc ion super capacitor has good mechanical property and stable electrochemical property and can adapt to different bending angles.
The supercapacitor made according to the invention was frozen at-75 ℃ and then connected to a clock and generated electricity, the results are shown in fig. 6. The results show that the prepared supercapacitor can continue to work without freezing at low temperature.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A hydrogel electrolyte, wherein the hydrogel electrolyte is prepared by the following method: under the action of an initiator, polymerizing a polymerizing monomer containing a polymerizing monomer, a high molecular polymer and water to form a hydrogel electrolyte polymer precursor, and then soaking the hydrogel electrolyte polymer precursor in an aqueous solution containing inorganic salt and zinc salt for crosslinking the high molecular polymer.
2. The hydrogel electrolyte of claim 1, wherein: the mass of the zinc salt in the aqueous solution is larger than that of the solvent water.
3. The hydrogel electrolyte of claim 1, wherein: the polymerization monomer is at least one of N, N-dimethylacrylamide, acrylamide, 3-sulfopropyl tetradecyl dimethyl betaine, 3-sulfopropyl hexadecyl dimethyl betaine, acrylic acid and 2-acrylamido-2-methyl-1-propane sulfonic acid; the high molecular polymer is one of carboxymethyl cellulose, cellulose acetate butyrate, cellulose powder, chitin and sodium alginate; the inorganic salt for crosslinking the high molecular polymer is one of zinc chloride, calcium chloride, aluminum chloride, cerium nitrate, magnesium chloride, copper chloride and silver chloride; the zinc salt is one of zinc chloride, zinc sulfate, zinc tetrafluoroborate, 2-mercaptopyridine-N-oxide zinc salt, zinc trifluoromethanesulfonate, disodium zinc ethylenediamine tetraacetate, zinc acetylacetonate and bis (trifluoromethylsulfonyl) imide zinc; the initiator is ammonium persulfate.
4. The hydrogel electrolyte of claim 1, wherein: the mass ratio of the polymerized monomer to the high molecular polymer to the water is 30:1:100-30:3: 200.
5. The hydrogel electrolyte of claim 1, wherein: the concentration of inorganic salt in the aqueous solution is 0.1-1M; the concentration of zinc salt is more than 7.5-12M.
6. The hydrogel electrolyte of claim 1, wherein: according to the mass ratio of 4: 30: 6000: 30: 300 respectively taking N, N-dimethylacrylamide, ammonium persulfate, acrylamide, deionized water and sodium alginate, stirring and dissolving, and heating and polymerizing in an oven; and soaking the polymerized hydrogel electrolyte precursor in a mixed solution of 10M zinc chloride and 0.1M calcium chloride for 1 hour to obtain the hydrogel electrolyte.
7. A supercapacitor, characterized in that: the electrolyte of the super capacitor is the hydrogel electrolyte prepared by any one of claims 1 to 5.
8. The ultracapacitor of claim 7, wherein: the cathode of the super capacitor is a zinc sheet, the anode takes titanium foil as an anode current collector, and active substances are coated on the current collector: conductive carbon black: the mass ratio of the adhesive polyvinylidene fluoride is 8: 1:1, substance (b).
9. The ultracapacitor of claim 8, wherein: the active substance is activated carbon.
10. The supercapacitor according to claim 8, wherein the positive electrode is prepared by a method comprising: the positive electrode was prepared by mixing 80 wt% of activated carbon, 10 wt% of carbon black and 10 wt% of polyvinylidene fluoride in an N-methylpyrrolidone solvent, and then coating the mixture on a titanium foil, followed by drying in a constant temperature oven at 80 ℃.
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| CN113745675B (en) * | 2021-09-07 | 2023-05-16 | 中新国际联合研究院 | Zinc electrode protected by negative framework hydrogel as modification layer and preparation method thereof |
| CN113851739B (en) * | 2021-10-25 | 2023-09-29 | 长春工业大学 | Preparation and application of gel electrolyte for antifreeze zinc-based battery |
| CN113851739A (en) * | 2021-10-25 | 2021-12-28 | 长春工业大学 | Preparation and application of gel electrolyte for anti-freezing zinc-based battery |
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| CN115331975B (en) * | 2022-09-08 | 2024-03-26 | 中国林业科学研究院林产化学工业研究所 | Integrated anti-freezing supercapacitor and preparation method thereof |
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