CN115548287A - Negative electrode active material, zinc ion battery and electronic device - Google Patents
Negative electrode active material, zinc ion battery and electronic device Download PDFInfo
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- CN115548287A CN115548287A CN202211125837.XA CN202211125837A CN115548287A CN 115548287 A CN115548287 A CN 115548287A CN 202211125837 A CN202211125837 A CN 202211125837A CN 115548287 A CN115548287 A CN 115548287A
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- China
- Prior art keywords
- zinc
- active material
- ion battery
- negative electrode
- positive electrode
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 50
- 239000011701 zinc Substances 0.000 claims abstract description 75
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 49
- 239000007774 positive electrode material Substances 0.000 claims description 39
- 239000011230 binding agent Substances 0.000 claims description 36
- 239000006258 conductive agent Substances 0.000 claims description 33
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000012528 membrane Substances 0.000 claims description 24
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 11
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000000661 sodium alginate Substances 0.000 claims description 7
- 235000010413 sodium alginate Nutrition 0.000 claims description 7
- 229940005550 sodium alginate Drugs 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 239000006182 cathode active material Substances 0.000 abstract description 6
- 238000002161 passivation Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 25
- 239000011669 selenium Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 13
- 238000000227 grinding Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000005388 borosilicate glass Substances 0.000 description 4
- 229960002303 citric acid monohydrate Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 229940091258 selenium supplement Drugs 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
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- 239000000499 gel Substances 0.000 description 2
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- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 241000258957 Asteroidea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- SDBOUNNVMSZUHW-UHFFFAOYSA-N S=[Cu]=[Se] Chemical compound S=[Cu]=[Se] SDBOUNNVMSZUHW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZUVGTYZBAKJUCH-UHFFFAOYSA-K [V+5].P(=O)([O-])([O-])[O-].[Zn+2] Chemical compound [V+5].P(=O)([O-])([O-])[O-].[Zn+2] ZUVGTYZBAKJUCH-UHFFFAOYSA-K 0.000 description 1
- XRFJZINEJXCFNW-UHFFFAOYSA-N [Zn+2].[O-][Mn]([O-])(=O)=O Chemical compound [Zn+2].[O-][Mn]([O-])(=O)=O XRFJZINEJXCFNW-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000012257 stirred material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- SWFBFRDZBFXEHJ-UHFFFAOYSA-N titanium diselenide Chemical compound [Se]=[Ti]=[Se] SWFBFRDZBFXEHJ-UHFFFAOYSA-N 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- 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 provides a negative electrode active material, a zinc ion battery and an electronic device. The chemical formula of the negative active material of the invention is A x B y The cathode active material is a layered compound, and compared with the existing zinc metal cathode which is used as a cathode, the cathode active material has better cycle stability, does not cause the problems of zinc dendrite, corrosion, passivation and the like, and improves the cycle performance of the battery; according to the zinc ion battery, the zinc-containing compound is used as the positive electrode, the layered compound is used as the negative electrode, and the zinc ion battery is used for a water system zinc ion battery without zinc metal, so that the application field of materials is widened; the zinc ion battery has the characteristics of safety, low cost, simple synthesis, long cycle life, no zinc dendrite and the like, and has good commercial prospect.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a negative electrode active material, a zinc ion battery and an electronic device.
Background
The problems of energy shortage and environmental deterioration due to excessive consumption of fossil fuels are becoming more severe, and development of new energy is one of effective strategies to solve the above problems. However, renewable energy power generation such as solar energy, wind energy, tidal energy, geothermal energy, etc. has intermittency and volatility, and an energy storage complement is required to smooth and stabilize the operation of the power system. Among the energy storage technologies, the electrochemical energy storage has the most outstanding comprehensive performance. As the most advanced electrochemical energy storage technology at present, lithium ion batteries have achieved great success in the markets of small electronic products and electric vehicles, but their application in the field of large-scale energy storage still needs to overcome the obstacles of high cost and poor safety.
The water system zinc ion battery has the advantages of high safety, rich raw materials, low cost, environmental protection and the like, and is one of ideal choices of large-scale energy storage batteries. However, the existing zinc metal negative electrode has the problems of dendrite, corrosion, passivation and the like, and in order to meet the requirement of long cycle, the usage amount of the zinc negative electrode in the battery is far beyond the required amount theoretically, so that the utilization rate of the zinc negative electrode is extremely low.
In view of the technical shortcomings of the current aqueous zinc ion batteries, there is a need for improvement.
Disclosure of Invention
In view of the above, the present invention provides a negative active material, a zinc ion battery and an electronic device, so as to solve or at least partially solve the technical problems in the prior art.
In a first aspect, the present invention providesA negative active material is disclosed, the chemical formula of the negative active material is A x B y Wherein A is one or more of Ti, cu, mo, fe and Bi, and B is S 2- ，Se 2- ，O 2- ，N 3- ，P 3- Wherein 0 is<x≤3，0<y≤8。
In a second aspect, the invention also provides a zinc ion battery comprising a negative electrode comprising the negative electrode active material.
Preferably, the zinc ion battery further comprises a positive electrode, a diaphragm and an electrolyte, wherein the positive electrode comprises a positive active material, and the chemical formula of the positive active material is Zn a M b N c Wherein M is one or more of V, mn, fe, cr, co, ni, zr, nb and Mo, and N is PO 4 3- ，P 2 O 7 4- ，SO 4 2- ，F - ，O 2- Wherein 0 is<a≤3，0<b≤5，0<c≤5。
Preferably, the zinc ion battery, the positive electrode and the negative electrode further comprise a conductive agent and a binder;
wherein the mass ratio of the positive active material, the conductive agent and the binder in the positive electrode is (5-9.5) to (0.3-3) to (0.2-2);
the mass ratio of the negative electrode active material, the conductive agent and the binder in the negative electrode is (5-9.5) to (0.3-3) to (0.2-2).
Preferably, in the zinc ion battery, the electrolyte is a liquid or gel material which takes soluble salt of zinc as a solute and water as a solvent and has ionic conductivity.
Preferably, in the zinc ion battery, the soluble salt of zinc includes one or more of zinc trifluoromethanesulfonate, zinc sulfate, zinc acetate, zinc chloride, zinc perchlorate, zinc nitrate, zinc bis (fluorosulfonyl) imide and zinc bis (trifluoromethanesulfonyl) imide.
Preferably, in the zinc ion battery, the separator comprises one of non-woven fabric, glass fiber, porous PP/PE separator, PTFE membrane and glass fiber filter paper.
Preferably, in the zinc ion battery, the conductive agent includes one or more of graphite, carbon black, ketjen black, carbon nanotubes, and graphene.
Preferably, in the zinc ion battery, the adhesive comprises one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, sodium alginate, polyacrylic acid, polyvinyl alcohol and styrene-butadiene latex.
In a third aspect, the invention also provides an electronic device comprising the zinc ion battery.
Compared with the prior art, the negative electrode active material and the zinc ion battery have the following beneficial effects:
1. the chemical formula of the negative active material of the invention is A x B y The cathode active material is a layered compound, and compared with the existing zinc metal cathode which is used as a cathode, the cathode active material has better cycle stability, does not cause the problems of zinc dendrite, corrosion, passivation and the like, and improves the cycle performance of the battery;
2. according to the zinc ion battery, the zinc-containing compound is used as the positive electrode, the layered compound is used as the negative electrode, and the zinc ion battery is used for a water system zinc ion battery without zinc metal, so that the application field of materials is widened; the zinc ion battery has the characteristics of safety, low cost, simple synthesis, long cycle life, no zinc dendrite and the like, and has good commercial prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 shows a positive electrode active material Zn prepared in example 1 of the present invention 3 V 4 (PO 4 ) 3 Sweep of (2)A scanning electron microscope image;
FIG. 2 shows a positive electrode active material Zn prepared in example 1 of the present invention 3 V 4 (PO 4 ) 3 XRD pattern of (a);
FIG. 3 shows TiS as an anode active material prepared in example 1 of the present invention 2 Scanning electron microscopy images of (a);
FIG. 4 shows TiS as a positive electrode active material prepared in example 1 of the present invention 2 XRD pattern of (a);
fig. 5 is a charge-discharge curve diagram of the zinc ion battery prepared in example 1 of the present invention;
FIG. 6 shows a positive electrode active material Zn prepared in example 2 of the present invention 0.5 VOPO 4 XRD pattern of (a);
FIG. 7 shows TiSe as a negative electrode active material prepared in example 2 of the present invention 2 XRD pattern of (a);
fig. 8 is a charge-discharge curve diagram of the zinc ion battery prepared in example 2 of the present invention;
FIG. 9 shows a positive electrode active material Zn prepared in example 3 of the present invention 3 V 3 O 8 XRD pattern of (a);
FIG. 10 shows a negative active material Cu prepared in example 4 of the present invention 2-x Scanning electron microscopy of Se;
FIG. 11 shows a negative active material Cu prepared in example 4 of the present invention 2-x XRD pattern of Se;
fig. 12 is a graph showing the cycle curve at a current density of 1C for the zinc-ion battery prepared in example 1 of the present invention;
fig. 13 is a charge and discharge graph of the zinc-ion battery prepared in comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments.
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The embodiment of the application provides a negative active material with a chemical formula A x B y Wherein A is one or more of Ti, cu, mo, fe and Bi, and B is S 2- ，Se 2- ，O 2- ，N 3- ，P 3- Wherein 0 is<x≤3，0<y≤8。
The negative electrode active material of the present application has a chemical formula a x B y The negative electrode active material is a layered compound, and specifically, the negative electrode active material can be a layered compound such as titanium disulfide, titanium diselenide, molybdenum disulfide, copper selenide sulfide, and the like, which stores zinc ions. Adopt the negative pole active material of this application as the negative pole, compare current zinc metal and be the negative pole, it has better circulation stability, and can not cause zinc dendrite, corruption, passivation scheduling problem, improves the cyclicity ability of battery.
Based on the same inventive concept, the embodiment of the application also provides a zinc ion battery, which comprises a negative electrode, wherein the negative electrode comprises the negative electrode active material.
In some casesIn an embodiment, the zinc ion battery further comprises a positive electrode, a diaphragm and an electrolyte, wherein the positive electrode comprises a positive active material, and the chemical formula of the positive active material is Zn a M b N c Wherein M is one or more of V, mn, fe, cr, co, ni, zr, nb and Mo, and N is PO 4 3- ，P 2 O 7 4- ，SO 4 2- ，F - ，O 2- Wherein 0<a≤3，0<b≤5，0<c≤5。
Specifically, in the above embodiments, the chemical formula of the positive electrode active material is Zn a M b N c A polyanionic or oxide zinc-containing compound which can provide a zinc source to match a non-zinc metal negative electrode; specifically, the positive electrode active material may be a zinc-containing material such as vanadium zinc phosphate, vanadium zinc fluorophosphate, vanadyl zinc phosphate, zinc vanadate, zinc manganate, or the like, which is capable of reversibly extracting and inserting zinc ions.
In some embodiments, the positive and negative electrodes further comprise a conductive agent and a binder;
wherein, the mass ratio of the anode active material, the conductive agent and the binder in the anode is (5-9.5) to (0.3-3) to (0.2-2);
the mass ratio of the negative electrode active material, the conductive agent and the binder in the negative electrode is (5-9.5) to (0.3-3) to (0.2-2).
Specifically, the preparation method of the positive electrode comprises the following steps: mixing the positive active material, the conductive agent and the binder and then coating the mixture on a positive current collector; the preparation method of the cathode comprises the following steps: and mixing the negative electrode active material, the conductive agent and the binder, and coating the mixture on a negative electrode current collector. The positive and negative current collectors include one of various metal foils, metal meshes, carbon cloths, graphite foils, or graphite sheets.
In some embodiments, the electrolyte is a liquid or gel material having a soluble salt of zinc as a solute, water as a solvent, and ionic conductivity.
In some embodiments, the soluble salt of zinc includes one or more of zinc triflate, zinc sulfate, zinc acetate, zinc chloride, zinc perchlorate, zinc nitrate, zinc bis (fluorosulfonyl) imide, zinc bis (trifluoromethanesulfonyl) imide.
In some embodiments, the membrane comprises one of a non-woven fabric, a glass fiber, a porous PP/PE membrane, a PTFE membrane, and a glass fiber filter paper.
In some embodiments, the conductive agent comprises one or more of graphite, carbon black, ketjen black, carbon nanotubes, graphene.
In some embodiments, the binder comprises one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, sodium alginate, polyacrylic acid, polyvinyl alcohol, styrene butadiene latex.
According to the zinc ion battery, the zinc-containing compound is used as the positive electrode, the layered compound is used as the negative electrode, and the zinc ion battery is used for a water system zinc ion battery without zinc metal, so that the application field of materials is widened; the zinc ion battery has the characteristics of safety, low cost, simplicity in synthesis, long cycle life, no zinc dendrite and the like, and has a good commercial prospect.
Based on the same inventive concept, the embodiment of the application also provides an electronic device which comprises the zinc ion battery. Specifically, the electronic device may be an electronic device that performs various functions (e.g., playing music) using a zinc ion battery as a power source for operation; the electronic device can also be an electronic terminal device such as a mobile phone, a tablet personal computer, a capacitor, a charger and the like; the electronic device may also be a power tool that uses a zinc ion battery as a driving power source to move a part (e.g., a drill bit); the electronic devices also include electric vehicles that run on a zinc ion battery as a driving power source, and may be automobiles (including hybrid vehicles) equipped with other driving sources in addition to the zinc ion battery.
The negative electrode active material and the zinc ion battery of the present application will be described below with reference to specific examples. This section further illustrates the present invention with reference to specific examples, which should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Example 1
The embodiment of the application provides a positive active material, and the chemical formula of the positive active material is Zn 3 V 4 (PO 4 ) 6 The preparation method of the positive active material comprises the following steps:
by NH 4 VO 3 、NH 4 H 2 PO 4 、Zn(NO 3 ) 2 Oxalic acid dihydrate, citric acid monohydrate and graphene are used as raw materials; wherein NH 4 H 2 PO 4 Is a source of phosphorus, zn (NO) 3 ) 2 As a zinc source, oxalic acid dihydrate, citric acid monohydrate and graphene as carbon sources;
0.986g of NH 4 VO 3 2.016g of oxalic acid dihydrate is added into 200mL of water and dispersed for 3h under magnetic stirring to obtain a solution; to the above solution was added 1.38g of NH 4 H 2 PO 4 、1.317g Zn(NO 3 ) 2 Dispersing 0.6g of citric acid monohydrate and 0.1g of graphene for 3 hours under magnetic stirring, and then feeding at an air inlet speed of 80%, an air inlet temperature of 160 ℃ and a feeding speed of 0.5% for spray drying to obtain a precursor;
then putting the precursor in argon atmosphere, and calcining at 750 ℃ for 12h to obtain Zn 3 V 4 (PO 4 ) 6 。
The embodiment of the application also provides a negative active material with a chemical formula of TiS 2 The preparation method of the negative active material comprises the following steps:
ti powder, S powder and graphene are used as raw materials; wherein Ti powder is a titanium source, S powder is a sulfur source, and graphene is a carbon source.
Placing 0.4787g Ti powder, 0.6414g S powder and 0.0347g graphene in a ball milling tank, and grinding for 1h; and transferring the ground powder into a high borosilicate glass tube with an opening at one end, connecting the other end of the high borosilicate glass tube with a vacuum pump, and sealing the tube with isobutane while vacuumizing. Then placing the sealed tube in a muffle furnace, heating to 550 ℃ at room temperature for 5h, calcining for 72h, cooling to room temperature, and adding CS 2 、C 2 H 5 OH is washed for a plurality of times to obtain TiS 2 。
The embodiment of the application also provides a water system zinc ion battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm;
the preparation method of the anode comprises the following steps: weighing Zn according to the weight ratio of 80 3 V 4 (PO 4 ) 6 The conductive carbon black conductive anode material comprises a positive electrode active material, a conductive agent and a binder, wherein the conductive agent is conductive carbon black SP, and the binder is 60 wt% of PTFE emulsion; firstly Zn is added 3 V 4 (PO 4 ) 6 Grinding the positive active material and the conductive carbon black SP uniformly in an agate mortar to obtain a powder material for later use; putting the binder PTFE emulsion in a beaker, adding isopropanol for demulsification, adding the ground powder material, mixing the slurry under an infrared lamp, drying, rolling the slurry on a roll-to-roll machine to form a membrane, putting the membrane in a vacuum oven at 80 ℃ for more than 6 hours, and pressing the membrane on a stainless steel mesh to obtain the anode;
the preparation method of the negative electrode comprises the following steps: weighing TiS according to the weight ratio of 80 2 The negative electrode comprises a negative electrode active material, a conductive agent and a binder, wherein the conductive agent is conductive carbon black SP, and the binder is 60 wt% of PTFE emulsion; firstly TiS 2 Uniformly grinding the negative active material and the conductive carbon black SP in an agate mortar to obtain a powder material for later use; putting the binder PTFE emulsion in a beaker, adding isopropanol for demulsification, adding the ground powder material, mixing the slurry under an infrared lamp, drying, rolling the mixture into a membrane on a roll machine, putting the membrane in a vacuum oven at 80 ℃ for keeping for more than 6 hours, and pressing the membrane on a stainless steel net to obtain a negative electrode;
the electrolyte is 3 mol.L -1 Aqueous solution of zinc trifluoromethanesulfonate (b).
A separator, which is glass fiber.
And assembling the positive electrode, the negative electrode, the electrolyte and the diaphragm into the button type water-based zinc ion battery.
Example 2
The embodiment of the application provides a positive active material, and the chemical formula of the positive active material is Zn 0.5 VOPO 4 The preparation method of the positive active material comprises the following steps:
with H 3 PO 4 、HNO 3 、V 2 O 5 、ZnI 2 Ethylene glycol dimethyl ether is used as a raw material; wherein H 3 PO 4 As a source of phosphorus, V 2 O 5 Is a source of vanadium, znI 2 Is a zinc source, HNO 3 Is an oxidant, and ethylene glycol dimethyl ether is a solvent;
mixing 2.4g V 2 O 5 、13.3mL H 3 PO 4 、10mL HNO 3 Adding into 55.7mL of water, reacting in an oil bath kettle at 110 ℃ under magnetic stirring for 16h, cooling, filtering, washing with acetone and water for three times, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain VOPO 4 ·2H 2 O; 0.5g of the obtained VOPO 4 ·2H 2 O and 4.625g ZnI 2 And adding 20mL of ethylene glycol dimethyl ether into a 100mL hydrothermal reaction kettle, reacting for 10h at 140 ℃, cooling, filtering, washing with ethylene glycol dimethyl ether for three times, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain Zn 0.5 VOPO 4 。
The embodiment of the application also provides a negative active material with a chemical formula of TiSe 2 The preparation method of the negative active material comprises the following steps:
ti powder, se powder and graphene are used as raw materials; wherein Ti powder is a titanium source, se powder is a selenium source, and graphene is a carbon source.
Placing 0.2393g Ti powder and 0.7896g Se powder in a mortar, and grinding to uniformly mix the powders; and transferring the mixed powder into a high borosilicate glass tube with an opening at one end, connecting the other end of the high borosilicate glass tube with a vacuum pump, and sealing the tube with isobutane while vacuumizing. Then placing the sealed tube in a muffle furnace, heating to 450 ℃ at room temperature for 4h, calcining for 72h, cooling to room temperature, and adding ethylenediamine and C 2 H 5 OH is washed for a plurality of times to obtain the TiSe 2 。
The embodiment of the application also provides a water system zinc ion battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm;
the preparation method of the positive electrode comprises the following steps: weighing Zn according to the weight ratio of 50 0.5 VOPO 4 Positive active material, conductive agent and adhesive, wherein the conductive agent is graphite, and the adhesive is sodium carboxymethylcellulose solution with weight percentage of 2%(ii) a Firstly Zn is added 0.5 VOPO 4 Uniformly grinding the positive active material and graphite in an agate mortar to obtain a powder material for later use; putting the sodium carboxymethylcellulose solution in a beaker, adding isopropanol for demulsification, adding the ground powder material, mixing under an infrared lamp, drying, rolling into a membrane on a roll machine, putting the membrane in a vacuum oven at 100 ℃ for more than 6 hours, and pressing on a titanium mesh to obtain the anode;
the preparation method of the negative electrode comprises the following steps: weighing the TiSe according to the weight ratio of 50 2 The cathode active material, a conductive agent and a binder, wherein the conductive agent is graphite, and the binder is a sodium carboxymethylcellulose solution with the weight percentage of 2%; firstly, tiSe is added 2 Uniformly grinding the negative active material and graphite in an agate mortar to obtain a powder material for later use; putting the sodium carboxymethylcellulose solution in a beaker, adding isopropanol for demulsification, adding the ground powder material, mixing under an infrared lamp, drying, rolling into a membrane on a roll machine, putting the membrane in a vacuum oven at 100 ℃ for more than 6 hours, and pressing on a titanium mesh to obtain a negative electrode;
the electrolyte contains 1 mol.L -1 Zinc sulfate and 0.5 mol. L -1 An aqueous solution of glucose;
the diaphragm is made of glass fiber;
and assembling the positive electrode, the negative electrode, the electrolyte and the diaphragm into the button type aqueous solution zinc ion battery.
Example 3
The embodiment of the application provides a positive active material, and the chemical formula of the positive active material is Zn 3 V 3 O 8 The preparation method of the positive active material comprises the following steps:
with Zn (COOCH) 3 ) 2 ·2H 2 O、V 2 O 5 Citric acid is used as a raw material; wherein Zn (COOCH) 3 ) 2 ·2H 2 O is a zinc source, V 2 O 5 Is a vanadium source, and citric acid is a carbon source;
1.0975g Zn (COOCH) 3 ) 2 ·2H 2 O、0.906g V 2 O 5 0.6g of citric acid monohydrate was added to the ball mill pot andadding acetone, mixing uniformly, and stirring at 300r/min for 6h to fully mix the materials; taking out the uniformly stirred materials, and drying the materials in a drying box at the temperature of 80 ℃ for 12 hours to obtain a precursor; putting the precursor in argon atmosphere, calcining for 3h at 500 ℃, and then calcining for 8h at 800 ℃ to obtain Zn 3 V 3 O 8 ；
The embodiment of the application also provides a water system zinc ion battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm;
the preparation method of the positive electrode comprises the following steps: weighing Zn according to the weight ratio of 95 3 V 3 O 8 The conductive material is a carbon nano tube, and the binder is sodium alginate emulsion; firstly Zn is added 3 V 3 O 8 Uniformly grinding the positive active material and the carbon nano tube in an agate mortar to obtain a powder material for later use; putting the sodium alginate emulsion serving as the binder into a beaker, adding the ground powder material, mixing the slurry under an infrared lamp, drying, rolling the mixture into a membrane on a double-roll machine, putting the membrane into a vacuum oven at 100 ℃ for more than 6 hours, and pressing the membrane on a titanium foil to obtain a positive electrode;
the preparation method of the negative electrode comprises the following steps: weighing TiS according to the weight ratio of 95 2 A negative electrode active material (the preparation method is the same as that of the embodiment 1), a conductive agent and a binder, wherein the conductive agent is a carbon nano tube, and the binder is sodium alginate emulsion; firstly TiS 2 Uniformly grinding the negative active material and the carbon nano tube in an agate mortar to obtain a powder material for later use; putting the sodium alginate emulsion serving as the binder into a beaker, adding the ground powder material, mixing the slurry under an infrared lamp, drying, rolling the mixture into a membrane on a double-roll machine, putting the membrane into a vacuum oven at 100 ℃ for more than 6 hours, and pressing the membrane on a titanium foil to obtain a negative electrode;
the electrolyte contains 2 mol/L -1 Zinc nitrate and 0.5 mol. L -1 An aqueous solution of ammonium acetate;
the diaphragm is a porous PP diaphragm;
and assembling the positive electrode, the negative electrode, the electrolyte and the diaphragm into the square aqueous solution zinc ion battery.
Example 4
The embodiment of the application also provides a negative active material with a chemical formula of Cu 2-x Se, the preparation method of the negative active material comprises the following steps:
with Cu (COOCH) 3 ) 2 ·H 2 O (copper acetate monohydrate), na 2 SeO 3 Sodium selenite and C 2 H 8 N 2 (ethylenediamine) as a raw material; wherein, cu (COOCH) 3 ) 2 ·H 2 O is a copper source, na 2 SeO 3 Is a source of selenium, C 2 H 8 N 2 As a reducing agent for high-valence selenium.
Cu with starfish morphology is prepared by a one-step hydrothermal method 2-x Se, specifically: 0.8g of Cu (COOCH) 3 ) 2 ·H 2 O、0.346g Na 2 SeO 3 、3mL C 2 H 8 N 2 Adding into 22mL deionized water, stirring vigorously for 30min, mixing thoroughly and dissolving to obtain a mixed solution; transferring the mixed solution into a Teflon-lined stainless steel reaction kettle with the volume of 100mL, and keeping the temperature at 180 ℃ for 24 hours; washing black precipitate at the bottom of the reaction kettle for multiple times by using deionized water and absolute ethyl alcohol, performing centrifugal separation, and then performing vacuum drying at 60 ℃ to obtain Cu 2-x Se。
The embodiment of the application also provides a water system zinc ion battery, which comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm;
the preparation method of the positive electrode comprises the following steps: weighing Zn according to the weight ratio of 60 0.5 VOPO 4 A positive electrode active material (the preparation method is the same as that of example 2), a conductive agent and a binder, wherein the conductive agent is graphene, and the binder is polyacrylic emulsion; firstly Zn is added 0.5 VOPO 4 Uniformly grinding the positive active material and the graphene in an agate mortar to obtain a powder material for later use; placing polyacrylic acid emulsion in a beaker, adding the ground powder material, mixing under an infrared lamp, dipping on a graphite sheet, and placing the graphite sheet containing the active material in a vacuum oven at 100 ℃ for more than 6 hours to obtain a positive electrode;
the preparation method of the negative electrode comprises the following steps: according to the weightWeighing Cu according to the weight ratio of 60 2-x The Se cathode material comprises a Se cathode active material, a conductive agent and a binder, wherein the conductive agent is graphene, and the binder is polyacrylic emulsion; firstly, cu is added 2-x Uniformly grinding the Se negative active material and the graphene in an agate mortar to obtain a powder material for later use; putting the polyacrylic acid emulsion in a beaker, adding the ground powder material, mixing under an infrared lamp, dipping on a graphite sheet, and putting the graphite sheet containing the active material in a vacuum oven at 100 ℃ for more than 6 hours to obtain a negative electrode;
the electrolyte is ZnSO 4 The preparation method of the polyacrylamide hydrogel electrolyte comprises the following steps: soaking the synthesized polyacrylamide hydrogel in 1 mol.L -1 ZnSO 4 Obtaining ZnSO in the solution for 24 hours 4 The polyacrylamide hydrogel electrolyte of (a);
the diaphragm is filter paper;
and assembling the positive electrode, the negative electrode, the electrolyte and the diaphragm into a soft-package type aqueous solution zinc ion battery.
Example 5
The embodiment of the application provides a water-based zinc ion battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm;
the preparation method of the anode comprises the following steps: weighing Zn according to the weight ratio of 70 3 V 4 (PO 4 ) 6 A positive electrode active material (the preparation method is the same as that of example 1), a conductive agent and a binder, wherein the conductive agent is acetylene black, and the binder is 2% sodium carboxymethylcellulose solution; firstly Zn is added 3 V 4 (PO 4 ) 6 Grinding the positive active material and the acetylene black uniformly in an agate mortar to obtain a powder material for later use; putting the sodium carboxymethylcellulose solution in a beaker, adding the ground powder material, mixing under an infrared lamp, dipping on carbon cloth, and putting the carbon cloth containing the active material in a vacuum oven at 100 ℃ for more than 6 hours to obtain an anode;
the preparation method of the negative electrode comprises the following steps: weighing Cu according to the weight ratio of 70 2-x Se negative active material (preparation method is same as example 4), conductive agent, binder, whereinThe conductive agent is acetylene black, and the binder is 2% sodium carboxymethyl cellulose solution; firstly, cu is added 2-x Uniformly grinding the Se negative electrode active material and the acetylene black in an agate mortar to obtain a powder material for later use; putting the sodium carboxymethylcellulose solution in a beaker, adding the ground powder material, mixing under an infrared lamp, dipping on carbon cloth, and putting the carbon cloth containing the active material in a vacuum oven at 100 ℃ for more than 6 hours to obtain a cathode;
the electrolyte contains 3 mol/L -1 And 0.5 mol.L of zinc trifluoromethanesulfonate (b) -1 An aqueous solution of monopotassium phosphate;
the diaphragm is made of glass fiber;
and assembling the anode, the cathode, the electrolyte and the diaphragm into the button type aqueous solution zinc ion battery.
Comparative example 1
The present comparative example provides an aqueous zinc-ion battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator;
wherein, the preparation method of the positive electrode is the same as that of the embodiment 1;
the negative active material is zinc powder; the preparation method of the negative electrode comprises the following steps: weighing a zinc powder negative electrode active material, a conductive agent and a binder according to the weight ratio of 80; firstly, uniformly grinding a zinc powder negative active material and conductive carbon black SP in an agate mortar to obtain a powder material for later use; putting the binder PTFE emulsion in a beaker, adding isopropanol for demulsification, then adding the ground powder material, performing size mixing and drying under an infrared lamp, finally rolling the mixture into a membrane on a roll machine, putting the membrane in a vacuum oven at 80 ℃ for more than 6 hours, and pressing the membrane on a titanium mesh to obtain a cathode; the utilization ratio of the zinc negative electrode in this comparative example was 20%;
the electrolyte is 3 mol.L -1 An aqueous solution of zinc trifluoromethanesulfonate of (1);
the diaphragm is made of glass fiber;
and assembling the positive electrode, the negative electrode, the electrolyte and the diaphragm into the button type aqueous solution zinc ion battery.
Performance testing
The positive electrode active material Zn prepared in example 1 was tested 3 V 4 (PO 4 ) 6 The surface morphology and the X-ray diffraction of (2) show that, as shown in fig. 1 and 2, the positive electrode active material Zn 3 V 4 (PO 4 ) 6 Is spherical with uniform size, and the size is between 1 and 4 mu m approximately.
Test of TiS negative electrode active Material obtained in example 1 2 The surface morphology and the X-ray diffraction results of (A) are shown in fig. 3 and 4, and it can be seen from fig. 3 to 4 that the negative electrode active material TiS 2 Is a pure compound, all peaks are in agreement with TiS 2 The structure (JCPDS No. 70-6204) is consistent, the appearance is flaky, graphene is coated, and the size is approximately between 3 and 8 mu m.
The water-based zinc ion battery assembled in example 1 was subjected to a charge and discharge test, and the results are shown in fig. 5, in which the test was performed using a constant current charge and discharge mode, with a charge cutoff voltage of 1.6V and a discharge cutoff voltage of 0.1V. As can be seen from FIG. 5, the zinc ion discharge capacity of this example can reach 94.6mAh g -1 。
Testing of positive electrode active material Zn prepared in example 2 0.5 VOPO 4 As shown in fig. 6, the positive electrode active material Zn is shown in fig. 6 as a result of X-ray diffraction of 0.5 VOPO 4 Characteristic peak of and VOPO 4 ·2H 2 The O structure (JCPDS No. 84-0111) has a more pronounced offset, demonstrating Zn intercalation.
Testing of negative active Material TiSe obtained in example 2 2 The surface morphology and the X-ray diffraction of (A) are shown in fig. 7, and it can be seen from fig. 7 that the negative electrode active material, tiSe 2 Is a pure compound, all peaks are in contact with TiSe 2 The structure (JCPDS No. 65-2037) is identical.
The charge and discharge test of the aqueous solution zinc ion battery assembled in example 2 was performed using a constant current charge and discharge mode, and the result is shown in fig. 8, in which the test was performed using the constant current charge and discharge mode until the charge voltage was 1.6V and the discharge voltage was 0.1V; as can be seen from FIG. 8, the zinc ion discharge capacity of this example can reach 107mAh·g -1 。
The positive electrode active material Zn prepared in example 3 was tested 3 V 3 O 8 As shown in fig. 9, the positive electrode active material Zn is shown in fig. 9 as a result of X-ray diffraction of 3 V 3 O 8 Is a pure compound.
Test example 4 negative electrode active material Cu obtained 2-x The surface morphology and X-ray diffraction results of Se are shown in FIGS. 10 and 11, and it is understood from FIGS. 10 to 11 that the negative electrode active material Cu 2-x Se is a pure compound, all peaks are in contact with Cu 2-x The Se structure (JCPDS No. 06-0680) is consistent, the appearance is in a starry shape, and the size is about 3-6 mu m.
The cycle curve of the water-based zinc-ion battery assembled in example 1 at a current density of 1C was measured, and as a result, as shown in fig. 12, it is understood from fig. 12 that the initial capacity of the zinc-ion battery obtained in this example at a current density of 1C was 94.6mAh g -1 And the capacity retention rate after 100 cycles is 94.3%, so that the composite material has good performance.
The result of the charge and discharge test of the aqueous zinc-ion battery assembled in comparative example 1 is shown in fig. 13, in which the test was performed using a constant current charge and discharge mode, and the charge cutoff voltage was 1.9V and the discharge cutoff voltage was 0.3V. As can be seen from FIG. 13, the zinc ion discharge capacity of this comparative example was 37.1mAh g -1 The capacity after 3 weeks of circulation is only 16mAh g -1 . Both reversible capacity and cycling performance are much lower than the cell in example 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A negative electrode active material, characterized in that the negative electrode active material has a chemical formula A x B y Wherein A is one or more of Ti, cu, mo, fe and Bi, and B is S 2- ，Se 2- ，O 2- ，N 3- ，P 3- Wherein 0 is<x≤3，0<y≤8。
2. A zinc ion battery comprising a negative electrode comprising the negative electrode active material according to claim 1.
3. The zinc-ion battery of claim 2, further comprising a positive electrode, a separator, and an electrolyte, wherein the positive electrode comprises a positive electrode active material having a chemical formula of Zn a M b N c Wherein M is one or more of V, mn, fe, cr, co, ni, zr, nb and Mo, and N is PO 4 3- ，P 2 O 7 4- ，SO 4 2- ，F - ，O 2- Wherein 0 is<a≤3，0<b≤5，0<c≤5。
4. The zinc-ion battery of claim 3, wherein the positive electrode and the negative electrode further comprise a conductive agent and a binder;
wherein the mass ratio of the positive active material, the conductive agent and the binder in the positive electrode is (5-9.5) to (0.3-3) to (0.2-2);
the mass ratio of the negative electrode active material, the conductive agent and the binder in the negative electrode is (5-9.5) to (0.3-3) to (0.2-2).
5. The zinc-ion battery of claim 3, wherein the electrolyte is a liquid or gel material having ionic conductivity with a soluble salt of zinc as a solute and water as a solvent.
6. The zinc-ion battery of claim 5, wherein the soluble salt of zinc comprises one or more of zinc triflate, zinc sulfate, zinc acetate, zinc chloride, zinc perchlorate, zinc nitrate, zinc bis (fluorosulfonyl) imide, and zinc bis (trifluoromethanesulfonyl) imide.
7. The zinc-ion battery of claim 3, wherein the separator comprises one of a non-woven fabric, a glass fiber, a porous PP/PE separator, a PTFE membrane, and a glass fiber filter paper.
8. The zinc-ion battery of claim 4, wherein the conductive agent comprises one or more of graphite, carbon black, ketjen black, carbon nanotubes, graphene.
9. The zinc-ion battery of claim 4, wherein the binder comprises one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, sodium alginate, polyacrylic acid, polyvinyl alcohol, styrene butadiene latex.
10. An electronic device comprising the zinc-ion battery according to any one of claims 2 to 9.
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