CN114725324B - Preparation and application of zinc metal anode integrated by coordination supermolecular grid material - Google Patents
Preparation and application of zinc metal anode integrated by coordination supermolecular grid material Download PDFInfo
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- CN114725324B CN114725324B CN202210212661.5A CN202210212661A CN114725324B CN 114725324 B CN114725324 B CN 114725324B CN 202210212661 A CN202210212661 A CN 202210212661A CN 114725324 B CN114725324 B CN 114725324B
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- tsa
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- thiosalicylic acid
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- 239000011701 zinc Substances 0.000 title claims abstract description 117
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 92
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 title abstract description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229940103494 thiosalicylic acid Drugs 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 150000003751 zinc Chemical class 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-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
- 238000001035 drying Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 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 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 2
- 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
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 210000001787 dendrite Anatomy 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 4
- 238000009713 electroplating Methods 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 16
- 239000010410 layer Substances 0.000 description 14
- 238000007747 plating Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
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- 239000011241 protective layer Substances 0.000 description 2
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- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- YOJJTXUAVALXQC-UHFFFAOYSA-N 2-sulfanyloxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OS YOJJTXUAVALXQC-UHFFFAOYSA-N 0.000 description 1
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000408529 Libra Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 241000722270 Regulus Species 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of zinc metal batteries or zinc ion batteries, and particularly relates to preparation and application of a zinc metal negative electrode integrated by a coordination supermolecular grid material. The Zn-TSA layer with good hydrophobicity can reduce diffusion of solvated water and anions through the Zn-TSA, thereby inhibiting hydrogen evolution and zinc dendrite growth on the zinc cathode. Meanwhile, the generation of harmful byproducts can be restrained, so that the assembled symmetrical battery has better electroplating/stripping stability without dendrite formation, and meanwhile, the zinc corrosion reaction is greatly reduced. In addition, the zinc cathode can be successfully applied to Zn-MoS 2 and Zn-V2O 5 full batteries, and a new idea is provided for constructing a Zn-metal cathode compact interface.
Description
Technical Field
The invention belongs to the technical field of zinc metal batteries or zinc ion batteries, and particularly relates to preparation and application of a zinc metal anode integrated by a coordination supermolecular grid material.
Background
In the latter lithium era, aqueous zinc metal batteries are considered one of the most promising alternatives. Because the zinc metal cathode has the advantages of large specific/volume capacity (820 mAh g -1,5855mAm-3), compatibility with the oxidation-reduction potential (-0.76V relative to a standard hydrogen electrode) of electrolyte in aqueous solution, excellent chemical stability, good resource richness and the like.
At present, despite the significant progress in the use of zinc metal battery anodes in aqueous solutions, commercialization of zinc metal battery devices is still considered impractical because zinc negative electrode applications still suffer from a number of drawbacks, such as Hydrogen Evolution Reactions (HER), zinc dendrite growth, zinc corrosion, and the like, and thus protection of the zinc negative electrode is required. In the strategy of protecting the zinc cathode, an electronic insulation and ionic conduction artificial interface can not only prevent the zinc cathode from being in direct contact with electrolyte and avoid side reactions (such as decomposition and zinc corrosion) related to the electrolyte, but also regulate transport ions so as to regulate electroplating/stripping reactions. However, current zinc cathode artificial interface layers can only inhibit zinc dendrite growth to a certain extent, and as the circulation is carried out and the volume is changed, the interface layers can crack or degrade, because the artificial interface layers cannot form self-healing in situ, so that the protection function is gradually lost, and zinc dendrites still grow on the surface. Meanwhile, gaps and cracks between the zinc metal negative electrode and the artificial interface layer can lead to uneven current distribution, thereby exacerbating zinc dendrite growth and by-product formation. In addition, current artificial interfacial layers often have inherent voids that reduce their mechanical strength and ionic conductivity. Thus, there is an urgent need for a new strategy to solve the above-mentioned disadvantages of the zinc anode, rather than simply inhibiting the occurrence of side reactions and the growth of zinc dendrites with a separate coating layer.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a simple and extensible wet chemical method for preparing a zinc metal negative electrode, and the interface of the zinc negative electrode is regulated by closely arranged Zn-TSA (TSA=thiosalicylic acid) coordination supermolecular grids, so that zinc dendrites and harmful byproducts are avoided, zinc corrosion reaction is reduced, and the zinc metal negative electrode has very important promotion effect on commercialization of zinc metal batteries.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The invention provides a preparation method of a zinc metal negative electrode, which comprises the following steps: one surface of zinc foil is soaked in zinc salt solution, zinc ions are adsorbed on the surface of the zinc foil and then transferred into thiosalicylic acid solution for soaking, the thiosalicylic acid reacts with the zinc ions on the surface of the zinc foil, and finally, the zinc metal negative electrode (namely Zn-TSA@Zn negative electrode) is prepared through washing and drying.
Preferably, the zinc salt comprises zinc sulphate, zinc trifluoromethane sulphonate, zinc acetate, zinc chloride or zinc perchlorate. More preferably, the zinc salt is zinc sulfate.
Preferably, the thiosalicylic acid is 2-thiosalicylic acid.
In the research, thiosalicylic acid (H2-TSA) is used as a ligand, zn is used as central metal, and the two-dimensional lamellar coordination compound material (Zn-TSA@Zn) is obtained by in-situ vertical growth on the surface of zinc foil. The Zn-TSA and the zinc foil are closely interacted to form a uniform and compact protective layer. The closely packed Zn-TSA layer prevents solvated water and anions from diffusing through the Zn-TSA, thereby promoting uniform Zn 2+ flux and thus regulating dendrite-free zinc deposition. Meanwhile, in a Zn-TSA@Zn negative electrode plating/stripping test, the Zn-TSA@Zn|Zn-TSA@Zn symmetrical battery shows high electroplating/stripping stability, can effectively inhibit the generation of harmful byproducts such as Zn x(OTF-)y(OH)2x-y·nH2 O and the like, and reduces zinc corrosion reaction. In addition, the practical application of the Zn-TSA@Zn negative electrode is verified by assembling a MoS 2 -Zn (2000 cycles) full battery with ultra-long cycle stability and a V 2O5 -Zn (1500 cycles), and the Zn-TSA@Zn negative electrode has strong potential as a long-cycle and dendrite-free negative electrode in a practical ZMB water device.
Preferably, the process of zinc salt solution soaking and thiosalicylic acid solution soaking is repeated 5 to 6 times.
Preferably, the concentration of the zinc salt solution is 0.5M-2M; the concentration of the thiosalicylic acid solution is 0.5M-2M, and the pH value is 6.8-7.2. More preferably, the concentration of the zinc salt solution is 0.1M and the concentration of the thiosalicylic acid solution is 0.05M.
Preferably, the zinc salt solution is soaked for 20s-60s, and the thiosalicylic acid solution is soaked for 1min-2min. More preferably, the zinc salt solution is soaked for 30 seconds and the thiosalicylic acid solution is soaked for 1 minute.
Preferably, the zinc salt solution soaking and the thiosalicylic acid solution soaking are both carried out at normal temperature and normal pressure.
Preferably, the zinc foil is cut before use and the soaked side is polished.
Preferably, the zinc foil has a thickness of 10-100 μm and a purity of greater than 99.99%.
Preferably, the zinc salt can also be replaced by cobalt salts, manganese salts, nickel salts, iron salts, copper salts, and the like. That is, manganese ion, nickel ion, iron ion, copper ion and mercaptosalicylic acid TSA may be coordinated.
The invention also provides a zinc metal negative electrode (namely a Zn-TSA@Zn negative electrode) prepared by adopting the preparation method.
The invention also provides application of the zinc metal negative electrode (namely Zn-TSA@Zn negative electrode) in a zinc metal battery or a zinc ion battery.
Preferably, the zinc metal cell or zinc ion cell includes, but is not limited to, ZMB devices (aqueous zinc metal cell devices).
Further, the ZMB device is a Zn-MoS 2 full cell or a Zn-V 2O5 full cell.
Compared with the prior art, the invention has the beneficial effects that:
The invention discloses a preparation method of a zinc metal anode integrated by a coordination supermolecular grid material, which is characterized in that a tightly arranged Zn-TSA (TSA=thiosalicylic acid) coordination supermolecular grid is prepared by a simple and extensible wet chemical method to regulate a zinc anode interface. The Zn-TSA layer with good hydrophobicity can reduce diffusion of solvated water and anions through the Zn-TSA, thereby inhibiting hydrogen evolution and zinc dendrite growth on the zinc cathode. Meanwhile, the generation of harmful byproducts such as Zn x(OTF-)y(OH)2x-y·nH2 O and the like can be inhibited, and the reasonably prepared anode/electrolyte interface further ensures that the assembled symmetrical battery has better electroplating/stripping stability without dendrite formation, and meanwhile, the zinc corrosion reaction is greatly reduced. In addition, the zinc cathode can be successfully applied to Zn-MoS 2 and Zn-V 2O5 full batteries, and a new thought is provided for constructing a compact interface of a Zn-metal cathode.
Drawings
FIG. 1 is a simulated structure of Zn-TSA@Zn negative electrode material;
FIG. 2 is a characterization of the properties of Zn-TSA@Zn negative electrode material;
In FIG. 2, a is a cross-sectional SEM of a Zn-TSA@Zn electrode; b is SEM image of Zn-TSA@Zn electrode surface; c is the XRD pattern of the Zn-TSA@Zn electrode; d is a thermal weight curve of the Zn-TSA@Zn electrode, and e is a nitrogen adsorption/desorption isothermal line diagram of the Zn-TSA@Zn electrode.
FIG. 3 is a TEM image of a Zn-TSA@Zn negative electrode material;
FIG. 4 is an in situ plating/stripping optical microscope image;
In fig. 4, each graph shows the front surface of the bare Zn electrode (a) and Zn-tsa@zn electrode (b), and the prescribed number of plating/stripping cycles and corresponding current curves: zn||Zn (c) and Zn-TSA@Zn|Zn-TSA@Zn (d).
FIG. 5 is an electrokinetic polarization curve of a bare Zn foil and Zn-TSA@Zn electrode in 3M Zn (CF 3SO3)2 in aqueous solution;
FIG. 6 is the electrochemical performance of a ZMB full cell;
In fig. 6, each graph is a charge-discharge curve of MoS 2 |zn battery (a) and MoS 2 |zn-tsa@zn battery (b) at a current rate of 2Ag -1, respectively; (c) Long-term cycling stability of both cells at 2Ag -1 and corresponding Ces; charging and discharging curves of V 2O5 Zn battery (d) and V 2O5 Zn-TSA@Zn battery (e) in 1, 10, 50 and 100 cycles; (f) Long-term cycling stability at 2A g -1 and corresponding CEs for both cells.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Example 1 preparation method of coordinated supermolecular grid Material-Integrated Zinc Metal negative electrode (Zn-TSA@Zn negative electrode)
(1) Cutting zinc foil (250 μm thick, purity greater than 99.99%) into rectangular pieces of 3cm×5cm, and polishing one side with fine sand paper;
(2) 2mmol of zinc sulfate was dissolved in 20mL of water as solution A;1mmol of 2-thiosalicylic acid (H 2 -TSA) was dissolved in 20mL of water and the pH of the solution was adjusted to about 7 with 0.1M potassium hydroxide solution as solution B;
(3) The polished side of the zinc foil was first immersed in solution a (the other side was not immersed as much as possible), held for 30s, to allow zinc ions to adsorb on the zinc foil surface, and then transferred to solution B for 1min of immersion to allow TSA to react with zinc ions on the zinc foil surface. After the reaction, removing the zinc foil, washing with water, flushing off the Zn-TSA which is not firm in growth, repeating the soaking-washing steps for 5 times, uniformly growing the Zn-TSA on the surface of zinc metal, and finally drying in a constant-temperature oven at 60 ℃ for 2 hours to obtain the Zn-TSA@Zn cathode. The simulated atomic configuration is shown in FIG. 1, wherein the molecular formula of Zn-TSA is [ Zn (C 6H4(CO2) (S) -1, 2) ].
The reaction growth process of the Zn-TSA is carried out at normal temperature and normal pressure, and the prepared Zn-TSA@Zn negative electrode can be directly used without further treatment.
Experimental example 1 characterization of the properties of Zn-TSA@Zn negative electrode
1. Test method
(1) The crystal structure of Zn-tsa@zn was determined by measurement of x-ray diffraction (XRD) with cukα radiation (λ= 1.5405 a), with a scan range of 5 ° to 50 °, and a scan rate of 10 ° min -1.
(2) The specific surface area of Zn-TSA@Zn Brunauere-Emmette-Teller (BET) was determined using ASAP 2460. The pore size distribution was derived using the Barrett-Joyner-Halenda (BJH) model.
(3) Thermogravimetric analysis (TGA) of Zn-tsa@zn was performed on the Libra TG209F1 in an atmosphere of N 2 at a scan rate of 10 k/min.
(4) The microstructure of Zn-TSA@Zn was studied using a transmission electron microscope (JEOL-2001 FTEM).
(5) The morphology and structural features of the Zn-TSA@Zn samples were observed with a cold field emission scanning electron microscope (FESEM, hitachi Regulus 8230) in combination with an energy dispersive x-ray spectrometer (EDS).
2. Test results
Cross-sectional Scanning Electron Microscopy (SEM) images of Zn-tsa@zn (2 a) visually show a uniform tight coating (thickness about 6 μm) on the zinc foil; FIG. 2b shows that the uniformly and closely distributed Zn-TSA flakes are perpendicular to the zinc surface and have a thickness of about 50-200 nm. Transmission Electron Microscopy (TEM) images showed that Zn-TSA has a uniform lamellar structure with a smooth surface (FIG. 3).
Coordinated Supermolecular Network (CSNs) is considered to be an excellent material for artificial zinc negative electrode interface. In general, CSN consists of hydrogen bonds, pi-pi stacking, ionic interactions, and metal-ligand interactions, and exhibits various good characteristics such as grid flexibility, self-healing ability, and dynamic reversibility. The present invention analyzes the crystal structure of Zn-TSA@Zn by X-ray diffraction (XRD) (FIG. 2C), showing that Zn-TSA CSN has a remarkable CSN structure, and sharp XRD peaks verify the high crystallinity of Zn-TSA CSN (coordinated supermolecular grid), which can well conform to the simulation mode of [ Zn (C 6H4(CO2) (S) -1, 2) ] (CCDC No. 231141) without impurities. FIG. 1 illustrates the simulated atomic configuration of Zn-TSA@Zn, the extended structure of Zn-TSA@Zn being a zinc sulfate based "zigzag" chain in which chains of aromatic rings alternate side to side, the chains being further stacked into various sheets, the aromatic rings in adjacent chains being arranged in such a way that the aromatic rings in adjacent chains are well separated by coordination of carboxylate with zinc (II) ions in adjacent chains, each two-dimensional sheet being formed in the form of a secondary layer of 8-membered rings in the bc plane, wherein each ring is formed of repeating units (-Zn 1-O1-Zn 1-S1-) and the chains of metal centers being parallel to the c-axis of the crystal, each individual sheet being separated by a layer of double aromatic layers, the layered structure being crosslinked by zinc (II) because the central metal can grow vertically and be closely packed. Thus, when Zn-TSA@Zn is used as the surface coating layer of the zinc anode, dense Zn-TSA@Zn can suppress the uneven diffusion of Zn 2+, thereby regulating dendrite-free zinc deposition.
In addition, thermogravimetry (TG) experiments performed in the range of 33-800 ℃ showed that Zn-tsa@zn has a higher thermal stability (fig. 2 d). Notably, zn-TSA was prepared in aqueous solution without high temperature vacuum drying. From 350 ℃, only one mass loss plateau (54.1% weight loss) was detected, due to the decomposition of the Zn-tsa@zn component, indicating a higher thermal stability of Zn-tsa@zn. Furthermore, no water related mass loss was observed, indicating that Zn-tsa@zn has good hydrophobicity, no water crystallized, coordinated or adsorbed in the structure. In addition, the physical properties of Zn-TSA were characterized using Brunauere-Emmette-Teller (BET) and Barrett-Joyner-Halenda (BJH) (FIG. 2 e). The results show that Zn-TSA@Zn has a nonporous characteristic, the specific surface area is low and is 9.6m 2 g-1, and the compact structure of Zn-TSA@Zn helps to prevent water penetration, so that a unique protective layer is established on the surface of zinc.
Experimental example 2 electrochemical measurement of Zn-TSA@Zn negative electrode
1. Experimental method
(1) Synthesis of molybdenum disulfide
Molybdenum disulfide is prepared by a typical hydrothermal method: first, 0.151g of thioacetamide, 0.206g of sodium molybdate dihydrate and 0.05g (0.14 mmol) of cetyltrimethylammonium bromide were dissolved in 20mL of deionized water, followed by magnetic stirring for 10 minutes until complete dissolution gave a homogeneous solution. Then, the homogeneous solution was transferred to a 50mL polytetrafluoroethylene autoclave and stored at 200 ℃ for 24 hours, and after the autoclave was cooled to room temperature, the product was washed three times with deionized water and absolute ethanol, respectively. Finally, the cells were dried in an oven at 60 ℃ for 12 hours, further characterized and used as battery positive electrode materials.
(2) Electrochemical characterization of Zn-TSA@Zn negative electrode
1) Plating/stripping test:
The symmetric zinc and Zn-tsa@zn cells were subjected to plating/stripping tests using a 2032 type button cell. Molybdenum disulfide or vanadium pentoxide (purity not less than 98%, an Naiji, without purification), ketjen Black (KB) and polyvinylidene fluoride (PVDF) were prepared at a ratio of 7:2:1, and then adding a certain amount of N-methyl-2-pyrrolidone (NMP), and continuing grinding for a period of time to obtain uniform slurry. On this basis, the slurry was uniformly coated on a stainless steel foil current collector and dried in an oven at 60 ℃ for 12 hours. Finally, a stainless steel foil was cut into Φ14mm electrodes and loaded with about 1.0mg of active material (Zn-tsa@zn), and the plating/stripping test was performed with the prepared stainless steel foil as the positive electrode, with zinc foil (purity ∈ 99.99%, thickness =0.1 mm) as the negative electrode (all bare zinc negative electrodes were polished with sandpaper), with medium-speed qualitative filter paper as the separator, and with 3M zinc trifluoromethane sulfonate Zn (CF 3SO3)2 aqueous solution as the electrolyte.
2) Linear polarization measurement:
The linear polarization measurement adopts a three-electrode structure, wherein bare zinc or Zn-TSA@Zn is used as a working electrode, a zinc plate is used as a counter electrode, and a saturated thermal electrode (SCE) is used as a reference electrode. The corrosion potential and corrosion current were calculated using Tafel fitting system for the electrochemical workstation.
3) Electrochemical performance of ZMB full cell:
To demonstrate the feasibility of Zn-TSA@Zn negative electrode in practical application, zn-TSA@Zn was used as the negative electrode, and two different positive electrode materials (MoS 2 and V 2O5) were used for assembling and evaluating the electrochemical characteristics of an all-ZMB device (aqueous zinc metal battery device). And (3) placing the full battery with V 2O5/MoS2 Zn-TSA@Zn in a voltage range of 0.25-1.25V (molybdenum disulfide) or 0.2-1.6V (vanadium pentoxide) for current charge and discharge, calculating Zn/Zn 2+ under different current densities on a NEWARECT-4008T battery tester, calculating specific capacity according to the active quality of the molybdenum disulfide or vanadium pentoxide positive electrode, and recording EIS and CV data of the battery on an electrochemical workstation (CHI 760E, china).
2. Experimental results
The hydrophobic, electronically insulating Zn-TSA layer can effectively separate zinc metal from the bulk liquid electrolyte, blocking the charge transfer of zinc metal to water, thereby inhibiting chemical oxidation of zinc and electrochemical water decomposition on the Zn-TSA@Zn electrode. In situ optical microscopy images provided direct evidence of zinc plating/stripping mediated by the medium Zn-TSA layer of 3M Zn (OTF) 2 electrolyte (fig. 4a and 4 b). As expected, irregular zinc particles appeared on the bare zinc surface, accumulating moss dendrites over 8 cycles. In the coating process on bare zinc, a large number of bubbles are generated, and after 8 hours, the corresponding voltage polarization of bare zinc can reach 192.7mV (FIG. 4 c), because the resistance is increased due to the formation of a large number of byproducts (such as Zn x(OTF-)y(OH)2x-y·nH2 O and ZnO), and dead zinc is detected to be separated from the electrode after 10 cycles. In sharp contrast, the interface between the Zn-tsa@zn negative electrode and the electrolyte remained smooth during the 10 cycles plating/stripping test, no zinc dendrites or bubbles were formed on the Zn-tsa@zn electrode (i.e., no by-product generation), and the corresponding voltage polarization remained stable (about 152.5 mV) (fig. 4 d).
In addition to dendrite growth, zinc corrosion reactions are also a key cause of aqueous cell failure. For this purpose, the effect of the Zn-TSA layer on the protection against zinc corrosion was analyzed by linear electrokinetic polarization experiments performed in 3M Zn (OTF) 2 aqueous solution (fig. 5). The results show that the Zn-TSA@Zn electrode [ 0.909Vvs. saturated thermal electrode (SCE) ] has a more positive corrosion potential [ 0.919Vvs. Saturated Calomel Electrode (SCE) ] value than the bare zinc electrode, and it is noted that the corrosion current density of the Zn-TSA@Zn electrode (0.92 μAcm -2) is greatly reduced compared to the zinc foil (25.05 μAcm -2). The lower the corrosion current, the lower the corrosion rate, which shows that the zinc corrosion reaction of the Zn-TSA@Zn electrode is greatly reduced.
Fig. 6a and 6b compare the cycling performance of MoS 2 Zn and MoS 2 Zn-tsa@zn full cells at 2Ag -1. It can be seen that the MoS 2 i Zn cell failed after 342 charge and discharge cycles due to zinc dendrite growth across the filter paper membrane. In sharp contrast, a MoS 2 Zn-tsa@zn battery can stably run for 600 charge and discharge cycles, but the cycling stability of a MoS 2 Zn-tsa@zn device is limited by degradation of the molybdenum disulfide positive electrode structure. Therefore, the invention replaces the positive electrode of the device with a new MoS 2 positive electrode, and the performance of the battery can be kept stable for more than 2000 cycles.
Likewise, FIGS. 6d and 6e show the cycling performance of V 2O5 Zn and V 2O5 Zn-TSA@Zn full cell at 2Ag -1. The specific capacity of both devices experienced an upward trend during the initial cycle due to the activation process of the V 2O5 positive electrode and reached a maximum of about 350mAh g -1 after 100 cycles. Then, a failure of the V 2O5 Zn battery was immediately observed, whereas the Zn-tsa@zn battery was able to operate for more than 1500 charge-discharge cycles. The above results demonstrate that the Zn-TSA@Zn negative electrode of the invention has strong potential as a long-cycle and dendrite-free negative electrode in an actual ZMB water device.
In summary, the invention adopts an easily-extensible wet chemical method, the Zn-TSA CSN is used for adjusting the zinc cathode interface, and the Zn-TSA layer effectively prevents solvated water and anions from diffusing through the Zn-TSA, thereby promoting uniform Zn 2+ flux, further avoiding dendrite-free zinc deposition and the generation of harmful byproducts, and reducing zinc corrosion reaction. Meanwhile, the feasibility of Zn-TSA in a Zn electrode is verified in ZMB, the circulation capacities of a full battery of MoS 2 Zn-TSA@Zn and V 2O5 Zn-TSA@Zn are obviously improved, and the method has very important promotion effect on commercialization of zinc metal batteries.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (7)
1. A preparation method of a zinc metal negative electrode is characterized in that one surface of a zinc foil is soaked in zinc salt solution, zinc ions are adsorbed on the surface of the zinc foil and then transferred into thiosalicylic acid solution for soaking, so that the thiosalicylic acid reacts with the zinc ions on the surface of the zinc foil, wherein the thiosalicylic acid is 2-thiosalicylic acid, and the concentration of the zinc salt solution is 0.01M-2M; the concentration of the thiosalicylic acid solution is 0.01M-2M, and the pH value is 6.8-7.2; the soaking time of the zinc salt solution is 10s-60min, and the soaking time of the thiosalicylic acid solution is 10s-60min; finally, washing and drying to obtain the zinc metal cathode.
2. The method for preparing a zinc metal anode according to claim 1, wherein the zinc salt comprises zinc sulfate, zinc trifluoromethane sulfonate, zinc acetate, zinc chloride or zinc perchlorate.
3. The method for preparing a zinc metal anode according to claim 1, wherein the process of immersing the zinc salt solution and immersing the thiosalicylic acid solution is repeated 5 to 6 times.
4. The method for preparing a zinc metal negative electrode according to claim 1, wherein the zinc salt solution soaking and the thiosalicylic acid solution soaking are carried out at normal temperature and normal pressure.
5. The method for preparing a zinc metal anode according to claim 1, wherein the zinc foil is cut before use and the soaked side is polished.
6. A zinc metal anode prepared by the preparation method of any one of claims 1 to 5.
7. Use of the zinc metal negative electrode of claim 6 in a zinc metal battery or a zinc ion battery.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007033815A2 (en) * | 2005-09-20 | 2007-03-29 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Electrochemical method for producing nanoscalar metal compounds |
| CN111933912A (en) * | 2020-08-14 | 2020-11-13 | 华中科技大学 | Zinc cathode with zinc ion conductivity interface modification layer, battery and preparation method |
| CN113363410A (en) * | 2021-05-27 | 2021-09-07 | 哈尔滨工业大学 | Preparation method and application of in-situ fast-growth multifunctional zinc cathode protective layer |
| CN113410453A (en) * | 2021-07-05 | 2021-09-17 | 西北工业大学 | Preparation method of metal-organic coordination film modified zinc cathode |
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| WO2007033815A2 (en) * | 2005-09-20 | 2007-03-29 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Electrochemical method for producing nanoscalar metal compounds |
| CN111933912A (en) * | 2020-08-14 | 2020-11-13 | 华中科技大学 | Zinc cathode with zinc ion conductivity interface modification layer, battery and preparation method |
| CN113363410A (en) * | 2021-05-27 | 2021-09-07 | 哈尔滨工业大学 | Preparation method and application of in-situ fast-growth multifunctional zinc cathode protective layer |
| CN113410453A (en) * | 2021-07-05 | 2021-09-17 | 西北工业大学 | Preparation method of metal-organic coordination film modified zinc cathode |
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