CN117438528A - Zinc phytate-polyanion gel coating zinc cathode and preparation method and application thereof - Google Patents
Zinc phytate-polyanion gel coating zinc cathode and preparation method and application thereof Download PDFInfo
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- CN117438528A CN117438528A CN202311613438.2A CN202311613438A CN117438528A CN 117438528 A CN117438528 A CN 117438528A CN 202311613438 A CN202311613438 A CN 202311613438A CN 117438528 A CN117438528 A CN 117438528A
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- 239000011701 zinc Substances 0.000 title claims abstract description 281
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 274
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 268
- 238000000576 coating method Methods 0.000 title claims abstract description 98
- 239000011248 coating agent Substances 0.000 title claims abstract description 97
- 229920000447 polyanionic polymer Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 60
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 55
- 239000007864 aqueous solution Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000467 phytic acid Substances 0.000 claims abstract description 22
- 229940068041 phytic acid Drugs 0.000 claims abstract description 22
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 13
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 11
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 11
- 244000137852 Petrea volubilis Species 0.000 claims description 10
- -1 2-hydroxyethoxy Chemical group 0.000 claims description 5
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
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- 239000010406 cathode material Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 90
- 239000000243 solution Substances 0.000 description 35
- 210000004027 cell Anatomy 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 22
- 239000010410 layer Substances 0.000 description 21
- 238000004806 packaging method and process Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 210000001787 dendrite Anatomy 0.000 description 14
- 238000004506 ultrasonic cleaning Methods 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
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- 238000007789 sealing Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
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- 238000007086 side reaction Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 230000008021 deposition Effects 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 238000004807 desolvation Methods 0.000 description 3
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- 230000004907 flux Effects 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- OPRIWFSSXKQMPB-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)CC(C)(C)NC(=O)C=C OPRIWFSSXKQMPB-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GBSRRQISIWGCNC-UHFFFAOYSA-N methyl propane-1-sulfonate Chemical compound CCCS(=O)(=O)OC GBSRRQISIWGCNC-UHFFFAOYSA-N 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of zinc ion battery cathode materials, and particularly relates to a zinc phytate-polyanion gel coating zinc cathode, and a preparation method and application thereof, wherein the preparation method comprises the following steps: after pretreatment of zinc sheets, immersing the zinc sheets in a phytic acid aqueous solution to prepare zinc coated zinc sheets of phytic acid; mixing acrylamide, sodium 2-acrylamide-2-methylpropanesulfonate, N' -methylenebisacrylamide, a photoinitiator and water to prepare a pre-gel aqueous solution; and covering the surface of the zinc sheet with the pre-gel aqueous solution, and initiating to form a polyanion gel coating by ultraviolet light to prepare the zinc phytate-polyanion gel coating zinc cathode. The invention utilizes a chemical conversion method to generate the zinc phytate coating in situ; the zinc phytate coating and the polyanion gel layer form hydrogen bond connection, so that the polyanion gel layer and the zinc phytate are tightly combined, the impedance is reduced, and the cycling stability of the zinc cathode coating is improved.
Description
Technical Field
The invention belongs to the technical field of zinc ion battery negative electrode materials, and particularly relates to a zinc phytate-polyanion gel coating zinc negative electrode, a preparation method and application thereof.
Background
With the rapid development of battery energy storage technology, researchers continuously explore and develop novel secondary battery technologies with high safety, stable performance, low cost and environmental protection based on the great demands in the fields of energy storage, electric automobiles, electronic equipment and the like. One of the water-based zinc ion batteries is a high-safety battery, and attention is paid to the characteristics of low cost, high capacity and the like. However, the formation of zinc dendrites at the negative electrode of the aqueous zinc ion battery and the side reaction of interface corrosion seriously obstruct the commercial application of the aqueous zinc ion battery, and the generation of dendrites greatly reduces the safety and the cycle life of the battery. The solution and optimization of zinc dendrite formation and interface corrosion are the requisite ways for realizing commercial application of the water-based zinc ion battery, and are the key directions of research of current scientific researchers.
Among the zinc anode stabilization strategies, the construction of a solid interface protection layer is the most direct and effective strategy. While inorganic interface coatings have received great attention because of having uniform ion transport channels or zinc-philic sites that can guide uniform deposition of zinc ions. However, during cycling, particularly at high capacity cycling, the change in volume of the negative electrode can easily cause cracking or even falling of the rigid inorganic coating, leading to failure of the interfacial coating protection, and difficulty in maintaining durable protection. In addition, low Zn of the coating 2+ Conductivity limits the performance of the anode in high current cycles.
Disclosure of Invention
In order to solve the technical problems, the invention provides a zinc phytate-polyanion gel coating zinc cathode, a preparation method and application thereof.
The invention is realized by the following technical scheme.
The first object of the invention is to provide a preparation method of zinc phytate-polyanion gel coating zinc cathode, comprising the following steps:
after pretreatment of zinc sheets, immersing the zinc sheets in a phytic acid aqueous solution to prepare zinc coated zinc sheets of phytic acid;
mixing acrylamide, sodium 2-acrylamide-2-methylpropanesulfonate, N' -methylenebisacrylamide, a photoinitiator and water to prepare a pre-gel aqueous solution;
and covering the surface of the zinc sheet with the pre-gel aqueous solution, and initiating to form a polyanion gel coating by ultraviolet light to prepare the zinc phytate-polyanion gel coating zinc cathode.
In some embodiments of the invention, the aqueous phytic acid solution has a mass concentration of 5% to 10%.
In some embodiments of the invention, the time of immersion in the aqueous phytic acid solution is 1 to 5 minutes.
In some embodiments of the invention, after the impregnation of the phytic acid aqueous solution is completed, the zinc sheet is alternately washed with ethanol and water and then dried.
In some embodiments of the invention, the photoinitiator comprises 2-hydroxy-2-methyl-1-phenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2 '-azobisisobutylamidine dihydrochloride or 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone.
In some embodiments of the invention, the molar ratio of acrylamide monomer, sodium 2-acrylamido-2-methylpropanesulfonate monomer is from 0.5 to 2:1, a step of; in the pre-coagulation aqueous solution, the total mass fraction of the monomers is 30-70%, the mass of N, N' -methylene bisacrylamide accounts for 0.01-0.1% of the total mass of the monomers, and the mass of the photoinitiator accounts for 0.01-0.5% of the total mass of the monomers.
In some embodiments of the invention, the pretreatment refers to polishing the zinc sheet with 2000 mesh sandpaper, followed by ultrasonic cleaning with ethanol and drying.
In some embodiments of the invention, the ultraviolet light is 365-410 nm ultraviolet light and the photoinitiation time is 1-4 hours.
Specifically, the pre-gel aqueous solution is dripped on a zinc phytate coating-zinc sheet, and is compressed and sealed into a glass mold, so that the solution is ensured to cover the surface of the zinc sheet, and the mold containing the zinc sheet and the pre-gel aqueous solution is irradiated by 365-410 nm ultraviolet light for 1-4 hours, so that the zinc phytate-polyanion gel coating zinc cathode is obtained.
The second object of the invention is to provide a zinc phytate-polyanion gel coating zinc anode prepared by the preparation method.
The third object of the invention is to provide the application of the zinc phytate-polyanion gel coating zinc cathode in preparing a water-based zinc ion battery.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the defects of an inorganic coating and the practical application requirements of large-current and large-capacity circulation of a water-based zinc ion battery, the invention introduces organic components into the coating and constructs a polyanion gel-inorganic protective layer with a similar SEI structure. Specifically, the invention utilizes a chemical conversion method to firstly generate a zinc phytate coating in situ on a zinc sheet, then forms a polyanion gel layer outside the zinc phytate coating, and the zinc phytate coating and the polyanion gel layer form hydrogen bond connection to promote the polyanion gel layer to be tightly combined with the zinc phytate, thereby reducing impedance and improving the cycling stability of the zinc cathode coating; the outer layer of the outer layer polyanion gel can play a role of glue, so that the coating has certain flexibility and the stability of the coating under high-capacity circulation is improved. Meanwhile, polyanion gel is coated on Zn 2+ Can effectively promote Zn in the deposition process 2+ Desolvation, the hydrogel skeleton can keep uniform ion flux, avoid overhigh local electric field density and effectively inhibit dendrites and side reactions. The design of the SEI-like structure organic-inorganic coating provides a new design idea for the surface modification of the zinc anode.
Drawings
FIG. 1 is a comparative example 1 bare zinc and example 1 zinc phytate-polyanion gel coated zinc negative electrode symmetric cell long cycle control (1 mA/cm 2 ～1mAh/cm 2 )。
FIG. 2 is a comparative example 1 bare zinc, example 1 zinc phytate-polyanion gel coated zinc negative electrode symmetric cell long cycle control (10 mA/cm 2 ～5mAh/cm 2 )。
FIG. 3 is a comparative example 1 bare zinc, example 1 zinc phytate-polyanion gel coated zinc negative electrode zinc dendrite growth behavior control (2 mAh/cm 2 -150 cycles).
FIG. 4 is a comparative example 1 bare zinc, example 1 zinc phytate-polyanionic gel coated zinc negative electrode full cell control (5A/g).
FIG. 5 is a comparative example 1 bare zinc, example 1 zinc phytate-polyanionic gel coated zinc negative electrode full cell control (10A/g).
FIG. 6 is a comparative example 2 zinc phytate coated zinc sheet (PA@Zn), comparative example 3 polyanionic gel coated zinc negative electrode symmetric cell long cycle control (1 mA/cm) 2 ～1mAh/cm 2 )。
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
The water-based zinc ion battery is widely paid attention to as a novel secondary battery, and has the advantages of good safety, low cost, high capacity and the like. However, the current research shows that dendrites are easy to appear on the negative electrode of the water-based zinc ion battery, and the problem of interface corrosion also appears, and the phenomenon seriously hinders the application of the water-based zinc ion battery. The current method for solving the problems is to construct an inorganic coating on the surface of the zinc anode, wherein the inorganic coating can guide zinc ions to be uniformly deposited and has positive effects on alleviating the problems. However, similar to general inorganic materials, the toughness of the inorganic coating is poor, and particularly when the inorganic coating is used in a negative electrode material, the volume change of the negative electrode is often caused when the battery is subjected to high-capacity circulation, the inorganic coating with poor toughness is cracked or even falls off due to the volume change of the negative electrode, and further, the inorganic coating cannot be formed on the surface of the negative electrode effectively for a long time.
In order to solve the problems, the invention builds an organic coating, namely a polyanion gel layer, on the surface of the inorganic coating on the basis of building the inorganic coating on the surface of the anode material, thereby effectively solving the problems.
The inorganic coating is a zinc phytate coating, and Phytic Acid (PA) is a sustainable organic acid containing 6 phosphoric acid carboxyl groups and 12 hydroxyl groups, has inherent metal chelating capacity, and can form PA-metal complex compounds. The zinc phytate coating can effectively inhibit side reaction of an interface so as to stabilize an electrode-electrolyte interface, and form an even and compact interface protection layer with good zinc affinity by utilizing chelation between Zn and PA, promote even deposition of zinc metal, and effectively inhibit zinc dendrite growth and negative electrode corrosion.
Then forming a polyanion gel layer outside the zinc phytate coating, wherein the zinc phytate coating and the polyanion gel layer form hydrogen bond connection, so that the polyanion gel layer and the zinc phytate are tightly combined, the impedance is reduced, and the cycling stability of the zinc cathode coating is improved; the outer layer of the outer layer polyanion gel can play a role of glue, so that the coating has certain flexibility and the stability of the coating under high-capacity circulation is improved. Meanwhile, polyanion gel is coated on Zn 2+ Can effectively promote Zn in the deposition process 2+ Desolvation, the hydrogel skeleton can keep uniform ion flux, avoid overhigh local electric field density and effectively inhibit dendrites and side reactions.
In the invention, the method for forming the polyanion gel layer adopts ultraviolet light to initiate reaction, firstly prepares pre-gel aqueous solution, specifically prepares acrylamide, 2-acrylamide-2-methylpropanesulfonic acid sodium salt, N' -methylene bisacrylamide, photoinitiator and water by mixing, and then adopts 365-410 nm ultraviolet light to initiate polymerization reaction.
In a preferred embodiment of the present invention, the photoinitiator comprises 2-hydroxy-2-methyl-1-phenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2 '-azobisisobutylamidine dihydrochloride or 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone.
In a preferred embodiment of the invention, the ultraviolet light is 365-410 nm ultraviolet light and the photoinitiation time is 1-4 hours.
Specifically, the invention provides a preparation method of a zinc phytate-polyanion gel coating zinc cathode, which comprises the following steps:
s1, cutting a zinc sheet to a proper size, polishing with 2000-mesh sand paper, performing ultrasonic cleaning with a proper amount of ethanol, immersing in a 5% -10% phytic acid solution for 1-5 min, preparing a zinc phytate coating on the surface of the zinc sheet in situ by using a chemical conversion method, and cleaning the surface of the zinc sheet with ethanol and deionized water to prepare a zinc phytate coating-zinc sheet;
mixing acrylamide, 2-acrylamide-2-methylpropanesulfonic acid sodium salt, N' -methylenebisacrylamide, a photoinitiator and water to prepare a pre-gel aqueous solution; the 2-acrylamide-2-methylpropanesulfonic acid sodium is 50% of 2-acrylamido-2-methylpropanesulfonic acid sodium water solution by mass percentage, and the photoinitiator comprises 2-hydroxy-2-methyl-1-phenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2 '-azo diisobutyl amidine dihydrochloride or 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone.
The molar ratio of the acrylamide monomer to the 2-acrylamide-2-sodium methylpropanesulfonate monomer is 0.5-2: 1, a step of; in the pre-coagulation aqueous solution, the total mass fraction of the monomers is 30-70%, the mass of N, N' -methylene bisacrylamide accounts for 0.01-0.1% of the total mass of the monomers, and the mass of the photoinitiator accounts for 0.01-0.5% of the total mass of the monomers.
S2, covering the zinc phytate coating surface of the zinc phytate coating-zinc sheet with the S1 pregelatinized water solution, and initiating formation of the polyanion gel coating by ultraviolet light to finally obtain the zinc phytate-polyanion gel coating zinc cathode. Specifically, the pre-gel aqueous solution is dripped on a zinc phytate coating-zinc sheet, and is compressed and sealed into a glass mold, so that the solution is ensured to cover the surface of the zinc sheet, and the mold containing the zinc sheet and the pre-gel aqueous solution is irradiated by 365-410 nm ultraviolet light for 1-4 hours, so that the zinc phytate-polyanion gel coating zinc cathode is obtained.
The invention also provides a water-based zinc ion battery, wherein the negative electrode of the battery adopts the zinc phytate-polyanion gel coating zinc negative electrode prepared by the method, and the battery assembly method comprises the following steps:
and finally, packaging by using a button cell packaging machine according to the placing sequence of the positive electrode shell, the positive electrode plate, the diaphragm, the zinc phytate-polyanion gel coating zinc negative electrode, the gasket, the elastic sheet and the negative electrode shell, wherein the pressure is 500psi.
The following examples and comparative examples are provided to illustrate the present invention.
Example 1
The preparation method of the zinc phytate-polyanion gel coating zinc cathode comprises the following steps:
(1) Cutting zinc sheet, grinding with 2000 mesh sand paper, and ultrasonic cleaning with ethanol.
(2) Immersing the treated zinc sheet into a phytic acid aqueous solution with the mass concentration of 10% for 2min, washing the surface of the zinc sheet by using ethanol and deionized water, and placing the zinc sheet into a vacuum drying oven for drying.
(3) Preparing a pregel solution: a pre-gel aqueous solution was prepared by dissolving 7.2g of acrylamide, 45.85g of sodium 2-acrylamido-2-methylpropanesulfonate (added as a 50% aqueous solution of sodium 2-acrylamido-2-methylpropanesulfonate), 0.0143g of N, N' -methylenebisacrylamide, and 1-hydroxy-cyclohexyl-phenyl ketone (0.0224 g) in 70ml of deionized water.
(4) And (3) dripping the prepared pregelatinized solution on the zinc sheet treated in the step (2) after treatment, and compressing and sealing the zinc sheet into a glass die to ensure that the solution completely covers the surface of the zinc sheet. And (3) irradiating a die containing the zinc sheet and the pregelatinized water solution for 2 hours by using 365nm ultraviolet light to obtain the zinc phytate-polyanion gel coating zinc cathode.
And finally, packaging by using a button cell packaging machine according to the placing sequence of the positive electrode shell, the positive electrode plate, the diaphragm, the zinc phytate-polyanion gel coating zinc negative electrode, the gasket, the elastic sheet and the negative electrode shell, wherein the pressure is 500psi.
Example 2
The preparation method of the zinc phytate-polyanion gel coating zinc cathode comprises the following steps:
(1) Cutting zinc sheet, grinding with 2000 mesh sand paper, and ultrasonic cleaning with ethanol.
(2) Immersing the treated zinc sheet in 10% phytic acid aqueous solution for 2min, washing the surface of the zinc sheet with ethanol and deionized water, and drying the zinc sheet in a vacuum drying oven.
(3) Preparing a pregel solution: a pre-gel aqueous solution was prepared by dissolving 7.2g of acrylamide, 45.85g of sodium 2-acrylamido-2-methylpropanesulfonate (added as a 50% aqueous solution of sodium 2-acrylamido-2-methylpropanesulfonate), 0.0143g of N, N' -methylenebisacrylamide, and 1-hydroxy-cyclohexyl-phenyl ketone (0.0224 g) in 70ml of deionized water.
(4) And (3) dripping the prepared pregelatinized solution on the zinc sheet treated in the step (2), and compressing and sealing the zinc sheet into a specific glass die to ensure that the solution completely covers the surface of the zinc sheet. And (3) irradiating a die containing the zinc sheet and the pregelatinized water solution for 1 hour by using 365nm ultraviolet light to obtain the zinc phytate-polyanion gel coating zinc cathode.
And finally, packaging by using a button cell packaging machine according to the placing sequence of the positive electrode shell, the positive electrode plate, the diaphragm, the zinc phytate-polyanion gel coating zinc negative electrode, the gasket, the elastic sheet and the negative electrode shell, wherein the pressure is 500psi.
Example 3
The preparation method of the zinc phytate-polyanion gel coating zinc cathode comprises the following steps:
(1) Cutting zinc sheet, grinding with 2000 mesh sand paper, and ultrasonic cleaning with ethanol.
(2) Immersing the treated zinc sheet in 10% phytic acid aqueous solution for 2min, washing the surface of the zinc sheet with ethanol and deionized water, and drying the zinc sheet in a vacuum drying oven.
(3) Preparing a pregel solution: a pre-gel aqueous solution was prepared by dissolving 7.2g of acrylamide, 45.85g of sodium 2-acrylamido-2-methylpropanesulfonate (added as a 50% aqueous solution of sodium 2-acrylamido-2-methylpropanesulfonate), 0.0143g of N, N' -methylenebisacrylamide, and 1-hydroxy-cyclohexyl-phenyl ketone (0.0224 g) in 70ml of deionized water.
(4) And (3) dripping the prepared pregelatinized solution on the treated zinc sheet, and compressing and sealing the zinc sheet into a specific glass die to ensure that the solution is completely covered on the surface of the zinc sheet. And (3) irradiating a die containing the zinc sheet and the pregelatinized water solution for 4 hours by using 365nm ultraviolet light to obtain the zinc phytate-polyanion gel coating zinc cathode.
And finally, packaging by using a button cell packaging machine according to the placing sequence of the positive electrode shell, the positive electrode plate, the diaphragm, the zinc phytate-polyanion gel coating zinc negative electrode, the gasket, the elastic sheet and the negative electrode shell, wherein the pressure is 500psi.
Example 4
The preparation method of the zinc phytate-polyanion gel coating zinc cathode comprises the following steps:
(1) Cutting zinc sheet, grinding with 2000 mesh sand paper, and ultrasonic cleaning with ethanol.
(2) Immersing the treated zinc sheet into 5% phytic acid aqueous solution for 5min, washing the surface of the zinc sheet with ethanol and deionized water, and drying the zinc sheet in a vacuum drying oven.
(3) Preparing a pregel solution: a pre-gel aqueous solution was prepared by dissolving 7.2g of acrylamide, 45.85g of sodium 2-acrylamido-2-methylpropanesulfonate (added as a 50% aqueous solution of sodium 2-acrylamido-2-methylpropanesulfonate), 0.0143g of N, N' -methylenebisacrylamide, and 1-hydroxy-cyclohexyl-phenyl ketone (0.0224 g) in 70ml of deionized water.
(4) And (3) dripping the prepared pregelatinized solution on the zinc sheet treated in the step (2), and compressing and sealing the zinc sheet into a specific glass die to ensure that the solution completely covers the surface of the zinc sheet. And (3) irradiating a die containing the zinc sheet and the pregelatinized water solution for 2 hours by using 365nm ultraviolet light to obtain the zinc phytate-polyanion gel coating zinc cathode.
And finally, packaging by using a button cell packaging machine according to the placing sequence of the positive electrode shell, the positive electrode plate, the diaphragm, the zinc phytate-polyanion gel coating zinc negative electrode, the gasket, the elastic sheet and the negative electrode shell, wherein the pressure is 500psi.
Example 5
The preparation method of the zinc phytate-polyanion gel coating zinc cathode comprises the following steps:
(1) Cutting zinc sheet, grinding with 2000 mesh sand paper, and ultrasonic cleaning with ethanol.
(2) Immersing the treated zinc sheet into 5% phytic acid aqueous solution for 5min, washing the surface of the zinc sheet with ethanol and deionized water, and drying the zinc sheet in a vacuum drying oven.
(3) Preparing a pregel solution: a pre-gel aqueous solution was prepared by dissolving 7.2g of acrylamide, 45.85g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt solution (added as 50% by mass aqueous solution of 2-acrylamido-2-methylpropanesulfonic acid sodium salt), 0.0143g of N, N' -methylenebisacrylamide, and 1-hydroxy-cyclohexyl-phenyl ketone (0.0224 g) in 70ml of deionized water.
(4) And (3) dripping the prepared pregelatinized solution on the treated zinc sheet, and compressing and sealing the zinc sheet into a specific glass die to ensure that the solution is completely covered on the surface of the zinc sheet. And (3) irradiating a die containing the zinc sheet and the pregelatinized water solution for 4 hours by using 365nm ultraviolet light to obtain the zinc phytate-polyanion gel coating zinc cathode.
And finally, packaging by using a button cell packaging machine according to the placing sequence of the positive electrode shell, the positive electrode plate, the diaphragm, the zinc phytate-polyanion gel coating zinc negative electrode, the gasket, the elastic sheet and the negative electrode shell, wherein the pressure is 500psi.
Example 6
The preparation method of the zinc phytate-polyanion gel coating zinc cathode comprises the following steps:
(1) Cutting zinc sheet, grinding with 2000 mesh sand paper, and ultrasonic cleaning with ethanol.
(2) Immersing the treated zinc sheet into 5% phytic acid aqueous solution for 5min, washing the surface of the zinc sheet with ethanol and deionized water, and drying the zinc sheet in a vacuum drying oven.
(3) Preparing a pregel solution: a pre-gel aqueous solution was prepared by dissolving 7.2g of acrylamide, 45.85g of a sodium 2-acrylamido-2-methylpropanesulfonate solution (added as a 50% aqueous solution of sodium 2-acrylamido-2-methylpropanesulfonate), 0.0143g of N, N' -methylenebisacrylamide, and 1-hydroxy-cyclohexyl-phenyl ketone (0.0224 g) in 70ml of deionized water.
(4) And (3) dripping the prepared pregelatinized solution on the zinc sheet treated in the step (2), and compressing and sealing the zinc sheet into a specific glass die to ensure that the solution completely covers the surface of the zinc sheet. And (3) irradiating a die containing the zinc sheet and the pregelatinized water solution for 1 hour by using 365nm ultraviolet light to obtain the zinc phytate-polyanion gel coating zinc cathode.
And finally, packaging by using a button cell packaging machine according to the placing sequence of the positive electrode shell, the positive electrode plate, the diaphragm, the zinc phytate-polyanion gel coating zinc negative electrode, the gasket, the elastic sheet and the negative electrode shell, wherein the pressure is 500psi.
Comparative example 1
Bare zinc sheet, i.e. zinc sheet without zinc phytate-polyanion gel coating.
Comparative example 2
The zinc phytate coating is prepared on the zinc sheet only, and specifically comprises the following steps:
(1) Cutting zinc sheet, grinding with 2000 mesh sand paper, and ultrasonic cleaning with ethanol.
(2) Immersing the treated zinc sheet in 10% phytic acid solution for 2min, washing the surface of the zinc sheet with ethanol and deionized water, and drying the zinc sheet in a vacuum drying oven to prepare the zinc sheet with the zinc phytate coating.
Comparative example 3
The preparation method of the polyanion gel coating only on the zinc sheet specifically comprises the following steps:
(1) Cutting zinc sheet, grinding with 2000 mesh sand paper, and ultrasonic cleaning with ethanol.
(2) Preparing a pregel solution: a pre-gel aqueous solution was prepared by dissolving 7.2g of acrylamide, 45.85g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt aqueous solution (added as 50% by mass concentration of 2-acrylamido-2-methylpropanesulfonic acid sodium salt aqueous solution), 0.0143g of N, N' -methylenebisacrylamide, and 1-hydroxy-cyclohexyl-phenyl ketone (0.0224 g) in 70ml of deionized water.
(3) And (3) dripping the prepared pregelatinized solution on the zinc sheet treated in the step (1) after treatment, and compressing and sealing the zinc sheet into a glass die to ensure that the solution completely covers the surface of the zinc sheet. And (3) irradiating a die containing the zinc sheet and the pregelatinized water solution for 2 hours by using 365nm ultraviolet light to obtain the polyanion gel coating zinc cathode.
The negative zinc sheets prepared in the above examples and comparative examples were first characterized, and the negative zinc sheets were assembled into a battery as described above, specifically: and finally, packaging by using a button cell packaging machine according to the placing sequence of the positive electrode shell, the positive electrode plate, the diaphragm, the zinc phytate-polyanion gel coating zinc negative electrode, the gasket, the elastic sheet and the negative electrode shell, wherein the pressure is 500psi. The assembled battery is subjected to performance detection, and the specific contents are as follows:
FIG. 1 is a symmetric cell long-cycle control (1 mA/cm) prepared for comparative example 1 bare zinc, example 1 zinc phytate-polyanion gel coated zinc anode (PA-AMPS) 2 ～1mAh/cm 2 ) As can be seen from FIG. 1, the temperature is 1mA/cm 2 ～1mAh/cm 2 Under the test condition, the zinc phytate-polyanion gel coating zinc symmetrical battery has longer cycle life (cycle 2400 h) compared with a bare zinc symmetrical battery.
FIG. 6 is a symmetrical cell long-cycle control (1 mA/cm) prepared for comparative example 2 zinc phytate coated zinc sheet (PA@Zn), comparative example 3 polyanionic gel coated zinc negative electrode (AMPS@Zn) 2 ～1mAh/cm 2 ) As can be seen from FIG. 6, the temperature is 1mA/cm 2 ～1mAh/cm 2 Under the test condition, after being modified by zinc phytate, the polarization voltage of the symmetrical battery is obviously reduced; the cycle life of the symmetrical battery after the modification of the polyanion gel coating is improved to 1200h.
As can be obtained by combining fig. 1 and fig. 6, after modification by adopting zinc phytate and an anionic gel coating respectively, the performance of the battery can be improved, and when the performance of the battery is synergistically improved by adopting the combination modification of the zinc phytate and the anionic gel coating, the cycle life is detected to be up to 2400h, which indicates that the synergistic effect of the zinc phytate and the anionic gel coating is good. The analysis is that the phytic acid has inherent metal chelating capacity, a PA-metal complex compound can be formed, the zinc phytate coating can effectively inhibit side reaction of an interface so as to stabilize an electrode-electrolyte interface, a uniform and compact interface protection layer with good zinc affinity is formed by utilizing chelation between Zn and PA, uniform deposition of zinc metal is promoted, zinc dendrite growth and negative electrode corrosion are effectively inhibited, and further battery performance is improved. Polyanionic gel in Zn 2+ Can effectively promote Zn in the deposition process 2+ Desolvation, the hydrogel skeleton can maintain uniform ion flux, avoid overhigh local electric field density, and effectively inhibit dendrite and side reaction, so that the battery performance can be improved.
In addition, in fig. 1, the life of the bare zinc cell of comparative example 1 was about 120h, the life of the zinc sheet cell of comparative example 2 was about 350h, the life of the zinc sheet cell of comparative example 3 was 1200h, and the cycle life of the zinc-polyanionic gel coating zinc symmetrical cell of example 1 was 2400h. The increased lifetime of example 1 compared to comparative example 1 is much greater than the sum of the effects of comparative examples 2 and 3, which demonstrates that the effect of providing both a zinc phytate coating and a polyanionic gel layer is significantly improved, and a 1+1>2 effect is achieved, compared to providing either a zinc phytate coating or a polyanionic gel layer on the zinc sheet surface alone. After the polyanion gel layer is constructed on the surface of the zinc phytate coating, the zinc phytate coating and the polyanion gel layer can also have synergistic effect besides the respective functions, so that the battery performance is obviously improved. The specific reason is that the zinc phytate coating and the polyanion gel layer form hydrogen bond connection, so that the polyanion gel layer and the zinc phytate are tightly combined, the impedance is reduced, and the cycling stability of the zinc cathode coating is improved.
To demonstrate the modifying effect of the coating according to the invention, the following performance characterization was further carried out:
FIG. 2 is a symmetric cell long-cycle control (10 mA/cm) prepared for comparative example 1 bare zinc, example 1 zinc phytate-polyanion gel coated zinc anode (PA-AMPS) 2 ～5mAh/cm 2 ) As can be seen from FIG. 2, the temperature is 10mA/cm 2 ～5mAh/cm 2 Under the condition of larger current test, the zinc phytate-polyanion gel coating zinc symmetrical battery has a longer cycle life (600 h) compared with a bare zinc symmetrical battery although the polarization voltage is slightly increased.
FIG. 3 shows a zinc dendrite growth behavior control (2 mAh/cm 2 -150 cycles), it can be seen from fig. 3 that the upper left and right panels are zinc dendrite growth conditions in example 1 at different magnifications, respectively, and the lower left and right panels are zinc dendrite growth conditions in comparative example 1 bare zinc at different magnifications, respectively, and that the dendrite growth is significantly reduced after modification by zinc phytate-polyanion gel coating.
FIG. 4 shows a full cell control (5A/g), and as can be seen from FIG. 4, after matching the positive electrode, the full cell has a starting capacity of 233mAh/g after modification of the zinc phytate-polyanion gel of example 1, and a capacity of 164mAh/g after 3000 cycles (the bare zinc full cell is reduced to 69 mAh/g), and the capacity retention rate is 68.7%.
FIG. 5 is a full cell control (10A/g), and as can be seen from FIG. 5, the initial capacity of the full cell after modification of the zinc phytate-polyanion gel of example 1 is 165.8mAh/g at a current density of 10A/g, the capacity after 3000 cycles is still kept at 96.3mAh/g (the bare zinc full cell is reduced to 35.5 mAh/g), and the capacity retention is 60%.
The characterization results prove that the polyanion gel-inorganic protective layer with the SEI-like structure constructed by the invention can obviously improve the performance of the zinc cathode and provide an improvement thought for the further development of the water-based zinc ion battery. The performance of the other embodiments is similar to that of embodiment 1, and will not be described in detail.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that such modifications and variations be included herein within the scope of the appended claims and their equivalents.
Claims (10)
1. The preparation method of the zinc phytate-polyanion gel coating zinc cathode is characterized by comprising the following steps of:
after pretreatment of zinc sheets, immersing the zinc sheets in a phytic acid aqueous solution to prepare zinc coated zinc sheets of phytic acid;
mixing an acrylamide monomer, a 2-acrylamide-2-methylpropanesulfonic acid sodium monomer, N' -methylenebisacrylamide, a photoinitiator and water to prepare a pre-gel aqueous solution;
and covering the surface of the zinc sheet with the pre-gel aqueous solution, and initiating to form a polyanion gel coating by ultraviolet light to prepare the zinc phytate-polyanion gel coating zinc cathode.
2. The method according to claim 1, wherein the mass concentration of the aqueous solution of phytic acid is 5% to 10%.
3. The method according to claim 1, wherein the time for immersion in the aqueous solution of phytic acid is 1 to 5 minutes.
4. The method according to claim 1, wherein after the completion of the impregnation with the aqueous phytic acid solution, the zinc sheet is alternately washed with ethanol and water and then dried.
5. The preparation method according to claim 1, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2 '-azobisisobutylamidine dihydrochloride or 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone.
6. The preparation method according to claim 1, wherein the molar ratio of the acrylamide monomer to the sodium 2-acrylamido-2-methylpropanesulfonate monomer is 0.5-2: 1, a step of; in the pre-coagulation aqueous solution, the total mass fraction of the monomers is 30-70%, the mass of N, N' -methylene bisacrylamide accounts for 0.01-0.1% of the total mass of the monomers, and the mass of the photoinitiator accounts for 0.01-0.5% of the total mass of the monomers.
7. The method according to claim 1, wherein the ultraviolet light is 365-410 nm ultraviolet light, and the photoinitiation time is 1-4 hours.
8. The preparation method according to claim 1, wherein the pretreatment is to sand a zinc sheet with 2000 mesh sand paper, and then ultrasonically clean the zinc sheet with ethanol and dry the zinc sheet.
9. A zinc phytate-polyanion gel coated zinc anode prepared according to the preparation method of any one of claims 1 to 8.
10. Use of the zinc phytate-polyanionic gel coating zinc anode according to claim 9 for the preparation of an aqueous zinc ion battery.
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