CN116425189A - ZnO@ZnS@C composite negative electrode material for zinc-nickel secondary battery and preparation method and application thereof - Google Patents
ZnO@ZnS@C composite negative electrode material for zinc-nickel secondary battery and preparation method and application thereof Download PDFInfo
- Publication number
- CN116425189A CN116425189A CN202211043296.6A CN202211043296A CN116425189A CN 116425189 A CN116425189 A CN 116425189A CN 202211043296 A CN202211043296 A CN 202211043296A CN 116425189 A CN116425189 A CN 116425189A
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- Prior art keywords
- zinc
- zns
- zno
- sulfate
- secondary battery
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Links
- 239000002131 composite material Substances 0.000 title claims abstract description 92
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010405 anode material Substances 0.000 claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000010439 graphite Substances 0.000 claims abstract description 74
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 74
- 239000002699 waste material Substances 0.000 claims abstract description 61
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- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 32
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 32
- 239000011701 zinc Substances 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000010406 cathode material Substances 0.000 claims abstract description 17
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 17
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- 229960001545 hydrotalcite Drugs 0.000 claims description 17
- 238000012216 screening Methods 0.000 claims description 17
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- 239000010949 copper Substances 0.000 claims description 14
- WJPZDRIJJYYRAH-UHFFFAOYSA-N [Zn].[Mo] Chemical compound [Zn].[Mo] WJPZDRIJJYYRAH-UHFFFAOYSA-N 0.000 claims description 13
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 5
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 5
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
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- 239000006258 conductive agent Substances 0.000 claims description 4
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 4
- 238000007580 dry-mixing Methods 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 4
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 4
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 4
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910000379 antimony sulfate Inorganic materials 0.000 claims description 3
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
- KVCOOBXEBNBTGL-UHFFFAOYSA-H ytterbium(3+);trisulfate Chemical compound [Yb+3].[Yb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KVCOOBXEBNBTGL-UHFFFAOYSA-H 0.000 claims description 3
- 229910000347 yttrium sulfate Inorganic materials 0.000 claims description 3
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229940050390 benzoate Drugs 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 2
- SYDXSHCNMKOQFW-UHFFFAOYSA-H erbium(3+);trisulfate Chemical compound [Er+3].[Er+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SYDXSHCNMKOQFW-UHFFFAOYSA-H 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 174
- 239000011787 zinc oxide Substances 0.000 description 87
- 229910052984 zinc sulfide Inorganic materials 0.000 description 70
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- 239000006256 anode slurry Substances 0.000 description 26
- 239000012299 nitrogen atmosphere Substances 0.000 description 25
- 239000012266 salt solution Substances 0.000 description 14
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- 238000004088 simulation Methods 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 13
- 238000005096 rolling process Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910052745 lead Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 238000005187 foaming Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
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- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
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- 239000002174 Styrene-butadiene Substances 0.000 description 2
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- 239000002000 Electrolyte additive Substances 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 239000005083 Zinc sulfide Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- 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
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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Abstract
The invention discloses a ZnO@ZnS@C composite negative electrode material for a zinc-nickel secondary battery and a preparation method and application thereof, and belongs to the technical field of recycling of resources of alkaline secondary battery negative electrode materials and waste graphite negative electrode materials. Zinc sulfate and waste graphite cathode materials are used as main raw materials, are uniformly mixed with functional metal salts and nitrogenous polymer organic matters, and are calcined in inert atmosphere to obtain the ZnO@ZnS@C composite cathode material for the zinc-nickel secondary battery. The novel zinc-nickel secondary battery negative electrode material can reduce deformation of a zinc electrode, inhibit growth of zinc dendrites, improve stability of a zinc negative electrode in alkali liquor, and greatly prolong the cycle service life of the zinc-nickel secondary battery. Meanwhile, the invention uses the waste graphite anode material as the raw material, so that the resource recovery and reutilization of the waste graphite anode material can be realized, and good economic benefit and environmental benefit are generated.
Description
Technical Field
The invention belongs to the technical field of recycling of alkaline secondary battery negative electrode materials and waste battery negative electrode materials, and particularly relates to a ZnO@ZnS@C composite negative electrode material for a zinc-nickel secondary battery, a preparation method and application thereof.
Background
The zinc-nickel secondary battery has the advantages of high working voltage, high specific power, environmental friendliness, low production cost and the like, and is a battery system with good application prospect. The negative electrode material zinc has the advantages of abundant reserves in nature, high theoretical specific capacity, low price and the like, and has good application prospect. However, the zinc cathode active material and the discharge product thereof have high solubility in alkaline electrolyte, and the zinc electrode can generate damages such as deformation, dendrite, self-corrosion, passivation and the like in the charge and discharge process, so that the cycle service life of the battery is reduced, and the industrialized development of the zinc-nickel secondary battery is severely limited.
Aiming at the problems of high solubility, easy dendrite formation, extremely easy electrode deformation and the like of the zinc cathode of the alkaline secondary battery in alkaline electrolyte. Many researches are made by many scientific researchers, and the research is mainly reflected in the aspects of use of additives, improvement of electrolyte, development of novel anode materials and the like. In the aspect of additives of the electrode, calcium hydroxide, magnesium chloride, aluminum hydroxide and titanium dioxide are proposed as additives for zinc cathodes, and experiments show that the additives can also effectively slow down deformation, dendrite formation and dissolution of the electrode. Electrolyte additives are typically fluorides, arsenates, chromates, etc., which can inhibit passivation and improve capacity retention. In addition, researchers have also found that some novel negative electrode materials such as calcium zincate, zinc aluminum hydrotalcite, etc. are used for the zinc negative electrode of the alkaline secondary battery, and although these novel materials improve the cycle stability performance of the alkaline secondary battery to some extent, they limit the rate capability of the alkaline secondary battery. At present, developing a novel zinc anode material is still an important means for solving the problems existing in the current zinc anode and promoting the rapid development of a zinc-nickel secondary battery.
Disclosure of Invention
The invention solves the technical problem of providing the ZnO@ZnS@C composite negative electrode material for the zinc-nickel secondary battery and the preparation method thereof, and the adoption of the composite negative electrode material for the zinc-nickel secondary battery can effectively reduce the deformation of a zinc electrode, inhibit the growth of zinc dendrites and improve the stability of the zinc negative electrode in alkali liquor, so that the cycle service life of the zinc-nickel secondary battery is greatly prolonged.
The invention adopts the following technical proposal to solve the technical problems, and the preparation method of the ZnO@ZnS@C composite anode material for the zinc-nickel secondary battery is characterized by comprising the following specific steps:
zinc sulfate and waste graphite cathode materials are used as main raw materials, and are subjected to high-temperature calcination in an inert gas atmosphere after being uniformly mixed by adopting dry mixing treatment or wet mixing treatment to prepare a ZnO@ZnS@C composite cathode material;
or zinc sulfate and waste graphite cathode materials are used as main raw materials, and are uniformly mixed with functional metal salts or/and nitrogen-containing high polymer organic matters by adopting dry mixing treatment or wet mixing treatment, and the ZnO@ZnS@C composite cathode material or metal doped ZnO@ZnS@C composite cathode material is prepared by high-temperature calcination in an inert gas atmosphere;
the functional metal salt is one or more of aluminum sulfate, titanium sulfate, bismuth sulfate, lead sulfate, indium sulfate, tin sulfate, antimony sulfate, ytterbium sulfate, yttrium sulfate, erbium sulfate, lanthanum sulfate, zirconium sulfate or chromium sulfate, and the nitrogen-containing high polymer organic matter is one or more of acrylamide, polyacrylamide, melamine or dopamine hydrochloride.
Further defined, the preparation method of the ZnO@ZnS@C composite anode material for the zinc-nickel secondary battery is characterized by comprising the following specific steps of:
step S1, soaking a waste graphite anode material in a dilute acid solution, leaching, adding the waste graphite anode material into deionized water or deionized water containing nitrogen-containing high polymer organic matters, and stirring to form viscous waste graphite slurry with good fluidity for later use;
step S2, zinc sulfate is dissolved in deionized water or zinc sulfate and functional metal salt are dissolved in deionized water, the solution is prepared by stirring and mixing uniformly, the waste graphite slurry obtained in the step S1 is added into the solution under continuous stirring, and the solution is dried for standby after stirring and mixing uniformly;
and S3, placing the mixture obtained in the step S2 into a tube furnace, heating to 120-200 ℃ at a heating rate of 1-10 ℃/min under an inert gas atmosphere, keeping the temperature for 10-120min, heating to 500-850 ℃ at a heating rate of 1-10 ℃/min, keeping the temperature for 1-24h, cooling to room temperature, crushing, and screening to obtain the ZnO@ZnS@C composite anode material or the metal doped ZnO@ZnS@C composite anode material.
Further defined, the preparation method of the ZnO@ZnS@C composite anode material for the zinc-nickel secondary battery is characterized by comprising the following specific steps of:
step S1, soaking a waste graphite anode material in a dilute acid solution, leaching, and drying for later use;
step S2, uniformly mixing zinc sulfate with the waste graphite anode material obtained in the step S1 or zinc sulfate, the waste graphite anode material obtained in the step S1 and functional metal salt or/and nitrogenous polymer organic matters, and performing high-energy ball milling on the mixture for later use;
and S3, placing the mixture obtained in the step S2 into a tube furnace, heating to 120-200 ℃ at a heating rate of 1-10 ℃/min under an inert gas atmosphere, keeping the temperature for 10-120min, heating to 500-850 ℃ at a heating rate of 1-10 ℃/min, keeping the temperature for 1-24h, cooling to room temperature, crushing, and screening to obtain the ZnO@ZnS@C composite anode material or the metal doped ZnO@ZnS@C composite anode material.
Further defined, the dilute acid solution is dilute sulfuric acid, dilute nitric acid, or dilute hydrochloric acid.
Further defined, the mass ratio of the zinc sulfate to the waste graphite anode material to the functional metal salt to the nitrogen-containing high polymer organic matter is 10:1-10:0-1:0-0.4.
The ZnO@ZnS@C composite negative electrode material for the zinc-nickel secondary battery is characterized by being prepared by the method.
The negative plate of the zinc-nickel secondary battery is characterized by being prepared from the ZnO@ZnS@C composite negative electrode material for the zinc-nickel secondary battery.
The preparation method of the negative plate of the zinc-nickel secondary battery is characterized by comprising the following specific steps: mixing 50-85 wt% of the composite anode material, 2-35 wt% of the additive and 3-20 wt% of the conductive agent uniformly, adding the mixture into an aqueous binder solution prepared from 1-5 wt% of the binder, stirring uniformly to obtain active material slurry, coating the prepared active material slurry on an anode substrate, drying, tabletting and punching to obtain the negative plate of the zinc-nickel secondary battery.
Further defined, the additive is one or more of antimony oxide, antimony doped tin oxide, antimony stannate, bismuth stannate, zinc molybdenum hydrotalcite or copper aluminum hydrotalcite; the conductive agent is one or two of graphene, carbon nano tubes, acetylene black, crystalline flake graphite, nitrogen carbide, titanium carbide, niobium carbide or titanium nitride; the binder is one or more of polytetrafluoroethylene, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyvinyl alcohol, acrylate or hydroxypropyl methyl cellulose; the negative electrode matrix is copper mesh, tinned copper mesh, zinc foil, copper-zinc alloy mesh, foam copper or foam zinc.
Further defined, the molecular formula of the zinc molybdenum hydrotalcite material is [ Zn x Mo y (OH) 2 ]·[(B a- ) b ·mH 2 O]Wherein B is a- Is OH − 、Cl - 、F - 、S 2- 、PO 4 3- 、SO 4 2- 、CO 3 2− 、NO 3 − 、BO 2 - 、MoO 4 2- Or WO 4 2- One or more of citrate, borate, benzoate, dodecylbenzenesulfonate, dodecylsulfate or dodecylsulfonate, 0.9 ∈0.5, y ∈0.1, x+y=1, b>0，m>0。
The utility model provides a zinc-nickel secondary battery, includes battery housing, seals the polar plate group and electrolyte in battery housing, polar plate group include positive plate, negative plate and diaphragm, its characterized in that: the negative plate adopts the negative plate of the zinc-nickel secondary battery.
Compared with the prior art, the invention has the advantages and beneficial effects that: according to the invention, zinc sulfate and waste graphite cathode materials are used as main raw materials, wherein the zinc sulfate is used as a zinc source, the waste graphite cathode materials realize the concept of recycling resources, and the zinc sulfate, the functional metal salt and the nitrogen-containing high polymer organic matters are uniformly mixed according to a certain mass ratio, and then are subjected to high-temperature calcination in an inert gas atmosphere to prepare the ZnO@ZnS@C composite cathode material for the zinc-nickel secondary battery. The composite anode material prepared by the invention effectively improves the cycle stability and the multiplying power performance of the zinc anode.
Drawings
FIG. 1 is an XRD pattern of the ZnO@ZnS@C composite negative electrode material prepared in example 1;
fig. 2 is an SEM image of the zno@zns@c composite anode material prepared in example 1.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
Preparation of ZnO@ZnS@C composite anode material:
soaking the waste graphite anode material in sulfuric acid solution with the molar concentration of 0.2mol/L for 20min, leaching, and drying at 120 ℃ for later use. Adding 3.5g of the treated waste graphite anode material and 0.2g of dopamine hydrochloride into 30mL of deionized water, and stirring to form viscous waste graphite slurry with good fluidity for later use; gradually adding 10g of zinc sulfate into the waste graphite slurry, stirring and mixing uniformly, and drying for 3 hours for later use; placing the mixture in a tube furnace, and heating to 130 ℃ for 30min at a heating rate of 5 ℃/min under a nitrogen atmosphere; and continuously placing the mixture in a tube furnace under a nitrogen atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min for 150min at constant temperature, cooling to room temperature, crushing, and screening to obtain the ZnO@ZnS@C composite anode material.
Zinc molybdenum hydrotalcite [ Zn ] x Mo y (OH) 2 ]·[(B a- ) b ·mH 2 O] (Zn/Mo=2/1，B a- =Cl - B=0.2, m=2):
1.09g of zinc chloride, 1.09g of molybdenum pentachloride and 6g of urea are dissolved in 200mL of deionized water, and magnetically stirred for 1h at room temperature to prepare a mixed solution; transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction for 48 hours at 120 ℃; and after the precursor is cooled to room temperature, filtering, washing and drying at 80 ℃ for 5 hours to obtain white powder, namely the zinc-molybdenum hydrotalcite.
Application of ZnO@ZnS@C composite anode material:
83g of synthesized ZnO@ZnS@C composite anode material, 4g of zinc molybdenum hydrotalcite, 5g of acetylene black, 1.5g of polyvinyl alcohol solution with the mass concentration of 4% and 0.2g of PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of a copper-emitting net through a slurry drawing die, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 2
Preparation of In-doped ZnO@ZnS@C composite anode material:
soaking the waste graphite anode material in hydrochloric acid solution with the molar concentration of 0.3mol/L for 10min, leaching, and drying at 120 ℃ for later use. Adding 1.8g of the treated waste graphite anode material and 0.4g of melamine into 23mL of deionized water, and stirring to form viscous waste graphite slurry with good fluidity for later use; dissolving 10g of zinc sulfate and 0.7g of indium sulfate into deionized water, stirring and mixing uniformly to prepare a salt solution, gradually adding the obtained waste graphite slurry into the salt solution under continuous stirring, stirring and mixing uniformly, and drying for 1h for later use; placing the mixture into a tube furnace, and heating to 150 ℃ for 30min at a heating rate of 5 ℃/min under the nitrogen atmosphere; and continuously placing the mixture In a tube furnace under a nitrogen atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature constant for 60min, cooling to room temperature, crushing, and screening to obtain the In-doped ZnO@ZnS@C composite anode material.
Application of In-doped ZnO@ZnS@C composite anode material:
68g of the synthesized In doped ZnO@ZnS@C composite anode material, 12g of antimony stannate, 5g of superconductive carbon black, 5g of zinc powder, 1.4g of HPMC solution with the mass concentration of 2.5% and 0.2g of PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of a copper mesh through a slurry pulling die, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 3
Preparing a Bi-doped ZnO@ZnS@C composite anode material:
soaking the waste graphite anode material in sulfuric acid solution with the molar concentration of 0.2mol/L for 30min, leaching, and drying at 120 ℃ for later use. Adding 3.3g of the treated waste graphite anode material and 0.1g of polyacrylamide into 25mL of deionized water, and stirring to form viscous waste graphite slurry with good fluidity for later use; dissolving 10g of zinc sulfate and 0.8g of bismuth sulfate into 38mL of deionized water, stirring and mixing uniformly to prepare a salt solution, gradually adding the obtained waste graphite slurry into the salt solution under continuous stirring, stirring and mixing uniformly, and drying for 80min for later use; placing the mixture into a tube furnace, and heating to 160 ℃ for 30min at a heating rate of 10 ℃/min under the nitrogen atmosphere; and continuously placing the mixture in a tube furnace under the nitrogen atmosphere after the constant temperature, heating to 750 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 90min, cooling to room temperature, crushing, and screening to obtain the Bi-doped ZnO@ZnS@C composite anode material.
Application of Bi-doped ZnO@ZnS@C composite anode material:
62g of the synthesized Bi-doped ZnO@ZnS@C composite anode material, 2.5g of antimony oxide, 5g of tin oxide and 1.5g of a polyvinyl alcohol solution with the mass concentration of 4% are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of foaming nickel through a slurry drawing die, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 4
Preparing a Sn-doped ZnO@ZnS@C composite anode material:
soaking the waste graphite anode material in nitric acid solution with the molar concentration of 0.05mol/L for 10min, leaching, and drying at 100 ℃ for later use. Taking 1.5g of the treated waste graphite anode material and 0.1g of acrylamide into 33mL of deionized water, and stirring to form viscous waste graphite slurry with good fluidity for later use; dissolving 10g of zinc sulfate and 0.3g of tin sulfate into 43mL of deionized water, stirring and mixing uniformly to prepare a salt solution, gradually adding the obtained waste graphite slurry into the salt solution under continuous stirring, stirring and mixing uniformly, and drying for 100min for later use; placing the mixture into a tube furnace, and heating to 200 ℃ for 80min at a heating rate of 10 ℃/min under a nitrogen atmosphere; and continuously placing the mixture in a tube furnace under the nitrogen atmosphere after the constant temperature, heating to 650 ℃ at the heating rate of 10 ℃/min for 120min, cooling to room temperature, crushing, and screening to obtain the Sn-doped ZnO@ZnS@C composite anode material.
Application of Sn-doped ZnO@ZnS@C composite anode material:
and (3) uniformly mixing 60g of the synthesized Sn-doped ZnO@ZnS@C composite anode material, 8g of copper-aluminum hydrotalcite and 2g of a polyvinyl alcohol solution with the mass concentration of 4%, preparing anode slurry, coating the anode slurry on two sides of foaming nickel by a slurry drawing die, and drying, rolling and cutting to prepare the anode plate. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 5
Preparation of Al-doped ZnO@ZnS@C composite anode material:
soaking the waste graphite anode material in sulfuric acid solution with the molar concentration of 0.2mol/L for 20min, leaching, and drying at 120 ℃ for later use. Taking 2.8g of the treated waste graphite anode material and 0.1g of polyacrylamide into 35mL of deionized water, and stirring to form viscous waste graphite slurry with good fluidity for later use; dissolving 10g of zinc sulfate and 0.15g of aluminum sulfate into 43mL of deionized water, stirring and mixing uniformly to prepare a salt solution, gradually adding the obtained waste graphite slurry into the salt solution under continuous stirring, stirring and mixing uniformly, and drying for 50min for later use; placing the mixture into a tube furnace, and heating to 150 ℃ for 70min at a heating rate of 5 ℃/min under a nitrogen atmosphere; and continuously placing the mixture in a tube furnace under a nitrogen atmosphere after constant temperature, heating to 750 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 110min, cooling to room temperature, crushing, and screening to obtain the Al-doped ZnO@ZnS@C composite anode material.
Application of Al-doped ZnO@ZnS@C composite anode material:
80g of the synthesized Al-doped ZnO@ZnS@C composite anode material, 2g of tin oxide, 3g of bismuth antimonate, 3g of carbon nano tube, 0.9g of 4% polyvinyl alcohol solution and 0.15g of 60% PTFE aqueous solution are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of foaming nickel through a slurry pulling mold, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 6
Preparation of Pb and Ti doped ZnO@ZnS@C composite anode material:
recovery of spent graphite anode material was the same as in example 1. Adding 3g of the treated waste graphite anode material and 0.15g of polyacrylamide into 30mL of deionized water, and stirring to form viscous waste graphite slurry with good fluidity for later use; dissolving 10g of zinc sulfate, 0.25g of lead sulfate and 0.15g of titanium sulfate into 60mL of deionized water, stirring and uniformly mixing to prepare a salt solution, gradually adding the obtained waste graphite slurry into the salt solution under continuous stirring, stirring and uniformly mixing, and drying for 70min for later use; placing the mixture into a tube furnace, and heating to 120 ℃ for 80min at a heating rate of 5 ℃/min under a nitrogen atmosphere; and continuously placing the mixture in a tube furnace under a nitrogen atmosphere after constant temperature, heating to 750 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 110min, cooling to room temperature, crushing, and screening to obtain the Pb and Ti doped ZnO@ZnS@C composite anode material.
Application of Pb and Ti doped ZnO@ZnS@C composite anode material:
82g of a composite anode material of ZnO@ZnS@C doped with Pb and Ti, 1.5g of antimony oxide, 3g of antimony stannate, 2.2g of niobium carbide, 1.3g of a polyvinyl alcohol solution with the mass concentration of 4% and 0.16g of a PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of foaming nickel through a slurry pulling mold, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 7
Preparation of ZnO@ZnS@C composite anode material doped with In and Sn:
recovery of spent graphite anode material was the same as in example 1. Adding 2g of the treated waste graphite anode material and 0.25g of polyacrylamide into 20mL of deionized water, and stirring to form viscous waste graphite slurry with good fluidity for later use; dissolving 10g of zinc sulfate, 0.35g of indium sulfate and 0.05g of tin sulfate into 55mL of deionized water, stirring and uniformly mixing to prepare a salt solution, gradually adding the obtained waste graphite slurry into the salt solution under continuous stirring, stirring and uniformly mixing, and drying for 60min for later use; placing the mixture into a tube furnace, and heating to 150 ℃ for 70min at a heating rate of 10 ℃/min under the nitrogen atmosphere; and continuously placing the mixture In a tube furnace under the nitrogen atmosphere after the constant temperature, heating to 800 ℃ at the heating rate of 10 ℃/min for 100min, cooling to room temperature, crushing, and screening to obtain the ZnO@ZnS@C composite anode material doped with In and Sn.
Application of ZnO@ZnS@C composite anode material doped with In and Sn:
84g of the synthesized ZnO@ZnS@C composite anode material doped with In and Sn, 3.3g of bismuth antimonate, 1.6g of antimony stannate, 2.8g of nitrogen carbide, 1.2g of a polyvinyl alcohol solution with the mass concentration of 4% and 0.18g of a PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of foaming nickel through a slurry pulling mold, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 8
Preparing a Bi, sn and Y doped ZnO@ZnS@C composite anode material:
recovery of spent graphite anode material was the same as in example 1. Adding 2.5g of the treated waste graphite anode material and 0.1g of acrylamide into 25mL of deionized water, and stirring to form viscous waste graphite slurry with good fluidity for later use; dissolving 10g of zinc sulfate, 0.15g of bismuth sulfate, 0.25g of tin sulfate and 0.35g of yttrium sulfate into 45mL of deionized water, stirring and mixing uniformly to prepare a salt solution, gradually adding the obtained waste graphite slurry into the salt solution under continuous stirring, stirring and mixing uniformly, and drying for 40min for later use; placing the mixture in a tube furnace, and heating to 130 ℃ for 80min at a heating rate of 10 ℃/min under a nitrogen atmosphere; and continuously placing the mixture in a tube furnace under the nitrogen atmosphere after the constant temperature, heating to 850 ℃ at the heating rate of 10 ℃/min for 70min, cooling to room temperature, crushing, and screening to obtain the ZnO@ZnS@C composite anode material doped with Bi, sn and Y.
Application of Bi, sn and Y doped ZnO@ZnS@C composite anode material:
62g of the synthesized Bi, sn and Y doped ZnO@ZnS@C composite anode material, 3g of antimony oxide, 2.5g of antimony stannate, 3.2g of tin oxide, 1.8g of titanium nitride, 0.8g of 4% polyvinyl alcohol solution and 0.14g of 60% PTFE aqueous solution are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of a copper mesh through a slurry pulling mold, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 9
Preparation of ZnO@ZnS@C composite anode material:
recovery of spent graphite anode material was the same as in example 1. 10g of zinc sulfate and 3.8g of treated waste graphite cathode material are mixed, the mixture is subjected to high-energy ball milling for 12 hours for standby, and the obtained mixture is placed in a tube furnace and heated to 120 ℃ for 60 minutes at a heating rate of 5 ℃/min under nitrogen atmosphere; and continuously placing the mixture in a tube furnace under a nitrogen atmosphere after constant temperature, heating to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 60min, cooling to room temperature, crushing, and screening to obtain the ZnO@ZnS@C composite anode material.
Application of ZnO@ZnS@C composite anode material:
82g of synthesized ZnO@ZnS@C composite anode material, 4g of antimony oxide, 5g of crystalline flake graphite, 1.4g of HPMC solution with the mass concentration of 2.5% and 0.2g of PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of a copper mesh through a slurry drawing die, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 10
Preparation of Ti-doped ZnO@ZnS@C composite anode material:
recovery of spent graphite anode material was the same as in example 1. Mixing 10g of zinc sulfate, 2.6g of treated waste graphite anode material and 0.3g of titanium sulfate, and performing high-energy ball milling on the mixture for 18 hours for later use; placing the obtained mixture into a tube furnace, and heating to 140 ℃ for 40min at a heating rate of 10 ℃/min under the nitrogen atmosphere; and (3) after keeping the temperature of the obtained mixture constant, continuously placing the mixture in a tube furnace, heating to 800 ℃ for 90 minutes at a heating rate of 10 ℃/min, cooling to room temperature, crushing, and screening to obtain the Ti-doped ZnO@ZnS@C composite anode material.
Zinc molybdenum hydrotalcite [ Zn ] x Mo y (OH) 2 ]·[(B a- ) b ·mH 2 O] (Zn/Mo=4/1，B a- =Cl - B=0.1, m=1):
2.18g of zinc chloride, 1.09g of molybdenum pentachloride and 6g of urea are dissolved in 200mL of deionized water, and magnetically stirred for 1.5h at room temperature to prepare a mixed solution; transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction for 45h at 130 ℃; and after the precursor is cooled to room temperature, filtering, washing and drying at 90 ℃ for 4 hours to obtain white powder, namely the zinc-molybdenum hydrotalcite.
Application of Ti-doped ZnO@ZnS@C composite anode material:
65g of the synthesized Ti-doped ZnO@ZnS@C composite anode material, 2.4g of antimony stannate, 4g of zinc molybdenum hydrotalcite, 3.5g of acetylene black, 1.5g of CMC solution with the mass concentration of 2.5%, 0.9g of polyvinyl alcohol solution with the mass concentration of 4% and 0.65g of SBR aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry, and the anode slurry is coated on two sides of a copper mesh through a slurry pulling mold, and is dried, rolled and cut to prepare a negative plate. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 11
Preparation of Cr and Sb doped ZnO@ZnS@C composite anode material:
recovery of spent graphite anode material was the same as in example 1. 10g of zinc sulfate, 3.2g of treated waste graphite anode material, 0.09g of dopamine hydrochloride, 0.18g of cadmium sulfate and 0.18g of antimony sulfate are mixed, and the mixture is subjected to high-energy ball milling for 15 hours for later use; placing the mixture into a tube furnace, and heating to 140 ℃ for 40min at a heating rate of 5 ℃/min under the nitrogen atmosphere; and continuously placing the mixture in a tube furnace under a nitrogen atmosphere after constant temperature, heating to 700 ℃ at a heating rate of 5 ℃/min for 100min, cooling to room temperature, crushing, and screening to obtain the Cr and Sb doped ZnO@ZnS@C composite anode material.
Application of Cr and Sb doped ZnO@ZnS@C composite anode material:
64g of the synthesized Cr and Sb doped ZnO@ZnS@C composite anode material, 4.5g of tin oxide, 3.2g of crystalline flake graphite, 2.5g of zinc powder, 2.6g of HPMC solution with the mass concentration of 2.5% and 0.8g of PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of a copper mesh through a slurry pulling die, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 12
Preparation of ZnO@ZnS@C composite anode material doped with Zr, yb and Ti:
recovery of spent graphite anode material was the same as in example 1. 10g of zinc sulfate, 2.4g of waste graphite, 0.2g of zirconium sulfate, 0.2g of ytterbium sulfate and 0.2g of titanium sulfate are mixed, and the mixture is subjected to high-energy ball milling for 20 hours for later use; placing the mixture in a tube furnace, and heating to 130 ℃ for 50min at a heating rate of 10 ℃/min under a nitrogen atmosphere; and continuously placing the mixture in a tube furnace under a nitrogen atmosphere after constant temperature, heating to 750 ℃ at a heating rate of 10 ℃/min, keeping the temperature constant for 90min, cooling to room temperature, crushing, and screening to obtain the ZnO@ZnS@C composite anode material doped with Zr, yb and Ti.
Application of ZnO@ZnS@C composite anode material doped with Zr, yb and Ti:
82g of a synthesized ZnO@ZnS@C composite anode material doped with Zr, yb and Ti, 2.4g of tin oxide, 1.8g of antimony oxide, 2.5g of titanium carbide, 2.1g of niobium carbide, 1.9g of HPMC solution with the mass concentration of 2.5% and 0.9g of PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of a copper mesh through a slurry pulling mold, and a negative plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Example 13
Preparation of Pb, bi and La doped ZnO@ZnS@C composite anode material:
recovery of spent graphite anode material was the same as in example 1. 10g of zinc sulfate, 2.1g of treated waste graphite anode material, 0.16g of lead sulfate, 0.17g of bismuth sulfate and 0.18g of lanthanum sulfate are mixed, and the mixture is subjected to high-energy ball milling for 24 hours for later use; placing the mixture into a tube furnace, and heating to 120 ℃ for 50min at a heating rate of 10 ℃/min under a nitrogen atmosphere; and continuously placing the mixture in a tube furnace under a nitrogen atmosphere after constant temperature, heating to 800 ℃ at a heating rate of 10 ℃/min for 90min, cooling to room temperature, crushing, and screening to obtain the Pb, bi and La doped ZnO@ZnS@C composite anode material.
Zinc molybdenum hydrotalcite [ Zn ] x Mo y (OH) 2 ]·[(B a- ) b ·mH 2 O] (Zn/Mo=5/1，B a- =Cl - B=0.2, m=2):
2.726g of zinc chloride, 1.09g of molybdenum pentachloride and 6g of urea are dissolved in 200mL of deionized water, and magnetically stirred for 2 hours at room temperature to prepare a mixed solution; transferring the obtained mixed solution into a reaction kettle, and performing hydrothermal reaction for 30 hours at 140 ℃; and after the precursor is cooled to room temperature, filtering, washing and drying at 60 ℃ for 8 hours to obtain white powder, namely the zinc-molybdenum hydrotalcite.
Application of ZnO@ZnS@C composite negative electrode material doped with Pb, bi and La
63g of a composite anode material of ZnO@ZnS@C doped with Pb, bi and La, 2.1g of zinc molybdenum hydrotalcite, 2.7 g of bismuth antimonate g, 2.6g of niobium titanate, 2.1g of carbon nano tube, 1.6g of HPMC solution with the mass concentration of 2.5% and 1.1g of PTFE aqueous solution with the mass concentration of 60% are uniformly mixed to prepare anode slurry, the anode slurry is coated on two sides of a copper mesh through a slurry pulling mold, and the anode plate is prepared through drying, rolling and cutting. The conventional sintered positive plate and negative plate are placed into a special simulation battery shell through an alkaline battery diaphragm, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Comparative example 1
Commercial zinc oxide was used as the active material.
Manufacturing a negative plate: 84g of commercial zinc oxide negative electrode material, 3.2g of bismuth oxide, 5g of conductive graphite, 1g of CMC solution with the mass concentration of 2.5%, 0.5g of polyvinyl alcohol solution with the mass concentration of 4% and 0.3g of SBR aqueous solution with the mass concentration of 60% are uniformly mixed to prepare negative electrode slurry, the negative electrode slurry is coated on two sides of a copper strip through a slurry pulling die, and a negative plate is prepared through drying, rolling and cutting.
And (3) battery assembly: the conventional sintered positive plate and negative plate are placed into a special simulation battery shell through a special diaphragm of a zinc-nickel battery, and are injected with KOH with the mass concentration of 30% and LiOH electrolyte with the mass concentration of 2% which are saturated by ZnO, so that the semi-sealed zinc-nickel secondary battery is assembled.
Cell performance test: the zinc-nickel secondary batteries fabricated using specific examples 1 to 13 and comparative example 1 were activated at 0.2C, then charged at 0.2C for 6 hours, after which the batteries were left to stand for 30 minutes, and then discharged at 0.2C and 5C to voltages of 1.4V and 1.2V, respectively, and the capacity properties of the negative electrode materials were measured. Battery cycle performance test: the zinc-nickel secondary batteries assembled by the composite anode materials prepared in examples 1 to 13 were respectively subjected to 1C charge-discharge test at an ambient temperature of 25C, and the capacity fade was terminated at 80% of the highest capacity. The battery electrical properties test results are shown in table 1.
Table 1 battery charge and discharge test
From the test results, the composite anode material prepared by the method has higher gram capacity, excellent cycle stability and higher volumetric specific energy, and can meet the requirements of commercial batteries, particularly high-capacity batteries. The improvement of the performances is mainly due to the fact that the waste graphite anode material and zinc sulfate react at high temperature in situ to generate zinc sulfide and zinc oxide heterojunction structures, the novel additive is favorable for improving the cycle stability of the battery, the conductivity of carbon-coated and carbon-doped zinc oxide is improved, the polarization of an electrode is inhibited, a large amount of beneficial metal elements exist, the deformation of the zinc anode is greatly reduced, the hydrogen evolution reaction of the zinc anode is obviously inhibited, and therefore the overall performance of the zinc anode, particularly the multiplying power performance and the cycle stability performance are improved. The zinc cathode material synthesized by the invention is used for preparing the alkaline secondary battery, and has the advantages of good multiplying power performance and long cycle service life.
The foregoing embodiments illustrate the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the scope of the principles of the invention, which are defined in the appended claims.
Claims (10)
1. The preparation method of the ZnO@ZnS@C composite negative electrode material for the zinc-nickel secondary battery is characterized by comprising the following specific steps of:
zinc sulfate and waste graphite cathode materials are used as main raw materials, and are subjected to high-temperature calcination in an inert gas atmosphere after being uniformly mixed by adopting dry mixing treatment or wet mixing treatment to prepare a ZnO@ZnS@C composite cathode material;
or zinc sulfate and waste graphite cathode materials are used as main raw materials, and are uniformly mixed with functional metal salts or/and nitrogen-containing high polymer organic matters by adopting dry mixing treatment or wet mixing treatment, and the ZnO@ZnS@C composite cathode material or metal doped ZnO@ZnS@C composite cathode material is prepared by high-temperature calcination in an inert gas atmosphere;
the functional metal salt is one or more of aluminum sulfate, titanium sulfate, bismuth sulfate, lead sulfate, indium sulfate, tin sulfate, antimony sulfate, ytterbium sulfate, yttrium sulfate, erbium sulfate, lanthanum sulfate, zirconium sulfate or chromium sulfate, and the nitrogen-containing high polymer organic matter is one or more of acrylamide, polyacrylamide, melamine or dopamine hydrochloride.
2. The preparation method of the ZnO@ZnS@C composite negative electrode material for a zinc-nickel secondary battery according to claim 1, which is characterized by comprising the following specific steps of:
step S1, soaking a waste graphite anode material in a dilute acid solution, leaching, adding the waste graphite anode material into deionized water or deionized water containing nitrogen-containing high polymer organic matters, and stirring to form viscous waste graphite slurry with good fluidity for later use;
step S2, zinc sulfate is dissolved in deionized water or zinc sulfate and functional metal salt are dissolved in deionized water, the solution is prepared by stirring and mixing uniformly, the waste graphite slurry obtained in the step S1 is added into the solution under continuous stirring, and the solution is dried for standby after stirring and mixing uniformly;
and S3, placing the mixture obtained in the step S2 into a tube furnace, heating to 120-200 ℃ at a heating rate of 1-10 ℃/min under an inert gas atmosphere, keeping the temperature for 10-120min, heating to 500-850 ℃ at a heating rate of 1-10 ℃/min, keeping the temperature for 1-24h, cooling to room temperature, crushing, and screening to obtain the ZnO@ZnS@C composite anode material or the metal doped ZnO@ZnS@C composite anode material.
3. The preparation method of the ZnO@ZnS@C composite negative electrode material for a zinc-nickel secondary battery according to claim 1, which is characterized by comprising the following specific steps of:
step S1, soaking a waste graphite anode material in a dilute acid solution, leaching, and drying for later use;
step S2, uniformly mixing zinc sulfate with the waste graphite anode material obtained in the step S1 or zinc sulfate, the waste graphite anode material obtained in the step S1 and functional metal salt or/and nitrogenous polymer organic matters, and performing high-energy ball milling on the mixture for later use;
and S3, placing the mixture obtained in the step S2 into a tube furnace, heating to 120-200 ℃ at a heating rate of 1-10 ℃/min under an inert gas atmosphere, keeping the temperature for 10-120min, heating to 500-850 ℃ at a heating rate of 1-10 ℃/min, keeping the temperature for 1-24h, cooling to room temperature, crushing, and screening to obtain the ZnO@ZnS@C composite anode material or the metal doped ZnO@ZnS@C composite anode material.
4. The method for producing a zno@zns@c composite negative electrode material for a zinc-nickel secondary battery according to claim 2 or 3, characterized by: the dilute acid solution is dilute sulfuric acid, dilute nitric acid or dilute hydrochloric acid; the mass ratio of the zinc sulfate, the waste graphite anode material, the functional metal salt and the nitrogen-containing high polymer organic matter is 10:1-10:0-1:0-0.4.
5. A zno@zns@c composite negative electrode material for a zinc-nickel secondary battery, characterized by being prepared by the method of any one of claims 1 to 4.
6. A negative electrode plate of a zinc-nickel secondary battery, characterized in that it is produced from the zno@zns@c composite negative electrode material for a zinc-nickel secondary battery according to claim 5.
7. A method for preparing a negative plate of a zinc-nickel secondary battery according to claim 6, which is characterized by comprising the following specific steps: uniformly mixing 50-85 wt% of ZnO@ZnS@C composite negative electrode material for zinc-nickel secondary batteries, 2-35 wt% of additive and 3-20 wt% of conductive agent, then adding into an aqueous binder solution prepared from 1-5 wt% of binder, uniformly stirring to obtain active material slurry, coating the prepared active material slurry on a negative electrode substrate, drying, tabletting and punching to obtain the negative plate of the zinc-nickel secondary battery.
8. The method for producing a negative electrode plate for a zinc-nickel secondary battery according to claim 7, wherein: the additive is one or more of antimony oxide, antimony doped tin oxide, antimony stannate, bismuth stannate, zinc molybdenum hydrotalcite or copper aluminum hydrotalcite; the conductive agent is one or two of graphene, carbon nano tubes, acetylene black, crystalline flake graphite, nitrogen carbide, titanium carbide, niobium carbide or titanium nitride; the binder is one or more of polytetrafluoroethylene, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyvinyl alcohol, acrylate or hydroxypropyl methyl cellulose; the negative electrode matrix is copper mesh, tinned copper mesh, zinc foil, copper-zinc alloy mesh, foam copper or foam zinc.
9. The method for producing a negative electrode plate for a zinc-nickel secondary battery according to claim 8, wherein: the molecular formula of the zinc-molybdenum hydrotalcite material is [ Zn ] x Mo y (OH) 2 ]·[(B a- ) b ·mH 2 O]Wherein B is a- Is OH − 、Cl - 、F - 、S 2- 、PO 4 3- 、SO 4 2- 、CO 3 2− 、NO 3 − 、BO 2 - 、MoO 4 2- Or WO 4 2- One or more of citrate, borate, benzoate, dodecylbenzenesulfonate, dodecylsulfate or dodecylsulfonate, 0.9 ∈0.5, y ∈0.1, x+y=1, b>0，m>0。
10. The utility model provides a zinc-nickel secondary battery, includes battery housing, seals the polar plate group and electrolyte in battery housing, polar plate group include positive plate, negative plate and diaphragm, its characterized in that: the negative plate adopts the negative plate of the zinc-nickel secondary battery.
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