CN107245729A - Manganese electrodeposition carbon fiber-based graded composite anode material and preparation method thereof - Google Patents
Manganese electrodeposition carbon fiber-based graded composite anode material and preparation method thereof Download PDFInfo
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- CN107245729A CN107245729A CN201710478157.9A CN201710478157A CN107245729A CN 107245729 A CN107245729 A CN 107245729A CN 201710478157 A CN201710478157 A CN 201710478157A CN 107245729 A CN107245729 A CN 107245729A
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- carbon fiber
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- anode material
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- 239000002131 composite material Substances 0.000 title claims abstract description 151
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 129
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 129
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 128
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011572 manganese Substances 0.000 title claims abstract description 45
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 44
- 239000010405 anode material Substances 0.000 title claims abstract description 43
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 17
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 14
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007747 plating Methods 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 229910006654 β-PbO2 Inorganic materials 0.000 claims description 30
- 229910006531 α-PbO2 Inorganic materials 0.000 claims description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 11
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 11
- 229940038773 trisodium citrate Drugs 0.000 claims description 11
- 229910006648 β-MnO2 Inorganic materials 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 10
- 239000012798 spherical particle Substances 0.000 claims description 10
- 229910006529 α-PbO Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000020 Nitrocellulose Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 230000001680 brushing effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002242 deionisation method Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 229920001220 nitrocellulos Polymers 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010981 drying operation Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 18
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 17
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 12
- 235000013339 cereals Nutrition 0.000 description 10
- 239000005543 nano-size silicon particle Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 239000011775 sodium fluoride Substances 0.000 description 6
- 235000013024 sodium fluoride Nutrition 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 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 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- LKIXMJFYKZVZER-UHFFFAOYSA-N [As].[Sn].[Sb] Chemical compound [As].[Sn].[Sb] LKIXMJFYKZVZER-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/1266—Particles formed in situ
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
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- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Ceramic Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Manganese electrodeposition carbon fiber-based graded composite anode material and preparation method thereof, the anode material includes carbon fiber substrate (1), is compounded in the α PbO for introducing nano-graphene particle on carbon fiber substrate surface2Composite deposite (2), it is compounded in α PbO2Composite deposite (2) surface introduces SiO2The β PbO of particle2Composite deposite (3), it is covered in β PbO2Composite deposite (3) surface introduces RuO2The β MnO of particle2Composite coating (4).Carbon fiber-based graded composite anode material electro catalytic activity prepared by the present invention is good, tank voltage is low, service life length, cost are low, electric effect is high.
Description
Technical field
The present invention relates to a kind of manganese electrodeposition anode material and preparation method thereof technical field.
Background technology
Metallurgical industry is still big power consumer in industrial production, and energy consumption is high, and its main specific energy consumption average specific is external
Advanced level is high by 40%.In the smelting process of manganese metal, more than 90% manganese is extracted by hydrometallurgical technology, electrolyzing gold
The current efficiency for belonging to manganese is low, typically only reaches 75% or so, the electrolysis nearly 7500kWh of manganese product power consumption per ton, is famous
Electricity-eating tiger, if in terms of 2,000,000 tons of domestic production manganese ingot in 2016, it would be desirable to energy consumption close to 15,000,000,000 degree electricity.Electrolytic metal
Although the production technology of manganese is a ripe production technology, but still has very big potentiality to dig.For the development of electrolytic manganese anode,
Positive plate develops into present cold rolling type from initial cast moulding, and alloying component also develops into existing from the silver-colored bianry alloy of initial lead
The silver-colored tin antimony arsenic multicomponent alloy of lead, 18-22 months from 4-6 months till now of use time, it should say and make rapid progress.But
It is that, with the fast development in recent years of electrolytic manganese industry, scale constantly expands, and most domestic manganese resource has started to gradually
Exhaustion, although and domestic existing some larger still undeveloped manganese ores and partial Ore Imported grade are higher,
But it is a kind of challenge for current domestic production technology because chlorine contained in ore, fluorine element are higher.Existing production work
Can not effectively it be removed in chlorine therein, fluorine element, electrolytic process in skill, chlorine, fluorine element form chlorine, fluorine ion just in the electrolytic solution
Normal value can seriously be exceeded, and chemical reaction is produced with the positive plate of metal, lead chloride and lead fluoride crystallization is formed, lead is damaged significantly
The service life of alloy anode.
Carbon fiber phosphorus content ratio is high, and (carbon fibrous body resistivity is 1.2 × 10 to good conductivity-3Ω cm), specific surface area
Greatly, it is a kind of good electrochemical reactor.Carbon fiber composite resin material, not only with good electric conductivity, also has concurrently
Excellent mechanical performance, carbon fiber composite resin material has good corrosion resistance, especially in high chloride ion environment moderate resistance
Corrosivity is excellent.However, because carbon fiber is a kind of microcrystalline graphite material, consumption is also easy to produce when separately as anode.Tradition
The lead silver alloy anode corrosion resistance used is not strong, and lead can be dissolved in the impurity for being electrolysed molten middle increase cathode product on a small quantity in anode,
Reduce product quality.Therefore conductive good, corrosion-resistant, high intensity, long-life, the new inertia of low cost Mn electrodeposition are further developed
Composite anode materials are very necessary.
The content of the invention
The invention aims to overcome above-mentioned prior art presence shortcoming there is provided a kind of electro catalytic activity it is good,
Tank voltage is low, service life length, cost are low, electric effect is high manganese electrodeposition carbon fiber-based graded composite anode material and its preparation side
Method.
The purpose of the present invention is achieved through the following technical solutions：
A kind of manganese electrodeposition carbon fiber-based graded composite anode material, including carbon fiber substrate, it is compounded in carbon fiber substrate
α-the PbO for introducing nano-graphene particle on surface2Composite deposite, it is compounded in α-PbO2Composite deposite surface is introduced
SiO2β-the PbO of particle2Composite deposite, it is covered in β-PbO2Composite deposite surface introduces RuO2β-the MnO of particle2It is compound to apply
Layer.
α-PbO of the present invention2Graphene particles composition in composite deposite is 1.57~4wt%, β-PbO2Composite deposite
In SiO2Particle group turns into 2.01~5wt%, β-MnO2RuO in composite coating2Particle group turns into 5~25wt%.Compound sun
The gross thickness of pole material is 4~13mm, and the thickness of carbon fiber substrate is 3~11mm, α-PbO2Thickness of multiple plating be 0.1~
0.5mm, β-PbO2Thickness of multiple plating is 0.39~2mm, β-MnO2Composite coating thickness is 0.01~0.2mm.
Manganese electrodeposition is as follows with the preparation method of carbon fiber-based graded composite anode material：
(1) removing glue is carried out to carbon fiber substrate first, under the protection of nitrogen or argon gas, at 400~800 DEG C of heating
Reason, makes the activity of carbon fiber than surface increase, while avoiding the fracture of wire of carbon fiber in processing procedure from damaging；
(2) it is 25% the carbon fiber substrate after step (1) processing to be placed in into temperature -10~15 DEG C, mass percent concentration
~60% HNO340min~2h is aoxidized in the aqueous solution, carbon fiber substrate striated corrosion is occurred；
(3) the carbon fiber substrate surface after step (2) processing is coated into elargol, be placed in baking oven, it is 60 to control temperature
~180 DEG C, drying time is 2~20min；Coating more than repeating and drying process 3~8 times, obtain carbon fiber substrate surface
Uniform active nano Argent grain；
(4) carbon fiber substrate that surface made from step (3) is coated with into active nano Argent grain is placed in after ultrasonic disperse
Alkaline composite plating solution in, using stainless steel as negative electrode, temperature be 30~60 DEG C, current density be 0.1~0.8A/dm2,
Electroplated 4~8 hours under mechanical agitation, the α-PbO for obtaining introducing nano-graphene particle are deposited on carbon fiber substrate surface2It is multiple
Close coating；Contain 20~40g/L of PbO, 100~160g/L of NaOH, K in described alkaline composite plating solution2Cr2O75~30g/
L, 1~4g/L of nano-graphene particle；
(5) the obtained surface deposition of step (4) processing there are into α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point
In acid composite plating solution after dissipating, using titanium mesh plate as negative electrode, temperature is 50~90 DEG C, and current density is 6~9A/dm2,
Electroplated 2~6 hours under mechanical agitation, in α-PbO2Composite deposite surface deposition obtains introducing SiO2β-the PbO of particle2It is compound
Coating；Contain Pb (NO in described acid composite plating solution3)2220~400g/L, HNO32~15g/L, 3~10g/ of NaF
L, Nano-meter SiO_225~20g/L；
(6) the obtained surface deposition of step (5) processing there are into β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality
In the hydrofluoric acid solution of degree 5%~30%, temperature is 0~30 DEG C, and soak time is 5~40min, and deionization washing is dried, so
Uniform brushing is dissolved in the quality hundred being configured in organic solvent with ruthenium trichloride and manganese nitrate on carbon fiber substrate surface afterwards
Divide the coating liquid that specific concentration is 20%~50%, then 5~25min, sky are decomposed in drying under conditions of temperature is 120~200 DEG C
It is cooled to room temperature, coating above and drying operation 3~20 times is repeated, in β-PbO2Composite deposite surface forms and introduces RuO2Particle
β-MnO2Composite coating, produces manganese electrodeposition carbon fiber-based graded composite anode material.
Elargol described in above-mentioned steps (3) is silver nitrate and the sol solutionses of trisodium citrate composition, and silver colloidal partical size is
20nm~80nm, the preparation method of silver colloidal partical is as follows：In flask add 1L distilled water, add 0.05mmol/L~
0.1mol/L silver nitrate, is heated to boiling, and quick stirring is lower to add the citric acid three that solution quality percentage is 0.5~20%
Sodium, continues back flow reaction 10min~1h, and natural cooling is stirred to room temperature, is filtered, obtained with acetic acid nitrocellulose O.22 μm
To the elargol in yellow green.Nano-graphene particle described in step (4) is sheet or spherical particle, particle diameter 10nm~
100nm.Step (5) described Nano-meter SiO_22For spherical particle, particle diameter is in 60nm~100nm.Step (6) ruthenium trichloride and nitre
The molal weight ratio of sour manganese is 1:20~1:5.
The present invention has the following advantages that compared with prior art：
1st, carbon fiber surface covers Nano Silver, greatly improves the electric conductivity of anode, makes carbon fiber bad with electric conductivity
α-PbO2Layer will not produce interface resistance.
2nd, composite electrodeposition α-PbO2Potassium bichromate is added in plating solution, prevents from separating out lead on negative electrode, lead in solution is reduced
The concentration polarization of ion, and avoid red Pb3O4The generation of material.
3rd, nano-graphene particle introduces α-PbO2The internal stress in coating is reduced in coating, it is to avoid coating crackle
Produce, and drastically increase the electric conductivity and decay resistance of composite deposite, extend the service life of anode.
4th, composite electrodeposition β-PbO at higher current densities2, coating is more evenly distributed in porous state, introduce nanometer
SiO 2 powder, the hardness that coating can be kept high improves β-PbO2Inoxidizability and thermal shock resistance, make coating high
At a temperature of will not decompose.
5th, the β-MnO that thermal decomposition method is obtained2With intermediate layer β-PbO2Coating formation solid solution, conducting efficiency high, and β-
MnO2-RuO2With higher catalytic activity, the overpotential that oxygen is analysed in electrolytic process can be reduced as composite anode.
6th, carbon fiber substrate is difficult passivation, and service life is long, because carbon fiber is the super good conductor material of a decay resistance
Material, therefore exceed more than one times of positive plate life-span using lead as representative on service life；Containing chlorion and fluoride solution
Middle operation, with good corrosion resistance, can be made lead-free high-grade manganese dioxide and metal manganese product, this be lead electrode not
It is likely to be breached.
Carbon fiber-based graded composite anode material prepared by the present invention is not changing compared with traditional lead-based multi-component alloy
On the basis of cell construction, electrolyte composition and working specification, electric conductivity is significantly improved, and tank voltage can reduce by 12%, material
Cost reduction by 20%, current efficiency improves 3-6%.
Brief description of the drawings
Fig. 1 is the structural representation of carbon fiber-based graded composite anode material；
In figure it is each marked as：1- carbon fiber substrates, 2- α-PbO2Composite deposite, 3- β-PbO2Composite deposite, 4- β-MnO2It is multiple
Close coating.
Embodiment
The inventive method is described in further detail below by embodiment, but the scope of the present invention is not limited to institute
State content.
Embodiment 1
As shown in figure 1, the manganese electrodeposition of present invention carbon fiber-based graded composite anode material includes carbon fiber substrate 1, answered
Close the α-PbO for introducing nano-graphene particle on carbon fiber substrate surface2Composite deposite 2, it is compounded in α-PbO2Composite deposite
2 surfaces introduce SiO2β-the PbO of particle2Composite deposite 3, it is covered in β-PbO2Composite deposite 3 surface introduces RuO2
β-the MnO of grain2Composite coating 4.
α-PbO described in the present embodiment2Graphene particles composition in composite deposite 2 is 2wt%, β-PbO2In composite deposite 3
SiO2Particle group turns into 3.5wt%, β-MnO2RuO in composite coating 42Particle group turns into 15wt%.Composite anode materials
Gross thickness is 8mm, and the thickness of carbon fiber substrate is 4.8mm, α-PbO2Thickness of multiple plating is 0.5mm, β-PbO2Composite Coatings thickness
Spend for 1mm, β-MnO2Composite coating thickness is 0.1mm.
Manganese electrodeposition is as follows with the preparation method of carbon fiber-based graded composite anode material：
(1) removing glue is carried out to carbon fiber substrate 1 first, under the protection of nitrogen or argon gas, at 400~600 DEG C of heating
Reason, makes the activity of carbon fiber than surface increase, while avoiding the fracture of wire of carbon fiber in processing procedure from damaging；
(2) carbon fiber substrate after step (1) processing is placed in the HNO that -5 DEG C of temperature, mass percent concentration are 50%3
1h is aoxidized in the aqueous solution, carbon fiber substrate striated corrosion is occurred；
(3) the carbon fiber substrate surface after step (2) processing is coated into elargol, be placed in baking oven, it is 60 to control temperature
DEG C, drying time is 20min；Coating more than repeating and drying process 5 times, make carbon fiber substrate surface obtain uniform activity and receive
Rice Argent grain.Described elargol is the sol solutionses that silver nitrate and trisodium citrate are constituted, and silver colloidal partical size is 20nm~50nm,
The preparation method of silver colloidal partical is as follows：1L distilled water is added in flask, 0.08mol/L silver nitrate is added, boiling is heated to
Rise, quick stirring is lower to add the trisodium citrate that solution quality percentage is 10%, continues back flow reaction 30min, natural cooling
Stirring is filtered with acetic acid nitrocellulose O.22 μm, obtains the elargol in yellow green to room temperature；
(4) carbon fiber substrate that surface made from step (3) is coated with into active nano Argent grain is placed in after ultrasonic disperse
Alkaline composite plating solution in, using stainless steel as negative electrode, temperature be 60 DEG C, current density is 0.5A/dm2, in mechanical agitation
Lower plating 8 hours, the α-PbO for obtaining introducing nano-graphene particle are deposited on carbon fiber substrate surface2Composite deposite 2；Institute
Contain lead monoxide PbO 30g/L, sodium hydroxide NaOH 100g/L, potassium bichromate K in the alkaline composite plating solution stated2Cr2O7
15g/L, nano-graphene particle 3g/L；Described nano-graphene particle is sheet-like particle, and particle diameter is in 80nm~100nm；
(5) the obtained surface deposition of step (4) processing there are into α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point
In acid composite plating solution after dissipating, using titanium mesh plate as negative electrode, temperature is 50~60 DEG C, and current density is 9A/dm2, in machine
The lower plating of tool stirring 4 hours, in α-PbO2The surface of composite deposite 2 deposition obtains introducing SiO2β-the PbO of particle2Composite deposite
3；Contain plumbi nitras Pb (NO in described acid composite plating solution3)2300g/L, nitric acid HNO310g/L, sodium fluoride NaF8g/
L, nano silicon SiO215g/L；The nano silicon is spherical particle, and particle diameter is in 60nm~80nm；
(6) the obtained surface deposition of step (5) processing there are into β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality
In the hydrofluoric acid solution of degree 30%, temperature is 20 DEG C, and soak time is 30min, and deionization washing is dried, then in carbon fiber
Uniform brushing is dissolved in the mass percent concentration being configured in organic solvent with ruthenium trichloride and manganese nitrate and is on matrix surface
30% coating liquid, then 25min is decomposed in drying under conditions of temperature is 150 DEG C, is air-cooled to room temperature, is repeated coating above and is dried
Dry run 10 times, in β-PbO2Composite deposite surface forms and introduces RuO2β-the MnO of particle2Composite coating 4, produces manganese electrodeposition
With carbon fiber-based graded composite anode material.The molal weight ratio of the ruthenium trichloride and manganese nitrate is 1:20.
Manganese electrodeposition manufactured in the present embodiment is with carbon fiber-based graded composite anode material in manganese electrolyte, and electrolytic condition is
Catholyte manganese ion concentration is 40g/L, and ammonium sulfate concentrations are 120g/L, and electrolysis temperature is 30 DEG C, and pH is 6.50, anode electricity
It is 20g/L to solve liquid manganese ion concentration, and ammonium sulfate concentrations are 120g/L, less than 100mg/L fluorides, 600mg/L C1-Ion, sulphur
Acid is 30g/L, and electrolysis temperature is 30 DEG C, using anion membrane electrolytic bath electrodeposit metals manganese, the electricity effect of the graded composite anode
4%, the low 180mV of tank voltage, 1 times of life are improved than traditional lead silver alloy anode plate.
Embodiment 2
The manganese electrodeposition of the present embodiment carbon fiber-based graded composite anode material structure be the same as Example 1.α-the PbO2It is multiple
The graphene particles composition closed in coating 2 is 1.57wt%, β-PbO2SiO in composite deposite 32Particle group turn into 5wt%, β-
MnO2RuO in composite coating 42Particle group turns into 10wt%.The gross thickness of composite anode materials is 13mm, carbon fiber substrate
Thickness is 11mm, α-PbO2Thickness of multiple plating is 0.3mm, β-PbO2Thickness of multiple plating is 0.5mm, β-MnO2Composite coating
Thickness is 0.2mm.
Manganese electrodeposition is as follows with the preparation method of carbon fiber-based graded composite anode material：
(1) removing glue is carried out to carbon fiber substrate 1 first, under the protection of nitrogen or argon gas, at 700~800 DEG C of heating
Reason, makes the activity of carbon fiber than surface increase, while avoiding the fracture of wire of carbon fiber in processing procedure from damaging；
(2) it is 60% the carbon fiber substrate after step (1) processing to be placed in into -10 DEG C of temperature, mass percent concentration
HNO340min is aoxidized in the aqueous solution, carbon fiber substrate striated corrosion is occurred；
(3) the carbon fiber substrate surface after step (2) processing is coated into elargol, be placed in baking oven, it is 100 to control temperature
DEG C, drying time is 10min；Coating more than repeating and drying process 3 times, make carbon fiber substrate surface obtain uniform activity and receive
Rice Argent grain.Described elargol is the sol solutionses that silver nitrate and trisodium citrate are constituted, and silver colloidal partical size is 50nm~80nm,
The preparation method of silver colloidal partical is as follows：1L distilled water is added in flask, 0.05mmol/L silver nitrate is added, boiling is heated to
Rise, quick stirring is lower to add the trisodium citrate that solution quality percentage is 20%, continues back flow reaction 1h, natural cooling stirring
To room temperature, filtered with acetic acid nitrocellulose O.22 μm, obtain the elargol in yellow green；
(4) carbon fiber substrate that surface made from step (3) is coated with into active nano Argent grain is placed in after ultrasonic disperse
Alkaline composite plating solution in, using stainless steel as negative electrode, temperature be 40 DEG C, current density is 0.8A/dm2, in mechanical agitation
Lower plating 6 hours, the α-PbO for obtaining introducing nano-graphene particle are deposited on carbon fiber substrate surface2Composite deposite 2；Institute
Contain lead monoxide PbO 20g/L, sodium hydroxide NaOH 150g/L, potassium bichromate K in the alkaline composite plating solution stated2Cr2O7
30g/L, nano-graphene particle 4g/L；Described nano-graphene particle is spherical particle, and particle diameter is in 10nm~40nm；
(5) the obtained surface deposition of step (4) processing there are into α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point
In acid composite plating solution after dissipating, using titanium mesh plate as negative electrode, temperature is 60~80 DEG C, and current density is 7A/dm2, in machine
The lower plating of tool stirring 6 hours, in α-PbO2The surface of composite deposite 2 deposition obtains introducing SiO2β-the PbO of particle2Composite deposite
3；Contain plumbi nitras Pb (NO in described acid composite plating solution3)2220g/L, nitric acid HNO315g/L, sodium fluoride NaF3g/
L, nano silicon SiO25g/L；The nano silicon is spherical particle, and particle diameter is in 80nm~100nm；
(6) the obtained surface deposition of step (5) processing there are into β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality
In the hydrofluoric acid solution of degree 20%, temperature is 0 DEG C, and soak time is 40min, and deionization washing is dried, then in carbon fiber-based
Uniform brushing is dissolved in the mass percent concentration being configured in organic solvent with ruthenium trichloride and manganese nitrate and is on body surface face
50% coating liquid, then 20min is decomposed in drying under conditions of temperature is 120 DEG C, is air-cooled to room temperature, is repeated coating above and is dried
Dry run 3 times, in β-PbO2Composite deposite surface forms and introduces RuO2β-the MnO of particle2Composite coating 4, produces manganese electrodeposition use
Carbon fiber-based graded composite anode material.The molal weight ratio of the ruthenium trichloride and manganese nitrate is 1:10.
Manganese electrodeposition manufactured in the present embodiment is with carbon fiber-based graded composite anode material in manganese electrolyte, and electrolytic condition is
Catholyte manganese ion concentration is 40g/L, and ammonium sulfate concentrations are 120g/L, and electrolysis temperature is 40 DEG C, and pH is 6.50, anode electricity
It is 20g/L to solve liquid manganese ion concentration, and ammonium sulfate concentrations are 120g/L, less than 100mg/L fluorides, 800mg/L Cl-Ion, sulphur
Acid is 30g/L, and electrolysis temperature is 30 DEG C, using anion membrane electrolytic bath electrodeposit metals manganese, the electricity effect of the graded composite anode
4%, the low 240mV of tank voltage, 2 times of life are improved than traditional lead silver alloy anode plate.
Embodiment 3
The manganese electrodeposition of the present embodiment carbon fiber-based graded composite anode material structure be the same as Example 1.α-the PbO2It is multiple
The graphene particles composition closed in coating 2 is 4wt%, β-PbO2SiO in composite deposite 32Particle group turn into 2.01wt%, β-
MnO2RuO in composite coating 42Particle group turns into 25wt%.The gross thickness of composite anode materials is 4mm, the thickness of carbon fiber substrate
Spend for 3mm, α-PbO2Thickness of multiple plating is 0.1mm, β-PbO2Thickness of multiple plating is 0.39mm, β-MnO2Composite coating is thick
Spend for 0.01mm.
Manganese electrodeposition is as follows with the preparation method of carbon fiber-based graded composite anode material：
(1) removing glue is carried out to carbon fiber substrate 1 first, under the protection of nitrogen or argon gas, at 600~700 DEG C of heating
Reason, makes the activity of carbon fiber than surface increase, while avoiding the fracture of wire of carbon fiber in processing procedure from damaging；
(2) carbon fiber substrate after step (1) processing is placed in the HNO that 15 DEG C of temperature, mass percent concentration are 25%3
2h is aoxidized in the aqueous solution, carbon fiber substrate striated corrosion is occurred；
(3) the carbon fiber substrate surface after step (2) processing is coated into elargol, be placed in baking oven, it is 180 to control temperature
DEG C, drying time is 2min；Coating more than repeating and drying process 8 times, make carbon fiber substrate surface obtain uniform activity and receive
Rice Argent grain.Described elargol is the sol solutionses that silver nitrate and trisodium citrate are constituted, and silver colloidal partical size is 60nm~80nm,
The preparation method of silver colloidal partical is as follows：1L distilled water is added in flask, 0.1mol/L silver nitrate is added, boiling is heated to
Rise, quick stirring is lower to add the trisodium citrate that solution quality percentage is 0.5%, continues back flow reaction 10min, natural cooling
Stirring is filtered with acetic acid nitrocellulose O.22 μm, obtains the elargol in yellow green to room temperature；
(4) carbon fiber substrate that surface made from step (3) is coated with into active nano Argent grain is placed in after ultrasonic disperse
Alkaline composite plating solution in, using stainless steel as negative electrode, temperature be 30 DEG C, current density is 0.6A/dm2, in mechanical agitation
Lower plating 7 hours, the α-PbO for obtaining introducing nano-graphene particle are deposited on carbon fiber substrate surface2Composite deposite 2；Institute
Contain lead monoxide PbO 40g/L, sodium hydroxide NaOH 160g/L, potassium bichromate K in the alkaline composite plating solution stated2Cr2O7
5g/L, nano-graphene particle 1g/L；Described nano-graphene particle is spherical particle, and particle diameter is in 10nm~30nm；
(5) the obtained surface deposition of step (4) processing there are into α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point
In acid composite plating solution after dissipating, using titanium mesh plate as negative electrode, temperature is 80~90 DEG C, and current density is 6A/dm2, in machine
The lower plating of tool stirring 5 hours, in α-PbO2The surface of composite deposite 2 deposition obtains introducing SiO2β-the PbO of particle2Composite deposite
3；Contain plumbi nitras Pb (NO in described acid composite plating solution3)2400g/L, nitric acid HNO32g/L, sodium fluoride NaF 10g/
L, nano silicon SiO220g/L；The nano silicon is spherical particle, and particle diameter is in 70nm~80nm；
(6) the obtained surface deposition of step (5) processing there are into β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality
In the hydrofluoric acid solution of degree 5%, temperature is 30 DEG C, and soak time is 5min, and deionization washing is dried, then in carbon fiber-based
Uniform brushing is dissolved in the mass percent concentration being configured in organic solvent with ruthenium trichloride and manganese nitrate and is on body surface face
20% coating liquid, then 5min is decomposed in drying under conditions of temperature is 200 DEG C, is air-cooled to room temperature, is repeated coating above and is dried
Dry run 20 times, in β-PbO2Composite deposite surface forms and introduces RuO2β-the MnO of particle2Composite coating 4, produces manganese electrodeposition
With carbon fiber-based graded composite anode material, also referred to as carbon fiber/α-PbO2- graphene/β-PbO2-SiO2/β-MnO2-RuO2Ladder
Spend composite inert anode material.The molal weight ratio of the ruthenium trichloride and manganese nitrate is 1:5.
Embodiment 4
The manganese electrodeposition of the present embodiment carbon fiber-based graded composite anode material structure be the same as Example 1.α-the PbO2It is multiple
The graphene particles composition closed in coating 2 is 2.5wt%, β-PbO2SiO in composite deposite 32Particle group turn into 2.5wt%, β-
MnO2RuO in composite coating 42Particle group turns into 5wt%.The gross thickness of composite anode materials is 10mm, the thickness of carbon fiber substrate
Spend for 5.1mm, α-PbO2Thickness of multiple plating is 0.3mm, β-PbO2Thickness of multiple plating is 2mm, β-MnO2Composite coating thickness
For 0.15mm.
Manganese electrodeposition is as follows with the preparation method of carbon fiber-based graded composite anode material：
(1) removing glue is carried out to carbon fiber substrate 1 first, under the protection of nitrogen or argon gas, at 500~600 DEG C of heating
Reason, makes the activity of carbon fiber than surface increase, while avoiding the fracture of wire of carbon fiber in processing procedure from damaging；
(2) carbon fiber substrate after step (1) processing is placed in the HNO that 8 DEG C of temperature, mass percent concentration are 40%3
1.5h is aoxidized in the aqueous solution, carbon fiber substrate striated corrosion is occurred；
(3) the carbon fiber substrate surface after step (2) processing is coated into elargol, be placed in baking oven, it is 150 to control temperature
DEG C, drying time is 15min；Coating more than repeating and drying process 5 times, make carbon fiber substrate surface obtain uniform activity and receive
Rice Argent grain.Described elargol is the sol solutionses that silver nitrate and trisodium citrate are constituted, and silver colloidal partical size is 30nm~50nm,
The preparation method of silver colloidal partical is as follows：1L distilled water is added in flask, 0.1mol/L silver nitrate is added, boiling is heated to
Rise, quick stirring is lower to add the trisodium citrate that solution quality percentage is 15%, continues back flow reaction 40min, natural cooling
Stirring is filtered with acetic acid nitrocellulose O.22 μm, obtains the elargol in yellow green to room temperature；
(4) carbon fiber substrate that surface made from step (3) is coated with into active nano Argent grain is placed in after ultrasonic disperse
Alkaline composite plating solution in, using stainless steel as negative electrode, temperature be 50 DEG C, current density is 0.1A/dm2, in mechanical agitation
Lower plating 4 hours, the α-PbO for obtaining introducing nano-graphene particle are deposited on carbon fiber substrate surface2Composite deposite 2；Institute
Contain lead monoxide PbO 25g/L, sodium hydroxide NaOH 120g/L, potassium bichromate K in the alkaline composite plating solution stated2Cr2O7
10g/L, nano-graphene particle 2g/L；Described nano-graphene particle is sheet-like particle, and particle diameter is in 70nm~80nm；
(5) the obtained surface deposition of step (4) processing there are into α-PbO2The carbon fiber substrate of composite deposite is placed in ultrasound point
In acid composite plating solution after dissipating, using titanium mesh plate as negative electrode, temperature is 70~80 DEG C, and current density is 8A/dm2, in machine
The lower plating of tool stirring 2 hours, in α-PbO2The surface of composite deposite 2 deposition obtains introducing SiO2β-the PbO of particle2Composite deposite
3；Contain plumbi nitras Pb (NO in described acid composite plating solution3)2300g/L, nitric acid HNO38g/L, sodium fluoride NaF6g/L,
Nano silicon SiO29g/L；The nano silicon is spherical particle, and particle diameter is in 60nm~80nm；
(6) the obtained surface deposition of step (5) processing there are into β-PbO2It is dense that the carbon fiber substrate of composite deposite is placed in quality
In the hydrofluoric acid solution of degree 15%, temperature is 25 DEG C, and soak time is 15min, and deionization washing is dried, then in carbon fiber
Uniform brushing is dissolved in the mass percent concentration being configured in organic solvent with ruthenium trichloride and manganese nitrate and is on matrix surface
40% coating liquid, then 15min is decomposed in drying under conditions of temperature is 150 DEG C, is air-cooled to room temperature, is repeated coating above and is dried
Dry run 8 times, in β-PbO2Composite deposite surface forms and introduces RuO2β-the MnO of particle2Composite coating 4, produces manganese electrodeposition use
Carbon fiber-based graded composite anode material.The molal weight ratio of the ruthenium trichloride and manganese nitrate is 1:15.
Claims (8)
1. manganese electrodeposition carbon fiber-based graded composite anode material, it is characterised in that the anode material includes carbon fiber substrate
(1) α-PbO for introducing nano-graphene particle on carbon fiber substrate surface, are compounded in2Composite deposite (2), it is compounded in α-PbO2
Composite deposite (2) surface introduces SiO2β-the PbO of particle2Composite deposite (3), it is covered in β-PbO2Composite deposite (3) surface
Introduce RuO2β-the MnO of particle2Composite coating (4).
2. manganese electrodeposition according to claim 1 carbon fiber-based graded composite anode material, it is characterised in that：α-PbO2It is multiple
The graphene particles composition closed in coating (2) is 1.57~4wt%, β-PbO2SiO in composite deposite (3)2Particle group turns into
2.01~5wt%, β-MnO2RuO in composite coating (4)2Particle group turns into 5~25wt%.
3. manganese electrodeposition according to claim 1 carbon fiber-based graded composite anode material, it is characterised in that described compound
The gross thickness of anode material is 4~13mm, and the thickness of carbon fiber substrate is 3~11mm, α-PbO2Thickness of multiple plating be 0.1~
0.5mm, β-PbO2Thickness of multiple plating is 0.39~2mm, β-MnO2Composite coating thickness is 0.01~0.2mm.
4. the preparation method of the manganese electrodeposition carbon fiber-based graded composite anode material as described in claims 1 to 3, its feature exists
In method and step is as follows：
(1) removing glue is carried out to carbon fiber substrate (1) first, under the protection of nitrogen or argon gas, heated at 400~800 DEG C,
Make the activity of carbon fiber than surface increase, while avoiding the fracture of wire of carbon fiber in processing procedure from damaging；
(2) by step (1) processing after carbon fiber substrate be placed in temperature -10~15 DEG C, mass percent concentration be 25%~
60% HNO340min~2h is aoxidized in the aqueous solution, carbon fiber substrate striated corrosion is occurred；
(3) the carbon fiber substrate surface after step (2) processing is coated into elargol, be placed in baking oven, it is 60~180 to control temperature
DEG C, drying time is 2~20min；Coating more than repeating and drying process 3~8 times, make carbon fiber substrate surface obtain uniformly
Active nano Argent grain；
(4) alkali that the carbon fiber substrate that surface made from step (3) is coated with into active nano Argent grain is placed in after ultrasonic disperse
Property composite plating solution in, using stainless steel as negative electrode, temperature be 30~60 DEG C, current density be 0.1~0.8A/dm2, in machinery
The lower plating of stirring 4~8 hours, the α-PbO for obtaining introducing nano-graphene particle are deposited on carbon fiber substrate surface2Composite Coatings
Layer (2)；Contain 20~40g/L of PbO, 100~160g/L of NaOH, K in described alkaline composite plating solution2Cr2O75~30g/
L, 1~4g/L of nano-graphene particle；
(5) the obtained surface deposition of step (4) processing there are into α-PbO2The carbon fiber substrate of composite deposite is placed in after ultrasonic disperse
In acid composite plating solution, using titanium mesh plate as negative electrode, temperature is 50~90 DEG C, and current density is 6~9A/dm2, stirred in machinery
Lower plating 2~6 hours is mixed, in α-PbO2Composite deposite (2) surface deposition obtains introducing SiO2β-the PbO of particle2Composite deposite
(3)；Contain Pb (NO in described acid composite plating solution3)2220~400g/L, HNO32~15g/L, 3~10g/L of NaF,
Nano-meter SiO_225~20g/L；
(6) the obtained surface deposition of step (5) processing there are into β-PbO2The carbon fiber substrate of composite deposite is placed in mass concentration 5%
In~30% hydrofluoric acid solution, temperature is 0~30 DEG C, and soak time is 5~40min, and deionization washing is dried, Ran Hou
Uniform brushing is dissolved in the mass percent being configured in organic solvent with ruthenium trichloride and manganese nitrate on carbon fiber substrate surface
Concentration is 20%~50% coating liquid, then 5~25min is decomposed in drying under conditions of temperature is 120~200 DEG C, is air-cooled to
Room temperature, repeats coating above and drying operation 3~20 times, in β-PbO2Composite deposite surface forms and introduces RuO2The β of particle-
MnO2Composite coating (4), produces manganese electrodeposition carbon fiber-based graded composite anode material.
5. the preparation method of the manganese electrodeposition carbon fiber-based graded composite anode material according to claims 4, its feature
Be, the elargol described in step (3) is the sol solutionses that silver nitrate and trisodium citrate are constituted, silver colloidal partical size be 20nm~
80nm, the preparation method of silver colloidal partical is as follows：1L distilled water is added in flask, adds 0.05mmol/L~0.1mol/L's
Silver nitrate, is heated to boiling, and quick stirring is lower to add the trisodium citrate that solution quality percentage is 0.5~20%, continues back
Stream reaction 10min~1h, natural cooling stirred to room temperature, is filtered, is obtained in yellowish green with acetic acid nitrocellulose O.22 μm
The elargol of color.
6. the preparation method of the manganese electrodeposition carbon fiber-based graded composite anode material according to claims 4, its feature
It is, the nano-graphene particle described in step (4) is sheet or spherical particle, and particle diameter is in 10nm~100nm.
7. the preparation method of the manganese electrodeposition carbon fiber-based graded composite anode material according to claims 4, its feature
It is, step (5) described Nano-meter SiO_22For spherical particle, particle diameter is in 60nm~100nm.
8. the preparation method of the manganese electrodeposition carbon fiber-based graded composite anode material according to claims 4, its feature
It is：The molal weight ratio of step (6) ruthenium trichloride and manganese nitrate is 1:20~1:5.
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