CN105895383A - Supercapacitor-used alloy/amorphous nickel cobalt hydroxide composite electrode and preparation method thereof - Google Patents
Supercapacitor-used alloy/amorphous nickel cobalt hydroxide composite electrode and preparation method thereof Download PDFInfo
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- CN105895383A CN105895383A CN201610220370.5A CN201610220370A CN105895383A CN 105895383 A CN105895383 A CN 105895383A CN 201610220370 A CN201610220370 A CN 201610220370A CN 105895383 A CN105895383 A CN 105895383A
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- Prior art keywords
- nickel
- cobalt
- alloy
- cobalt hydroxide
- amorphous
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Links
- 239000000956 alloy Substances 0.000 title claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 43
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title abstract 5
- 239000006260 foam Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 238000004070 electrodeposition Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 4
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021584 Cobalt(II) iodide Inorganic materials 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 claims description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 4
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 4
- CTIHZTFULZJBGQ-UHFFFAOYSA-L cobalt(2+);decanoate Chemical compound [Co+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O CTIHZTFULZJBGQ-UHFFFAOYSA-L 0.000 claims description 4
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 claims description 4
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 4
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 4
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims description 4
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 4
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- -1 graphite alkene Chemical class 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002238 carbon nanotube film Substances 0.000 claims description 2
- 229910052729 chemical element Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 1
- 229960001763 zinc sulfate Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000010410 layer Substances 0.000 description 11
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses a method of preparing a supercapacitor-used alloy/amorphous nickel cobalt hydroxide composite electrode. The method comprises steps: (1) foam metal is cleaned; (2) a foam metal-based alloy is prepared; (3) nickel cobalt hydroxide is electrodeposited on th e foam alloy; and (4) a metal/amorphous nickel cobalt hydroxide composite electrode is prepared. In addition, the invention also discloses a composite electrode prepared by adopting the above preparation method. Compared with the prior art, the composite electrode can effectively improve the mass specific capacity and the cycle stability of the supercapacitor and has high practical value and wide application prospect.
Description
Technical field
The present invention relates to a kind of combination electrode, specifically, relate to a kind of ultracapacitor alloy/amorphous
Nickel cobalt hydroxide combination electrode and preparation method thereof.
Background technology
Ultracapacitor not only has the advantage that power density is high, energy density is big, charge-discharge velocity is fast, and
And have that efficiency is high, have extended cycle life, the advantage such as electrode material environmental protection and operating temperature range width,
The fields such as information technology, mobile communication, electric automobile, fuel combination automobile, Aero-Space and science and techniques of defence,
There is huge market potential, be the scientific research focus of society.
According to the difference of electric charge energy storage mechnism, ultracapacitor can be divided into double layer capacitor and fake capacitance electric capacity
Device.In the electrode material of double layer capacitor, graphite is to study electricity that is more and that obtained business application
Pole material, its theoretical specific capacity can reach 400F/g.But, by pore-size distribution, configuration of surface and with
The impact of the factors such as electrolyte wellability, electric charge is obstructed in transmittance process, and substantial amounts of compound phenomenon occurs,
Its actual specific capacity is caused to be only about 200F/g.Transistion metal compound relies on the fake capacitance characteristic of its excellence,
Scientific research has presented good development trend, particularly Ni (OH)2/Co(OH)2Film, shows
High initial mass specific capacity.But, fake capacitance electrode material is in charge and discharge process, by electrolyte
Ion orientation and the restriction of charge migration speed, the multiplying power property of its high current charge-discharge is poor, limits it
The further raising of chemical property.How to give full play to the fake capacitance characteristic of nickel cobalt metal, be to change further
The key of its chemical property kind, is also the emphasis studied of people.
Summary of the invention
It is an object of the invention to provide a kind of ultracapacitor alloy/amorphous nickel cobalt hydroxide compound electric
Pole, utilizes foam metal base alloy to be obviously improved the electric conductivity of nickel cobalt hydroxide, and then promotes super electricity
The specific discharge capacity of container and cyclical stability.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of ultracapacitor alloy/amorphous nickel cobalt hydroxide combination electrode, by foam metal base alloy with
Amorphous nickel cobalt hydroxide two parts are uniformly composited.
Further, the molecular formula of described amorphous nickel cobalt hydroxide is NixCoy(OH)2(x+y), and
X:y=1:(0.5～2).
The present invention additionally provides above-mentioned ultracapacitor alloy/amorphous nickel cobalt hydroxide combination electrode simultaneously
Preparation method, comprise the steps:
(1) foam metal is put in concentrated hydrochloric acid and carry out ultrasonic cleaning, remove the oxide on foam metal surface
Layer is then clean by deionized water and alcohol flushing；
(2) by metal salt solution or graphene suspension or carbon nano tube suspension as presoma, regulation
Solution ph, on foam metal, alloy/graphite alkene/carbon nano-tube film conductive layer is prepared in electro-deposition in situ,
Then clean by deionized water and alcohol flushing；
(3) sample of step (2) gained is placed in the mixed solvent of nickel salt and cobalt salt, regulates pH value,
Original position electric deposition nickel cobalt hydroxide thereon；
(4) by clean to sample deionized water and the ethanol purge of step (3) gained, after drying, to obtain final product
Alloy/amorphous nickel cobalt hydroxide combination electrode.
Further, in step (1), described foam metal is in nickel foam, foam copper, foamed aluminium
A kind of.The time of described ultrasonic cleaning is 30min.
Further, in step (2), in described presoma, slaine is silver nitrate, zinc nitrate, sulfuric acid
Zinc, aluminum nitrate, aluminum sulfate, aluminium chloride, cobaltous iodide, cobaltous bromide, cobalt chloride, cobaltous fluoride, cobaltous sulfate,
Cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt phosphate, cobalt naphthenate, cobaltous octadecanate, new cobalt decanoate, boron are acylated
Cobalt, nickel iodide, nickelous bromide, nickel chloride, nickel fluoride, nickel sulfate, ammonium nickel sulfate, nickelous carbonate, nickel nitrate,
One or more in nickel acetate, citric acid nickel, nickel sulfide, copper chloride, copper nitrate, copper sulphate；Described
The solvent of presoma is water, methyl alcohol, ethanol, isopropanol, the tert-butyl alcohol, chloroform, ethylene glycol, dimethyl
Acetamide, dimethyl sulfoxide, benzyl ether, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, N, N-dimethyl
One or more in formamide；The concentration of described metal salt solution is 0.005～0.5mol/L, described electro-deposition
Time is 1-100min.
Further, in step (2), the pH value of solution being adjusted to faintly acid, described pH regulates
Agent is one or more in acetic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
Further, in step (3), described nickel salt be nickel iodide, nickelous bromide, nickel chloride, nickel fluoride,
One or more in nickel sulfate, ammonium nickel sulfate, nickelous carbonate, nickel nitrate, nickel acetate, citric acid nickel；Institute
Stating cobalt salt is cobaltous iodide, cobaltous bromide, cobalt chloride, cobaltous fluoride, cobaltous sulfate, cobalt carbonate, cobalt nitrate, acetic acid
One or more in cobalt, cobalt phosphate, cobalt naphthenate, cobaltous octadecanate, new cobalt decanoate, cobalt boracylate；Institute
Stating in the mixed solution of nickel salt and cobalt salt, nickel is 1:2 with the chemical element metering ratio of cobalt, and its solvent is water, first
Alcohol, ethanol, isopropanol, the tert-butyl alcohol, chloroform, ethylene glycol, dimethylacetylamide, dimethyl sulfoxide, two
One or more in benzyl oxide, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, N,N-dimethylformamide.
Yet further, in step (4), after regulation, the pH value of solution is 6～10, regulation pH value
Electrolyte is one or more in sodium carbonate, sodium acid carbonate, sodium acetate, sodium phosphate, potassium carbonate etc.；
The final solution concentration of described step (4) is 0.005～0.5mol/L, and described electrodeposition time is 1-100min.
Preferably, in step (4), dry run is protected in environment in vacuum environment or nitrogen and is carried out,
Drying time is 1～15h, and baking temperature is 30～120 DEG C.
In the present invention, the principle of alloy/amorphous nickel cobalt hydroxide combination electrode high specific capacitance is: nickel cobalt
High fake capacitance reserves and the high conductivity of alloy.Wherein, nickle atom and the cobalt atom of transition group provides respectively
Abundant redox active point, it is ensured that fake capacitance capacity；The high conductivity of foaming structure alloy,
Ensure that the quick exchange of its electric charge；Alloy particularly comprises high activity and the high conductivity being different from nickel cobalt
During the third metal, in capacitor charging/discharging cyclic process, this third metal can participate in fake capacitance storage
Can process, uniform after be deposited on nickel cobalt hydroxide surfaces, thus play rapid electric charge exchange and transmission
Effect.
Compared with prior art, the method have the advantages that
(1) present invention utilizes the high fake capacitance reserves of nickel cobalt and the structure of alloy and high conductivity, with
Foam metal, as skeleton, prepares the foamed alloy of high-specific surface area and high conductivity by original position electrodeposition process,
In situ electro-deposition amorphous nickel cobalt hydroxide on foamed alloy again, eventually pass cleaning, be dried to obtain compound
Electrode, its preparation method science, rationally, the specific discharge capacity and the circulation that substantially increase ultracapacitor are steady
Qualitative, there is the highest practical value and wide application prospect.
(2) in the present invention, nickle atom and the cobalt atom of transition group each provides abundant redox
Active site, it is possible to fully ensure that the fake capacitance capacity of nickel cobalt metal, and then ensure the electrochemistry of ultracapacitor
Promoting smoothly of performance and being effectively improved of practical value.
(3) in the present invention, the high conductivity of foaming structure alloy, it is ensured that the quick exchange of its electric charge；Special
It not foaming structure alloy when comprising the third metal being different from the high activity of nickel cobalt and high conductivity, super
In level capacitor charging/discharging cyclic process, this third metal can participate in fake capacitance thermal energy storage process, equably
After be deposited on nickel cobalt hydroxide surfaces, thus play raising charge-exchange and the effect of transfer rate so that
The performance of ultracapacitor has obtained significantly promoting.
(4) preparation method of the present invention, reaction temperature is low, react controlled, there is not production safety hidden
Suffer from, less demanding to the technology of producers, it is especially suitable for large-scale promotion application.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, and embodiments of the present invention include but not limited to
The following example.
Embodiment
Combination electrode disclosed by the invention, equal with amorphous nickel cobalt hydroxide two parts by foam metal base alloy
Even being composited, wherein, the molecular formula of amorphous nickel cobalt hydroxide is NixCoy(OH)2(x+y), and
X:y=1:(0.5～2).This combination electrode compared with prior art, can not only be effectively improved the matter of ultracapacitor
Amount specific capacity and cyclical stability, and preparation method is simple, is suitable for large-scale production and application.Its preparation side
Method can be summarized as following step in general:
(1) foam metal is cleaned；
(2) foam metal base alloy is prepared；
(3) at foamed alloy substrates nickel cobalt hydroxide；
(4) metal/amorphous nickel cobalt hydroxide combination electrode is prepared.
In above-mentioned several steps, each side factor involved by each step all has multiple choices, especially exists
Selection, solution concentration and the factor aspect such as temperature, time, have extremely flexible change space, in reality
When border produces, free change can be carried out according to the needs of final products.Under above-mentioned principle, it is set forth below
Example is to illustrate creativeness and the practical value of present aspect.
Embodiment 1
First, the nickel foam of 2cm*2cm*1.6mm is placed in Ultrasonic Cleaning in 6Mol concentrated hydrochloric acid
30min, removes the NiO layer on nickel foam surface, cleaner by deionized water and alcohol flushing.Secondly, use
50ml concentration be the copper sulfate solution of 0.01mol/L as presoma, utilizing sulfuric acid to regulate its pH value is 5.
Then, use three-electrode method, copper conductive layer thick for electro-deposition 20nm in situ in nickel foam；Wherein, clean
Clean nickel foam is as working electrode, and the Pt sheet of 2cm*2cm*0.2mm is as to electrode, and saturated calomel is electric
Pole is as reference electrode.The DC voltage of conducting-1V, at 25 DEG C, electro-deposition 5min；Again by obtained
Sample deionized water and ethanol purge clean, being placed in 20ml concentration is 0.02mol/L nickel nitrate and 40ml
Concentration is in the mixed aqueous solution of 0.04mol/L cobalt nitrate, utilizes sodium carbonate buffer, and regulation pH value is to 9
Left and right, electro-deposition 5min, thereon the nickel cobalt hydroxide of original position one layer of amorphous of electro-deposition.Finally, by institute
The sample deionized water obtained and ethanol purge are clean, be dried 10h, obtain bubble under 60 DEG C of vacuum environments
The Ni-based copper alloy of foam/nickel cobalt hydroxide combination electrode.
The combination electrode made is assembled into three-electrode system and carries out performance detection, test this super capacitor electrode
The specific discharge capacity of pole and charge-discharge performance.Test result: the Ni-based copper of foam prepared by the present embodiment closes
Gold/amorphous nickel cobalt hydroxide combination electrode high specific capacity reaches 1258F/g；After circulating 2000 times, specific volume
Amount keeps more than 95.3%.
Changing synthesis presoma composition and the preparation condition of the Ni-based copper alloy of foam, other condition is constant, obtains
Alloy/amorphous nickel cobalt hydroxide combination electrode performance as shown in table 1.As it can be seen from table 1 change bubble
Foam metal species, alloy presoma composition and the factor such as pH value, electrodeposition time, can significantly affect prepared
The specific discharge capacity of combination electrode and cyclical stability.Metal electrode is as a support group of combination electrode among these
Plate, its Structure and stability has important function for formation and the pattern of combination electrode；Conductive layer presoma
Composition and pH value directly determine composition and the uniformity of alloy nano-wire, and then determine its electricity counterfeit to cobalt nickel
The facilitation of capacitive energy；And electrodeposition time directly affects conductive layer thickness.Particularly, copper is owing to existing
Univalent copper ion and bivalent cupric ion, electro-chemical activity is higher.When in alloy containing copper, it is possible to participate in
In the chemical reaction of nickel cobalt energy storage, it is obviously improved its charge-exchange and transfer rate, makes the electrochemistry of nickel cobalt store up
Performance can be not fully exerted, thus the specific discharge capacity obtained is higher.
Measurement result under table 1 different-alloy and presoma composition, preparation condition
Embodiment 2
According to the step described in embodiment 1, one layer of 20nm thickness of the nickel foam surface electro-deposition after cleaning up
Copper conductive layer.Then, obtained sample being placed in 20ml concentration is 0.02mol/L nickel nitrate and 40ml
Concentration is in the mixed aqueous solution of 0.04mol/L cobalt nitrate, utilizes sodium carbonate buffer, and regulation pH value is to 9
Left and right, electro-deposition 5min, thereon the nickel cobalt hydroxide of original position one layer of amorphous of electro-deposition.Finally, by institute
The sample deionized water obtained and ethanol purge are clean, be dried 10h, obtain bubble under 60 DEG C of vacuum environments
The Ni-based copper alloy of foam/nickel cobalt hydroxide combination electrode.Respectively change nickel cobalt hydroxide precursor composition,
Preparation condition and drying condition, keep other conditions constant, and the electrode of super capacitor performance obtained is such as
Shown in table 2 below.
Measurement result under the different nickel cobalt hydroxide precursor composition of table 2, preparation condition and dried treatment conditions
From table 2 it can be seen that change the composition of presoma, preparation condition and dried treatment conditions, meeting
Significantly affect specific discharge capacity and the cyclical stability of obtained combination electrode, in any case but change, this
Bright prepared combination electrode, its specific discharge capacity compared with prior art, all has and significantly improves, and energy
Enough keep a metastable cyclicity.As can be seen here, the present invention compared with prior art, has prominent
Substantive distinguishing features and significant technological progress, there is the highest creativeness.
Above-described embodiment is only the preferred embodiments of the present invention, not limiting the scope of the invention, but
The design principle of all employing present invention, and carry out non-creativeness work on this basis and the change made,
Within protection scope of the present invention all should being belonged to.
Claims (10)
1. ultracapacitor alloy/amorphous nickel cobalt hydroxide combination electrode, it is characterised in that be uniformly composited with amorphous nickel cobalt hydroxide two parts by foam metal base alloy.
A kind of ultracapacitor alloy/amorphous nickel cobalt hydroxide combination electrode the most according to claim 1, it is characterised in that the molecular formula of described amorphous nickel cobalt hydroxide is NixCoy (OH)2(x+y), and x:y=1:(0.5 ~ 2).
3. the preparation method of ultracapacitor alloy/amorphous nickel cobalt hydroxide combination electrode, it is characterised in that comprise the steps:
(1) foam metal is put in concentrated hydrochloric acid and carry out ultrasonic cleaning, remove the oxide skin(coating) on foam metal surface, then clean by deionized water and alcohol flushing；
(2) by metal salt solution or graphene suspension or carbon nano tube suspension as presoma, regulating solution ph, on foam metal, alloy/graphite alkene/carbon nano-tube film conductive layer is prepared in electro-deposition in situ, then clean by deionized water and alcohol flushing；
(3) sample of step (2) gained is placed in the mixed solvent of nickel salt and cobalt salt, regulates pH value, thereon original position electric deposition nickel cobalt hydroxide；
(4) by clean to sample deionized water and the ethanol purge of step (3) gained, after drying, alloy/amorphous nickel cobalt hydroxide combination electrode is obtained.
The preparation method of a kind of ultracapacitor alloy the most according to claim 3/amorphous nickel cobalt hydroxide combination electrode, it is characterised in that in step (1), described foam metal is the one in nickel foam, foam copper, foamed aluminium.
The preparation method of a kind of ultracapacitor alloy the most according to claim 3/amorphous nickel cobalt hydroxide combination electrode, it is characterised in that in step (1), the time of described ultrasonic cleaning is 30min.
The preparation method of a kind of ultracapacitor alloy the most according to claim 3/amorphous nickel cobalt hydroxide combination electrode, it is characterized in that, in step (2), in described presoma, slaine is silver nitrate, zinc nitrate, zinc sulfate, aluminum nitrate, aluminum sulfate, aluminium chloride, cobaltous iodide, cobaltous bromide, cobalt chloride, cobaltous fluoride, cobaltous sulfate, cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt phosphate, cobalt naphthenate, cobaltous octadecanate, new cobalt decanoate, cobalt boracylate, nickel iodide, nickelous bromide, nickel chloride, nickel fluoride, nickel sulfate, ammonium nickel sulfate, nickelous carbonate, nickel nitrate, nickel acetate, citric acid nickel, nickel sulfide, copper chloride, copper nitrate, one or more in copper sulphate；The solvent of described presoma is one or more in water, methyl alcohol, ethanol, isopropanol, the tert-butyl alcohol, chloroform, ethylene glycol, dimethylacetylamide, dimethyl sulfoxide, benzyl ether, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, N,N-dimethylformamide；The concentration of described metal salt solution is 0.005 ~ 0.5mol/L, and described electrodeposition time is 1-100min.
The preparation method of a kind of ultracapacitor alloy the most according to claim 3/amorphous nickel cobalt hydroxide combination electrode, it is characterized in that, in step (2), the pH value of solution is adjusted to faintly acid, and described pH adjusting agent is one or more in acetic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
The preparation method of a kind of ultracapacitor alloy the most according to claim 3/amorphous nickel cobalt hydroxide combination electrode, it is characterized in that, in step (3), one or more during described nickel salt is nickel iodide, nickelous bromide, nickel chloride, nickel fluoride, nickel sulfate, ammonium nickel sulfate, nickelous carbonate, nickel nitrate, nickel acetate, citric acid nickel；Described cobalt salt is one or more in cobaltous iodide, cobaltous bromide, cobalt chloride, cobaltous fluoride, cobaltous sulfate, cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt phosphate, cobalt naphthenate, cobaltous octadecanate, new cobalt decanoate, cobalt boracylate；In the mixed solution of described nickel salt and cobalt salt, nickel measures ratio for 1:2 with the chemical element of cobalt, its solvent is one or more in water, methyl alcohol, ethanol, isopropanol, the tert-butyl alcohol, chloroform, ethylene glycol, dimethylacetylamide, dimethyl sulfoxide, benzyl ether, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, DMF.
The preparation method of a kind of ultracapacitor alloy the most according to claim 3/amorphous nickel cobalt hydroxide combination electrode, it is characterized in that, in step (4), after regulation, the pH value of solution is 6 ~ 10, and the electrolyte of regulation pH value is one or more in sodium carbonate, sodium acid carbonate, sodium acetate, sodium phosphate, potassium carbonate etc.；The final solution concentration of described step (4) is 0.005 ~ 0.5mol/L, and described electrodeposition time is 1-100min.
The preparation method of a kind of ultracapacitor alloy the most according to claim 3/amorphous nickel cobalt hydroxide combination electrode; it is characterized in that, in step (4), dry run is protected in environment in vacuum environment or nitrogen and is carried out; drying time is 1 ~ 15h, and baking temperature is 30 ~ 120 DEG C.
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| CN114016103B (en) * | 2021-10-28 | 2022-11-01 | 浙江大学 | Amorphous transition metal hydroxide electrode material and preparation method thereof |
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Granted publication date: 20181207 |