CN109881217A - Manganese electrodeposition carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material and preparation method - Google Patents
Manganese electrodeposition carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material and preparation method Download PDFInfo
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- CN109881217A CN109881217A CN201910248123.XA CN201910248123A CN109881217A CN 109881217 A CN109881217 A CN 109881217A CN 201910248123 A CN201910248123 A CN 201910248123A CN 109881217 A CN109881217 A CN 109881217A
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- ruox
- carbon fiber
- amorphous state
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- manganese
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- 229910019897 RuOx Inorganic materials 0.000 title claims abstract description 98
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 96
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 96
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000011572 manganese Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 30
- 239000010405 anode material Substances 0.000 title claims abstract description 28
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 11
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 11
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 23
- 239000000701 coagulant Substances 0.000 claims description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- HPOIYBGFFZRZKK-UHFFFAOYSA-N lead;methanesulfonic acid Chemical compound [Pb].CS(O)(=O)=O HPOIYBGFFZRZKK-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 14
- 238000005660 chlorination reaction Methods 0.000 claims description 13
- 150000001868 cobalt Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 239000004615 ingredient Substances 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 10
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 10
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 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 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 235000005979 Citrus limon Nutrition 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- RUPZUFYOCDCMSA-UHFFFAOYSA-N manganese;methanesulfonic acid Chemical compound [Mn].CS(O)(=O)=O RUPZUFYOCDCMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 235000011151 potassium sulphates Nutrition 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002242 deionisation method Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 244000248349 Citrus limon Species 0.000 claims description 3
- 244000131522 Citrus pyriformis Species 0.000 claims description 3
- 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 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000460 chlorine Substances 0.000 abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 abstract 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 229940099607 manganese chloride Drugs 0.000 abstract 1
- 235000002867 manganese chloride Nutrition 0.000 abstract 1
- 239000011565 manganese chloride Substances 0.000 abstract 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 229910000978 Pb alloy Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Abstract
Manganese electrodeposition carbon fiber-based amorphous state Pb-Mn-RuOxGradient anode material and preparation method, the anode includes carbon fiber reinforced substrate, the Ni-Co that is overlying on carbon fiber reinforced substrate3O4Bottom, the Sn-Co-RuO being overlying on bottomxMiddle layer and it is overlying on Sn-Co-RuOxAmorphous state Pb-Mn-RuO in middle layerxActive layer.Carbon fiber-based amorphous state Pb-Mn-RuO prepared by the present inventionxGradient anode material is compared with traditional lead-based multi-component alloy, in manganese chloride system anion membrane electrodeposition manganese, on the basis of not changing cell construction, electrolyte composition and working specification, anode life and electric conductivity significantly improve, tank voltage can reduce by 20% or more, current efficiency improves 4-8%, and can inhibit the generation of chlorine.
Description
Technical field
The present invention relates to a kind of anode material and preparation method thereof technical fields, and in particular to applied to ammonium chloride system
Extract the preparation method of the anode material of non-ferrous metal.
Background technique
Since hydrometallurgy has many advantages, such as that high comprehensive resource utilization rate, process environmental protection and low-grade ore are adaptable,
The non-ferrous metals such as Cu, Zn, Ni, Mn extract shared share by wet process and are gradually increased.In the electrolytic process of non-ferrous metal
In, about 90% zinc, 30% or so copper and 100% manganese are extracted by hydrometallurgical technology.By taking wet method electrolysis manganese as an example, electrolyzing gold
The current efficiency for belonging to manganese is low, generally only reaches 75% or so, and the nearly 6200kWh of electrolysis manganese product power consumption per ton, is famous
Electricity-eating tiger, if in terms of annual 1400000 tons of domestic production manganese ingot, by the energy consumption of needs close to 86.8 hundred million degree electricity.In electrolyzing gold
In the production process for belonging to manganese, there is 95% or more power consumption to concentrate on electrolytic cell, in manganese electrowinning process, anode material property
Ionic discharge current potential, the variation of overpotential, current efficiency size, power consumption, anode life and cathode is directly affected to produce
The indexs such as quality.
Electrolytic manganese production with anode plate original adoption graphite be electrolysed, but because its in electrolysis be easy expansion, fall off and
It suffers exit, lead alloy plate is because it is easy molding, in sulfuric acid electrolyte the advantages that stable operation and in electrolytic manganese industry
It is applied, the use of lead alloy plate electrolysis is a large amount of particle MnO generated in anolyte2, MnO2It is because of lead alloy surface
Lead, which is precipitated with lead (II) ion in negative electrode electro-deposition, to be entered in manganese metal, makes that the purity of electrolytic manganese reduces, manganese metal surface is formed
Dendrite arm and keep anode and cathode short-circuit, power consumption is big, reduces direct current electrical efficiency；Lead electrode easily occurs bending and deformation simultaneously, reduces electricity
Efficiency is flowed, electrode life is shortened.Titanium plate have good electric conductivity, biggish intensity and strong corrosion resistant, hardly by
The corrosion of the major part organic acid such as dilute sulfuric acid, dilute hydrochloric acid, chlorine, while quality is much smaller compared to stereotype.But due to pure titanium
Plate is easy passivation at low temperature, and electrode plate electric conductivity is deteriorated, therefore needs to handle titanium plate surface, and ti-based coating price is high
Expensive, when realizing industrialization, one-time investment is big.
Summary of the invention
The purpose of the invention is to overcome the above-mentioned prior art there are the shortcomings that, provide a kind of electro catalytic activity it is good,
Electrode conductivuty is strong, the tank voltage in electrodeposition is low, long service life, the manganese electrodeposition carbon fiber-based amorphous state Pb-Mn- that low energy consumption
RuOx gradient anode material.The present invention also provides the preparation methods of this anode material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of manganese electrodeposition carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material, including carbon fiber reinforced substrate, be overlying on
Ni-Co on carbon fiber reinforced substrate3O4It bottom, the Sn-Co-RuOx middle layer being overlying on bottom and is overlying among Sn-Co-RuOx
Amorphous state Pb-Mn-RuOx active layer on layer.
Ni-Co of the present invention3O4Bottom is composite deposite, the Co in the composite deposite3O4Group become 2.85~
10wt%；Sn-Co-RuOx middle layer is coating, and the Sn:Co:Ru molar ratio in the coating is (54~80): (18~32): (1
~10)；Pb:Mn:Ru molar ratio in the amorphous state Pb-Mn-RuOx active layer is (42~70): (24~48): (2~
12).The overall thickness of the anode is 2~10mm, wherein bottom with a thickness of 20~200 μm, intermediate layer thickness is 10~100 μ
M, active layer thickness are 0.1~1mm.
Manganese electrodeposition of the present invention carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material the preparation method is as follows:
(1) pretreatment of carbon fiber substrate: carrying out first except glue, by carbon fiber substrate under the protection of nitrogen, 400~
800 DEG C of heat treatment, increase the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage, so
This carbon fiber substrate is placed in 40~90 DEG C of temperature afterwards, the H that mass percent concentration is 10%~20%2SO4It is aoxidized in aqueous solution
1~2h makes its surface in striated；
(2)Ni-Co3O4The preparation of bottom: by step (1), treated that carbon fiber substrate is placed in neutral nickel plating solution, control
Temperature processed is 30~60 DEG C, 0.5~2A/dm of cathode-current density2, 30~120min of electro-deposition obtains active nickel, deionized water
It is immediately placed in after washing in cobalt salt coagulant liquid under the conditions of 40~80 DEG C and stands 4~8h of growth, obtain zeolite imidazole frame, then be placed in
400~600 DEG C of 2~6h of calcining of temperature are controlled in Muffle furnace, obtain Ni-Co3O4Bottom；
(3) preparation of Sn-Co-RuOx middle layer: will contain citric acid: solvent: metal chlorination salt molar ratio is 1~3:5
The coagulant liquid of~8:0.1~1 is painted on the Ni-Co through step (2) treated carbon fiber substrate3O4Bottom surface controls temperature
It is dry 10min at 130 DEG C, is then placed in Muffle furnace, control temperature calcines 4~20min under the conditions of 300~500 DEG C, such as
This 10 times repeatedly, last time calcination time is 2h, obtains Sn-Co-RuOx middle layer；
(4) preparation of amorphous state Pb-Mn-RuOx active layer: Sn-Co-RuOx middle layer will be obtained after step (3) are handled
Carbon fiber substrate be placed in methane sulfonic acid lead solution, control 1~4A/dm of anodic current density2, under the conditions of 30~70 DEG C of temperature
1~4h of electro-deposition obtains Pb-Mn-RuOx coating, which is further heat-treated to 1~3h at 100~300 DEG C, is obtained non-
Crystalline state Pb-Mn-RuOx active layer, as carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode.
In above-mentioned steps, the neutrality nickel plating solution ingredient and formula are as follows: 150~200g/L nickel sulfate, 12~16g/L chlorine
Change potassium, 30~35g/L boric acid, 60~140g/L anhydrous potassium sulfate, 40~60g/L sodium citrate, 0.1~0.4g/L dodecyl
Sodium sulphate, pH are controlled 4.5~6.The cobalt salt coagulant liquid is by the cobalt nitrate of about 6g and 2-methylimidazole with quality percentage
For (20~60): (40~80) are dissolved in be sufficiently stirred in 300~800ml methanol after stand and obtain.When prepared by the middle layer
Solvent is one of ethylene glycol, ethyl alcohol, isopropanol and n-butanol or two kinds；The metal chlorination salt is stannic chloride, chlorination
One of cobalt, ruthenic chloride or two kinds；The methane sulfonic acid lead solution ingredient and formula are as follows: 100~300g/L methane sulfonic acid
Lead, 50~100g/L methane sulfonic acid manganese, 10~30g/L ruthenic chloride, 60~140g/L complexing agent, 10~30g/L methane sulfonic acid.Institute
State the one or more that complexing agent is sodium ethylene diamine tetracetate, acetylacetone,2,4-pentanedione, ascorbic acid and sodium acetate.
The present invention has abandoned existing for sulfate system that current efficiency is low, energy consumption is high, the shortcomings such as seriously polluted, uses
Chloride (MnCl2- NH4Cl-H2O) electrolysis system, makes full use of that its electrolyte conductivity is high, manganese deposition is high-efficient, production slot
The advantages of forcing down, while by the way that inhibition chlorine can be played with high activity and corrosion proof amorphous state Pb-Mn-RuOx oxide skin(coating)
The effect of the generation of gas and the inhibition earth of positive pole, solves the spilling and spilling of electrolysis of chloride system but existing anode chlorine
Etching problem of the chlorine to anode.Carbon fiber substrate of the invention has the formedness such as intensity is high, density is low, chlorine-resistant corrosivity is good
Can, by solving in its coating surface active layer, carbon fiber surface inertia is big, surface energy is low, lacks the official with catalytic activity
The deficiencies of energy is rolled into a ball, reactivity is weak, effectively increases the performance of entire anode material.
The present invention has the advantages that compared with prior art
1, use lightweight carbon fiber for matrix, electrodeposit metals Ni, Ni are firmly combined with C after substrate pretreatment, are then existed
Zeolite imidazole frame is grown on the surface Ni and calcines cobalt salt, obtains the Ni-Co of resistance to hydrochloric acid3O4Bottom improves the binding force at interface
With the corrosion resistance of coating, the service life of anode is extended.
2、Ni-Co3O4Bottom and Sn-Co-RuOXMiddle layer all contains cobalt, between them ionic radius deviation less than 30%,
It is readily formed gradient solid solution, reduces each oxide skin(coating) interface resistance greatly, improves the electric conductivity of electrode.
3, in Sn-Co-RuOXIn middle layer, the amorphous state Pb- being firmly combined is obtained by electrochemical deposition and thermal decomposition
Mn-RuOx active layer promotes MnO after thermal decomposition2With PbO2Phase counterdiffusion, improves MnO2With PbO2Be combined with each other power.
4, because amorphous state Pb-Mn-RuOx possesses nanocrystal, biggish specific surface area, lesser electronics transfer resistance, more
More crystal defects generates preferably catalytic performance.
5, the anode can avoid the passivation of matrix and when by external force, and coating is easy to produce the phenomenon that falling off, and extend electricity
Pole service life.
6, it in anion membrane electrolytic bath, is found in chloride system a kind of with high activity and corrosion proof amorphous state Pb-Mn-
RuOx oxide skin(coating) can play the effect for inhibiting the generation of chlorine and the inhibition earth of positive pole, greatly improve the production of electrolytic manganese
Efficiency, realize electrolytic manganese clean and effective production.
7, the base amorphous Pb-Mn-RuOx gradient anode material of novel carbon fiber operates in chloride containing manganese system, has good
Good corrosion resistance, can be made high-grade cathode product, and long service life, the cost of material is low, and tank voltage can reduce by 20% or more, electricity
It flows efficiency and improves 4~8%, be that lead electrode can not be attainable.
Detailed description of the invention
Fig. 1 is the surface topography of carbon fiber after pre-treatment；
Fig. 2 is carbon fiber/Ni surface topography；
Fig. 3 is carbon fiber/Ni/ZIF67 surface topography；
Fig. 4 is carbon fiber/Ni-Co3O4Surface topography.
Specific embodiment
Below by embodiment, invention is further described in detail, but the scope of the present invention is not limited in described
Hold.
Embodiment 1
The carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material of the present embodiment by carbon fiber reinforced substrate, be overlying on carbon fiber
Ni-Co on substrate3O4It bottom, the Sn-Co-RuOx middle layer being overlying on bottom and is overlying in Sn-Co-RuOx middle layer
Amorphous state Pb-Mn-RuOx active layer.The Ni-Co3O4Bottom is composite deposite, the Co in the composite deposite3O4Group becomes
2.85~10wt%, the Sn:Co:Ru molar ratio in middle layer, that is, Sn-Co-RuOx coating is (54~80): (18~32): (1~
10)；Pb:Mn:Ru molar ratio in amorphous state Pb-Mn-RuOx active layer is (42~70): (24~48): (2~12).
The preparation method of the carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material of the present embodiment, specific steps are such as
Under:
(1) pretreatment of carbon fiber substrate: carrying out first except glue, by carbon fiber substrate under the protection of nitrogen, 400~
800 DEG C of heat treatment, increase the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage, so
This carbon fiber substrate is placed in 40~90 DEG C of temperature afterwards, mass percent concentration is 10%~20%H2SO4Aqueous solution in aoxidize
1~2h makes its surface in striated.
(2)Ni-Co3O4The preparation of bottom: by step (1), treated that carbon fiber substrate is placed in neutral nickel plating solution, control
Temperature processed is 30~60 DEG C, 0.5~2A/dm of cathode-current density2, 30~120min of electro-deposition obtains active nickel, deionized water
It is immediately placed in after washing in cobalt salt coagulant liquid under the conditions of 40~80 DEG C and stands 4~8h of growth, obtain zeolite imidazole frame
(ZIF67), then control 400~600 DEG C of 2~6h of calcining of temperature in Muffle furnace are placed in, obtain Ni-Co3O4Bottom；The neutral plating
Nickel solution ingredient and formula are as follows: 150~200g/L nickel sulfate (NiSO4·7H2O), 12~16g/L potassium chloride (KC1), 30~
35g/L boric acid (H3BO3), 60~140g/L anhydrous potassium sulfate (K2SO4), 40~60g/L sodium citrate, 0.1~0.4g/L 12
Sodium alkyl sulfate, pH are controlled 4.5~6.The cobalt salt coagulant liquid preparation: the cobalt nitrate and 2- methyl miaow of 6g or so will be weighed
Azoles with quality percentage be (20~60): (40~80) are dissolved in be sufficiently stirred in 300~800ml methanol after stand obtain coagulant liquid.
(3) preparation of Sn-Co-RuOx middle layer: will contain citric acid: solvent: metal chlorination salt molar ratio is 1~3:5
What the coagulant liquid of~8:0.1~1 was painted on that step (2) obtains is coated with Ni-Co3O4The carbon fiber substrate surface of bottom controls temperature
It is dry 10min at 130 DEG C, is then placed in control temperature in Muffle furnace and calcines 4~20min under the conditions of 300~500 DEG C, such as
This 10 times repeatedly, last time calcination time is 2h, obtains Sn-Co-RuOx middle layer.The solvent is ethylene glycol, ethyl alcohol, different
One of propyl alcohol and n-butanol or two kinds.The metal chlorination salt be one of stannic chloride, cobalt chloride and ruthenic chloride or
It is several.
(4) preparation of amorphous state Pb-Mn-RuOx active layer: the carbon fiber substrate after step (3) is obtained is placed in methyl sulphur
In lead plumbate solution, 1~4A/dm of anodic current density is controlled2, 1~4h of electro-deposition under the conditions of 30~70 DEG C of temperature obtains Pb-Mn-
The coating is further heat-treated 1~3h by RuOx coating at 100~300 DEG C, obtains amorphous state Pb-Mn-RuOx active layer,
As carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode.The methane sulfonic acid lead solution ingredient and formula: 100~300g/L
Methane sulfonic acid lead, 50~100g/L methane sulfonic acid manganese, 10~30g/L ruthenic chloride, 60~140g/L complexing agent, 10~30g/L first
Base sulfonic acid.The complexing agent be sodium ethylene diamine tetracetate, one or both of acetylacetone,2,4-pentanedione, ascorbic acid and sodium acetate with
On.
The overall thickness for the anode that the present embodiment is prepared be 2~10mm, wherein bottom with a thickness of 20~200 μm, in
For interbed with a thickness of 10~100 μm, active layer thickness is 0.1~1mm.
Embodiment 2
The carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material of the present embodiment by carbon fiber reinforced substrate, be overlying on carbon fiber
Ni-Co on substrate3O4It bottom, the Sn-Co-RuOx middle layer being overlying on bottom and is overlying in Sn-Co-RuOx middle layer
Amorphous state Pb-Mn-RuOx active layer.Wherein, Ni-Co3O4Co in composite deposite3O4Group becomes 8wt%, Sn-Co-RuOx plating
Sn:Co:Ru molar ratio in layer is 60:28:10；Pb:Mn:Ru molar ratio in amorphous state Pb-Mn-RuOx active layer is 50:
36:10.
The preparation method of the carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material of the present embodiment, specific steps are such as
Under:
(1) pretreatment of carbon fiber substrate: carrying out first except glue, under the protection of nitrogen, heats at 500 DEG C, makes
The active specific surface of carbon fiber increases, while the fracture of wire of carbon fiber in treatment process being avoided to damage, then by this carbon fiber substrate
It is placed in temperature 60 C, mass percent concentration 15%H2SO4Aqueous solution in aoxidize 1.5h, make its surface in striated (see figure
1)。
(2)Ni-Co3O4The preparation of bottom: by step (1), treated that carbon fiber substrate is placed in neutral nickel plating solution, control
Temperature processed is 40 DEG C, cathode-current density 1A/dm2, electro-deposition 120min is obtained active nickel (see Fig. 2), vertical after deionization washing
It is put into cobalt salt coagulant liquid under the conditions of 60 DEG C and stands growth 6h, obtain zeolite imidazole frame (ZIF67) (see Fig. 3), then set
500 DEG C of calcining 4h of temperature are controlled in Muffle furnace, obtain Ni-Co3O4Bottom (see Fig. 4).The neutrality and is matched at nickel plating solution ingredient
Side: 180g/L nickel sulfate (NiSO4·7H2O), 14g/L potassium chloride (KC1), 30g/L boric acid (H3BO3), 80g/L anhydrous potassium sulfate
(K2SO4), 50g/L sodium citrate, 0.2g/L lauryl sodium sulfate, pH control is 5 or so.The cobalt salt coagulant liquid is to weigh
The cobalt nitrate and 2-methylimidazole of 6g or so with quality percentage be 40:60 be dissolved in be sufficiently stirred in 400ml methanol after stand and obtain
Coagulant liquid.
(3) preparation of Sn-Co-RuOx middle layer: citric acid will be contained: ethylene glycol: metal chlorination salt (stannic chloride, chlorination
The mixture of cobalt and ruthenic chloride) molar ratio be 1:6:0.6 coagulant liquid in be painted on that step (2) obtains be coated with Ni-Co3O4Bottom
The carbon fiber substrate surface of layer is then placed in Muffle furnace controlled at 10min dry at 130 DEG C and controls temperature at 400 DEG C
Under the conditions of calcine 10min, 10 times repeatedly, last time calcination time be 2h, obtain Sn-Co-RuOx middle layer.
(4) preparation of amorphous state Pb-Mn-RuOx active layer: Sn-Co-RuOx middle layer is coated with by what step (3) obtained
Carbon fiber substrate is placed in methane sulfonic acid lead solution, controls anodic current density 2A/dm2, electro-deposition 2h under the conditions of temperature 50 C,
Pb-Mn-RuOx coating is obtained, the coating is further heat-treated 2h at 200 DEG C, obtains amorphous state Pb-Mn-RuOx activity
Layer, as carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode.The methane sulfonic acid lead solution ingredient and formula are as follows: 200g/L
Methane sulfonic acid lead, 80g/L methane sulfonic acid manganese, 30g/L ruthenic chloride, 120g/L acetylacetone,2,4-pentanedione, 20g/L methane sulfonic acid.
The overall thickness for the anode that the present embodiment is prepared is 10mm, wherein bottom with a thickness of 100 μm, intermediate layer thickness
It is 50 μm, active layer thickness 0.5mm.
Carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material manufactured in the present embodiment is placed in chlorination manganese electrolyte
In, using electro-deposition manganese in anion exchange membrane electrolysis cells, electrolytic condition is that catholyte manganese ion concentration is 1mol/L, chlorine
Change ammonium concentration is 2mol/L, and electrolysis temperature is -10 DEG C, current density 500A/m2, pH 6.10, anolyte ammonium chloride
Concentration is 2mol/L, hydrochloric acid 1mol/L, and electricity effect improves 8% than traditional lead silver alloy anode plate, and tank voltage can reduce by 25%,
Service life extends 3 times.
Embodiment 3
The carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material of the present embodiment by carbon fiber reinforced substrate, be overlying on carbon fiber
Ni-Co on substrate3O4It bottom, the Sn-Co-RuOx middle layer being overlying on bottom and is overlying in Sn-Co-RuOx middle layer
Amorphous state Pb-Mn-RuOx active layer.Wherein Ni-Co3O4Co in composite deposite3O4Group becomes 2.85wt%, Sn-Co-RuOx
Sn:Co:Ru molar ratio in coating is 54:18:1；Pb:Mn:Ru molar ratio in amorphous state Pb-Mn-RuOx active layer is 42:
24:12.
The preparation method of the carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material of the present embodiment, specific steps are such as
Under:
(1) it the pretreatment of carbon fiber substrate: is carried out first except glue, by carbon fiber substrate under the protection of nitrogen, at 800 DEG C
Heat treatment, increases the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage, then by this
Carbon fiber substrate is placed in 40 DEG C of temperature, mass percent concentration 10%H2SO4Aqueous solution in aoxidize 2h, make its surface in item
Line shape.
(2)Ni-Co3O4The preparation of bottom: by step (1), treated that carbon fiber substrate is placed in neutral nickel plating solution, control
Temperature processed is 30 DEG C, cathode-current density 0.5A/dm2, electro-deposition 30min obtains active nickel, is immediately placed in after deionization washing
Growth 8h is stood in cobalt salt coagulant liquid under the conditions of 40 DEG C, obtains zeolite imidazole frame (ZIF67), then be placed in Muffle furnace and control
400 DEG C of calcining 6h of temperature, obtain Ni-Co3O4Bottom.The neutrality nickel plating solution ingredient and formula are as follows: 150g/L nickel sulfate
(NiSO4·7H2O), 12g/L potassium chloride (KC1), 35g/L boric acid (H3BO3), 60g/L anhydrous potassium sulfate (K2SO4), 40g/L lemon
Lemon acid sodium, 0.1g/L lauryl sodium sulfate, pH are controlled 4.5~5.The cobalt salt coagulant liquid be by the cobalt nitrate of 6g or so with
2-methylimidazole with quality percentage be 20:80 be dissolved in be sufficiently stirred in 300ml methanol after stand obtain coagulant liquid.
(3) preparation of Sn-Co-RuOx middle layer: will contain citric acid: ethyl alcohol: stannic chloride molar ratio is the solidifying of 2:5:0.1
Be painted on that step (2) obtains in glue is coated with Ni-Co3O4The carbon fiber substrate surface of bottom is done controlled at 130 DEG C
Dry 10min is then placed in control temperature in Muffle furnace and calcines 20min under the conditions of 300 DEG C, and 10 times repeatedly, last time
Calcination time is 2h, obtains Sn-Co-RuOx middle layer.
(4) preparation of amorphous state Pb-Mn-RuOx active layer: Sn-Co-RuOx middle layer is coated with by what step (3) obtained
Carbon fiber substrate is placed in methane sulfonic acid lead solution, controls anodic current density 1A/dm2, electro-deposition 4h under the conditions of 30 DEG C of temperature,
Pb-Mn-RuOx coating is obtained, the coating is further heat-treated 3h at 100 DEG C, obtains amorphous state Pb-Mn-RuOx activity
Layer, as carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode.The methane sulfonic acid lead solution ingredient and formula are as follows: 100g/L
Methane sulfonic acid lead, 50g/L methane sulfonic acid manganese, 10g/L ruthenic chloride, 140g/L sodium ethylene diamine tetracetate, 10g/L methane sulfonic acid.
The overall thickness for the anode that the present embodiment is prepared is 2mm, wherein bottom with a thickness of 20 μm, intermediate layer thickness is
10 μm, active layer thickness 0.1mm.
Carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material manufactured in the present embodiment is placed in chlorination manganese electrolyte
In, using electro-deposition manganese in anion exchange membrane electrolysis cells, electrolytic condition is that catholyte manganese ion concentration is 1mol/L, chlorine
Change ammonium concentration is 2mol/L, and electrolysis temperature is -10 DEG C, current density 500A/m2, pH 6.10, anolyte ammonium chloride
Concentration is 2mol/L, hydrochloric acid 1mol/L, and electricity effect improves 4% than traditional lead silver alloy anode plate, and tank voltage can reduce by 20%,
Service life extends 1.2 times.
Embodiment 4
The carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material of the present embodiment by carbon fiber reinforced substrate, be overlying on carbon fiber
Ni-Co on substrate3O4It bottom, the Sn-Co-RuOx middle layer being overlying on bottom and is overlying in Sn-Co-RuOx middle layer
Amorphous state Pb-Mn-RuOx active layer.Wherein Ni-Co3O4Co in composite deposite3O4Group becomes 10wt%, Sn-Co-RuOx plating
Sn:Co:Ru molar ratio in layer is 80:32:8；Pb:Mn:Ru molar ratio in amorphous state Pb-Mn-RuOx active layer is 70:
48:2.
The preparation method of the carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material of the present embodiment, specific steps are such as
Under:
(1) it the pretreatment of carbon fiber substrate: is carried out first except glue, by carbon fiber substrate under the protection of nitrogen, at 400 DEG C
Heat treatment, increases the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage, then by this
Carbon fiber substrate is placed in 90 DEG C of temperature, mass percent concentration 20%H2SO4Aqueous solution in aoxidize 1h, make its surface in item
Line shape.
(2)Ni-Co3O4The preparation of bottom: by step (1), treated that carbon fiber substrate is placed in neutral nickel plating solution, control
Temperature processed is 60 DEG C, cathode-current density 2A/dm2, electro-deposition 100min obtains active nickel, is immediately placed in after deionization washing
Growth 4h is stood in cobalt salt coagulant liquid under the conditions of 80 DEG C, obtains zeolite imidazole frame (ZIF67), then be placed in Muffle furnace and control
600 DEG C of calcining 2h of temperature, obtain Ni-Co3O4Bottom.The neutrality nickel plating solution ingredient and formula are as follows: 200g/L nickel sulfate
(NiSO4·7H2O), 16g/L potassium chloride (KC1), 33g/L boric acid (H3BO3), 140g/L anhydrous potassium sulfate (K2SO4), 60g/L lemon
Lemon acid sodium, 0.4g/L lauryl sodium sulfate, pH are controlled 6 or so.The cobalt salt coagulant liquid be by the cobalt nitrate of 6g or so with
2-methylimidazole with quality percentage be 60:40 be dissolved in be sufficiently stirred in 800ml methanol after stand obtain coagulant liquid.
(3) preparation of Sn-Co-RuOx middle layer: will contain citric acid: solvent: metal chlorination salt molar ratio is 3:8:1's
Be painted on that step (2) obtains in coagulant liquid is coated with Ni-Co3O4The carbon fiber substrate surface of bottom, controlled at 130 DEG C
Dry 10min is then placed in control temperature in Muffle furnace and calcines 4min under the conditions of 600 DEG C, and 10 times repeatedly, last time
Calcination time is 2h, obtains Sn-Co-RuOx middle layer.The solvent is the mixture of isopropanol and n-butanol.The metal chlorine
Salt dissolving is the mixture of cobalt chloride and ruthenic chloride.
(4) preparation of amorphous state Pb-Mn-RuOx active layer: Sn-Co-RuOx middle layer is coated with by what step (3) obtained
Carbon fiber substrate is placed in methane sulfonic acid lead solution, controls anodic current density 4A/dm2, electro-deposition 1h under the conditions of temperature 70 C,
Pb-Mn-RuOx coating is obtained, the coating is further heat-treated 1h at 300 DEG C, obtains amorphous state Pb-Mn-RuOx activity
Layer, as carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode.The methane sulfonic acid lead solution ingredient and formula are as follows: 300g/L
Methane sulfonic acid lead, 100g/L methane sulfonic acid manganese, 20g/L ruthenic chloride, 60g/L complex compound, sodium ethylene diamine tetracetate, 30g/L methyl
Sulfonic acid.The complex compound is the mixture of ascorbic acid and sodium acetate.
The overall thickness for the anode that the present embodiment is prepared is 8mm, wherein bottom with a thickness of 200 μm, intermediate layer thickness
It is 100 μm, active layer thickness 1mm.
Carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material manufactured in the present embodiment is placed in chlorination manganese electrolyte
In, using electro-deposition manganese in anion exchange membrane electrolysis cells, electrolytic condition is that catholyte manganese ion concentration is 1mol/L, chlorine
Change ammonium concentration is 2mol/L, and electrolysis temperature is -10 DEG C, current density 500A/m2, pH 6.10, anolyte ammonium chloride
Concentration is 2mol/L, hydrochloric acid 1mol/L, and electricity effect improves 6% than traditional lead silver alloy anode plate, and tank voltage can reduce by 22%,
Service life extends 1.5 times.
Claims (9)
1. a kind of manganese electrodeposition carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material, which is characterized in that including carbon fiber
Substrate, the Ni-Co being overlying on carbon fiber reinforced substrate3O4Bottom, the Sn-Co-RuOx middle layer being overlying on bottom and it is overlying on Sn-
Amorphous state Pb-Mn-RuOx active layer in Co-RuOx middle layer.
2. manganese electrodeposition according to claim 1 carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material, feature
It is, the Ni-Co3O4Bottom is composite deposite, the Co in the composite deposite3O4Group becomes 2.85~10wt%；Sn-Co-
RuOx middle layer is coating, and the Sn:Co:Ru molar ratio in the coating is (54~80): (18~32): (1~10)；The amorphous
Pb:Mn:Ru molar ratio in state Pb-Mn-RuOx active layer is (42~70): (24~48): (2~12).
3. manganese electrodeposition according to claim 1 or 2 carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material, special
Sign is, the overall thickness of the anode is 2~10mm, wherein bottom with a thickness of 20~200 μm, intermediate layer thickness is 10~
100 μm, active layer thickness is 0.1~1mm.
4. manganese electrodeposition as described in any one of claims 1-3 carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode material
Preparation method, which is characterized in that method and step is as follows:
(1) it the pretreatment of carbon fiber substrate: is carried out first except glue, by carbon fiber substrate under the protection of nitrogen, 400~800
DEG C heat treatment, increases the active specific surface of carbon fiber, while the fracture of wire of carbon fiber in treatment process being avoided to damage, then general
This carbon fiber substrate is placed in 40~90 DEG C of temperature, the H that mass percent concentration is 10%~20%2SO4In aqueous solution oxidation 1~
2h makes its surface in striated；
(2)Ni-Co3O4The preparation of bottom: by step (1), treated that carbon fiber substrate is placed in neutral nickel plating solution, control temperature
Degree is 30~60 DEG C, 0.5~2A/dm of cathode-current density2, 30~120min of electro-deposition obtains active nickel, after deionization washing
It is immediately placed in cobalt salt coagulant liquid under the conditions of 40~80 DEG C and stands 4~8h of growth, obtain zeolite imidazole frame, then be placed in Muffle
400~600 DEG C of 2~6h of calcining of temperature are controlled in furnace, obtain Ni-Co3O4Bottom；
(3) preparation of Sn-Co-RuOx middle layer: will contain citric acid: solvent: metal chlorination salt molar ratio is 1~3:5~8:
0.1~1 coagulant liquid is painted on the Ni-Co through step (2) treated carbon fiber substrate3O4Bottom surface, controlled at
Dry 10min, is then placed in Muffle furnace at 130 DEG C, and control temperature calcines 4~20min under the conditions of 300~500 DEG C, so
10 times repeatedly, last time calcination time is 2h, obtains Sn-Co-RuOx middle layer；
(4) preparation of amorphous state Pb-Mn-RuOx active layer: the carbon of Sn-Co-RuOx middle layer will be obtained after step (3) are handled
Fibrous matrix is placed in methane sulfonic acid lead solution, controls 1~4A/dm of anodic current density2, electricity is heavy under the conditions of 30~70 DEG C of temperature
1~4h of product, obtains Pb-Mn-RuOx coating, which is further heat-treated to 1~3h at 100~300 DEG C, obtains amorphous state
Pb-Mn-RuOx active layer, as carbon fiber-based amorphous state Pb-Mn-RuOx gradient anode.
5. the preparation method according to claim 4, which is characterized in that the neutrality nickel plating solution ingredient and formula are as follows: 150
~200g/L nickel sulfate, 12~16g/L potassium chloride, 30~35g/L boric acid, 60~140g/L anhydrous potassium sulfate, 40~60g/L lemon
Lemon acid sodium, 0.1~0.4g/L lauryl sodium sulfate, pH are controlled 4.5~6.
6. the preparation method according to claim 4, which is characterized in that the cobalt salt coagulant liquid is by the nitric acid of about 6g
Cobalt and 2-methylimidazole are with quality percentage for (20~60): (40~80) are dissolved in be sufficiently stirred in 300~800ml methanol after stand
It obtains.
7. the preparation method according to claim 4, which is characterized in that the middle layer prepare when solvent be ethylene glycol,
One of ethyl alcohol, isopropanol and n-butanol or two kinds；The metal chlorination salt is stannic chloride, in cobalt chloride, ruthenic chloride
It is one or two kinds of.
8. the preparation method according to claim 4, which is characterized in that the methane sulfonic acid lead solution ingredient and formula are as follows:
100~300g/L methane sulfonic acid lead, 50~100g/L methane sulfonic acid manganese, 10~30g/L ruthenic chloride, 60~140g/L complexing agent,
10~30g/L methane sulfonic acid.
9. preparation method according to claim 8, which is characterized in that the complexing agent is sodium ethylene diamine tetracetate, acetyl
The one or more of acetone, ascorbic acid and sodium acetate.
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| CN112553546A (en) * | 2020-09-18 | 2021-03-26 | 河北工业大学 | Preparation method and device of chopped carbon fiber reinforced amorphous composite material |
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| CN109881217B (en) | 2020-10-09 |
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