CN114824152B - Preparation method and application of zinc cathode modified by metal complex - Google Patents
Preparation method and application of zinc cathode modified by metal complex Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 129
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 125
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 16
- -1 metal complex modified zinc Chemical class 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 77
- 229910052799 carbon Inorganic materials 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 25
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 24
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 15
- 150000003751 zinc Chemical class 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 13
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 235000019253 formic acid Nutrition 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002134 carbon nanofiber Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 239000000123 paper Substances 0.000 claims description 5
- 239000002109 single walled nanotube Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 3
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 239000011135 tin Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000007853 buffer solution Substances 0.000 description 12
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000872 buffer Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
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
- H01M10/365—Zinc-halogen accumulators
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a zinc cathode modified by a metal complex, belonging to the technical field of electrochemical energy storage. The invention provides a method for preparing a metal complex modified zinc cathode by taking a metal compound as a raw material, and further provides application of the metal complex modified zinc cathode in an aqueous zinc-based battery. The preparation method has the advantages of simple process, wide and easily available experimental raw materials, low cost and suitability for large-scale production. The prepared water-based zinc-based battery has good electrochemical performance, the growth of dendrites of the negative electrode is obviously inhibited, and the cycle stability and the rate capability of electrochemical energy storage devices such as batteries are obviously improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a preparation method of a zinc negative electrode modified by a metal complex and application of the zinc negative electrode modified by the metal complex in a water-based zinc-based battery.
Background
At present, most of energy sources in the world are derived from fossil fuels, and with the progress of society, the demand of human beings on the energy sources is increasing day by day, which inevitably causes quite serious influence on the environment and the sustainable development of human beings, so that the development of novel energy sources capable of replacing the traditional fossil energy sources and the realization of high-efficiency energy storage technology are very important. Lithium ion batteries are attracting attention as an energy storage device for practical use in portable electronic products as well as vehicles. Lithium ion batteries have excellent characteristics such as flexibility, high efficiency, and long cycle life, compared to other secondary batteries. However, due to the high cost of metallic lithium and the flammable and toxic characteristics of organic electrolytes, these limitations greatly limit the development and application of lithium ion batteries.
Aqueous zinc ion batteries have become one of the most attractive candidates for energy storage due to the abundant reserves of zinc metal and the high safety of aqueous electrolytes. In recent years, zinc-based batteries have been focused on, and compared with other metal negative electrodes, zinc has a higher theoretical capacity and the lowest oxidation-reduction potential. However, the zinc electrode as a negative electrode is very prone to dendrite formation during continuous dissolution/deposition, and deposited zinc can selectively grow at the dendrite after the increase of the cycle number, and finally the short circuit of the pierced diaphragm or the peeling deactivation is caused, so that the cycle life is greatly reduced. The further development of the zinc ion battery is severely restricted, so that the optimization of the zinc cathode has important significance for improving the performance of the zinc ion battery.
Many efforts have been made to solve this problem. For example, electrolyte additives (sodium dodecyl sulfate (SDS), poly (ethylene glycol), ethyl phosphate (TEP), cetyltrimethylammonium bromide (CTAB), thiourea, and Polyacrylamide (PAM)) have been shown to have a positive effect on improving the stability of zinc negative electrodes. Furthermore, the application of a protective layer on the zinc negative electrode has proven to be an effective measure. For example, the prior art discloses a coating formed by calcium carbonate coating with nano-pores, a graphene oxide layer deposited in a sheet-like manner on the surface of a zinc negative electrode, and a TiO deposited on the surface of a zinc negative electrode by an atomic layer deposition method 2 Coatings, etc., to some extent eliminating the possibility of dendrite selective growth.
However, electrolyte additives may reduce the ionic conductivity of the electrolyte of an aqueous zinc ion battery, and coating a zinc anode by atomic layer deposition is too expensive and precise to be applied in large-scale industrial production. Therefore, a method for modifying a zinc negative electrode, which has the advantages of simple process and low cost, needs to be developed.
Disclosure of Invention
The invention aims to provide a zinc cathode modified by a metal complex and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a zinc negative electrode modified by a metal complex comprises the following steps:
s1: titrating the ammonium salt solution to acidity by using acid to obtain a mixed solution;
s2: adding a metal compound raw material into the mixed solution obtained in the step;
s3: carrying out ultrasonic dispersion on the solution obtained in the step, and then adding a zinc cathode;
s4: stirring the solution obtained in the step under the condition of oil bath, wherein the temperature of the oil bath is set to be 60-80 ℃, and the stirring time is 2-4 h;
s5: and washing the product obtained in the step for 2-3 times by using a washing solvent, and drying in a vacuum drying oven after washing to obtain the zinc cathode modified by the metal complex.
Preferably, the aqueous zinc-based battery is characterized by a battery in which a zinc sheet, porous zinc, a zinc/carbon composite material, or a zinc alloy is used as a negative electrode, and an aqueous solution is used as an electrolyte.
In any of the above schemes, preferably, in step S1, the acid is one or a combination of formic acid, acetic acid and oxalic acid.
In any of the above embodiments, in step S1, the ammonium salt is one or a combination of ammonium formate, ammonium chloride and ammonium sulfate, wherein the concentration of the ammonium salt is 0.1 to 0.5mol/L, and the pH of the mixed solution is 3.6 to 4.8.
In any of the above embodiments, in step S1, the concentration of the ammonium salt is preferably 0.1 to 0.3mol/L, and the pH of the mixed solution is preferably 4.2 to 4.6.
In any of the above embodiments, preferably, in step S1, the concentration of the ammonium salt is 0.2mol/L, and the pH of the mixed solution is 4.4.
In any of the above schemes, preferably, in step S2, the metal compound raw material comprises one or more of aluminum sulfate octadecahydrate, aluminum nitrate nonahydrate, aluminum trichloride and aluminum chloride hexahydrate.
In any of the above schemes, preferably, in step S2, the metal compound raw material includes one or more of ferric nitrate, ferric nitrate nonahydrate, ferric trichloride, and ferric chloride hexahydrate.
In any of the above schemes, preferably, in step S2, the metal compound raw material includes one or a combination of two of copper sulfate and copper chloride.
In any of the above schemes, preferably, in step S2, the metal compound raw material includes one or a combination of two of manganese acetate and manganese chloride.
In any of the above embodiments, preferably, in step S3, the zinc negative electrode includes: zinc flakes, porous zinc, zinc alloys, and zinc/carbon composites.
Preferably in any of the above aspects, the zinc alloy comprises an alloy of zinc and one or more of silver, copper, gold, mercury, tin, aluminum, magnesium, cadmium, lead, titanium and antimony metals
In any of the above embodiments, it is preferable that the carbon source in the zinc/carbon composite is derived from a combination of one or more of mesocarbon microbeads, natural graphite, expanded graphite, artificial graphite, glassy carbon, carbon fibers (e.g., carbon nanofibers), hard carbon, soft carbon, activated carbon, porous carbon, carbon cloth, carbon paper, three-dimensional graphite, carbon black, carbon nanotubes (e.g., single-walled carbon nanotubes, multi-walled carbon nanotubes), graphene (e.g., graphene sheets), and modified materials of the above carbon materials.
In any of the above solutions, preferably, the carbon source in the zinc/carbon composite material is one or a combination of more of activated carbon, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon paper, graphene sheets, and carbon cloth.
In any of the above schemes, the carbon source in the zinc/carbon composite material is preferably a combination of one or more of activated carbon, carbon nanofibers and graphene sheets.
The application of the zinc negative electrode modified by the metal complex in an aqueous zinc-based battery.
The invention has the technical effects and advantages that:
1. the preparation method has the advantages of simple process, wide and easily available experimental raw materials, low cost and suitability for large-scale production;
2. the zinc cathode modified by the technology provided by the invention is used for the water system zinc-based battery, so that the growth of zinc dendrites is obviously inhibited. After the zinc cathode is treated, the electrochemical performance of the battery is obviously improved, and the battery shows longer cycling stability and excellent rate performance.
Drawings
Fig. 1 is a cross-sectional SEM image of an aluminum metal complex modified zinc anode of example 1 of the present invention;
fig. 2 is a cross-sectional SEM image of a comparative example 1 zinc anode of the present invention;
FIG. 3 is a zinc ion deposition/dissolution voltage curve for an aluminum metal complex modified zinc symmetric cell of example 1 of the present invention and a zinc symmetric cell of comparative example 1;
FIG. 4 is an SEM image of the surface of an electrode after 50 hours cycling for a symmetrical cell of comparative example 1 in accordance with the invention;
FIG. 5 is an SEM image of the surface of an electrode after 740 hours of cycling for a symmetrical zinc cell modified with aluminum metal complex in example 1 of the present invention;
FIG. 6 is a graph showing the cycle performance of zinc (Zn/NaV) of the zinc negative electrode modified with aluminum metal complex of example 1 of the present invention and zinc of comparative example 1 3 O 8 ·1.5H 2 O cells);
FIG. 7 is a graph of the rate capability of the zinc modified with aluminum metal complex coating of example 1 of the invention and the zinc of comparative example 1 (Zn/NaV) 3 O 8 ·1.5H 2 O-cell).
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, and is not intended to limit the present invention. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the feature.
A preparation method of a zinc negative electrode modified by a metal complex comprises the following steps:
s1: titrating the ammonium salt solution to acidity by using acid to obtain a mixed solution;
s2: adding a metal compound raw material into the mixed solution obtained in the step;
s3: carrying out ultrasonic dispersion on the solution obtained in the step, and then adding a zinc cathode;
s4: stirring the solution obtained in the step under the condition of oil bath, wherein the temperature of the oil bath is set to be 60-80 ℃, and the stirring time is 2-4 h;
s5: and washing the product obtained in the step for 2-3 times by using a washing solvent, and drying in a vacuum drying oven after washing to obtain the zinc cathode modified by the metal complex.
Specifically, the water-based zinc-based battery is characterized in that a zinc sheet, porous zinc, a zinc/carbon composite material and a zinc alloy are used as a negative electrode, and an aqueous solution is used as an electrolyte.
Specifically, in step S1, the acid is one or a combination of formic acid, acetic acid and oxalic acid.
Specifically, in step S1, the ammonium salt is one or a combination of ammonium formate, ammonium chloride and ammonium sulfate, wherein the concentration of the ammonium salt is 0.1 to 0.5mol/L, and the pH of the mixed solution is 3.6 to 4.8.
Specifically, in step S1, the concentration of the ammonium salt is 0.1 to 0.3mol/L, and the pH of the mixed solution is 4.2 to 4.6.
Specifically, in step S1, the concentration of ammonium salt was 0.2mol/L, and the pH of the mixed solution was 4.4.
Specifically, in step S2, the metal compound raw material includes one or more of aluminum sulfate octadecahydrate, aluminum nitrate nonahydrate, aluminum trichloride and aluminum chloride hexahydrate.
Specifically, in step S2, the metal compound raw material includes one or more of ferric nitrate, ferric nitrate nonahydrate, ferric trichloride, and ferric chloride hexahydrate.
Specifically, in step S2, the metal compound raw material includes one or a combination of two of copper sulfate and copper chloride.
Specifically, in step S2, the metal compound raw material includes one or a combination of two of manganese acetate and manganese chloride.
Specifically, in step S3, the zinc negative electrode includes: zinc flakes, porous zinc, zinc alloys, and zinc/carbon composites.
Specifically, the zinc alloy comprises an alloy of zinc and one or more of silver, copper, gold, mercury, tin, aluminum, magnesium, cadmium, lead, titanium and antimony
Specifically, the carbon source in the zinc/carbon composite material is derived from a combination of one or more of mesocarbon microbeads graphite, natural graphite, expanded graphite, artificial graphite, glassy carbon, carbon fibers (e.g., carbon nanofibers), hard carbon, soft carbon, activated carbon, porous carbon, carbon cloth, carbon paper, three-dimensional graphite, carbon black, carbon nanotubes (e.g., single-walled carbon nanotubes, multi-walled carbon nanotubes), graphene (e.g., graphene sheets), and modified materials of the above carbon materials.
Specifically, the carbon source in the zinc/carbon composite material is preferably one or a combination of more of activated carbon, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon paper, graphene sheets and carbon cloth.
Specifically, the carbon source in the zinc/carbon composite material is more preferably a combination of one or more of activated carbon, carbon nanofibers, and graphene sheets.
The application of the zinc negative electrode modified by the metal complex in the zinc ion battery.
Example 1:
0.01mol of ammonium formate was weighed out and dissolved in 50ml of deionized water, and the ammonium formate solution was titrated to pH 4.4 using formic acid to obtain a buffer solution. After 0.06g of aluminum sulfate was added to the buffer and sonicated for 15min to completely dissolve, 8 commercial zinc plates (1cm. Times.1cm) were added to the solution, and the mixture was vigorously stirred in an oil bath at 70 ℃ for 3 hours. And taking out the stirred zinc sheet, washing the zinc sheet for 2 to 3 times by using ethanol and deionized water, placing the zinc cathode after reaction in a vacuum drying oven, and drying the zinc cathode for 12 hours at the temperature of 60 ℃ to obtain the aluminum metal complex modified zinc cathode.
Example 2:
0.02mol of ammonium formate was weighed out and dissolved in 50ml of deionized water, and the ammonium formate solution was titrated to pH 4.4 using formic acid to obtain a buffer solution. After 0.06g of aluminum sulfate was added to the buffer and sonicated for 15min to completely dissolve, 8 commercial zinc plates (1cm. Times.1cm) were added to the solution, and the mixture was vigorously stirred in an oil bath at 70 ℃ for 3 hours. And taking out the stirred zinc sheet, washing the zinc sheet for 2 to 3 times by using ethanol and deionized water, placing the zinc cathode after reaction in a vacuum drying oven, and drying the zinc cathode for 12 hours at the temperature of 60 ℃ to obtain the aluminum metal complex modified zinc cathode.
Example 3:
0.005mol of ammonium formate was weighed out and dissolved in 50ml of deionized water, and the ammonium formate solution was titrated to pH 4.4 using formic acid to obtain a buffer solution. After adding 0.06g of aluminum sulfate to the buffer and sonicating for 15min to complete dissolution, 8 commercial zinc plates at 1cm x 1cm were added to the solution and the mixture was placed in an oil bath at 70 ℃ and stirred vigorously for 3 hours. And taking out the stirred zinc sheet, washing the zinc sheet for 2 to 3 times by using ethanol and deionized water, placing the reacted zinc cathode in a vacuum drying oven, and drying the zinc cathode for 12 hours at the temperature of 60 ℃ to obtain the aluminum metal complex modified zinc cathode.
Example 4:
0.01mol of ammonium formate was weighed out and dissolved in 50ml of deionized water, and the ammonium formate solution was titrated to pH 3.6 using formic acid to obtain a buffer solution. After 0.06g of aluminum sulfate was added to the buffer and sonicated for 15min to completely dissolve, 8 commercial zinc plates (1cm. Times.1cm) were added to the solution, and the mixture was vigorously stirred in an oil bath at 70 ℃ for 3 hours. And taking out the stirred zinc sheet, washing the zinc sheet for 2 to 3 times by using ethanol and deionized water, placing the zinc cathode after reaction in a vacuum drying oven, and drying the zinc cathode for 12 hours at the temperature of 60 ℃ to obtain the aluminum metal complex modified zinc cathode.
Example 5:
0.01mol of ammonium formate was weighed out and dissolved in 50ml of deionized water, and the ammonium formate solution was titrated to pH 4.8 using formic acid to obtain a buffer solution. After adding 0.06g of aluminum sulfate to the buffer and sonicating for 15min to complete dissolution, 8 commercial zinc plates at 1cm x 1cm were added to the solution and the mixture was placed in an oil bath at 70 ℃ and stirred vigorously for 3 hours. And taking out the stirred zinc sheet, washing the zinc sheet for 2 to 3 times by using ethanol and deionized water, placing the zinc cathode after reaction in a vacuum drying oven, and drying the zinc cathode for 12 hours at the temperature of 60 ℃ to obtain the aluminum metal complex modified zinc cathode.
Example 6:
0.01mol of ammonium formate was weighed out and dissolved in 50ml of deionized water, and the ammonium formate solution was titrated to pH 4.4 using formic acid to obtain a buffer solution. After adding 0.06g of manganese sulfate to the buffer and sonicating for 15min to dissolve completely, 8 commercial zinc plates of 1cm x 1cm were added to the solution and the mixture was placed in a 70 ℃ oil bath and stirred vigorously for 3 hours. And taking out the stirred zinc sheet, washing the zinc sheet for 2-3 times by using ethanol and deionized water, placing the zinc cathode after reaction in a vacuum drying oven, and drying the zinc cathode for 12 hours at the temperature of 60 ℃ to obtain the zinc cathode modified by the manganese metal complex.
Example 7:
0.01mol of ammonium formate was weighed out and dissolved in 50ml of deionized water, and the ammonium formate solution was titrated to pH 4.4 using formic acid to obtain a buffer solution. Adding 0.06g of aluminum sulfate into a buffer solution, performing ultrasonic treatment for 15min until the aluminum sulfate is completely dissolved, adding a zinc/graphene composite material into the solution, and placing the mixed solution in an oil bath at 70 ℃ to be violently stirred for 3 hours. And taking out the stirred zinc cathode, washing the zinc cathode for 2 to 3 times by using ethanol and deionized water, placing the reacted zinc cathode in a vacuum drying oven, and drying the zinc cathode for 12 hours at the temperature of 60 ℃ to obtain the aluminum metal complex modified zinc cathode.
Example 8:
0.01mol of ammonium formate was weighed out and dissolved in 50ml of deionized water, and the ammonium formate solution was titrated to pH 4.4 using formic acid to obtain a buffer solution. Adding 0.06g of aluminum sulfate into the buffer solution, performing ultrasonic treatment for 15min until the aluminum sulfate is completely dissolved, adding a zinc/activated carbon composite material into the solution, and placing the mixed solution in an oil bath at 70 ℃ for vigorously stirring for 3 hours. And taking out the stirred zinc cathode, washing the zinc cathode for 2 to 3 times by using ethanol and deionized water, placing the reacted zinc cathode in a vacuum drying oven, and drying the zinc cathode for 12 hours at the temperature of 60 ℃ to obtain the aluminum metal complex modified zinc cathode.
Example 9:
0.01mol of ammonium formate was weighed out and dissolved in 50ml of deionized water, and the ammonium formate solution was titrated to pH 4.4 using formic acid to obtain a buffer solution. Adding 0.06g of aluminum sulfate into the buffer solution, performing ultrasonic treatment for 15min until the aluminum sulfate is completely dissolved, adding a zinc-copper alloy into the solution, and placing the mixed solution in an oil bath at 70 ℃ to be vigorously stirred for 3 hours. And taking out the stirred zinc cathode, washing the zinc cathode for 2 to 3 times by using ethanol and deionized water, placing the reacted zinc cathode in a vacuum drying oven, and drying the zinc cathode for 12 hours at the temperature of 60 ℃ to obtain the aluminum metal complex modified zinc cathode.
Comparative example 1:
an unmodified zinc cathode is used as the cathode.
The electrochemical properties of the samples obtained were determined as follows:
using zinc cathode modified by metal complex as electrode, glass fiber (Whatman) as diaphragm, and 2mol L -1 ZnSO 4 As the electrolyte of the symmetrical battery, the button type Zn// Zn symmetrical battery of CR2025 is assembled by the electrolyte, and the current density is 1mA cm -2 (1mAh cm -2 ) The electrochemical performance of the symmetrical cell was tested.
117mg of NaV were weighed out 3 O 8 ·1.5H 2 O (NVO for short) cathode material, 32mg of conductive carbon black is added and fully ground. Then 16mg of 60wt.% adhesive Polytetrafluoroethylene (PTFE) is weighed and dissolved in 5ml of ethanol, after ultrasonic treatment for 15 minutes, the mixture is fully dispersed, the ground material is added into the ethanol dispersion liquid for ultrasonic treatment for 2 hours, and the dispersed slurry is rolled into a pole piece. The prepared electrode sheet was vacuum-dried at 60 ℃ for 12 hours, and cut into 1mg electrode sheets for use. Taking an NVO pole piece as a positive electrode, a zinc negative electrode modified by a metal complex as a negative electrode, glass fiber (Whatman) as a diaphragm and 2mol L of the negative electrode -1 ZnSO 4 +0.1mol L -1 NaSO 4 The button type water-based zinc ion battery is assembled into a CR2025 battery as an electrolyte. The battery is tested for charge-discharge capacity and rate capability within the voltage range of 0.2-1.4V.
The cycling stability of the symmetrical cell and the full cell was determined and the specific results are shown in Table 1
TABLE 1
| Number of | Symmetric battery cycle time/h | Cycle number/n of full cell |
| Example 1 | 740 | 1520 |
| Example 2 | 620 | 890 |
| Example 3 | 590 | 840 |
| Example 4 | 350 | 660 |
| Example 5 | 470 | 740 |
| Example 6 | 320 | 630 |
| Example 7 | 540 | 820 |
| Example 8 | 420 | 710 |
| Example 9 | 570 | 830 |
| Comparative example 1 | 80 | 380 |
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. A preparation method of a zinc cathode modified by a metal complex is characterized by comprising the following steps: the method comprises the following steps:
s1: titrating the ammonium salt solution to acidity by using acid to obtain a mixed solution;
s2: adding a metal compound raw material into the mixed solution obtained in the step;
s3: carrying out ultrasonic dispersion on the solution obtained in the step, and then adding a zinc cathode;
s4: stirring the solution obtained in the step under the condition of oil bath, wherein the temperature of the oil bath is set to be 60-80 ℃, and the stirring time is 2-4 hours;
s5: washing the product obtained in the step for 2 to 3 times by using a washing solvent, and drying in a vacuum drying oven after washing to obtain a zinc negative electrode modified by a metal complex;
in the step S1, the ammonium salt is one or a combination of ammonium formate, ammonium chloride and ammonium sulfate, wherein the concentration of the ammonium salt is 0.1 to 0.5mol/L, and the pH value of the mixed solution is 3.6 to 4.8;
in step S2, the metal compound raw material comprises one or more of aluminum sulfate octadecahydrate, aluminum nitrate nonahydrate, aluminum trichloride and aluminum chloride hexahydrate;
or in step S2, the metal compound raw material includes one or more of ferric nitrate, ferric nitrate nonahydrate, ferric trichloride and ferric chloride hexahydrate;
or in the step S2, the metal compound raw material comprises one or two of copper sulfate and copper chloride;
or in step S2, the metal compound raw material comprises one or the combination of two of manganese acetate and manganese chloride;
in step S3, the zinc negative electrode includes: zinc flakes, porous zinc, zinc alloys, and zinc/carbon composites;
the carbon source in the zinc/carbon composite material is derived from one or more of mesocarbon microbeads, natural graphite, expanded graphite, glassy carbon, carbon fibers, hard carbon, soft carbon, activated carbon, porous carbon, carbon cloth, carbon paper, carbon black, carbon nanotubes, graphene and modified materials of the above carbon materials.
2. The method for preparing a zinc anode modified by a metal complex according to claim 1, wherein the method comprises the following steps: in step S1, the acid is one or a combination of formic acid, acetic acid, and oxalic acid.
3. The method for preparing a zinc anode modified by a metal complex according to claim 1, wherein the method comprises the following steps: in the step S1, the concentration of the ammonium salt is 0.1 to 0.3mol/L, and the pH of the mixed liquid is 4.2 to 4.6.
4. The method for preparing a zinc negative electrode modified by a metal complex according to claim 3, wherein the method comprises the following steps: in step S1, the concentration of the ammonium salt is 0.2mol/L, and the pH of the mixed solution is 4.4.
5. The method for preparing a zinc anode modified by a metal complex according to claim 1, wherein the method comprises the following steps: the zinc alloy comprises an alloy of zinc with one or more of silver, copper, gold, mercury, tin, aluminium, magnesium, cadmium, lead, titanium and antimony.
6. The method for preparing a zinc anode modified by a metal complex according to claim 1, wherein the method comprises the following steps: the carbon source in the zinc/carbon composite material is one or a combination of more of activated carbon, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon paper, graphene sheets and carbon cloth.
7. The method for preparing a zinc anode modified by a metal complex according to claim 1, wherein the method comprises the following steps: the carbon source in the zinc/carbon composite material is set as one or more of activated carbon, carbon nanofibers and graphene sheets.
8. Use of a method of preparing a metal complex modified zinc negative electrode according to any one of claims 1 to 7 in an aqueous zinc-based battery.
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