CN106450249B - 一种铋/氢氧化镍二次碱性电池及其制备方法 - Google Patents
一种铋/氢氧化镍二次碱性电池及其制备方法 Download PDFInfo
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- CN106450249B CN106450249B CN201611083383.9A CN201611083383A CN106450249B CN 106450249 B CN106450249 B CN 106450249B CN 201611083383 A CN201611083383 A CN 201611083383A CN 106450249 B CN106450249 B CN 106450249B
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- Prior art keywords
- bismuth
- nickel hydroxide
- battery
- solution
- nickel
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 131
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 67
- 239000000243 solution Substances 0.000 claims abstract description 53
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 229910001451 bismuth ion Inorganic materials 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 6
- 239000007774 positive electrode material Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000007773 negative electrode material Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000006258 conductive agent Substances 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229940036348 bismuth carbonate Drugs 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 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
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 229940049676 bismuth hydroxide Drugs 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002192 fatty aldehydes Chemical class 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- UFSKGOWRESQFBF-UHFFFAOYSA-N [Bi]=O.S(O)(O)(=O)=O Chemical compound [Bi]=O.S(O)(O)(=O)=O UFSKGOWRESQFBF-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims 1
- 235000015165 citric acid Nutrition 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910000104 sodium hydride Inorganic materials 0.000 claims 1
- 239000012312 sodium hydride Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000007246 mechanism Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 description 9
- 239000012279 sodium borohydride Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
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- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002127 nanobelt Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 241000219991 Lythraceae Species 0.000 description 2
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 2
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- 150000001621 bismuth Chemical class 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
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- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
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- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
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- 239000000725 suspension Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical group [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 1
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- 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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
本发明公开了一种铋/氢氧化镍二次碱性电池及其制备方法。本发明的电池以金属铋为电池的负极活性材料,以氢氧化镍为电池的正极活性材料,以碱溶液为电解质溶液,电池的电压窗口为0.2~1.4V。铋材料的制备为:在一定温度和搅拌条件下,按还原剂与铋离子的一定摩尔比将还原剂溶液滴加到含助剂的铋离子溶液中进行一定时间的反应,反应完成后将产物洗涤和固液分离,再将固体物进行真空干燥制备出铋材料,铋材料为0.005~5μm粒径的金属粉末,其比表面积为5~500m2/g。本发明的电池在5A/g电流密度下的比容量为254mAh/g。该电池具有大的电容量、良好的循环稳定性、环境友好,是一种具有广阔应用前景的新型化学电源。
Description
技术领域
本发明涉及一种铋/氢氧化镍二次碱性电池及其制备方法,属于电化学储能技术领域。
背景技术
随着工业的发展和人口的增长,人们对能源的需求也日益增长。由于近几十年来人们对化石能源的过度开采,能源逐渐枯竭,所以我们迫切地需要发展新的可再生能源。尽管在当代我们已经发展了多种可再生能源如风能、太阳能水能,但由于这些自然能源的不稳定性,限制了它们的用途,但是我们可以通过能量储存、转移、备份等方法来解决这些问题,其中化学电池由于转换效率高、能量密度高、环境污染少、携带使用方便且能量转换不受卡诺循环限制等特点成为储存能源最好的选择。镍电池是以氢氧化镍为正极的一系列电池,主要包括镍/氢电池、镍/镉电池、镍/铁电池、镍/锌电池等。镍/氢电池具有较高的容量、安全性能好、低记忆效应、工艺成熟等优点,但其负极一般采用稀土储氢合金,导致其成本高及电池装配工艺要求较高;镍/镉电池循环寿命长且贮存性能出色,由于镉的污染,其使用受到极大限制;镍/铁电池具有绿色环保、材料来源丰富、价格低廉、可耐过充过放电等独有的优点,缺点在于其自放电率大、低温性能差;镍/锌电池能快速充放电且成本较低,但锌电极在循环充放过程中容易变形、形成枝晶导致电池内部短路。因此,寻找新型的镍电池负极材料成为镍电池发展的关键。
电极是电池最重要的部分,而电极活性材料又是电极最核心的组成部分,决定了电池的性能。我国拥有十分丰富的铋资源,是世界上铋储量最大的国家,目前已探明的铋储量占世界总储量的70%以上。铋,83号元素,是一种具有共价键的典型的半金属元素,铋金属具有近似石墨的层状结构,熔点较低,仅有271℃,而沸点比熔点高1580℃,适宜用液相分散的方法制备纳米铋粉,且铋金属是一种绿色金属,含铋材料已在医药、环保、化妆品、陶瓷、染料、润滑油、功能材料等领域显现出潜在的应用价值。
Zeng等[Advanced Materials 304(2016)1-8.]采用电化学沉积法制备出稳定的单晶态铋单质,并以铋为正极,NiCo2O4为负极,1mol/L KOH为电解液,制备出二次碱性电池,且经10000次循环后容量基本无衰减。Zuo等[Nanomaterials 4(2015)1756-1765.]以Ti为基底,采用简单的水热法使制备出的铋单质均匀的分散在Ti基质上,并分别以LiOH或NaOH等为电解液,在三电极体系下,1mol/L KOH溶液中,0.5A/g电流密度下铋电极容量达170mAh/g。Timothy S.Arthur等[Electrochemistry Communications 16(2012)103-106.]采用电沉积法制备出单质Bi、Sb和Bi1-xSbx合金,并将其应用于Mg离子电池的正极材料。O.Crosnier等[Journal of Power Sources 94(2001)169-74.]在Ar-H2气氛下,采用直流电弧等离子技术制备出200nm左右的纯铋纳米粒,并将其用于锂离子电池的正极材料。Shao等[Nano letters 14(2013)255-260.]采用水热法制备出铋纳米管,将其应用于镁离子二次电池正极材料,这种纳米结构的铋电极具有高达350mAh/g的比容量,优越的稳定性及接近100%的库伦效率。Su等[Nano Energy 12(2015)88-95.]采用水热法制备出Bi@石墨烯纳米复合物,将其作为钠离子电池正极材料,在0.01-2.0V范围内,获得的钠储存容量高达561mAh/g。王彦敏等[山东交通学院学报4(2012)67-74.]以硝酸铋为原料,乙二醇为溶剂和还原剂,聚乙烯吡咯唍酮(PVP)为稳定剂,采用溶剂热法制备了单晶铋纳米带。赵彦保等[无机化学学报9(2003)997-1000.]以铋颗粒为起始原料,液体石蜡为溶剂,硬脂酸为修饰剂,采用分散法制备出硬脂酸修饰铋纳米微粒,并对其反应机理进行了研究。王轶等[延边大学学报:自然科学版3(2011)245-248.]以氯化铋为原料,水合肼为还原剂,油酸钠为表面活性剂,采用水相一步还原法制备出高纯度、粒径为20nm近似球形的超细金属铋纳米粒子,并探索了反应温度、还原剂浓度对铋纳米粒子的影响。唐春娟等[材料研究学报3(2011)273-277.]以五水硝酸铋为原料,水合肼为还原剂,CTAB为包覆剂,水和乙二胺为溶剂,详细研究了水和乙二胺的组分变化对产物的形貌和结构的影响。Dai等[Chemical Physics Letters591(2014)126–129.]通过改变表面活性剂的种类,制备出不同形貌的铋纳米粒子,其中采用P123为表面活性剂,能够制备出由六边形纳米棱柱组成的铋纳米花。Kim等[MaterialsChemistry and Physics 153(2015)316-322.]采用碱式碳酸铋为原料,在以四甘醇为溶剂、PVP为包覆剂的溶液中,通过两步煅烧法把直接碱式碳酸铋还原成球形铋纳米粒子。C JTang等[J Phys Chem C 113(2009)5422-5427.]分别以乙二醇和乙二胺为溶剂,通过溶剂热反应制备出铋纳米线和铋纳米花。Wang等[J Phys Chem B 110(2006)25702-25706.]通过改变PVP与铋原料的摩尔比,采用多元醇还原法,制备出不同形貌的单晶铋纳米粒子,并且在相同的合成条件下,通过引入痕量的Fe3+,能够把铋纳米立方体转换成铋纳米带。Wang等[J Phys Chem B 109(2005)7067-7072.]在室温下以DMF为溶剂,氯化铋为铋源,硼氢化钠为还原剂,PVP为封端剂剂,制备出铋纳米粒子。并详细探索了PVP与氯化铋的摩尔比及氯化铋的浓度对铋纳米粒子的尺寸和单分散性的影响。Ma等[Colloids and Surfaces A:Physicochem Eng Aspects 395(2012)276-283.]以硝酸铋为铋源,酒石酸为络合剂,NaH2PO2·H2O为还原剂,通过调整酒石酸和氢氧化钠的量,采用液相表面修饰还原法制备出直径10-50nm的铋纳米粒及长度约为10μm宽度约为100nm的铋纳米带。Cheng等[MaterialsLetters 63(2009)2239-2242.]采用乙二醇为溶剂,利用多元醇热法,在198℃下回流2小时,制备出铋微球或纳米球,并进一步研究了其可能的生长机理。
发明专利[申请公开号CN101569934A]公开了“一种金属铋纳米粒的制备方法”,通过混合可溶性铋盐水溶液和修饰剂有机溶液,加入还原剂,搅拌加热回流,制备出粒径分布比较均一的金属铋纳米粒。发明专利[申请公开号CN102212880A]公开了“一种Bi单质纳米结构材料及其制备方法与应用”,将表面活性剂、水合肼和铋盐溶于水制备成悬浊液;将所述悬浊液在80~120℃条件下反应18~30h,制备出由片状六方晶相Bi单质为结构单元组成的具有花朵状形貌的纳米颗粒,并将其制备成铋修饰电极,应用于水溶液中的重金属离子检测。发明专利[申请公开号CN102717095A]公开了“一种单分散铋纳米颗粒的制备方法”,本发明采用乙酸铋作为铋源,油胺或油酸作为包裹剂和表面活性稳定剂,在有机相体系中合成铋纳米颗粒,所制得的铋纳米颗粒具有较高的产率,很好的稳定性。发明专利[申请公开号CN102989507A]公开了“一种铋基光催化剂的制备及性能检测方法”,该发明首先将Bi(NO3)3·5H2O溶于醋酸,以乙二醇为反应介质,搅拌混匀,再加入一定体积的二甲基甲酰胺后,将得到的溶液经加热回流并搅拌即得到产物Bi-DMF花球。将制备的Bi-DMF花球在可见光条件下进行光催化性能测试,2h内罗丹明由紫色褪为无色,降解完全;表明此球形铋基催化剂在可见光范围内,具有良好的光催化性能。发明专利[申请公开号CN105312086A]公开了“一种石榴状碳包覆铋纳米复合材料和其制备方法”,该发明在密闭容器中,将水溶性糖类、硝酸铋和聚乙烯吡咯烷酮溶于水,再加入有机酸,在160℃~260℃反应,经洗涤、干燥得到石榴状碳包覆铋纳米复合材料。并且该材料对黑索金的热分解有明显的催化作用,可将其应用于推进剂燃烧催化。发明专利[申请公开号CN104475133A]公开了“一种Bi/BiOCl光催化剂的制备方法”,本发明采用一步燃烧法,以硝酸铋、氯化铵和柠檬酸为原料,通过硝酸盐和柠檬酸间的氧化还原反应,制备出Bi/BiOCl复合光催化剂。
目前已有不少关于铋作为光催化剂和润滑剂等应用方面的报道。但是,关于以金属铋为负极,氢氧化镍为正极的二次碱性电池的文献及专利研究仍未见报道。因此,新构造的铋/氢氧化镍二次碱性电池将进一步推进镍电池技术。
发明内容
本发明的目的在于提供一种新型的铋/氢氧化镍二次碱性电池及其制备方法。本发明以球形氢氧化镍为电池的正极活性材料,以金属铋为电池的负极活性材料,以碱溶液为电解质溶液。
本发明的技术方案为:
一种铋/氢氧化镍二次碱性电池,其特征在于,以金属铋材料为电池的负极活性材料,铋材料为0.005~5μm粒径的金属粉末,其比表面积为5~500m2/g;以氢氧化镍材料为电池的正极活性材料;以碱溶液为电解质溶液;电池的电压窗口为0.2~1.4V。
所述的氢氧化镍材料中所含元素的质量百分比为:镍48~63%、钴0.5~12%、锌0.5~6.5%、铈0~8.5%、其余为氢、氧等非金属元素;氢氧化镍材料的比表面积为5~100m2/g,粒径为1~15μm;氢氧化镍材料的松装密度为1.58~1.75g/cm3,振实密度为2.0~2.5g/cm3。
所述的铋材料,其制备方法包括如下步骤:
(1)将可溶性的铋原料溶于溶剂中,将其配制成铋离子浓度为0.01~5mol/L的铋离子溶液;或者将不溶性的铋原料溶于酸中,配制成铋离子浓度为0.01~5mol/L的铋离子溶液;
(2)将还原剂溶解于溶剂中配制成浓度为0.1~16mol/L的还原剂溶液;
(3)按助剂与铋离子(0~10):1的摩尔比,将助剂加入到铋离子溶液中,充分混合;
(4)在温度为0~100℃和搅拌条件下,按还原剂与铋离子的摩尔比为(1~100):1将步骤(2)所得还原剂溶液滴加到步骤(3)所得含助剂的铋离子溶液中,滴加完成后,继续搅拌0~360min将产物分别用水和乙醇洗涤,并进行固液分离,将固体物置于真空干燥箱中30~100℃干燥6~36h至恒重制备出铋材料;
进一步地,所述的溶剂为水、甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙三醇、聚乙二醇、三乙醇胺、四甘醇、二甲基甲酰胺(DMF)中一种或两种以上。
进一步地,所述的铋原料,包括金属铋、氧化铋、氢氧化铋、碳酸铋、碱式碳酸铋、硫酸氧铋、硝酸氧铋、硫酸铋、硝酸铋、卤化铋、乙酸铋、柠檬酸铋中的一种或两种以上。
进一步地,所述的酸溶液为盐酸、硫酸、醋酸或硝酸中的一种或两种以上,其浓度为1~10mol/L。
进一步地,所述的还原剂为硼氢化钠、硼氢化钾、次亚磷酸钠、烷基胺硼烷、水合肼、脂肪醛、芳香醛中的一种或两种以上。
进一步地,所述的助剂为聚乙二醇、乙二醇、丙三醇、三乙醇胺、柠檬酸、抗坏血酸、酒石酸、油酸钠、十六烷基三甲基溴化铵(CTAB)、聚乙烯吡咯烷酮(PVP)中的一种或两种以上。
上述的铋/氢氧化镍二次碱性电池的制备方法,包括如下步骤:
(1)铋电极和氢氧化镍电极的制备
铋电极的制备:将粘结剂溶于N-甲基吡咯烷酮中,配成0.02~1g/ml的溶液,再将铋材料、导电剂加入到粘结剂溶液中,搅拌均匀至膏状,涂覆在集流体上,再将其在80~150℃的干燥箱中5~36h,经辊压后裁成电极片,即得到铋电极,所述铋材料、导电剂及粘结剂满足如下质量百分比:铋材料70~95%、导电剂3~15%、粘结剂2~15%;
氢氧化镍电极的制备:按照氢氧化镍材料70~95%、导电剂3~15%、粘结剂2~15%的质量百分比称量备用,然后依次将粘结剂、导电剂、氢氧化镍材料混合均匀调成糊状涂抹于泡沫镍上,80~150℃干燥5~36h,辊压并裁剪后得到氢氧化镍电极片;
(2)铋/氢氧化镍二次碱性电池的组装
将步骤(1)中得到的电极片按铋电极片、隔膜、氢氧化镍电极片依次放入电池模具中构造成二电极的三明治结构,滴加电解液后将电池模具紧固密封,即构造成铋/氢氧化镍二次碱性电池。
进一步地,所述的导电剂为导电炭黑、乙炔黑、石墨、石墨烯中的一种或两种以上。
进一步地,所述的粘结剂为聚四氟乙烯乳液、聚偏氟乙烯、羧甲基纤维素钠或丁苯橡胶中的一种或两种以上。
进一步地,所述的集流体为多孔网状、箔状或织物状的高电子导电率材料,涉及到泡沫镍、镍箔或镍网、铜网或铜箔、不锈钢网、不锈钢冲孔钢带或不锈钢箔、钛箔或钛网、铅箔或铅布、石墨化碳布或石墨烯布材料中的一种或两种以上。
进一步地,所述的电解液为一种或两种以上碱金属氢氧化物的水溶液,其浓度为1~8mol/L。
进一步地,所述的隔膜为接枝聚丙烯无纺布、接枝PP微孔膜、玻璃纤维纸、尼龙无纺布、聚乙烯醇膜、石棉纸中的一种或两种以上。
所制备材料的结构与电化学性能测试:
采用JEOLJEM-3010型扫描电子显微镜对所制备材料进行微观形貌及大小的测试;采用D/MAX-3C型粉末X-射线衍射仪对所制备的材料进行晶相结构的测试。
采用上海辰华公司生产的CHI660A电化学工作站、深圳市新威尔电子有限公司生产的BTS-3000电池测试仪对所构造的电池进行循环伏安、恒流充放电、循环寿命、倍率性能测试。
本发明的有益效果在于:
(1)本发明以氢氧化镍材料为电池的正极活性材料,以金属铋材料为电池的负极活性材料,以碱溶液为电解质溶液,构造出了新型的铋/氢氧化镍二次碱性电池,电池的电压窗口为0.2~1.4V。
(2)本发明的铋/氢氧化镍二次碱性电池,在5A/g的电流密度下电容量达到254mAh/g,电池经过1000次循环之后电容量的保留率仍保持在73%以上,该电池具有电容量大、循环寿命长、环境友好等优点,是一种具有广阔应用前景的新型可逆二次化学电源。
附图说明
图1为实施例1所制备的铋材料的扫描电子显微镜图。
图2为实施例2所制备的铋材料的扫描电子显微镜图。
图3为实施例1、3~5所采用的氢氧化镍材料的扫描电子显微镜图。
图4为实施例1所制备的铋材料的X射线衍射图。
图5为实施例1中铋/氢氧化镍二次碱性电池的循环寿命图。
图6为实施例3中铋/氢氧化镍二次碱性电池在不同扫描速率下的循环伏安测试图。
图7为实施例3中铋/氢氧化镍二次碱性电池在0.5A/g电流密度下的恒电流充放电测试图。
图8为实施例4中铋/氢氧化镍二次碱性电池的在不同电流密度下的恒电流充放电测试图。
图9为实施例5中铋/氢氧化镍二次碱性电池在不同扫描速率下的循环伏安测试图。
具体实施方式
下面以具体实施例进一步说明本发明,但本发明并不局限于此。
实施例1
(1)称取一定质量Bi(NO3)3·5H2O,溶解于10ml浓硝酸溶液中,加水稀释后,配制成0.5mol/L的Bi(NO3)3溶液。
(2)将2.22gPVP、20mL 0.5mol/L的Bi(NO3)3溶液依次加入100mL圆底烧瓶中,混合均匀后,在室温下搅拌30min。
(3)按硼氢化钠和铋离子摩尔比为3:1,称取一定质量的硼氢化钠溶于20ml去离子水中配成硼氢化钠溶液,在室温下一边搅拌一边将硼氢化钠溶液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌5min,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH值为中性,放入真空干燥箱中60℃下干燥30h,制得铋材料。
(4)采用JEOLJEM-3010型扫描电子显微镜对实施例1所制备的铋材料进行测试,如图1所示,该铋材料由粒径约为20-50nm的纳米颗粒组成的花椰菜形貌。
(5)采用XRD-6000型X-射线衍射仪对实施例1所制备的铋材料进行测试,如图4所示,样品特征峰很明显,在2θ=22°,24°,27°,38°,40°,45°,46°,49°,56°和59°等位置均有较明显的特征峰,和标准卡片(JCPDS No.44-1246)一致,其所对应的晶面分别为003、101、012、104、110、015、113、202、024和107。
(6)铋电极及氢氧化镍电极的制备:
铋电极的制备:按照铋材料80%、粘结剂PVDF12%及导电剂乙炔黑8%的质量百分比,首先将粘结剂溶于N-甲基吡咯烷酮中,配成0.02g/ml的溶液,再将铋材料、导电剂加入到粘结剂溶液中,搅拌均匀至膏状,涂覆在泡沫镍集流体上,再将其置于真空干燥箱中100℃干燥12h,经辊压后裁成电极片,即得到铋材料电极片。
氢氧化镍电极的制备:按照氢氧化镍材料80%、导电剂10%、粘结剂10%的质量百分比称量备用,然后依次将PTEF乳液粘结剂、导电剂乙炔黑、氢氧化镍材料混合均匀调成糊状涂抹于泡沫镍上,120℃干燥12h,辊压并裁剪后得到氢氧化镍电极片。
(7)将已制备的铋电极片/隔膜/氢氧化镍电极片依次放入特制的电池模具中构造成二电极的三明治结构,再滴加6mol/L的KOH电解液后将电池模具紧固密封,即组装成所述的铋/氢氧化镍二次碱性电池。
(9)采用深圳市新威尔电子有限公司生产的BTS-3000电池测试仪,对所构造的铋/氢氧化镍二次碱性电池在室温下进行循环寿命测试,电池的电压窗口为0.2~1.4V。由图5可见,所制备的电池在5A/g的电流密度下,首次放电容量为254mAh/g,经过1000次充放电循环之后以后还能保持最初比电容的73.6%,这说明其具有良好的循环稳定性能。
(10)采用JEOLJEM-3010型扫描电子显微镜对实施例1、3~5所采用的氢氧化镍材料的形貌进行测试,如图3所示,该氢氧化镍材料由直径约为5~15μm球体组成,分布均匀,排列规整。
实施例2
(1)称取1.99g柠檬酸铋溶解于20ml乙二醇溶液中。
(2)将0.5g酒石酸、2.0g氢氧化钠依次加入加入到步骤(1)溶液中,混合均匀后,在室温下搅拌30min。
(3)按NaH2PO2和铋离子摩尔比为80:1,称取一定质量的NaH2PO2溶于40ml去离子水中配成NaH2PO2溶液,在90℃下一边搅拌一边将NaH2PO2溶液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌300min,直至溶液由澄清变为黑色,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH为中性,放入真空干燥箱中80℃下干燥24h,制得铋材料。
(4)采用JEOLJEM-3010型扫描电子显微镜对实施例2所制备的铋材料进行测试,如图2所示,该铋粉末材料由粒径约为500nm的纳米粒组成。
实施例3
(1)称取4.8507g Bi(NO3)3·5H2O,溶解于20ml乙二醇溶液中。
(2)将2.22gPVP加入到步骤(1)溶液中,混合均匀后,在室温下搅拌30min。
(3)按硼氢化钠和铋离子摩尔比为3:1,称取一定质量的硼氢化钠溶于20ml去离子水中配成硼氢化钠溶液,在室温下一边搅拌一边将硼氢化钠溶液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌5min,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH为中性,放入真空干燥箱中60℃下干燥30h,制得铋材料。
(4)同实施例1中的步骤(6)。
(5)将已制备的氢氧化镍电极片/隔膜/铋电极片依次放入特制的电池模具中构造成二电极的三明治结构,再滴加5mol/L的KOH和1mol/L的LiOH的混合电解液后将电池模具紧固密封,即组装成所述的铋/氢氧化镍二次碱性电池。
(6)采用上海辰华公司生产的CHI660A电化学工作站,对所构造的铋/氢氧化镍二次碱性电池在室温下进行循环伏安和恒流充放电测试,电池的电压窗口为0.2~1.4V。如图6所示,所制备的电池在不同扫描速率下(5、10、20、50mV/s)的伏安曲线,即使在较高的扫速下,氧化还原可逆性良好,表现出较好的电化学性能。由图7可见,该电池在电流密度为0.5A/g时的比电容达到260mAh/g。
实施例4
(1)称取2.4254g Bi(NO3)3··5H2O,溶解于20ml乙二醇和20mL丙三醇溶液中。
(2)将0.1g CTAB加入到步骤(1)溶液中,混合均匀后,在室温下搅拌30min。
(3)按硼氢化钾和铋离子摩尔比为5:1,称取一定质量的硼氢化钾溶于40ml去离子水中配成硼氢化钾溶液,在室温下一边搅拌一边将硼氢化钾溶液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌30min,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH为中性,放入真空干燥箱中90℃下干燥10h,制得铋材料。
步骤(4)、(5)分别同实施例1中的步骤(6)、(7)。
(6)采用上海辰华公司生产的CHI660A电化学工作站,对所构造的铋/氢氧化镍二次碱性电池在室温下进行恒流充放电测试,电池的电压窗口为0.2~1.4V。由图8可知,电池在0.5A/g的电流密度下比电容达到228mAh/g,在电流密度为1、2和5A/g时的比电容分别为216、213和208mAh/g。在0.5A/g的电流密度下时,91%的电容量集中在放电电压平台0.75~0.9V内。
实施例5
(1)称取一定质量BiCl3,溶解于10mL浓盐酸溶液中,配制成0.5mol/L的BiCl3溶液,备用。
(2)将0.1g油酸钠加入到步骤(1)溶液中,混合均匀后,在室温下搅拌30min。
(3)按水合肼和铋离子摩尔比为100:1,量取一定体积80wt%的水合肼,并转移到恒压滴液漏斗中,在90℃下,一边搅拌一边将水合肼溶液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌90min,直至溶液由澄清变为黑色,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH值为中性,放入真空干燥箱中60℃下干燥12h,制得铋材料。
步骤(4)、(5)分别同实施例1中的步骤(6)、(7)。
(6)采用上海辰华公司生产的CHI660A电化学工作站,对所构造的铋/氢氧化镍二次碱性电池在室温下进行循环伏安测试,电池的电压窗口为0.2~1.4V。如图9所示,所制备的电池在5mV/s扫描速率下不同周期(第一次循环和第二十次循环)的伏安曲线,其氧化峰电位为1.2V,还原峰电位分别为0.54V和0.85V,且曲线基本重合,说明此电池的稳定性和可逆性良好。
Claims (8)
1.一种铋/氢氧化镍二次碱性电池,其特征在于,以金属铋材料为电池的负极活性材料,以氢氧化镍材料为电池的正极活性材料,以碱溶液为电解质溶液,电池的电压窗口为0.2~1.4V;
所述的氢氧化镍材料中所含元素的质量百分比为:镍 48~63%、钴0.5~12%、锌0.5~6.5%、铈 0~8.5%、其余为氢、氧非金属元素;
氢氧化镍材料的比表面积为5~100m2/g,粒径为1~15μm;氢氧化镍材料的松装密度为1.58~1.75g/cm3,振实密度为2.0~2.5g/cm3;
所述的铋材料为0.005~5µm粒径的金属粉末,其比表面积为5~500m2/g;其制备方法包括如下步骤:
(1) 将可溶性的铋原料溶于溶剂中,将其配制成铋离子浓度为0.01~5mol/L的铋离子溶液;或者将不溶性的铋原料溶于酸溶液中,配制成铋离子浓度为0.01~5mol/L的铋离子溶液;
(2) 将还原剂溶解于溶剂中配制成浓度为0.1~16mol/L的还原剂溶液;
(3) 按助剂与铋离子的摩尔比为x,0<x≤10,将助剂加入到铋离子溶液中,充分混合;
(4) 在温度为0~100℃和搅拌条件下,按还原剂与铋离子的摩尔比为(1~100):1将步骤(2)所得还原剂溶液滴加到步骤(3)所得含助剂的铋离子溶液中,滴加完成后,继续搅拌5~360min将产物分别用水和乙醇洗涤,并进行固液分离,将固体物置于真空干燥箱中30~100℃干燥6~36h至恒重制备出铋材料。
2.根据权利要求1所述的铋/氢氧化镍二次碱性电池,其特征在于,所述的溶剂为水、甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙三醇、聚乙二醇、三乙醇胺、四甘醇、二甲基甲酰胺中一种或两种以上。
3.根据权利要求1所述的铋/氢氧化镍二次碱性电池,其特征在于,所述的铋原料,包括金属铋、氧化铋、氢氧化铋、碳酸铋、碱式碳酸铋、硫酸氧铋、硝酸氧铋、硫酸铋、硝酸铋、卤化铋、乙酸铋、柠檬酸铋中的一种或两种以上。
4.根据权利要求1所述的铋/氢氧化镍二次碱性电池,其特征在于,所述的酸溶液为盐酸、硫酸或硝酸中的一种或两种以上,其浓度为1~10mol/L。
5.根据权利要求1所述的铋/氢氧化镍二次碱性电池,其特征在于,所述的还原剂为硼氢化钠、硼氢化钾、次亚磷酸钠、烷基胺硼烷、水合肼、脂肪醛、芳香醛中的一种或两种以上。
6.根据权利要求1所述的铋/氢氧化镍二次碱性电池,其特征在于,所述的助剂为聚乙二醇、乙二醇、丙三醇、三乙醇胺、柠檬酸、抗坏血酸、酒石酸、油酸钠、十六烷基三甲基溴化铵、聚乙烯吡咯烷酮中的一种或两种以上。
7.权利要求1至6任一项所述的铋/氢氧化镍二次碱性电池的制备方法,其特征在于,包括如下步骤:
(1) 铋电极和氢氧化镍电极的制备
铋电极的制备:将粘结剂溶于N-甲基吡咯烷酮中,配成0.02~1g/ml的溶液,再将铋材料、导电剂加入到粘结剂溶液中,搅拌均匀至膏状,涂覆在集流体上,再将其置于干燥箱中80~150℃干燥5~36h,经辊压后裁成电极片,即得到铋电极,所述铋材料、导电剂及粘结剂满足如下质量百分比:铋材料70~95%、导电剂3~15%、粘结剂2~15%;
氢氧化镍电极的制备:按照氢氧化镍材料70~95%、导电剂3~15%、粘结剂2~15%的质量百分比称量备用,然后依次将粘结剂、导电剂、氢氧化镍材料混合均匀调成糊状涂抹于泡沫镍上,80~150℃干燥5~36h,辊压并裁剪后得到氢氧化镍电极片;
(2)铋/氢氧化镍二次碱性电池的组装
将步骤(1)中得到的电极片按铋电极片、隔膜、氢氧化镍电极片依次放入电池模具中构造成二电极的三明治结构,滴加电解液后将电池模具紧固密封,即制得铋/氢氧化镍二次碱性电池。
8.根据权利要求7所述的铋/氢氧化镍二次碱性电池的制备方法,其特征在于,所述的导电剂为导电炭黑、石墨、石墨烯中的一种或两种以上;所述的粘结剂为聚四氟乙烯乳液、聚偏氟乙烯、羧甲基纤维素钠或丁苯橡胶中的一种或两种以上;所述的集流体为泡沫镍、镍箔或镍网、铜网或铜箔、不锈钢网、不锈钢冲孔钢带或不锈钢箔、钛箔或钛网、铅箔或铅布、石墨化碳布或石墨烯布材料中的一种或两种以上;
所述的电解液为一种或两种以上碱金属氢氧化物的水溶液,其浓度为1~8mol/L;所述的隔膜为接枝聚丙烯无纺布、接枝PP微孔膜、玻璃纤维纸、尼龙无纺布、聚乙烯醇膜、石棉纸中的一种或两种以上。
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