CN112582578A - Zinc cathode with protective layer and preparation method and application thereof - Google Patents
Zinc cathode with protective layer and preparation method and application thereof Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 110
- 239000011701 zinc Substances 0.000 title claims abstract description 110
- 239000011241 protective layer Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000002086 nanomaterial Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- 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 6
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 3
- UISIYYCJKZNXDU-UHFFFAOYSA-L disodium;naphthalene-2,6-dicarboxylate Chemical compound [Na+].[Na+].C1=C(C([O-])=O)C=CC2=CC(C(=O)[O-])=CC=C21 UISIYYCJKZNXDU-UHFFFAOYSA-L 0.000 claims description 3
- MDGRUBNBPOYDKU-UHFFFAOYSA-K trisodium benzene-1,3,5-tricarboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 MDGRUBNBPOYDKU-UHFFFAOYSA-K 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- QAGQFDYITIKYIW-UHFFFAOYSA-L disodium;2,5-dicarboxybenzene-1,4-diolate Chemical compound [Na+].[Na+].OC1=CC(C([O-])=O)=C(O)C=C1C([O-])=O QAGQFDYITIKYIW-UHFFFAOYSA-L 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 244000137852 Petrea volubilis Species 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 5
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000013239 manganese-based metal-organic framework Substances 0.000 description 4
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010278 pulse charging Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- 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
-
- 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
Abstract
The invention relates to a preparation method of a zinc cathode with a protective layer, which comprises the following steps: reacting an aqueous solution containing metal salt and an organic ligand at the temperature of 20-80 ℃ for 4-12h, carrying out solid-liquid separation, washing and drying to obtain metal-MOFs; annealing the metal-MOFs at 400-600 ℃ for 3-5h under the protection of nitrogen atmosphere to obtain a metal-MOFs-based nano material; mixing the metal-MOFs-based nano material with an additive, a polymer and an organic solvent to prepare slurry, then coating the slurry on the surface of a clean zinc cathode, and drying to obtain the zinc-based composite cathode material. According to the invention, the inorganic-organic composite surface protection film is constructed on the surface of the zinc cathode, so that the direct contact between the zinc cathode and the electrolyte is avoided, the uniform distribution of an electric field on the surface of the zinc cathode is ensured, the zinc deposition is more uniform, and meanwhile, the inorganic-organic composite protection film has good flexibility, the growth of zinc dendrites is inhibited, and the cycle life of the zinc-based battery is greatly prolonged.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a metal zinc cathode with a protective layer on the surface, a preparation method thereof and application thereof in a secondary zinc-based battery.
Background
The metal zinc has high energy density (820 mAh/g), lower reduction potential (-0.76V vs. standard hydrogen electrode) and low cost, and is a negative electrode material of green batteries such as secondary zinc-based batteries, alkaline zinc-nickel batteries, alkaline zinc-silver batteries, neutral zinc-manganese batteries, zinc-nickel flow batteries, zinc-bromine batteries and the like. Therefore, the improvement of the electrochemical performance of the metallic zinc is receiving much attention from researchers and engineers.
However, since zinc has a more negative reduction potential than a standard hydrogen electrode, when metal zinc is in direct contact with an electrolyte, the metal zinc reacts with the electrolyte to release hydrogen gas; and zinc dendrite and large deformation of the zinc negative electrode can be generated in the battery circulation process, so that the internal short circuit of the secondary battery is caused, and the defects seriously limit the service life of the zinc-based battery. In order to solve these problems, researchers and engineers have developed various ways such as electrolyte modification, pulse charging, and zinc electrode replacement in order to achieve the goal of improving the cycle life of zinc-based batteries. However, the methods still have certain limitations, such as the method for modifying the electrolyte can only improve the cycle life of the zinc-based battery under certain conditions; the pulse charging method still cannot solve the reaction of the metal zinc and the electrolyte; the way of replacing the zinc electrode causes a great deal of waste of metal resources.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a metal zinc cathode with a protective layer on the surface, wherein an inorganic-organic composite surface protective film is constructed on the surface of the zinc cathode, so that the direct contact between the zinc cathode and an electrolyte is avoided, the uniform distribution of an electric field on the surface of the zinc cathode is ensured, the zinc deposition is more uniform, and meanwhile, the inorganic-organic composite protective film has good flexibility, the growth of zinc dendrites is inhibited, and the cycle life of a zinc-based battery is greatly prolonged.
The invention also provides a preparation method of the metal zinc negative electrode with the protective layer and application of the metal zinc negative electrode in a secondary zinc-based battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a zinc anode with a protective layer comprises the following steps:
1) Reacting an aqueous solution containing metal salt and an organic ligand at the temperature of 20-80 ℃ for 4-12h, carrying out solid-liquid separation, washing and drying to obtain metal-MOFs;
2) Annealing the metal-MOFs at 400-600 ℃ for 3-5h under the protection of nitrogen atmosphere to obtain a metal-MOFs-based nano material;
3) Mixing the metal-MOFs-based nano material with an additive, a polymer and an organic solvent to prepare slurry, then coating the slurry on the surface of a clean zinc cathode, and drying (generally drying in vacuum for 10-14h at 60-80 ℃) to obtain the zinc cathode with the protective layer.
Specifically, in step 1), the metal salt is a nitrate or sulfate of manganese, zinc, cobalt, and nickel, such as manganese sulfate, zinc nitrate, nickel nitrate, and cobalt nitrate. The organic ligand is one or more than two of dimethyl imidazole, pyromellitic acid tetrasodium salt, trimesic acid trisodium salt, 2, 5-dihydroxy terephthalic acid disodium salt and 2, 6-naphthalene dicarboxylic acid disodium salt; the mass ratio of the metal salt to the organic ligand is 1:0.5-5. The concentration of the metal salt in the aqueous solution containing the metal salt and the organic ligand may vary from 1 to 100mg/ml. The organic ligands of the present invention can be purchased directly or by reacting the acid with NaOH to obtain the corresponding sodium salt, which is a common technique in the art, e.g., reacting pyromellitic acid with NaOH to obtain pyromellitic acid tetrasodium salt.
Specifically, in the step 3), the additive comprises one or more of boron nitride, calcium carbonate, zirconium oxide, titanium oxide, aluminum oxide, acetylene black, carbon black, graphene and graphite; preferably boron nitride.
Specifically, in the step 3), the polymer comprises one or more of polyamide, polyvinyl butyral, polytetrafluoroethylene and polyvinylidene fluoride; preferably polyvinyl butyral.
Specifically, in the step 3), the organic solvent comprises one or more of ethanol, N-dimethylformamide, N-methylpyrrolidone, isopropanol, formic acid and dimethyl sulfoxide; ethanol is preferred.
Further preferably, in the step 3), the metal-MOFs-based nano material is mixed with an additive, a polymer and an organic solvent according to the mass ratio of (5) - (20): 10) - (25): 70) - (90) to prepare a slurry; the thickness of the protective layer is 5 to 50 μm.
In the invention, the clean zinc cathode is obtained by the following treatment: polishing the surface of the metal zinc by using 8000-mesh sand paper, then respectively cleaning the metal zinc with the polished surface by using deionized water, ethanol and acetone under an ultrasonic condition, wherein the treatment temperature is 25 ℃, the treatment time is 30 minutes, and after the treatment is finished, drying the metal zinc in a vacuum oven at 80 ℃ for 6 hours.
The invention provides a zinc cathode with a protective layer, which is prepared by the preparation method.
The invention also provides application of the zinc negative electrode with the protective layer in preparation of a secondary zinc-based battery. The zinc cathode with the protective layer provided by the invention has wide application prospects in alkaline, near-neutral and weak-acid secondary zinc-based batteries, and can remarkably prolong the cycle life of the zinc-based batteries.
According to the invention, the slurry containing the metal-MOFs-based nano material, the additive, the polymer and the organic solvent is used for coating the surface of the zinc cathode, and a layer of inorganic-organic composite surface protection film is formed on the surface of the zinc cathode in a vacuum drying mode, so that the direct contact between the zinc cathode and an electrolyte is avoided, the uniform distribution of an electric field on the surface of the zinc cathode is ensured, the deposition of zinc ions on the surface of the zinc cathode is more uniform, meanwhile, the inorganic-organic composite protection film has good flexibility, the growth of zinc dendrites is inhibited, the protection of the zinc cathode is realized, the inorganic-organic composite protection film is applied to the zinc-based battery, and the cycle life of the zinc-based battery is remarkably prolonged. Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for protecting a zinc cathode, namely a method for preparing the zinc cathode with a protective layer, which is simple to operate, low in cost and easy for large-scale production. The zinc cathode with the protective layer solves the problem of poor cycle performance of a zinc-based battery by avoiding the direct contact of the zinc cathode and electrolyte and inhibiting the formation of zinc dendrite. The zinc cathode protected by the invention is an ideal cathode material and can be widely applied to alkaline, neutral and weakly acidic zinc-based batteries.
Drawings
Fig. 1 is a graph of voltage versus cycle number for zinc symmetric cells of example 4 and comparative example 1 at a given current density and capacity.
Detailed Description
The invention will now be described in further detail with reference to specific embodiments and the accompanying drawings. The following examples are intended to provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the scope of the present invention. Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
In the following examples, the starting materials used were all common commercial products which were directly available.
Example 1
The preparation method of the zinc negative electrode with the protective layer in the embodiment includes the following steps:
s1, polishing the surface of metal zinc by using 8000-mesh sand paper, then respectively cleaning the polished metal zinc by using deionized water, ethanol and acetone under the ultrasonic condition, wherein the treatment temperature is 25 ℃, the treatment time is 30 minutes, and after the treatment is finished, drying the metal zinc in a vacuum oven at 80 ℃ for 6 hours to obtain a clean zinc cathode.
S2 Zinc nitrate (1 g) and dimethylimidazole (0.5 g) were dissolved in 40 mL of deionized water, respectively. Subsequently, the two solutions were mixed and stirred for 2 minutes to be mixed and reacted at room temperature for 4 hours. And after the reaction is finished, centrifuging, washing the precipitate with deionized water and ethanol respectively for three times, and drying at 60 ℃ to obtain the Zn-MOFs.
S3, placing the Zn-MOFs prepared in the S2 in a tube furnace, introducing nitrogen of 100 sccm (sccm is a standard liter per minute flow value), heating to 500 ℃ at a heating rate of 10 ℃/min, annealing for 4h, and naturally cooling to room temperature after the annealing is finished to obtain the Zn-MOFs-based nano material.
S4, mixing the Zn-MOFs-based nano material prepared in the S3, boron nitride and polyamide, adding formic acid to prepare slurry (the mass ratio of the Zn-MOFs-based nano material to the boron nitride to the polyamide to the formic acid is 5.
Example 2
The preparation method of the zinc negative electrode with the protective layer in the embodiment includes the following steps:
s1, polishing the surface of metal zinc by using 8000-mesh sand paper, then respectively cleaning the polished metal zinc by using deionized water, ethanol and acetone under the ultrasonic condition, wherein the treatment temperature is 25 ℃, the treatment time is 30 minutes, and after the treatment is finished, drying the metal zinc in a vacuum oven at 80 ℃ for 6 hours to obtain a clean zinc cathode.
S2 cobalt nitrate (1 g) and 2-methylimidazole (0.5 g) were dissolved in 40 mL of deionized water, respectively. Subsequently, the two solutions were mixed and stirred for 2 minutes to be well mixed, and reacted at room temperature for 4 hours. And after the reaction is finished, centrifuging, washing the precipitate with deionized water and ethanol respectively for three times, and drying at 60 ℃ to obtain the Co-MOFs.
S3, placing the Co-MOFs prepared in the S2 in a tube furnace, introducing 100 sccm nitrogen, heating to 500 ℃ at a heating rate of 10 ℃/minute, annealing for 4 hours, and naturally cooling to room temperature after the treatment is finished to obtain the Co-MOFs-based nano material.
S4, mixing the Co-MOFs-based nano material prepared in the S3, zirconia and polyamide, adding formic acid to prepare slurry (the mass ratio of the Co-MOFs-based nano material to the zirconia to the polyamide to the formic acid is 5.
Example 3
The preparation method of the zinc negative electrode with the protective layer in the embodiment includes the following steps:
s1, polishing the surface of the metal zinc by using 8000-mesh sand paper, then respectively cleaning the metal zinc with the polished surface by using deionized water, ethanol and acetone under the ultrasonic condition, wherein the treatment temperature is 25 ℃, the treatment time is 30 minutes, and after the treatment is finished, drying is carried out for 6 hours in a vacuum oven at 80 ℃ to obtain a clean zinc cathode.
S2 manganese sulfate (1.5 g) and trisodium trimesate (5 g) are dissolved in 40 mL of deionized water respectively. Subsequently, the two solutions were mixed and stirred for 30 minutes to be well mixed. Then transferred to a 100Ml reaction kettle and reacted for 12h at the temperature of 80 ℃. And after the reaction is finished, centrifuging, washing the precipitate with deionized water and ethanol respectively for three times, and drying at 60 ℃ to obtain the Mn-MOFs.
S3, placing the Mn-MOFs prepared in the S2 in a tubular furnace, introducing 100 sccm nitrogen, heating to 500 ℃ at the heating rate of 10 ℃/min, annealing for 4h, and naturally cooling to room temperature after the annealing is finished to obtain the Mn-MOFs-based nano material.
S4, mixing the Mn-MOFs-based nano material prepared in S3, zirconia and polyvinyl butyral according to a mass ratio of 10.
Example 4
The preparation method of the zinc negative electrode with the protective layer in the embodiment includes the following steps:
s1, polishing the surface of metal zinc by using 8000-mesh sand paper, then respectively cleaning the polished metal zinc by using deionized water, ethanol and acetone under the ultrasonic condition, wherein the treatment temperature is 25 ℃, the treatment time is 30 minutes, and after the treatment is finished, drying the metal zinc in a vacuum oven at 80 ℃ for 6 hours to obtain a clean zinc cathode.
S2 Nickel nitrate (1 g) and disodium 2, 6-naphthalenedicarboxylate (0.5 g) were dissolved in 40 mL of deionized water, respectively. Subsequently, the two solutions were mixed and stirred for 2 minutes to be well mixed. The reaction was carried out at 80 ℃ for 4h. After the reaction is finished, centrifuging, washing the precipitate with deionized water and ethanol respectively for three times, and drying at 60 ℃ to obtain the Ni-MOFs.
S3, placing the Ni-MOFs prepared in the S2 in a tube furnace, introducing 100 sccm nitrogen, heating to 500 ℃ at the heating rate of 10 ℃/minute, annealing for 4 hours, and naturally cooling to room temperature after the annealing is finished to obtain the Ni-MOFs-based nano material.
And S4, mixing the Ni-MOFs-based nano material prepared in the S3, boron nitride and polyvinyl butyral according to the mass ratio of 5.
Respectively using the metal zinc with the protective layer on the surface obtained in S4 as a positive electrode and a negative electrode, and using the metal zinc containing 1M ZnSO 4 Is an electrolyte and an alumina film is a diaphragm, and the zinc symmetrical battery with the protective layer is prepared.
Charge-discharge test of the symmetric battery was performed at room temperature with a current density of 1 mAh/cm 2 The charge-discharge capacity of the charge-discharge capacitor is 2 mAh/cm 2 The number of cycles was 1000, as shown in FIG. 1.
Comparative example 1
The method for preparing the zinc symmetrical cell without the protective layer in the comparative example comprises the following steps:
s1, polishing the surface of the metal zinc by using 8000-mesh sand paper, then respectively cleaning the metal zinc with the polished surface by using deionized water, ethanol and acetone under the ultrasonic condition, wherein the treatment temperature is 25 ℃, the treatment time is 30 minutes, and after the treatment is finished, drying is carried out for 6 hours in a vacuum oven at 80 ℃ to obtain a clean zinc cathode.
S2 respectively takes the clean metal zinc obtained in S1 as a positive electrode and a negative electrode and contains 1M ZnSO 4 The electrolyte and the alumina film are diaphragms, and the zinc symmetrical battery without the protective layer is prepared.
Charge-discharge test of the symmetric battery was performed at room temperature with a current density of 1 mAh/cm 2 The charge-discharge capacity of the charge-discharge capacitor is 2 mAh/cm 2 Under the condition of 110 cycles, the zinc symmetrical cell without the protective layer fails, as shown in fig. 1.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. A preparation method of a zinc cathode with a protective layer is characterized by comprising the following steps:
1) Reacting an aqueous solution containing metal salt and an organic ligand at the temperature of 20-80 ℃ for 4-12h, carrying out solid-liquid separation, washing and drying to obtain metal-MOFs;
2) Annealing the metal-MOFs at 400-600 ℃ for 3-5h under the protection of nitrogen atmosphere to obtain a metal-MOFs-based nano material;
3) Mixing the metal-MOFs-based nano material with an additive, a polymer and an organic solvent to prepare slurry, then coating the slurry on the surface of a clean zinc cathode, and drying to obtain the zinc cathode with the protective layer.
2. The method for preparing the zinc negative electrode with the protective layer according to claim 1, wherein in the step 1), the metal salt is nitrate or sulfate of metal manganese, zinc, cobalt and nickel; the organic ligand is one or more than two of dimethyl imidazole, pyromellitic acid tetrasodium salt, trimesic acid trisodium salt, 2, 5-dihydroxy terephthalic acid disodium salt and 2, 6-naphthalene dicarboxylic acid disodium salt; the mass ratio of the metal salt to the organic ligand is 1:0.5-5.
3. The method for preparing the zinc negative electrode with the protective layer according to claim 1, wherein the additive in step 3) comprises one or more of boron nitride, calcium carbonate, zirconium oxide, titanium oxide, aluminum oxide, acetylene black, carbon black, graphene and graphite.
4. The method for preparing the zinc negative electrode with the protective layer according to claim 1, wherein in the step 3), the polymer comprises one or more of polyamide, polyvinyl butyral, polytetrafluoroethylene and polyvinylidene fluoride.
5. The method for preparing a zinc negative electrode having a protective layer according to claim 1, wherein the organic solvent comprises one or more of ethanol, N-dimethylformamide, N-methylpyrrolidone, isopropanol, formic acid, and dimethylsulfoxide in step 3).
6. The method for preparing a zinc negative electrode with a protective layer according to claim 1, wherein in the step 3), the metal-MOFs-based nanomaterial is mixed with an additive, a polymer and an organic solvent according to a mass ratio of (5) - (20) - (10) - (25) - (70) - (90) to prepare a slurry; the thickness of the protective layer is 5 to 50 μm.
7. The zinc negative electrode with the protective layer prepared by the preparation method of any one of claims 1 to 6.
8. Use of a zinc negative electrode with a protective layer according to claim 7 for the preparation of a secondary zinc-based battery.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113410453A (en) * | 2021-07-05 | 2021-09-17 | 西北工业大学 | Preparation method of metal-organic coordination film modified zinc cathode |
| CN113583453A (en) * | 2021-07-22 | 2021-11-02 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of Mn-MOF/GO nano material |
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| CN114050261A (en) * | 2021-11-04 | 2022-02-15 | 浙江工业大学 | Preparation method of zinc-based battery negative electrode material |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080093243A (en) * | 2007-04-16 | 2008-10-21 | 엘에스엠트론 주식회사 | Anode active material for secondary battery and method for preparing thereof and secondary battery containing the same for anode |
| CN106784688A (en) * | 2016-12-21 | 2017-05-31 | 华中科技大学 | Preparation and application of Zn-C secondary battery composite material |
| CN108258241A (en) * | 2018-01-16 | 2018-07-06 | 北京工业大学 | A kind of cathode of lithium battery for inhibiting lithium dendrite growth using ZIF-8 porous carbon materials |
| CN108807961A (en) * | 2018-06-06 | 2018-11-13 | 上海电力学院 | A kind of zinc-base cell negative electrode material and preparation method thereof |
| CN109713213A (en) * | 2017-10-26 | 2019-05-03 | 中国科学院上海硅酸盐研究所 | A kind of metal zinc load and its preparation method and application with non-functional interface decorative layer |
| JP2019091531A (en) * | 2017-11-10 | 2019-06-13 | 住友金属鉱山株式会社 | Positive electrode active material for lithium ion secondary battery, lithium ion secondary battery, and manufacturing method of the positive electrode active material for lithium ion secondary battery |
| CN111900388A (en) * | 2020-05-26 | 2020-11-06 | 北京理工大学 | Zinc ion battery negative electrode material, preparation and application thereof |
| CN112133918A (en) * | 2020-09-16 | 2020-12-25 | 东北师范大学 | Application of metal-organic framework material as negative electrode protection material of alkali metal air battery and alkali metal air battery |
-
2020
- 2020-12-28 CN CN202011575025.6A patent/CN112582578B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080093243A (en) * | 2007-04-16 | 2008-10-21 | 엘에스엠트론 주식회사 | Anode active material for secondary battery and method for preparing thereof and secondary battery containing the same for anode |
| CN106784688A (en) * | 2016-12-21 | 2017-05-31 | 华中科技大学 | Preparation and application of Zn-C secondary battery composite material |
| CN109713213A (en) * | 2017-10-26 | 2019-05-03 | 中国科学院上海硅酸盐研究所 | A kind of metal zinc load and its preparation method and application with non-functional interface decorative layer |
| JP2019091531A (en) * | 2017-11-10 | 2019-06-13 | 住友金属鉱山株式会社 | Positive electrode active material for lithium ion secondary battery, lithium ion secondary battery, and manufacturing method of the positive electrode active material for lithium ion secondary battery |
| CN108258241A (en) * | 2018-01-16 | 2018-07-06 | 北京工业大学 | A kind of cathode of lithium battery for inhibiting lithium dendrite growth using ZIF-8 porous carbon materials |
| CN108807961A (en) * | 2018-06-06 | 2018-11-13 | 上海电力学院 | A kind of zinc-base cell negative electrode material and preparation method thereof |
| CN111900388A (en) * | 2020-05-26 | 2020-11-06 | 北京理工大学 | Zinc ion battery negative electrode material, preparation and application thereof |
| CN112133918A (en) * | 2020-09-16 | 2020-12-25 | 东北师范大学 | Application of metal-organic framework material as negative electrode protection material of alkali metal air battery and alkali metal air battery |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113410453A (en) * | 2021-07-05 | 2021-09-17 | 西北工业大学 | Preparation method of metal-organic coordination film modified zinc cathode |
| CN113410453B (en) * | 2021-07-05 | 2023-02-28 | 西北工业大学 | Preparation method of metal-organic coordination film modified zinc cathode |
| CN113583453A (en) * | 2021-07-22 | 2021-11-02 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of Mn-MOF/GO nano material |
| CN113851646A (en) * | 2021-09-29 | 2021-12-28 | 江南大学 | Zinc ion battery cathode material based on boron nitride film and preparation method thereof |
| CN114050261A (en) * | 2021-11-04 | 2022-02-15 | 浙江工业大学 | Preparation method of zinc-based battery negative electrode material |
| CN114899349A (en) * | 2022-05-05 | 2022-08-12 | 电子科技大学 | Method for inhibiting growth of zinc dendrite by modifying zinc of negative electrode of zinc ion battery |
| CN114899349B (en) * | 2022-05-05 | 2023-03-21 | 电子科技大学 | Method for inhibiting growth of zinc dendrite by modifying zinc of negative electrode of zinc ion battery |
| CN115000411A (en) * | 2022-08-05 | 2022-09-02 | 临沂华太电池有限公司 | Alkaline battery cathode material for marine environment and battery using same |
| CN115000411B (en) * | 2022-08-05 | 2022-11-15 | 临沂华太电池有限公司 | Alkaline battery cathode material for marine environment and battery using same |
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Application publication date: 20210330 Assignee: SUZHOU JINQIANG NEW MATERIALS Co.,Ltd. Assignor: ANYANG NORMAL University Contract record no.: X2023980053015 Denomination of invention: A zinc negative electrode with a protective layer and its preparation method and application Granted publication date: 20220705 License type: Common License Record date: 20231222 |
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