CN117175001A - Enhanced domain-limited zwitterionic gel electrolyte and preparation method and application thereof - Google Patents
Enhanced domain-limited zwitterionic gel electrolyte and preparation method and application thereof Download PDFInfo
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- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 12
- 150000003751 zinc Chemical class 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 8
- 229960001763 zinc sulfate Drugs 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- -1 polypropylene Polymers 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 2
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 229940117986 sulfobetaine Drugs 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims 2
- 229960003237 betaine Drugs 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 21
- 150000002500 ions Chemical class 0.000 abstract description 18
- 210000001787 dendrite Anatomy 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 6
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000009036 growth inhibition Effects 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000004134 energy conservation Methods 0.000 description 1
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- 230000037427 ion transport Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- WCEJONSMJDZUSV-UHFFFAOYSA-N trimethoxy(2-methylprop-1-enyl)silane Chemical compound CO[Si](OC)(OC)C=C(C)C WCEJONSMJDZUSV-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of electrochemical energy storage, and relates to an enhanced domain-limited amphoteric ion gel electrolyte, a preparation method and application thereof. The invention provides a zinc ion battery which is simple to operate and can be produced in a large scale, wherein electrolyte is prepared from an enhanced domain-limited amphoteric ion gel material, and the formula parameters of the electrolyte can be regulated and controlled by adjusting polymer monomers, cross-linking agents and initiators, so that the zinc ion battery is suitable for the requirements of different fields. The invention utilizes the action mechanisms of ionic conduction, gel stability, side reaction inhibition, dendrite growth inhibition and the like of the zwitterionic polymer monomer to obviously improve the performance and stability of the enhanced domain-limited zwitterionic gel electrolyte.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and relates to an enhanced domain-limited amphoteric ion gel electrolyte, a preparation method and application thereof.
Background
With the development of socioeconomic performance, batteries are becoming an important energy storage device, and there is an increasing demand in various fields. Zinc ion batteries have become an emerging battery technology due to the advantages of high specific capacity, low cost, environmental friendliness and the like. And as one of the core components of the zinc ion battery, the performance of the electrolyte directly determines the performance of the battery. However, conventional electrolytes still have some problems, and currently common electrolytes include organic electrolytes and inorganic electrolytes. The organic electrolyte has the defects of inflammability, volatility, short service life and the like; the disadvantages of poor conductivity, easy generation of precipitate and the like of the inorganic electrolyte limit the application of the inorganic electrolyte in zinc ion batteries. Therefore, improvement and improvement of the performance of the electrolyte are an important research direction.
In recent years, research and development of gel electrolyte materials have been advanced to a certain extent, so that performance indexes such as energy density, power density and cycle life of zinc ion batteries can be improved. Common materials such as polyvinyl alcohol and polyacrylamide have good water absorbability, but the materials have poor water retention property, low charge and discharge efficiency, are easily influenced by temperature and humidity, cannot inhibit side reactions and dendrite growth, and limit the application of the materials in zinc ion batteries.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides an enhanced domain-limited amphoteric ion gel electrolyte which solves the problems of poor mechanical property, low ion conductivity and the like of the electrolyte in the electrochemical energy storage field.
The aim of the invention can be achieved by the following technical scheme: an enhanced domain-limited zwitterionic gel electrolyte, the electrolyte raw materials comprise a porous support, a zwitterionic polymer monomer, a cross-linking agent, an initiator and a zinc salt solution.
Preferably, the mass ratio of the zwitterionic polymer monomer to the cross-linking agent to the initiator is 10-20:0.3-0.6:0.05-0.1.
In the enhanced domain-limiting zwitterionic gel electrolyte, the porous support comprises at least one of a nylon membrane, a hydrophilic polyvinylidene fluoride membrane, a polypropylene membrane, a polyimide membrane, a nanopore membrane and a non-woven fabric.
Preferably, the porous support has a thickness of 0.5 to 1.0mm, a pore diameter of 20 to 100 μm, and a porosity of 30 to 80%. The invention can effectively support gel by controlling the thickness, the pore diameter and the porosity of the porous support body, prevent the problems of gel leakage, expansion, shrinkage and the like, and can effectively inhibit side reaction and dendrite growth.
In one enhanced domain-limiting zwitterionic gel electrolyte described above, the zwitterionic polymer monomer comprises at least one of 3- (1-vinyl-1H-imidazol-3-yl) propane-1-sulfonate, 4- (1-vinyl-1H-imidazol-3-yl) butane-1-sulfonate, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide, sulfobetaine methyl methacrylate, and carboxybetaine methyl methacrylate.
Preferably, the zwitterionic polymer monomer is at least one of 3- (1-vinyl-1H-imidazol-3-yl) propane-1-sulfonate (VIM-PS) and 4- (1-vinyl-1H-imidazol-3-yl) butane-1-sulfonate (VIM-BS).
Wherein the structural formula of the 3- (1-vinyl-1H-imidazol-3-yl) propane-1-sulfonate (VIM-PS) and the structural formula of the 4- (1-vinyl-1H-imidazol-3-yl) butane-1-sulfonate (VIM-BS) are respectively as follows:
the ionic conduction of the zwitterionic polymer monomer is utilized, and the ionic groups in the zwitterionic polymer monomer can adsorb and release ions, so that the ionic conduction of the electrolyte is realized, and the ionic mobility and the ionic transmission rate of the electrolyte are improved; and then the gel stability of the zwitterionic polymer monomer is utilized, and the zwitterionic polymer monomer formed through the crosslinking reaction can construct a stable gel network structure, so that the shrinkage and expansion of the gel are prevented, the gel leakage is avoided, and the gel stability is critical to the long-term stability and reliability of the electrolyte.
The positive and negative ionic groups in the zwitterionic polymer monomer have the capability of adsorbing and neutralizing ions generated by side reaction, so that the occurrence of the side reaction is restrained, the chemical stability of the electrolyte is improved, and the energy loss of the battery is reduced; furthermore, the polymer chains of the zwitterionic polymer monomers can hinder the growth and diffusion of crystals, thereby inhibiting dendrite formation, which is of great importance for improving the interfacial stability of the electrolyte, preventing short circuits, and extending battery life.
In the enhanced domain-limiting zwitterionic gel electrolyte, the cross-linking agent is at least one of N, N' -methylenebisacrylamide, isobutenyl trimethoxysilane and dimethyl acryloyloxyethyl trimethoxysilane.
In the enhanced domain-limiting zwitterionic gel electrolyte, the initiator is at least one of potassium persulfate, ammonium persulfate and benzoyl peroxide.
In the enhanced domain-limiting zwitterionic gel electrolyte, the zinc salt is at least one of zinc sulfate, zinc trifluoromethane sulfonate, zinc tetrafluoroborate and zinc perchlorate.
The invention also provides a preparation method of the enhanced domain-limited zwitterionic gel electrolyte, which comprises the following steps:
s1, adding a zwitterionic monomer into deionized water, and then performing ultrasonic treatment to obtain a monomer solution;
s2, adding a cross-linking agent and an initiator into the monomer solution, and performing ultrasonic treatment to obtain a mixed solution;
s3, deoxidizing the mixed solution, pouring the deoxidized mixed solution into a die, and placing the die into a porous support body for curing treatment to obtain gel;
s4, freeze-drying the gel, and then soaking the gel in zinc salt solution to form gel electrolyte.
In the preparation method of the enhanced domain-limited zwitterionic gel electrolyte, the curing treatment in the step S3 is ultraviolet radiation or heat treatment.
In the preparation method of the enhanced domain-limited zwitterionic gel electrolyte, the concentration of the zinc salt solution in the step S4 is 1-3mol/L, and the soaking time is 0.5-4h.
When the enhanced domain-limited amphoteric ion gel electrolyte is prepared, the concentration of zinc salt is controlled to ensure good ion transmission capacity and stability of a gel structure, so that the comprehensive performance of a zinc ion battery is improved; too high a concentration of zinc salt increases the rejection between ions, reduces the mobility and conductivity of the ions, and high concentrations of zinc ions may cause uneven swelling of the gel, damage the stability of the gel, and increase the risk of shrinkage and leakage of the gel. Conversely, too low a zinc salt concentration limits ion migration and conduction, resulting in slower ion transport rates in the electrolyte, and too low a zinc ion concentration may result in incomplete or loose gel structure, which may reduce gel stability and mechanical strength.
The invention also provides a zinc battery, which comprises the enhanced domain-limited amphoteric ion gel electrolyte.
Preferably, the preparation method of the zinc ion battery comprises the following steps: attaching and fixing the positive pole piece and the negative pole piece to two sides of the battery shell respectively; placing the enhanced domain-limited amphoteric ion gel electrolyte above a positive pole piece in a battery shell; and finally, closing the battery shell and connecting the positive and negative electrode leads.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a zinc ion battery which is simple to operate and can be produced in a large scale, wherein electrolyte is prepared from an enhanced domain-limited amphoteric ion gel material, and the formula parameters of the electrolyte can be regulated and controlled by adjusting polymer monomers, cross-linking agents and initiators, so that the zinc ion battery is suitable for the requirements of different fields.
The invention utilizes the action mechanisms of ionic conduction, gel stability, side reaction inhibition, dendrite growth inhibition and the like of the zwitterionic polymer monomer to obviously improve the performance and stability of the enhanced domain-limited zwitterionic gel electrolyte.
The preparation method of the gel electrolyte can reduce the production cost, improve the production efficiency and has wide application prospect.
The invention aims to provide a high-performance zinc ion battery for the market so as to meet the requirements of the battery market on high-performance and low-cost products.
Drawings
FIG. 1 is an SEM image of an enhanced domain-restricted zwitterionic gel prepared using non-woven fabric as the porous support according to example 1 of the present invention after freeze-drying for 72 hours.
FIG. 2 is a graph showing the time voltage at 25℃for the zinc ion cells of examples 1-2 and comparative example 1 according to the present invention.
FIG. 3 shows the use of the enhanced domain-limited zwitterionic gel electrolyte and the single polyvinyl alcohol gel electrolyte of examples 1-2 and comparative example 1 of the present invention in a zinc ion battery at a current density of 0.5mA cm -2 SEM images of the zinc anode surface after 100 cycles of cycling under the conditions were compared.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Example 1:
s1, preparing the following raw materials in parts by weight: 15 parts of 3- (1-vinyl-1H-imidazol-3-yl) propane-1-sulfonate, 0.4 part of N, N' -methylenebisacrylamide, 0.07 part of ammonium persulfate, and a concentration of 2 mol.L -1 Zinc sulfate solution of (a);
s2, adding 3- (1-vinyl-1H-imidazole-3-yl) propane-1-sulfonate into 120ml deionized water, and performing ultrasonic treatment for 3 minutes to obtain a monomer solution;
s3, sequentially adding N, N' -methylene bisacrylamide and ammonium persulfate, and performing ultrasonic treatment for 1 minute to obtain a mixed solution;
s4, introducing high-purity argon into the mixed solution for 5 minutes, removing bubbles by ultrasonic treatment for 3 seconds, pouring into a die, putting a layer of non-woven fabric with the aperture of 100 mu m and the thickness of 0.5mm, and placing the non-woven fabric with the porosity of 80% into a blast oven at the temperature of 75 ℃ for reaction for 24 hours to form gel;
s5, freeze-drying the prepared gel for 72 hours to remove water, wherein an SEM image is shown as a figure 1, and soaking the gel in a zinc sulfate solution for 2 hours to form a gel electrolyte;
s6, using the prepared enhanced limited amphoteric ion gel electrolyte in a zinc ion battery, wherein the current condition is 0.5mA cm -2 The cycle performance was tested and the time voltage curve is shown in figure 2. SEM images of the surface of the zinc anode after circulation are shown in fig. 3-a, and the surface is uniform and compact, which shows that the gel electrolyte can effectively inhibit the growth of byproducts and dendrites.
Through tests, the enhanced domain-limited zwitterionic gel electrolyte prepared by the embodiment still maintains good stability and cycle performance after long-time cyclic charge and discharge.
Example 2:
s1, preparing the following raw materials in parts by weight: 15 parts of 4- (1-vinyl-1H-imidazol-3-yl) butane-1-sulfonate, 0.4 part of N, N' -methylenebisacrylamide, 0.07 part of ammonium persulfate, and a concentration of 2 mol.L -1 Zinc trifluoromethane sulfonate of (a);
s2, adding 3- (1-vinyl-1H-imidazole-3-yl) propane-1-sulfonate into 120ml deionized water, and performing ultrasonic treatment for 3 minutes to obtain a monomer solution;
s3, sequentially adding N, N' -methylene bisacrylamide and ammonium persulfate, and performing ultrasonic treatment for 1 minute to obtain a mixed solution;
s4, introducing high-purity argon into the mixed solution for 5 minutes, removing bubbles by ultrasonic for 3 seconds, pouring into a mold, placing a nylon film with the thickness of 0.5mm into the mold, and placing the nylon film into a blast oven at the temperature of 75 ℃ for reacting for 24 hours to form gel;
s5, freeze-drying the prepared gel for 72 hours to remove water, wherein an SEM image is shown as a figure 1, and soaking the gel in a 2mol/L zinc sulfate solution for 2 hours to form a gel electrolyte;
s6, using the prepared enhanced limited amphoteric ion gel electrolyte in a zinc ion battery, wherein the current condition is 0.5mA cm -2 Testing the cycle performance, the time voltage curve is as followsShown in fig. 2. SEM images of the surface of the zinc anode after circulation are shown in fig. 3-b, the surface of which is more uniform and compact than that of example 1, and the problems of peeling and the like do not occur, which indicates that the gel electrolyte has better effect in inhibiting the growth of byproducts and dendrites.
Through tests, the enhanced domain-limited zwitterionic gel electrolyte prepared in the embodiment has good stability and cycle performance when different zwitterionic monomers, porous supports and zinc salt solutions are used.
Example 3:
the difference from example 1 is only that the nonwoven fabric in step S4 has a pore size of 1. Mu.m.
Example 4:
the difference from example 1 is only that the nonwoven fabric in step S4 has a pore size of 200. Mu.m.
Example 5:
the difference from example 1 is only that the zinc sulfate solution concentration in step S5 is 0.5mol/L.
Example 6: the difference from example 1 is only that the zinc sulfate solution concentration in step S5 is 3mol/L.
Comparative example 1:
s1, preparing the following raw materials in parts by weight: 10 parts of polyvinyl alcohol, 0.2 part of N, N' -methylene bisacrylamide, 0.05 part of ammonium persulfate and concentration of 2 mol.L -1 Zinc trifluoromethane sulfonate of (a);
s2, adding polyvinyl alcohol into 90ml of deionized water, heating and stirring for 8 hours to obtain a monomer solution;
s3, sequentially adding N, N' -methylene bisacrylamide and ammonium persulfate, and performing ultrasonic treatment for 1 minute to obtain a mixed solution;
s4, introducing high-purity argon into the mixed solution for 5 minutes, removing bubbles by ultrasonic for 3 seconds, pouring into a mould, and placing into a 70 ℃ blast oven for reaction for 24 hours to form gel;
s5, freeze-drying the prepared gel for 72 hours to remove water, and soaking the gel in a zinc sulfate solution for 0.5 hour to form a gel electrolyte;
s6, using the prepared polyvinyl alcohol gel electrolyte for zinc ion batteries under current conditionsIs 0.5 mA.cm -2 The cycle performance was tested and the time voltage curve is shown in figure 2. SEM images of the surface of the zinc anode after cycling are shown in fig. 3-c, which are irregular and uneven compared with examples 1-2, showing that a large amount of zinc dendrites and by-products are generated, indicating that the gel electrolyte has limited effect in inhibiting the by-products and dendrite growth, etc.
Through testing, the polyvinyl alcohol gel electrolyte prepared in the comparative example 1 has poor water retention and mechanical properties, and shows poor cycle stability when used in zinc ion batteries.
Comparative example 2:
the only difference from example 1 is that the electrolyte raw material does not contain a zwitterionic polymer monomer. Comparative example 2 failed to form a gel without the zwitterionic polymer monomer.
Table 1: test results of the Performance of Zinc ion batteries prepared in examples 1-2 and comparative examples 1-2
| Examples | Cycle number | Cycle life (h) | Water retention property | Mechanical strength (elongation) |
| Example 1 | 595 | 1190 | 84％@360h | 2890％ |
| Implementation of the embodimentsExample 2 | 775 | 1550 | 90％@480h | 3000％ |
| Example 3 | 35 | 70 | 81％@100h | 2740％ |
| Example 4 | 420 | 840 | 87％@310h | 2410％ |
| Example 5 | 12 | 24 | 85％@270h | 2800％ |
| Example 6 | 325 | 650 | 88％@355h | 2850％ |
| Comparative example 1 | 50 | 100 | 42％@20h | 320％ |
In conclusion, the enhanced domain-limited zwitterionic gel electrolyte not only shows improvement on appearance, but also obtains iterative upgrade on performance. The mechanical strength and stability of the gel electrolyte are greatly improved by adding the porous support, and the problems of leakage, expansion, shrinkage and the like of the gel are avoided, so that the safe use of the gel electrolyte is effectively ensured. It is worth mentioning that the polymer monomer of the invention contains the zwitterionic monomers VIM-PS and VIM-BS which are helpful for improving the ion conductivity of the gel electrolyte, and simultaneously the nitrogen and sulfur elements have coordination function and can be coordinated with Zn 2+ A more stable complex is formed, thereby improving the operating efficiency of the battery. In addition, the electrolyte is not only suitable for zinc ion batteries, but also can be widely applied to other types of batteries, such as zinc air batteries, zinc metal batteries and the like, and provides more possibility for energy conservation, environmental protection and sustainable development. Therefore, the enhanced domain-limited zwitterionic gel electrolyte provided by the invention has remarkable practical value and is an innovative result which positively contributes to the development of the future energy storage and conversion field.
The point values in the technical scope of the present invention are not exhaustive, and the new technical solutions formed by equivalent substitution of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the present invention; meanwhile, in all the listed or unrecited embodiments of the present invention, each parameter in the same embodiment represents only one example of the technical scheme (i.e. a feasibility scheme), and no strict coordination and limitation relation exists between each parameter, wherein each parameter can be replaced with each other without violating axiom and the requirement of the present invention, except what is specifically stated.
The technical means disclosed by the scheme of the invention is not limited to the technical means disclosed by the technical means, and also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, and such changes and modifications are intended to be included within the scope of the invention.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. The enhanced domain-limited zwitterionic gel electrolyte is characterized in that the electrolyte raw material comprises a porous support, a zwitterionic polymer monomer, a cross-linking agent, an initiator and a zinc salt solution.
2. The enhanced domain-limited zwitterionic gel electrolyte of claim 1, wherein the porous support comprises at least one of nylon membrane, hydrophilic polyvinylidene fluoride membrane, polypropylene membrane, polyimide membrane, nanoporous membrane and nonwoven fabric.
3. The enhanced domain-limited zwitterionic gel electrolyte as recited in claim 1, wherein the porous support has a thickness of 0.5-1.0mm, a pore size of 20-100 μm and a porosity of 30-80%.
4. The enhanced domain-limited zwitterionic gel electrolyte of claim 1, wherein the zwitterionic polymer monomer comprises at least one of 3- (1-vinyl-1H-imidazol-3-yl) propane-1-sulfonate, 4- (1-vinyl-1H-imidazol-3-yl) butane-1-sulfonate, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, [3- (methacryloylamino) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide, sulfobetaine methyl methacrylate, and carboxylic betaine methyl methacrylate.
5. The enhanced domain-limited zwitterionic gel electrolyte as recited in claim 1, wherein the mass ratio of zwitterionic polymer monomer, cross-linking agent and initiator is 10-20:0.3-0.6:0.05-0.1.
6. The enhanced domain-limited zwitterionic gel electrolyte of claim 1, wherein the zinc salt is at least one of zinc sulfate, zinc trifluoromethane sulfonate, zinc tetrafluoroborate, and zinc perchlorate.
7. A method of preparing the enhanced domain-limited zwitterionic gel electrolyte as recited in any one of claims 1-6, comprising the steps of:
s1, adding a zwitterionic monomer into deionized water, and then performing ultrasonic treatment to obtain a monomer solution;
s2, adding a cross-linking agent and an initiator into the monomer solution, and performing ultrasonic treatment to obtain a mixed solution;
s3, deoxidizing the mixed solution, pouring the deoxidized mixed solution into a die, and placing the die into a porous support body for curing treatment to obtain gel;
s4, freeze-drying the gel, and then soaking the gel in zinc salt solution to form gel electrolyte.
8. A method for preparing the enhanced domain-limited zwitterionic gel electrolyte as recited in claim 7, wherein the step S3 curing treatment is ultraviolet radiation or heat treatment.
9. The method for preparing the enhanced domain-limited zwitterionic gel electrolyte as claimed in claim 7, wherein the concentration of the zinc salt solution in the step S4 is 1-3mol/L, and the soaking time is 0.5-4h.
10. A zinc cell comprising the enhanced domain zwitterionic gel electrolyte of claim 1.
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| CN118073727A (en) * | 2024-01-17 | 2024-05-24 | 黑龙江大学 | Low-temperature solid electrolyte and preparation method and application thereof |
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