CN115287737A - Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof - Google Patents
Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 427
- 239000010936 titanium Substances 0.000 title claims abstract description 325
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 325
- 239000002131 composite material Substances 0.000 title claims abstract description 216
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 138
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 138
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 49
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 49
- 238000004070 electrodeposition Methods 0.000 claims abstract description 43
- 239000010410 layer Substances 0.000 claims description 163
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 111
- 229910018316 SbOx Inorganic materials 0.000 claims description 102
- 239000011521 glass Substances 0.000 claims description 87
- 229910052799 carbon Inorganic materials 0.000 claims description 67
- 238000005245 sintering Methods 0.000 claims description 65
- 239000011248 coating agent Substances 0.000 claims description 63
- 238000000576 coating method Methods 0.000 claims description 63
- 239000011246 composite particle Substances 0.000 claims description 58
- 239000004005 microsphere Substances 0.000 claims description 58
- 239000002243 precursor Substances 0.000 claims description 56
- 229910003070 TaOx Inorganic materials 0.000 claims description 50
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 32
- 238000007747 plating Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- 238000003466 welding Methods 0.000 claims description 30
- 239000011324 bead Substances 0.000 claims description 29
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 150000003608 titanium Chemical class 0.000 claims description 25
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 23
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 21
- 239000004917 carbon fiber Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 18
- 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 18
- 238000002791 soaking Methods 0.000 claims description 17
- 235000006408 oxalic acid Nutrition 0.000 claims description 16
- 230000003213 activating effect Effects 0.000 claims description 15
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims description 15
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- -1 tin-ruthenium-tantalum Chemical compound 0.000 claims description 14
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 238000005488 sandblasting Methods 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims description 12
- 238000009713 electroplating Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000012212 insulator Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LTNGUMKBFWBWGY-UHFFFAOYSA-N [Sb][Sn][Pt] Chemical compound [Sb][Sn][Pt] LTNGUMKBFWBWGY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005098 hot rolling Methods 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 claims description 6
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000861 blow drying Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910020935 Sn-Sb Inorganic materials 0.000 claims description 4
- 229910008757 Sn—Sb Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical group [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims 1
- 230000002035 prolonged effect Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910000978 Pb alloy Inorganic materials 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 15
- 229910052725 zinc Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 238000007654 immersion Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 229910000989 Alclad Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 101100522123 Caenorhabditis elegans ptc-1 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229910001924 platinum group oxide Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
Abstract
The invention relates to a titanium-based gradient composite manganese dioxide anode plate and a preparation method thereof, belonging to the technical field of non-ferrous metal electrodeposition. The titanium-based gradient composite manganese dioxide anode plate comprises a titanium-clad aluminum conductive beam and a titanium-based oxide anode plate, wherein the titanium-based oxide anode plate comprises a titanium plate, titanium-clad aluminum composite rods, double-layer titanium nets and a titanium rod, the top end of the titanium plate is fixedly connected with the bottom end of the titanium-clad aluminum conductive beam, the titanium-clad aluminum composite rods are vertically arranged at the bottom end of the titanium plate, the double-layer titanium nets are arranged between the adjacent titanium-clad aluminum composite rods, the titanium rod is arranged at the bottom end of the titanium-clad aluminum composite rods, the top end of each double-layer titanium net is fixedly connected with the titanium plate, and the bottom end of each double-layer titanium net is fixedly connected with the titanium rod; the titanium plate, the titanium-clad aluminum composite rod, the double-layer titanium net and the titanium surface on the titanium rod are sequentially coated with a metal oxide intermediate layer and a composite manganese dioxide active layer. Compared with the traditional lead alloy anode, the invention has the advantages of reduced cell voltage, prolonged service life, improved current efficiency and high cathode product quality.
Description
Technical Field
The invention relates to a titanium-based gradient composite manganese dioxide anode plate and a preparation method thereof, belonging to the technical field of non-ferrous metal electrodeposition.
Background
In non-ferrous metallurgy, about 90% or more of zinc and about 30% of copper are extracted by hydrometallurgical techniques. Especially in the process of zinc hydrometallurgy, the energy consumption of the electrodeposition process consumes 2/3 of the whole zinc extraction process, and the production energy consumption of zinc hydrometallurgy per ton is 3200-4200 kwh/t.Zn. The oxygen evolution potential of industrial lead alloy anodes is as high as about 1V, which increases the useless power consumption by about 1000kWh, accounting for about 30% of the total energy consumption of zinc electrowinning.
The anode materials used at home and abroad at present mainly comprise the following four types:
first type lead alloy anode: the produced lead-based alloy has large anode pollution and is gradually eliminated by the market in accordance with national policies due to the defects of poor corrosion resistance, toxicity, harm to human bodies, solution pollution, easy deformation in the electrolytic process, precipitation at the cathode and the like;
second type titanium-based platinum group oxide coating anode: the noble metal coating titanium anode has better performance, is not consumed in the electrolytic process, has good stability, low oxygen evolution overpotential and high catalytic activity, but limits the large-scale application thereof due to higher price;
a third titanium-based lead dioxide coating anode: the titanium-based lead dioxide anode inherits the respective advantages of the coated titanium anode and the coated lead anode, fully combines the good shape stability of the titanium anode and the price advantage of the lead anode, and fully overcomes the defects of easy corrosion and bending of the lead anode, high price of the coated titanium anode and the like. However, the following problems arise in use: (1) PbO 2 The combination of the deposition layer and the surface of the electrode is not tight or the deposition layer is not uniform; (2) PbO 2 The deposition layer has ceramic brittleness, and the more compact the internal stress is, the larger the internal stress is; (3) Conductive corrosion-resistant beta-PbO 2 The deposited layer and the titanium matrix have low bonding force and are easy to fall off in the using process; (4) PbO 2 The cell voltage of the electrode is high in electrodeposition applications.
A fourth titanium-based manganese dioxide coating anode: the manganese dioxide coating anode has the advantages that: the oxygen evolution overpotential is low, the corrosion resistance is good, and the purity of the cathode product is high; the disadvantages are: the preparation process is complex and the cost is high; in addition, most manganese dioxide coating anodes have obvious cracks on the surface, the matrix is easy to expose in the long-time electrolytic process, the corrosion rate of the metal matrix is increased, and if the matrix is titanium-based, non-conductive titanium dioxide can be oxidized on the exposed matrix surface, so that the voltage is increased, and the energy consumption is increased.
In addition, the titanium-based anode produced industrially at present is easy to deform in actual use, so that the short circuit of the cathode and the anode is easily caused, the anode can be seriously damaged, the power consumption is increased, and the quality of a cathode product is reduced.
Therefore, there is an urgent need to develop an anode with high current efficiency, low energy consumption, low cost, simple process, and high quality (low lead content) of cathode product.
Disclosure of Invention
Aiming at the problems that in industrial production, a titanium-based anode is easy to deform in actual use, the short circuit of a cathode and an anode is easily caused, the anode can be seriously damaged seriously to cause the increase of power consumption and the reduction of the quality of a cathode product, the invention provides a titanium-based gradient composite manganese dioxide anode plate and a preparation method thereof, and the invention mixes Ag-carbon fiber-beta-PbO into the titanium-based gradient composite manganese dioxide anode plate 2 Composite particles embedded with tungsten-containing gamma-MnO 2 In the coating layer, the gamma-MnO is greatly improved 2 The conductivity and the internal stress of the plating layer are reduced, so that the service life of the composite manganese dioxide electrode is prolonged, and the cell voltage is reduced; simultaneously embedding Sn-Ru-TaOx coated hollow glass microspheres into tungsten-containing gamma-MnO 2 In the coating layer, not only the gamma-MnO is improved 2 And the catalytic activity of the catalyst is greatly reduced, and the gamma-MnO content is greatly reduced 2 The plating layer is brittle, so that the stability of the electrode is better in the using process; the titanium-based gradient composite manganese dioxide anode plate is applied to non-ferrous metal electrodeposition, compared with the traditional lead alloy anode, the bath voltage is reduced by more than 8%, the service life is prolonged by more than 1 time, the current efficiency is improved by more than 2%, and the quality of a cathode product is high.
A titanium-based gradient composite manganese dioxide anode plate comprises a titanium-coated aluminum conducting beam 1 and a titanium-based oxide anode plate 2, wherein the titanium-based oxide anode plate 2 is fixedly arranged at the bottom end of the titanium-coated aluminum conducting beam 1, and an insulator 7 is arranged on the titanium-based oxide anode plate 2;
the titanium-based oxide anode plate 2 comprises a titanium plate 3, a titanium-clad aluminum composite rod 4, a double-layer titanium net 5 and a titanium rod 6, the top end of the titanium plate 3 is fixedly connected with the bottom end of the titanium-clad aluminum conductive beam 1, the titanium-clad aluminum composite rod 4 is vertically arranged at the bottom end of the titanium plate 3, the titanium rod 6 is arranged at the bottom end of the titanium-clad aluminum composite rod 4, the titanium plate 3, the titanium-clad aluminum composite rod 4 and the titanium rod 6 form a titanium-based oxide anode plate frame, the double-layer titanium net 5 is arranged between the adjacent titanium-clad aluminum composite rods 4, the top end of the double-layer titanium net 5 is fixedly connected with the titanium plate 3, and the bottom end of the double-layer titanium net 5 is fixedly connected with the titanium rod 6; the titanium surface of the titanium-based oxide anode plate frame is sequentially coated with a metal oxide intermediate layer I and a composite manganese dioxide active layer, and the titanium surface of the double-layer titanium mesh 5 is sequentially coated with a metal oxide intermediate layer II and a composite manganese dioxide active layer.
The thickness of the titanium layer of the titanium-clad aluminum conductive beam 1 is 1-3 mm, one end of the titanium-clad aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head, the thickness of the titanium plate 3 is 3-5 mm, the thickness of the titanium layer of the titanium-clad aluminum composite rod 4 is 0.5-2 mm, the long axis of the double-layer titanium mesh 5 is 3-16 mm, the short axis is 1-6 mm, and the section thickness is 0.5-3 mm; the thickness of the metal oxide intermediate layer I and the metal oxide intermediate layer II is 1-5 mu m, and the thickness of the composite manganese dioxide active layer is 0.3-2 mm.
The metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-doped carbon fiber-beta-PbO 2 Composite particles, sn-Ru-TaOx coated hollow glass microspheres and gamma-MnO 2 。
Furthermore, the granularity of the carbon fiber is 1-10 mu m, and the Ag-carbon fiber-beta-PbO is doped 2 The particle size of the composite particles is 10-100 mu m, and the particle size of the hollow glass beads is 10-100 mu m.
Further, the molar ratio of Pt, sn and Sb in the Pt-Sn-SbOx is 1-7.
Further, the Ag-carbon fiber-beta-PbO is doped by taking the mass percent of the composite manganese dioxide active layer as 100 percent 2 1 to 6 percent of composite particles, 0.5 to 4 percent of Sn-Ru-TaOx coated hollow glass microspheres, 0.05 to 2 percent of W and the balance of gamma-MnO 2 (ii) a Ag-doped carbon fiber-beta-PbO 2 The composite particles comprise 0.5-5 wt% of Ag, 0.1-1 wt% of carbon fiber powder and the balance of beta-PbO 2 (ii) a The molar ratio of Sn to Ru to Ta in the Sn-Ru-TaOx coated hollow glass bead is (40-50).
Further, the Ag-doped carbon fiber-beta-PbO 2 The preparation method of the composite particles comprises the following specific steps:
stainless steel is used as an anode, a titanium mesh is used as a cathode, and acid is addedElectrodepositing for 4-8 h in the lead nitrate composite plating solution to obtain the Ag-doped carbon fiber-beta-PbO 2 Composite coating doped with Ag-carbon fiber-beta-PbO 2 Stripping the composite coating and then ball-milling to obtain the Ag-doped carbon fiber-beta-PbO 2 Composite particles; wherein the acid lead nitrate composite plating solution contains 50-200 g/L of lead nitrate, 0.5-20 g/L of silver nitrate, 4-20 g/L of thiourea and 4-20 g/L of carbon fiber particles, and the pH value of the acid lead nitrate composite plating solution is 0-2; the temperature of the electro-deposition is 60-90 ℃, and the current density is 6-12A/dm 2 。
Further, the preparation method of the Sn-Ru-TaOx coated hollow glass bead comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing moisture by rotary evaporation to obtain tin-ruthenium-tantalum precursor liquid;
2) Placing hollow glass beads at the temperature of 400-600 ℃, calcining for 0.5-2 h, immersing in a NaOH solution with the concentration of 5-10 wt.%, treating for 5-40 min at the temperature of 60-90 ℃, washing with deionized water, immersing in an HF solution with the concentration of 0.5-2 wt.% for treating for 1-5 min, deionizing, washing, and drying to obtain pretreated hollow glass beads;
3) Immersing the pretreated hollow glass microspheres into a tin-ruthenium-tantalum precursor liquid for ultrasonic soaking for 5-10 min, drying at the temperature of 100-150 ℃, then roasting at the temperature of 300-560 ℃ for 10-20 min, repeating the ultrasonic soaking and roasting processes for 6-12 times, and then sintering at the temperature of 400-480 ℃ for 1-2 h to obtain the Sn-Ru-TaOx coated hollow glass microsphere composite particles.
The preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) After oil removal and acid cleaning, the aluminum bar is immersed in NaOH solution for 1-5 min, washed by deionized water and then immersed in HNO 3 Activating in the solution for 4-8 min to obtain an activated aluminum bar; treating the inner wall of the titanium tube by using an HF solution, and cleaning by using deionized water to obtain a pretreated titanium tube; the pre-treated titanium pipe is sleeved outside the aluminum bar and is extruded, drawn and compounded, the titanium-clad aluminum composite bar is prepared through hot rolling, and the titanium-clad aluminum composite bar is welded with the aluminum-copper composite conductive head to obtain a titanium-clad aluminum conductive beam;
(2) Welding a titanium plate, a titanium-coated aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame in NaOH solution for 10-30 min, performing heat treatment on the titanium-based oxide anode plate frame after sand blasting surface treatment, then placing the titanium-based oxide anode plate frame in oxalic acid solution for activation for 0.5-2.0 h to obtain an activated titanium-based oxide anode plate frame, coating tin-antimony precursor liquid on the surface of the activated titanium-based oxide anode plate frame, drying, performing sintering pretreatment for 5-10 min, repeating the coating of the tin-antimony precursor liquid and the sintering process for 3-10 times, and then placing the titanium-based oxide anode plate frame at the temperature of 400-600 ℃ for sintering for 1-2 h to obtain the titanium-based oxide anode plate frame coated with a metal oxide interlayer;
(3) Immersing the titanium mesh formed by drawing into NaOH solution for 10-30 min, carrying out heat treatment after carrying out sand blasting surface treatment on the titanium mesh, then placing the titanium mesh in oxalic acid solution for activating for 0.5-2.0 h to obtain an activated titanium mesh, coating platinum-tin-antimony precursor solution or palladium-titanium-tin-antimony precursor solution on the surface of the activated titanium mesh, drying, sintering for 5-10 min, repeating the coating and sintering processes for 3-10 times, and then placing the titanium mesh at the temperature of 400-600 ℃ for sintering for 1-2 h to obtain the titanium mesh coated with Pt-Sn-SbOx or Pd-Ti-Sn-Sb; coating a tin-antimony precursor solution on the surface of a titanium net coated with Pt-Sn-SbOx or Pd-Ti-Sn-Sb, drying, sintering for 5-10 min, repeating the coating of the tin-antimony precursor solution and the sintering process for 3-10 times, and sintering at 400-600 ℃ for 1-2 h to obtain the titanium net coated with a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Welding a titanium mesh coated with a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer on a titanium-based oxide anode plate frame coated with a metal oxide intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-coated aluminum composite rods; placing the titanium-based oxide anode plate blank as an anode and the titanium plate as a cathode in manganese nitrate composite electroplating solution for composite electrodeposition, cleaning with deionized water, and blow-drying to obtain a titanium-based oxide anode plate;
(5) Welding the top end of a titanium plate of the titanium-based oxide anode plate at the bottom end of the titanium-coated aluminum conducting beam, and installing an insulator on the titanium-based oxide anode plate to obtain the titanium-based gradient composite manganese dioxide anode plate.
The concentration of the NaOH solution in the step (1) is 5-10 wt.%, the soaking temperature of the NaOH solution is 40-70 ℃, and HNO is added 3 The concentration of the solution is 10-40 wt.%, the concentration of the HF solution is 1-10 wt.%, the hot rolling temperature is 500-700 ℃, and the welding method is pulse argon protection aluminum-aluminum welding;
in the step (2), the concentration of the NaOH solution is 10-20 wt.%, the soaking temperature of the NaOH solution is 50-80 ℃, the heat treatment temperature is 400-700 ℃, the heat treatment time is 0.2-1.5 h, the concentration of the oxalic acid solution is 5-30 wt.%, the activation temperature is 80-100 ℃, and the sintering pretreatment temperature is 400-700 ℃;
in the step (3), the concentration of the NaOH solution is 10-20 wt.%, the soaking temperature of the NaOH solution is 50-80 ℃, the heat treatment temperature is 400-700 ℃, the heat treatment time is 0.2-1.5 h, the concentration of the oxalic acid solution is 5-30 wt.%, the activation temperature is 80-100 ℃, and the sintering pretreatment temperature is 400-700 ℃;
the temperature of the composite electrodeposition in the step (4) is 80-100 ℃, and the current density is 1-5A/dm 2 The stirring speed is 50-300 rpm, and the composite electrodeposition time is 4-20 h; the manganese nitrate composite electroplating solution contains 20-100 g/L of manganese nitrate (Mn (NO) 3 ) 2 ) 2-30 g/L nitric acid (HNO) 3 ) 10-40 g/L sodium tungstate (Na) 2 WO 4 ) 10-30 g/L of Ag-doped carbon fiber-beta-PbO 2 4-30 g/L of Sn-Ru-TaOx coated hollow glass microspheres.
Preparing the palladium-titanium-tin-antimony precursor solution: adding palladium chloride, tetrabutyl titanate, tin chloride and antimony chloride into concentrated hydrochloric acid according to a molar ratio until the palladium chloride, tetrabutyl titanate, tin chloride and antimony chloride are completely dissolved, then adding n-butyl alcohol solvent, and removing water in a coating solution by adopting a rotary evaporator to obtain a palladium-titanium-tin-antimony precursor solution;
preparing the platinum-tin-antimony precursor solution: chloroplatinic acid (H) 2 PtC1 6 ·6H 2 O), tin chloride and antimony chloride are added into concentrated hydrochloric acid according to the molar ratio until the tin chloride and the antimony chloride are completely dissolved, then n-butyl alcohol solvent is added, and a rotary evaporator is adopted to remove the moisture of the coating liquid, so that platinum-tin-antimony precursor liquid is obtained;
preparing the tin-antimony precursor liquid: adding tin chloride and antimony chloride into concentrated hydrochloric acid according to a molar ratio until the tin chloride and the antimony chloride are completely dissolved, then adding n-butyl alcohol solvent, and removing water of coating liquid by adopting a rotary evaporator to obtain tin-antimony precursor liquid.
The invention has the beneficial effects that:
(1) The titanium-based gradient composite manganese dioxide anode plate is used for non-ferrous metal electrodeposition, and has the advantages of good electrocatalytic activity, long service life, low cost and high electric efficiency; compared with the traditional lead-based multi-element alloy, on the basis of not changing the structure of an electrolytic cell, the composition of electrolyte and the operation specification, the cell voltage can be reduced by more than 8 percent, the service life is prolonged by more than 1 time, the current efficiency is improved by more than 2 percent, and the quality of a cathode product is high;
(2) The invention adopts the titanium-coated aluminum conductive beam/rod, which not only can reduce the material cost of the electrode, but also can avoid the introduction of impurity ions (Cu) into the cathode product 2+ )；
(3) The Pd and Pt elements are introduced into the metal oxide intermediate layer of the titanium-based gradient composite manganese dioxide anode plate, so that the surface area of the coating can be increased, the coating is easy to generate a net structure, the conductivity of the coating is increased, and the interface resistance between the titanium base and the coating is reduced;
(4) The invention adopts the double-layer titanium mesh electrode, so that the apparent area of the surface of the electrode is increased by 1 time, the catalytic activity of an active layer is improved, and the cell voltage of the electrode in the electrodeposition process is reduced;
(5) The invention mixes Ag-carbon fiber-beta-PbO 2 Composite particles embedded with tungsten-containing gamma-MnO 2 In the coating layer, the gamma-MnO is greatly improved 2 The conductivity is improved, the internal stress of the plating layer is reduced, the service life of the composite manganese dioxide electrode is prolonged, and the cell voltage is reduced; simultaneously embedding Sn-Ru-TaOx coated hollow glass microspheres into tungsten-containing gamma-MnO 2 In the coating layer, not only the gamma-MnO is improved 2 And the catalytic activity of the catalyst is greatly reduced, and the gamma-MnO content is greatly reduced 2 The plating layer is brittle, so that the stability of the electrode is better in the using process; ag-carbon fiber-beta-PbO doped in electro-deposition manganese dioxide plating solution 2 The addition of the composite particles and the Sn-Ru-TaOx coated hollow glass microspheres can increase the current density of the anode of the electrodeposition by 4More than twice of the gamma-MnO and no generation of roughness 2 And (7) plating.
Drawings
FIG. 1 is a schematic structural diagram of a titanium-based gradient composite manganese dioxide anode plate;
FIG. 2 isbase:Sub>A schematic sectional view taken along line A-A of FIG. 1;
FIG. 3 is a schematic cross-sectional view taken along line B-B of FIG. 2;
FIG. 4 is a schematic cross-sectional view taken along line C-C of FIG. 1;
in the figure: the composite material comprises, by weight, 1-a titanium-clad aluminum conductive beam, 1 a-a copper-aluminum composite conductive head, 2-a titanium-based oxide anode plate, 3-a titanium plate, 4-a titanium-clad aluminum composite rod, 5-a double-sided titanium net, 5 a-a titanium substrate, 5 b-a metal oxide intermediate layer, 5 c-a composite manganese dioxide active layer, 6-a titanium rod and 7-an insulator.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
The titanium-based gradient composite manganese dioxide anode plate (shown in figures 1-4) comprises a titanium-coated aluminum conductive beam 1 and a titanium-based oxide anode plate 2, wherein the titanium-based oxide anode plate 2 is fixedly arranged at the bottom end of the titanium-coated aluminum conductive beam 1, and an insulator 7 is arranged on the titanium-based oxide anode plate 2;
the titanium-based oxide anode plate 2 comprises a titanium plate 3, titanium-coated aluminum composite rods 4, a double-layer titanium net 5 and titanium rods 6, the top ends of the titanium plate 3 are fixedly connected with the bottom end of the titanium-coated aluminum conductive beam 1, the titanium-coated aluminum composite rods 4 are vertically arranged at the bottom end of the titanium plate 3, the titanium rods 6 are arranged at the bottom end of the titanium-coated aluminum composite rods 4, the titanium plate 3, the titanium-coated aluminum composite rods 4 and the titanium rods 6 form a titanium-based oxide anode plate frame, the double-layer titanium net 5 is arranged between the adjacent titanium-coated aluminum composite rods 4, the top ends of the double-layer titanium net 5 are fixedly connected with the titanium plate 3, and the bottom ends of the double-layer titanium net 5 are fixedly connected with the titanium rods 6; the titanium surface of the titanium-based oxide anode plate frame is sequentially coated with a metal oxide intermediate layer I and a composite manganese dioxide active layer, and the titanium surface of the double-layer titanium mesh 5, namely a titanium substrate 5a, is sequentially coated with a metal oxide intermediate layer II5b and a composite manganese dioxide active layer 5c;
the titanium-coated aluminum conductive beam 1 has the length of 600-1500 mm, the width of 20-50 mm and the height of 30 ∞60mm, the thickness of the titanium layer of the titanium-clad aluminum conductive beam 1 is 1-3 mm, one end of the titanium-clad aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head 1a, the length of the copper-aluminum composite conductive head 1a is 50-200 mm, the width of the copper-aluminum composite conductive head is 20-50 mm, the height of the copper-aluminum composite conductive head is 10-30 mm, the thickness of a titanium plate 3 is 3-5 mm, the titanium-clad aluminum composite rod 4 is round or square, wherein the diameter of round rod aluminum is round or square
The section length of the square aluminum is 4-10 mm, the width of the square aluminum is 1-4 mm, the thickness of a titanium layer of the titanium-coated aluminum composite rod 4 is 0.5-2 mm, the long axis of a double-layer titanium mesh of the double-layer titanium mesh 5 is 3-16 mm, and the short axis of the double-layer titanium mesh is 1-6 mm; the titanium rod 6 is a round rod or a square rod, wherein the diameter of the round rod is
The section length of the square bar is 4-10 mm, and the width is 3-5 mm; the thickness of the metal oxide intermediate layer I and the metal oxide intermediate layer II is 1-5 mu m, and the thickness of the composite manganese dioxide active layer is 0.3-2 mm;
the metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-doped carbon fiber-beta-PbO 2 Composite particles, sn-Ru-TaOx coated hollow glass microspheres and gamma-MnO 2 ；
The granularity of the carbon fiber is 1-10 mu m, and the Ag-carbon fiber-beta-PbO is doped 2 The particle size of the composite particles is 10-100 mu m, and the particle size of the hollow glass beads is 10-100 mu m;
the molar ratio of Pt, sn and Sb in the Pt-Sn-SbOx is 1-7;
the Ag-carbon fiber-beta-PbO is doped according to the mass percentage of the composite manganese dioxide active layer as 100 percent 2 1 to 6 percent of composite particles, 0.5 to 4 percent of Sn-Ru-TaOx coated hollow glass microspheres, 0.05 to 2 percent of W and the balance of gamma-MnO 2 (ii) a Ag-doped carbon fiber-beta-PbO 2 The composite particles contain 0.5-5% of Ag and carbon fiber powderThe amount is 0.1-1%, and the rest is beta-PbO 2 (ii) a The molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass bead is 40-50;
ag-doped carbon fiber-beta-PbO 2 The preparation method of the composite particles comprises the following specific steps:
taking stainless steel as an anode and a titanium mesh as a cathode, and electrodepositing for 4-8 h in an acidic lead nitrate composite plating solution to obtain the Ag-doped carbon fiber-beta-PbO 2 Composite coating doped with Ag-carbon fiber-beta-PbO 2 Stripping the composite coating and then ball-milling to obtain Ag-doped carbon fiber-beta-PbO 2 Composite particles; wherein the acid lead nitrate composite plating solution contains 50-200 g/L of lead nitrate, 0.5-20 g/L of silver nitrate, 4-20 g/L of thiourea and 4-20 g/L of carbon fiber particles, and the pH value of the acid lead nitrate composite plating solution is 0-2; the temperature of the electro-deposition is 60-90 ℃, and the current density is 6-12A/dm 2 ；
The preparation method of the Sn-Ru-TaOx coated hollow glass bead comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing moisture by rotary evaporation to obtain tin-ruthenium-tantalum precursor liquid;
2) Placing hollow glass beads at the temperature of 400-600 ℃, calcining for 0.5-2 h, immersing in a NaOH solution with the concentration of 5-10 wt.%, treating for 5-40 min at the temperature of 60-90 ℃, washing with deionized water, immersing in an HF solution with the concentration of 0.5-2 wt.% for treating for 1-5 min, deionizing, washing, and drying to obtain pretreated hollow glass beads;
3) Immersing the pretreated hollow glass microspheres in a tin-ruthenium-tantalum precursor liquid for 5-10min in an ultrasonic manner, drying at 100-150 ℃, then roasting at 300-560 ℃ for 10-20 min, repeating the ultrasonic immersion and roasting processes for 6-12 times, and then sintering at 400-480 ℃ for 1-2 h to obtain Sn-Ru-TaOx coated hollow glass microsphere composite particles;
the invention mixes Ag-carbon fiber-beta-PbO 2 Composite particles embedded with tungsten-containing gamma-MnO 2 In the coating layer, the gamma-MnO is greatly improved 2 Conducting performance and reducing internal stress of plating layer to make them be combinedThe service life of the manganese dioxide electrode is prolonged, and the cell voltage is reduced; simultaneously embedding Sn-Ru-TaOx coated hollow glass microspheres into tungsten-containing gamma-MnO 2 In the coating layer, not only the gamma-MnO is improved 2 And the catalytic activity of the catalyst is greatly reduced, and the gamma-MnO content is greatly reduced 2 The plating layer is brittle, so that the stability of the electrode is better in the using process; ag-carbon fiber-beta-PbO doped in electro-deposition manganese dioxide plating solution 2 The addition of the composite particles and the Sn-Ru-TaOx coated hollow glass microspheres can increase the current density of the anode of the electrodeposition by more than 4 times without generating coarse gamma-MnO 2 And (4) plating.
Example 1: the titanium-based gradient composite manganese dioxide anode plate of the embodiment (see figures 1-4);
the length of the titanium-clad aluminum conductive beam 1 is 1200mm, the width is 40mm, the height is 50mm, the thickness of the titanium layer of the titanium-clad aluminum conductive beam 1 is 2mm, one end of the titanium-clad aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head 1a, the length of the copper-aluminum composite conductive head 1a is 100mm, the width is 36mm, the height is 46mm, the thickness of a titanium plate 3 is 4mm, the titanium-clad aluminum composite rod 4 is round, and the diameter of round rod aluminum is round
The titanium layer of the titanium-coated aluminum composite rod 4 is 1.5mm in thickness, the long axis of the double-layer titanium mesh 5 is 10mm, the short axis of the double-layer titanium mesh is 5mm, and the section thickness of the double-layer titanium mesh is 1.0mm; the titanium rod 6 is a round rod, wherein the diameter of the round rod is
The thickness of the metal oxide intermediate layer I is 2 micrometers, the thickness of the metal oxide intermediate layer II is 3 micrometers, and the thickness of the composite manganese dioxide active layer is 0.4mm;
the metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-doped carbon fiber-beta-PbO 2 Composite particles, sn-Ru-TaOx coated hollow glass microspheres and gamma-MnO 2 ；
The granularity of the carbon fiber is 1 mu m, and the Ag-carbon fiber-beta-PbO is doped 2 The particle size of the composite particles is 10 mu m, and the particle size of the hollow glass beads is 10 mu m;
the molar ratio of Pt, sn and Sb in Pt-Sn-SbOx is 3;
the Ag-carbon fiber-beta-PbO is doped according to the mass percentage of the composite manganese dioxide active layer as 100 percent 2 1.0 percent of composite particles, 0.5 percent of Sn-Ru-TaOx coated hollow glass microspheres, 0.1 percent of W and the balance of gamma-MnO 2 (ii) a Ag-doped carbon fiber-beta-PbO 2 The composite particles comprise 0.5 mass percent of Ag, 0.1 mass percent of carbon fiber powder and the balance of beta-PbO 2 (ii) a The molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass bead is 30, and the mass of the Sn-Ru-TaOx oxide accounts for 1.0 percent of that of the Sn-Ru-TaOx coated hollow glass bead;
ag-doped carbon fiber-beta-PbO 2 The preparation method of the composite particles comprises the following specific steps:
taking stainless steel as an anode and a titanium mesh as a cathode, and carrying out electrodeposition for 4 hours in an acidic lead nitrate composite plating solution to obtain Ag-doped carbon fiber-beta-PbO 2 Composite coating doped with Ag-carbon fiber-beta-PbO 2 Stripping the composite coating and then ball-milling to obtain Ag-doped carbon fiber-beta-PbO 2 Composite particles; the acid lead nitrate composite plating solution contains 50g/L of lead nitrate, 0.5g/L of silver nitrate, 4g/L of thiourea and 4g/L of carbon fiber particles, and the pH value of the acid lead nitrate composite plating solution is 0; the temperature of the electrodeposition is 60 ℃ and the current density is 6A/dm 2 ；
The preparation method of the Sn-Ru-TaOx coated hollow glass bead comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing moisture by rotary evaporation to obtain tin-ruthenium-tantalum precursor liquid;
2) Placing hollow glass microspheres at 400 ℃ for calcining for 0.5h, immersing into a NaOH solution with the concentration of 5wt.%, treating at 60 ℃ for 5min, washing with deionized water, immersing into an HF solution with the concentration of 0.5wt.% for 1min, deionizing, washing, and drying to obtain pretreated hollow glass microspheres;
3) Immersing the pretreated hollow glass beads into a tin-ruthenium-tantalum precursor liquid for ultrasonic immersion for 5min, drying at 100 ℃, then roasting at 300 ℃ for 10min, repeating the ultrasonic immersion and roasting processes for 6 times, and then sintering at 480 ℃ for 1h to obtain Sn-Ru-TaOx coated hollow glass bead composite particles;
the preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) Degreasing and pickling the aluminum bar, immersing the aluminum bar into a NaOH solution with the concentration of 5wt.%, immersing the aluminum bar for 1min at the temperature of 40 ℃, cleaning the aluminum bar by using deionized water, and immersing the aluminum bar into HNO with the concentration of 10wt.% 3 Activating in the solution for 4min to obtain an activated aluminum bar; treating the inner wall of the titanium tube by using an HF solution with the concentration of 1wt.%, and cleaning by using deionized water to obtain a pretreated titanium tube; sleeving a pretreated titanium pipe outside an aluminum rod, extruding, drawing and compounding, performing hot rolling at 500 ℃ to obtain a titanium-coated aluminum composite rod, and welding the titanium-coated aluminum composite rod and an aluminum-copper composite conductive head (pulse argon protection aluminum-aluminum welding) to obtain a titanium-coated aluminum conductive beam;
(2) Welding a titanium plate, a titanium-clad aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame into a NaOH solution with the concentration of 10wt.%, immersing for 10min at the temperature of 50 ℃, carrying out heat treatment on the titanium-based oxide anode plate frame at the temperature of 400 ℃ after carrying out sand blasting surface treatment, carrying out heat treatment for 0.2h, then placing the titanium-based oxide anode plate frame into an oxalic acid solution with the concentration of 5wt.%, activating for 0.5h at the temperature of 80 ℃ to obtain an activated titanium-based oxide anode plate frame, coating a tin-antimony precursor solution on the surface of the activated titanium-based oxide anode plate frame, drying for 8min at the temperature of 100-120 ℃, placing the activated titanium-based oxide anode plate frame into a sintering pretreatment for 5min at the temperature of 400 ℃, repeating the processes of coating the tin-antimony precursor solution and sintering for 5 times, and then placing the activated titanium-based oxide anode plate frame into the temperature of 400 ℃ for sintering for 1h to obtain the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer;
(3) Immersing a titanium mesh formed by drawing into a NaOH solution with the concentration of 10wt.%, soaking for 10min at the temperature of 50 ℃, performing sand blasting surface treatment on the titanium mesh, performing heat treatment for 0.2h at the temperature of 400 ℃, then placing the titanium mesh into an oxalic acid solution with the concentration of 5wt.%, activating for 0.5h at the temperature of 80 ℃ to obtain an activated titanium mesh, coating platinum-tin-antimony precursor solution on the surface of the activated titanium mesh, drying for 8min at the temperature of 100-120 ℃, placing the titanium mesh in a sintering pretreatment for 5min at the temperature of 400 ℃, repeating the coating of the platinum-tin-antimony precursor solution and the sintering process for 5 times, and then placing the titanium mesh in the temperature of 400 ℃ for sintering for 1h to obtain the titanium mesh coated with Pt-Sn-SbOx; coating tin-antimony precursor liquid on the surface of the titanium net coated with Pt-Sn-SbOx, drying for 8min at the temperature of 100-120 ℃, sintering and pretreating for 5min at the temperature of 400 ℃, repeating the coating of the tin-antimony precursor liquid and the sintering process for 5 times, and then sintering for 1h at the temperature of 400 ℃ to obtain the titanium net coated with a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Argon arc welding the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer on the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-coated aluminum composite rods; placing a titanium-based oxide anode plate blank serving as an anode and a titanium plate serving as a cathode in a manganese nitrate composite electroplating solution, performing composite electrodeposition for 4 hours at the temperature of 80 ℃, cleaning by using deionized water, and blow-drying to obtain a titanium-based oxide anode plate; wherein the current density of the composite electrodeposition is 1A/dm 2 The stirring speed is 50rpm; the manganese nitrate composite electroplating solution contains 40g/L of manganese nitrate (Mn (NO) 3 ) 2 ) 10g/L nitric acid (HNO) 3 ) 10g/L sodium tungstate (Na) 2 WO 4 ) 10g/L Ag-doped carbon fiber-beta-PbO 2 The composite particles and the 4g/L Sn-Ru-TaOx coat the hollow glass microspheres;
(5) Welding the top end of a titanium plate of the titanium-based oxide anode plate at the bottom end of the titanium-clad aluminum conducting beam, and mounting an insulator on the titanium-based oxide anode plate to obtain a titanium-based gradient composite manganese dioxide anode plate;
the titanium-based gradient composite manganese dioxide anode plate is used for non-ferrous metal (zinc) electrodeposition, and the zinc ion concentration in zinc electrolyte is 50g/L, the sulfuric acid concentration is 150g/L, and 600mg/L C1 - The zinc electrodeposition is carried out at the temperature of 40 ℃, the electrical efficiency of the gradient composite manganese dioxide anode plate is improved by 3 percent compared with the traditional lead-silver (0.75 wt.%) alloy anode plate, the cell voltage is reduced by 8 percent, the service life is prolonged by 1.5 times, and the zinc of a cathode product 0# reaches more than 99 percent.
Example 2: the titanium-based gradient composite manganese dioxide anode plate of the embodiment (see fig. 1-4);
the titanium-clad aluminum conductive beam 1 has the length of 1200mm and the width of 40mm,The height is 50mm, the thickness of 1 titanium layer of titanium alclad aluminium conducting beam is 2mm, the welding of one end of titanium alclad aluminium conducting beam 1 has compound conductive head 1a of copper aluminium, the compound conductive head 1a of copper aluminium is long for 100mm, wide for 36mm, the height is 46mm, the thickness of titanium plate 3 is 4mm, compound stick 4 of titanium alclad aluminium is circular, wherein the diameter of pole aluminium is for the diameter of circle stick
The titanium layer of the titanium-coated aluminum composite rod 4 is 1.5mm in thickness, the long axis of the double-layer titanium mesh 5 is 10mm, the short axis of the double-layer titanium mesh is 5mm, and the section thickness of the double-layer titanium mesh is 1.5mm; the titanium rod 6 is a round rod, wherein the diameter of the round rod is
The thickness of the metal oxide intermediate layer I is 3 micrometers, the thickness of the metal oxide intermediate layer II is 4 micrometers, and the thickness of the composite manganese dioxide active layer is 1mm;
the metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-doped carbon fiber-beta-PbO 2 Composite particles, sn-Ru-TaOx coated hollow glass microspheres and gamma-MnO 2 (ii) a The granularity of the carbon fiber is 5 mu m, and the Ag-carbon fiber-beta-PbO is doped 2 The particle size of the composite particles is 50 microns, and the particle size of the hollow glass beads is 50 microns; the molar ratio of Pt, sn and Sb in Pt-Sn-SbOx is 5;
the Ag-carbon fiber-beta-PbO is doped according to the mass percentage of the composite manganese dioxide active layer as 100 percent 2 3 percent of composite particles, 0.5 percent of Sn-Ru-TaOx coated hollow glass microspheres, 1.0 percent of W and the balance of gamma-MnO 2 (ii) a Ag-doped carbon fiber-beta-PbO 2 The composite particles comprise 3 mass percent of Ag, 0.5 mass percent of carbon fiber powder and the balance of beta-PbO 2 (ii) a The molar ratio of Sn to Ru to Ta in the Sn-Ru-TaOx coated hollow glass bead is 45;
ag-doped carbon fiber-beta-PbO 2 The preparation method of the composite particles comprises the following specific steps:
by stainless steelTaking steel as an anode and a titanium mesh as a cathode, and electrodepositing for 6 hours in the acidic lead nitrate composite plating solution to obtain the Ag-doped carbon fiber-beta-PbO 2 Composite coating doped with Ag-carbon fiber-beta-PbO 2 Stripping the composite coating, and ball-milling to obtain Ag-doped carbon fiber-beta-PbO 2 Composite particles; the acid lead nitrate composite plating solution contains 150g/L of lead nitrate, 10g/L of silver nitrate, 16g/L of thiourea and 12g/L of carbon fiber particles, and the pH value of the acid lead nitrate composite plating solution is 1; the electrodeposition temperature was 75 ℃ and the current density was 10A/dm 2 ；
The preparation method of the Sn-Ru-TaOx coated hollow glass bead comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing moisture by rotary evaporation to obtain tin-ruthenium-tantalum precursor liquid;
2) Calcining the hollow glass microspheres at 500 ℃ for 1.5h, immersing the hollow glass microspheres in a NaOH solution with the concentration of 8wt.%, treating the hollow glass microspheres at 70 ℃ for 20min, washing the hollow glass microspheres with deionized water, immersing the hollow glass microspheres in a HF solution with the concentration of 1.2wt.% for 3min, and performing deionization washing and drying to obtain pretreated hollow glass microspheres;
3) Immersing the pretreated hollow glass microsphere into tin-ruthenium-tantalum precursor liquid for 8min by ultrasonic immersion, drying at 120 ℃, roasting for 15min at 500 ℃, repeating the ultrasonic immersion and roasting processes for 10 times, and sintering for 2h at 480 ℃ to obtain Sn-Ru-TaOx coated hollow glass microsphere composite particles;
the preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) Degreasing and pickling the aluminum bar, immersing the aluminum bar into 8wt.% NaOH solution, immersing the aluminum bar for 3min at the temperature of 60 ℃, cleaning the aluminum bar by using deionized water, and immersing the aluminum bar into 20wt.% HNO 3 Activating in the solution for 6min to obtain an activated aluminum bar; treating the inner wall of the titanium tube by using an HF solution with the concentration of 5wt.%, and cleaning by using deionized water to obtain a pretreated titanium tube; pre-processing a titanium pipe, sleeving the titanium pipe outside an aluminum rod, extruding, drawing and compounding, hot rolling at the temperature of 600 ℃ to obtain a titanium-coated aluminum composite rod, and welding the titanium-coated aluminum composite rod and an aluminum-copper composite conductive head (pulse argon protection aluminum-aluminum welding) to obtain a titanium-coated aluminum conductorAn electric beam;
(2) Welding a titanium plate, a titanium-clad aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame in a NaOH solution with the concentration of 15wt.%, immersing the titanium-based oxide anode plate frame for 20min at the temperature of 60 ℃, performing sand blasting surface treatment on the titanium-based oxide anode plate frame, performing heat treatment for 1.0h at the temperature of 600 ℃, then placing the titanium-based oxide anode plate frame in an oxalic acid solution with the concentration of 20wt.%, activating the titanium-based oxide anode plate frame for 1.0h at the temperature of 100 ℃ to obtain an activated titanium-based oxide anode plate frame, coating a tin-antimony precursor solution on the surface of the activated titanium-based oxide anode plate frame, drying the activated titanium-based oxide anode plate frame for 10min at the temperature of 120 ℃, placing the activated titanium-based oxide anode plate frame at the temperature of 600 ℃ for sintering pretreatment for 8min, repeating the processes of coating the tin-antimony precursor solution and sintering for 7 times, and then placing the titanium-based oxide anode plate frame at the temperature of 550 ℃ for sintering for 1.5h to obtain the titanium-based oxide anode plate frame coated with a metal oxide Sn-SbOx intermediate layer;
(3) Soaking a titanium net formed by drawing in a NaOH solution with the concentration of 15wt.%, soaking for 20min at the temperature of 70 ℃, performing sand blasting surface treatment on the titanium net, performing heat treatment for 1.0h at the temperature of 600 ℃, then placing the titanium net in an oxalic acid solution with the concentration of 20wt.%, activating for 1.0h at the temperature of 100 ℃ to obtain an activated titanium net, coating platinum-tin-antimony precursor solution on the surface of the activated titanium net, drying for 10min at the temperature of 100 ℃, placing the titanium net in sintering pretreatment for 8min at the temperature of 600 ℃, repeating the coating of the platinum-tin-antimony precursor solution and the sintering process for 7 times, and then placing the titanium net in sintering for 1.5h at the temperature of 550 ℃ to obtain the titanium net coated with Pt-Sn-SbOx; coating tin-antimony precursor liquid on the surface of the titanium mesh coated with Pt-Sn-SbOx, drying at 100 ℃ for 10min, sintering at 600 ℃ for 8min, repeating the coating of the tin-antimony precursor liquid and the sintering process for 7 times, and sintering at 500 ℃ for 1.5h to obtain the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Argon arc welding the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer on the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-coated aluminum composite rods; placing the titanium-based oxide anode plate blank as an anode and the titanium plate as a cathode in manganese nitrate composite electroplating solution at a temperaturePerforming composite electrodeposition for 10 hours at the temperature of 90 ℃, cleaning by using deionized water, and blow-drying to obtain a titanium-based oxide anode plate; wherein the current density of the composite electrodeposition is 3A/dm 2 The stirring speed is 150rpm; the manganese nitrate composite electroplating solution contains 80g/L of manganese nitrate (Mn (NO) 3 ) 2 ) 20g/L nitric acid (HNO) 3 ) 30g/L sodium tungstate (Na) 2 WO 4 ) 20g/L Ag-doped carbon fiber-beta-PbO 2 The composite particles and the Sn-Ru-TaOx with the concentration of 20g/L coat the hollow glass microspheres;
(5) Welding the top end of a titanium plate of the titanium-based oxide anode plate at the bottom end of the titanium-clad aluminum conducting beam, and mounting an insulator on the titanium-based oxide anode plate to obtain a titanium-based gradient composite manganese dioxide anode plate;
the titanium-based gradient composite manganese dioxide anode plate is used for non-ferrous metal (zinc) electrodeposition, and the zinc ion concentration in zinc electrolyte is 50g/L, the sulfuric acid concentration is 150g/L, and 600mg/L C1 - The zinc electrodeposition is carried out at the temperature of 40 ℃, the electrical efficiency of the gradient composite manganese dioxide anode plate is improved by 4 percent compared with the traditional lead-silver (0.75 wt.%) alloy anode plate, the cell voltage is reduced by 18 percent, the service life is prolonged by 2 times, and the zinc of the cathode product No. 0 reaches more than 99 percent.
Example 3: the titanium-based gradient composite manganese dioxide anode plate of the embodiment (see fig. 1-4);
the length of the titanium-clad aluminum conductive beam 1 is 1300mm, the width is 20mm, the height is 40mm, the thickness of a titanium layer of the titanium-clad aluminum conductive beam 1 is 1mm, one end of the titanium-clad aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head 1a, the length of the copper-aluminum composite conductive head 1a is 100mm, the width is 18mm, the height is 38mm, the thickness of a titanium plate 3 is 3mm, a titanium-clad aluminum composite rod 4 is square, the section length of the square aluminum is 4mm, the width is 1mm, the thickness of a titanium layer of the titanium-clad aluminum composite rod 4 is 0.5mm, the long axis of a double-layer titanium mesh 5 is 3mm, the short axis is 1mm, and the section thickness is 0.5mm; the titanium rod 6 is a square rod, wherein the section of the square rod is 4mm in length and 3mm in width, the thickness of the metal oxide intermediate layer I is 1 micrometer, the thickness of the metal oxide intermediate layer II is 2 micrometers, and the thickness of the composite manganese dioxide active layer is 0.3mm;
the metal oxide interlayer I is Sn-SbOx, the metal oxide interlayer II is Pd-Ti-Sn-SbOx/Sn-SbOx oxide interlayer,the active layer of the composite manganese dioxide contains Ag-doped carbon fiber-beta-PbO 2 Composite particles, sn-Ru-TaOx coated hollow glass microspheres and gamma-MnO 2 (ii) a The granularity of the carbon fiber is 1 mu m, and the Ag-carbon fiber-beta-PbO is doped 2 The particle size of the composite particles is 10 mu m, and the particle size of the hollow glass beads is 10 mu m; the mole ratio of Pt, ti, sn and Sb in Pd-Ti-Sn-SbOx is 3;
the Ag-carbon fiber-beta-PbO is doped according to the mass percentage of the composite manganese dioxide active layer as 100 percent 2 1 percent of composite particles, 0.5 percent of Sn-Ru-TaOx coated hollow glass microspheres, 0.1 percent of W and the balance of gamma-MnO 2 (ii) a Ag-doped carbon fiber-beta-PbO 2 The composite particles comprise 0.5 percent of Ag, 0.1 percent of carbon fiber powder and the balance of beta-PbO 2 (ii) a The molar ratio of Sn to Ru to Ta in the Sn-Ru-TaOx coated hollow glass bead is 30, and the mass of Sn-Ru-TaOx oxide accounts for 1 percent of that of the Sn-Ru-TaOx coated hollow glass bead;
ag-doped carbon fiber-beta-PbO 2 The preparation method of the composite particles comprises the following specific steps:
taking stainless steel as an anode and a titanium mesh as a cathode, and carrying out electrodeposition for 4 hours in an acidic lead nitrate composite plating solution to obtain Ag-doped carbon fiber-beta-PbO 2 Composite coating doped with Ag-carbon fiber-beta-PbO 2 Stripping the composite coating and then ball-milling to obtain the Ag-doped carbon fiber-beta-PbO 2 Composite particles; wherein the acid lead nitrate composite plating solution contains 50g/L of lead nitrate, 0.5g/L of silver nitrate, 4g/L of thiourea and 4g/L of carbon fiber particles, and the pH value of the acid lead nitrate composite plating solution is; the electrodeposition temperature was 60 ℃ and the current density was 6A/dm 2 ；
The preparation method of the Sn-Ru-TaOx coated hollow glass bead comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing moisture by rotary evaporation to obtain tin-ruthenium-tantalum precursor liquid;
2) Calcining the hollow glass microspheres at 400 ℃ for 0.5h, immersing the hollow glass microspheres in a NaOH solution with the concentration of 5wt.% for 5min at 60 ℃, washing the hollow glass microspheres with deionized water, immersing the hollow glass microspheres in an HF solution with the concentration of 0.5wt.% for 1min, and then carrying out deionization washing and drying to obtain pretreated hollow glass microspheres;
3) Immersing the pretreated hollow glass microsphere into tin-ruthenium-tantalum precursor liquid for ultrasonic immersion for 5min, drying at 100 ℃, roasting at 300 ℃ for 10min, repeating the ultrasonic immersion and roasting processes for 6 times, and sintering at 480 ℃ for 1h to obtain Sn-Ru-TaOx coated hollow glass microsphere composite particles;
the preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) Degreasing and acid washing an aluminum bar, immersing the aluminum bar into a NaOH solution with the concentration of 5wt.%, immersing the aluminum bar for 1min at the temperature of 40 ℃, cleaning the aluminum bar by using deionized water, and immersing the aluminum bar into HNO with the concentration of 10wt.% 3 Activating in the solution for 4min to obtain an activated aluminum bar; treating the inner wall of the titanium tube by using an HF solution with the concentration of 1wt.%, and cleaning by using deionized water to obtain a pretreated titanium tube; sleeving a pretreated titanium pipe outside an aluminum rod, extruding, drawing and compounding, performing hot rolling at 500 ℃ to obtain a titanium-coated aluminum composite rod, and welding the titanium-coated aluminum composite rod and an aluminum-copper composite conductive head (pulse argon protection aluminum-aluminum welding) to obtain a titanium-coated aluminum conductive beam;
(2) Welding a titanium plate, a titanium-coated aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame into a NaOH solution with the concentration of 10wt.%, immersing for 10min at the temperature of 50 ℃, performing heat treatment on the titanium-based oxide anode plate frame at the temperature of 400 ℃ after sand blasting surface treatment, then placing the titanium-based oxide anode plate frame into an oxalic acid solution with the concentration of 5wt.%, activating for 0.5h at the temperature of 80 ℃ to obtain an activated titanium-based oxide anode plate frame, coating a tin-antimony precursor solution on the surface of the activated titanium-based oxide anode plate frame, drying for 5min at the temperature of 120 ℃, placing the activated titanium-based oxide anode plate frame at the temperature of 400 ℃ for sintering pretreatment for 5min, repeating the processes of coating the tin-antimony precursor solution and sintering for 3 times, and then placing the activated titanium-based oxide anode plate frame at the temperature of 400 ℃ for sintering for 1h to obtain the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer;
(3) Immersing a titanium net formed by drawing into a NaOH solution with the concentration of 10wt.%, soaking for 10min at the temperature of 50 ℃, performing sand blasting surface treatment on the titanium net, performing heat treatment for 0.2h at the temperature of 400 ℃, then placing the titanium net into an oxalic acid solution with the concentration of 5wt.%, activating for 0.5h at the temperature of 80 ℃ to obtain an activated titanium net, coating palladium-titanium-tin-antimony precursor solution on the surface of the activated titanium net, drying for 8min at the temperature of 100-120 ℃, placing the titanium net in a sintering pretreatment for 5min at the temperature of 400 ℃, repeating the coating of the palladium-titanium-tin-antimony precursor solution and the sintering process for 3 times, and then placing the titanium net in the sintering process for 1h at the temperature of 400 ℃ to obtain the titanium net coated with Pd-Ti-Sn-SbOx; coating tin-antimony precursor liquid on the surface of the titanium mesh coated with Pd-Ti-Sn-SbOx, drying at 100-120 ℃ for 8min, sintering at 400 ℃ for 5min, repeating the coating of tin-antimony precursor liquid and the sintering process for 3 times, and sintering at 400 ℃ for 1.0h to obtain the titanium mesh coated with the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Argon arc welding the titanium mesh coated with the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer on the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-coated aluminum composite rods; placing a titanium-based oxide anode plate blank serving as an anode and a titanium plate serving as a cathode in manganese nitrate composite electroplating solution, performing composite electrodeposition for 4 hours at the temperature of 80 ℃, cleaning by using deionized water, and blow-drying to obtain a titanium-based oxide anode plate; wherein the current density of the composite electrodeposition is 1A/dm 2 The stirring speed is 50rpm; the manganese nitrate composite electroplating solution contains 20g/L of manganese nitrate (Mn (NO) 3 ) 2 ) 10g/L nitric acid (HNO) 3 ) 10g/L sodium tungstate (Na) 2 WO 4 ) 10g/L Ag-doped carbon fiber-beta-PbO 2 The composite particles and the 4g/LSn-Ru-TaOx coat the hollow glass microspheres;
(5) Welding the top end of a titanium plate of the titanium-based oxide anode plate at the bottom end of the titanium-clad aluminum conducting beam, and mounting an insulator on the titanium-based oxide anode plate to obtain a titanium-based gradient composite manganese dioxide anode plate;
the titanium-based gradient composite manganese dioxide anode plate is used for electrodeposition of nonferrous metal (copper), the concentration of copper ions in copper electrolyte is 45g/L, the concentration of sulfuric acid is 180g/L, and the concentration is 100mg/L C1 - Ions, copper electrodeposition is carried out at the temperature of 50 ℃, and the electrical efficiency of the gradient composite manganese dioxide anode plate is higher than that of the traditional lead-calcium (0.07 wt.%) -tin(1.25 wt.%) the alloy anode plate is improved by 3%, the cell voltage is reduced by 10%, the service life is prolonged by 1 time, and the zinc of cathode product No. 0 reaches more than 99%.
Example 4: the titanium-based gradient composite manganese dioxide anode plate of the embodiment (see fig. 1-4);
the length of the titanium-clad aluminum conductive beam 1 is 1300mm, the width of the titanium-clad aluminum conductive beam is 50mm, the height of the titanium layer of the titanium-clad aluminum conductive beam 1 is 60mm, the thickness of the titanium layer of the titanium-clad aluminum conductive beam 1 is 3mm, one end of the titanium-clad aluminum conductive beam 1 is welded with a copper-aluminum composite conductive head 1a, the length of the copper-aluminum composite conductive head 1a is 120mm, the width of the copper-aluminum composite conductive head is 44mm, the height of the copper-aluminum composite conductive head is 54mm, the thickness of a titanium plate 3 is 2mm, the titanium-clad aluminum composite rod 4 is square, the section length of the square aluminum is 10mm, the width of the square aluminum is 4mm, the thickness of the titanium layer of the titanium-clad aluminum composite rod 4 is 2mm, the long axis of a double-layer titanium mesh of the double-layer titanium mesh 5 is 16mm, the short axis is 6mm, and the section thickness of the double-layer titanium mesh is 0.7mm; the titanium rod 6 is a square rod, wherein the cross section of the square rod is 10mm in length and 5mm in width, the thickness of the metal oxide intermediate layer I is 5 micrometers, the thickness of the metal oxide intermediate layer II is 5 micrometers, and the thickness of the composite manganese dioxide active layer is 2mm;
the metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-doped carbon fiber-beta-PbO 2 Composite particles, sn-Ru-TaOx coated hollow glass microspheres and gamma-MnO 2 (ii) a The granularity of the carbon fiber is 10 mu m, and the Ag-carbon fiber-beta-PbO is doped 2 The particle size of the composite particles is 100 microns, and the particle size of the hollow glass beads is 100 microns; the molar ratio of Pt, sn and Sb in Pd-Ti-Sn-SbOx is 3;
the Ag-carbon fiber-beta-PbO is doped according to the mass percentage of the composite manganese dioxide active layer as 100 percent 2 6 percent of composite particles, 4 percent of Sn-Ru-TaOx coated hollow glass microspheres, 1.8 percent of W and the balance of gamma-MnO 2 (ii) a Ag-doped carbon fiber-beta-PbO 2 The composite particles comprise 5 mass percent of Ag, 1 mass percent of carbon fiber powder and the balance of beta-PbO 2 (ii) a The molar ratio of Sn to Ru to Ta in the Sn-Ru-TaOx coated hollow glass bead is 1;
ag-doped carbon fiber-β-PbO 2 The preparation method of the composite particles comprises the following specific steps:
taking stainless steel as an anode and a titanium mesh as a cathode, and carrying out electrodeposition for 8 hours in an acidic lead nitrate composite plating solution to obtain Ag-doped carbon fiber-beta-PbO 2 Composite coating doped with Ag-carbon fiber-beta-PbO 2 Stripping the composite coating and then ball-milling to obtain Ag-doped carbon fiber-beta-PbO 2 Composite particles; wherein the acid lead nitrate composite plating solution contains 150g/L of lead nitrate, 20g/L of silver nitrate, 20g/L of thiourea and 20g/L of carbon fiber particles, and the pH value of the acid lead nitrate composite plating solution is 2; the temperature of the electrodeposition is 90 ℃, and the current density is 12A/dm 2 ；
The preparation method of the Sn-Ru-TaOx coated hollow glass bead comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing moisture by rotary evaporation to obtain tin-ruthenium-tantalum precursor liquid;
2) Calcining the hollow glass microspheres at 600 ℃ for 2h, immersing the hollow glass microspheres in a NaOH solution with the concentration of 10wt.%, treating the hollow glass microspheres at 90 ℃ for 40min, washing the hollow glass microspheres with deionized water, immersing the hollow glass microspheres in an HF solution with the concentration of 2wt.% for 5min, deionizing, washing and drying to obtain pretreated hollow glass microspheres;
3) Immersing the pretreated hollow glass microsphere into tin-ruthenium-tantalum precursor liquid for ultrasonic immersion for 10min, drying at 100 ℃, then roasting for 20min at 560 ℃, repeating the ultrasonic immersion and roasting processes for 12 times, and then sintering for 2h at 480 ℃ to obtain Sn-Ru-TaOx coated hollow glass microsphere composite particles;
the preparation method of the titanium-based gradient composite manganese dioxide anode plate comprises the following specific steps:
(1) Degreasing and pickling the aluminum bar, immersing the aluminum bar into a NaOH solution with the concentration of 15wt.%, immersing the aluminum bar for 5min at the temperature of 70 ℃, cleaning the aluminum bar by using deionized water, and immersing the aluminum bar into HNO with the concentration of 40wt.% 3 Activating in the solution for 8min to obtain an activated aluminum bar; treating the inner wall of the titanium tube by using an HF solution with the concentration of 10wt.%, and cleaning by using deionized water to obtain a pretreated titanium tube; sleeving a pretreated titanium pipe outside an aluminum rod, extruding, drawing and compounding, and hot rolling at 700 ℃ to obtain a titanium-coated aluminum composite rodWelding the composite rod with an aluminum-copper composite conductive head (pulse argon protection aluminum-aluminum welding) to obtain a titanium-clad aluminum conductive beam;
(2) Welding a titanium plate, a titanium-coated aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, immersing the titanium-based oxide anode plate frame into a NaOH solution with the concentration of 20wt.%, soaking the titanium-based oxide anode plate frame at the temperature of 80 ℃ for 30min, performing sand blasting surface treatment on the titanium-based oxide anode plate frame, performing heat treatment at the temperature of 700 ℃ for 1.5h, then placing the titanium-based oxide anode plate frame into an oxalic acid solution with the concentration of 30wt.%, activating the titanium-based oxide anode plate frame at the temperature of 100 ℃ for 2.0h to obtain an activated titanium-based oxide anode plate frame, coating a tin-antimony precursor solution on the surface of the activated titanium-based oxide anode plate frame, drying the activated titanium-based oxide anode plate frame at the temperature of 110 ℃ for 8min, placing the activated titanium-based oxide anode plate frame at the temperature of 700 ℃ for sintering pretreatment for 10min, repeating the tin-antimony precursor solution coating and sintering processes for 10 times, and then placing the activated titanium-based oxide anode plate frame at the temperature of 600 ℃ for sintering for 2h to obtain the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer;
(3) Immersing a titanium mesh formed by drawing in a NaOH solution with the concentration of 20wt.%, soaking for 30min at the temperature of 80 ℃, performing sand blasting surface treatment on the titanium mesh, performing heat treatment for 1.5h at the temperature of 700 ℃, then placing the titanium mesh in an oxalic acid solution with the concentration of 30wt.%, activating for 2.0h at the temperature of 80 ℃ to obtain an activated titanium mesh, coating a palladium-titanium-tin-antimony precursor solution on the surface of the activated titanium mesh, drying for 8min at the temperature of 120 ℃, placing the titanium mesh in a sintering pretreatment for 10min at the temperature of 600 ℃, repeating the coating of the palladium-titanium-tin-antimony precursor solution and the sintering process for 10 times, and then placing the titanium mesh in the sintering process at the temperature of 600 ℃ for 2h to obtain the titanium mesh coated with Pd-Ti-Sn-SbOx; coating tin-antimony precursor liquid on the surface of the titanium mesh coated with Pd-Ti-Sn-SbOx, drying at 120 ℃ for 8min, sintering at 600 ℃ for 10min, repeating the coating of tin-antimony precursor liquid and the sintering process for 10 times, and sintering at 600 ℃ for 2h to obtain the titanium mesh coated with the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Argon arc welding the titanium mesh coated with the Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer on the titanium-based oxide anode plate frame coated with the metal oxide Sn-SbOx intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer is positioned between adjacent titanium-coated aluminum composite rods; with titanium basePlacing the oxide anode plate blank as an anode and a titanium plate as a cathode in manganese nitrate composite electroplating solution, performing composite electrodeposition at 100 ℃ for 20 hours, cleaning with deionized water, and blow-drying to obtain a titanium-based oxide anode plate; wherein the current density of the composite electrodeposition is 5A/dm 2 The stirring speed is 300rpm; the manganese nitrate composite plating solution contains 100g/L of manganese nitrate (Mn (NO) 3 ) 2 ) 30g/L nitric acid (HNO) 3 ) 40g/L sodium tungstate (Na) 2 WO 4 ) 30g/L Ag-doped carbon fiber-beta-PbO 2 The composite particles and 30g/L Sn-Ru-TaOx coat the hollow glass microspheres;
(5) Welding the top end of a titanium plate of the titanium-based oxide anode plate at the bottom end of the titanium-clad aluminum conducting beam, and mounting an insulator on the titanium-based oxide anode plate to obtain a titanium-based gradient composite manganese dioxide anode plate;
the titanium-based gradient composite manganese dioxide anode plate is used for electrodeposition of nonferrous metal (copper), the concentration of copper ions in copper electrolyte is 45g/L, the concentration of sulfuric acid is 180g/L, and the concentration is 100mg/L C1 - And ions are subjected to copper electrodeposition at the temperature of 50 ℃, the electrical efficiency of the gradient composite manganese dioxide anode plate is improved by 3 percent compared with that of the traditional lead-calcium (0.07 wt.%) -tin (1.25 wt.%) alloy anode plate, the cell voltage is reduced by 15 percent, the service life is prolonged by 2 times, and the zinc of a cathode product No. 0 reaches more than 99 percent.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A titanium-based gradient composite manganese dioxide anode plate is characterized in that: the conductive beam comprises a titanium-coated aluminum conductive beam (1) and a titanium-based oxide anode plate (2), wherein the titanium-based oxide anode plate (2) is fixedly arranged at the bottom end of the titanium-coated aluminum conductive beam (1), and an insulator (7) is arranged on the titanium-based oxide anode plate (2);
the titanium-based oxide anode plate (2) comprises a titanium plate (3), a titanium-coated aluminum composite rod (4), a double-layer titanium net (5) and a titanium rod (6), the top end of the titanium plate (3) is fixedly connected with the bottom end of the titanium-coated aluminum conductive beam (1), the titanium-coated aluminum composite rod (4) is vertically arranged at the bottom end of the titanium plate (3), the titanium rod (6) is arranged at the bottom end of the titanium-coated aluminum composite rod (4), the titanium plate (3), the titanium-coated aluminum composite rod (4) and the titanium rod (6) form a titanium-based oxide anode plate frame, the double-layer titanium net (5) is arranged between the adjacent titanium-coated aluminum composite rods (4), the top end of the double-layer titanium net (5) is fixedly connected with the titanium plate (3), and the bottom end of the double-layer titanium net (5) is fixedly connected with the titanium rod (6); the titanium surface of the titanium-based oxide anode plate frame is sequentially coated with a metal oxide intermediate layer I and a composite manganese dioxide active layer, and the titanium surface of the double-layer titanium net (5) is sequentially coated with a metal oxide intermediate layer II and a composite manganese dioxide active layer.
2. The titanium-based gradient composite manganese dioxide anode plate of claim 1, characterized in that: the thickness of a titanium layer of the titanium-clad aluminum conductive beam (1) is 1-3 mm, one end of the titanium-clad aluminum conductive beam (1) is welded with a copper-aluminum composite conductive head, the thickness of a titanium plate (3) is 3-5 mm, the thickness of a titanium layer of a titanium-clad aluminum composite rod (4) is 0.5-2 mm, a long double-layer titanium mesh hole of a double-layer titanium mesh (5) is 3-16 mm, a short shaft is 1-6 mm, and the thickness of the cross section is 0.5-3 mm; the thickness of the metal oxide intermediate layer I and the metal oxide intermediate layer II is 1-5 mu m, and the thickness of the composite manganese dioxide active layer is 0.3-2 mm.
3. The titanium-based gradient composite manganese dioxide anode plate of claim 1, characterized in that: the metal oxide intermediate layer I is Sn-SbOx, the metal oxide intermediate layer II is a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer, and the composite manganese dioxide active layer contains Ag-doped carbon fiber-beta-PbO 2 Composite particles, sn-Ru-TaOx coated hollow glass microspheres and gamma-MnO 2 。
4. The titanium-based gradient composite manganese dioxide anode plate of claim 3, wherein: the granularity of the carbon fiber is 1-10 mu m, and the Ag-carbon fiber-beta-PbO is doped 2 The particle size of the composite particles is 10-100 mu m, and the particle size of the hollow glass beads is 10-100 mu m.
5. The titanium-based gradient composite manganese dioxide anode plate of claim 3, wherein: the molar ratio of Pt, sn and Sb in the Pt-Sn-SbOx is 1-7.
6. The titanium-based gradient composite manganese dioxide anode plate of claim 3, wherein: the Ag-carbon fiber-beta-PbO is doped according to the mass percentage of the composite manganese dioxide active layer as 100 percent 2 1 to 6 percent of composite particles, 0.5 to 4 percent of Sn-Ru-TaOx coated hollow glass microspheres, 0.05 to 2 percent of W and the balance of gamma-MnO 2 (ii) a Ag-doped carbon fiber-beta-PbO 2 The composite particles comprise 0.5-5 wt% of Ag, 0.1-1 wt% of carbon fiber powder and the balance of beta-PbO 2 (ii) a The molar ratio of Sn, ru and Ta in the Sn-Ru-TaOx coated hollow glass bead is 40-50.
7. The titanium-based gradient composite manganese dioxide anode plate of claim 3, wherein: ag-doped carbon fiber-beta-PbO 2 The preparation method of the composite particles comprises the following specific steps:
taking stainless steel as an anode and a titanium mesh as a cathode, and electrodepositing for 4-8 h in the acidic lead nitrate composite plating solution to obtain the Ag-doped carbon fiber-beta-PbO 2 Composite coating doped with Ag-carbon fiber-beta-PbO 2 Stripping the composite coating and then ball-milling to obtain the Ag-doped carbon fiber-beta-PbO 2 Composite particles; wherein the acid lead nitrate composite plating solution contains 50-200 g/L of lead nitrate, 0.5-20 g/L of silver nitrate, 4-20 g/L of thiourea and 4-20 g/L of carbon fiber particles, and the pH value of the acid lead nitrate composite plating solution is 0-2; the temperature of the electro-deposition is 60-90 ℃, and the current density is 6-12A/dm 2 。
8. The titanium-based gradient composite manganese dioxide anode plate of claim 3, wherein: the preparation method of the Sn-Ru-TaOx coated hollow glass bead comprises the following specific steps:
1) Dissolving tin chloride, ruthenium chloride and tantalum chloride in concentrated hydrochloric acid, adding n-butanol solvent, and removing moisture by rotary evaporation to obtain tin-ruthenium-tantalum precursor liquid;
2) Placing the hollow glass microspheres at 400-600 ℃ for calcining for 0.5-2 h, immersing into a NaOH solution with the concentration of 5-10 wt.%, treating at 60-90 ℃ for 5-40 min, washing with deionized water, immersing into an HF solution with the concentration of 0.5-2 wt.% for treating for 1-5 min, deionizing, washing, and drying to obtain pretreated hollow glass microspheres;
3) Immersing the pretreated hollow glass microspheres in a tin-ruthenium-tantalum precursor liquid for ultrasonic soaking for 5-10 min, drying, roasting at the temperature of 300-560 ℃ for 10-20 min, repeating the ultrasonic soaking and roasting processes for 6-12 times, and sintering at the temperature of 400-480 ℃ for 1-2 h to obtain the Sn-Ru-TaOx coated hollow glass microsphere composite particles.
9. The preparation method of the titanium-based gradient composite manganese dioxide anode plate of claims 1 to 8 is characterized in that: the method comprises the following specific steps:
(1) After oil removal and acid cleaning, the aluminum bar is immersed into NaOH solution for 1-5 min, washed by deionized water and then immersed into HNO 3 Activating in the solution for 4-8 min to obtain an activated aluminum bar; treating the inner wall of the titanium tube by using an HF solution, and cleaning by using deionized water to obtain a pretreated titanium tube; the titanium-coated aluminum composite bar is prepared by hot rolling, and the titanium-coated aluminum composite bar is welded with the aluminum-copper composite conductive head to obtain a titanium-coated aluminum conductive beam;
(2) Welding a titanium plate, a titanium-clad aluminum composite rod and a titanium rod to form a titanium-based oxide anode plate frame, soaking the titanium-based oxide anode plate frame in NaOH solution for 10-30 min, carrying out heat treatment on the titanium-based oxide anode plate frame after sand blasting surface treatment, then placing the titanium-based oxide anode plate frame in oxalic acid solution for activation for 0.5-2.0 h to obtain an activated titanium-based oxide anode plate frame, coating tin-antimony precursor liquid on the surface of the activated titanium-based oxide anode plate frame, drying, carrying out sintering pretreatment for 5-10 min, repeating the coating of the tin-antimony precursor liquid and the sintering process for 3-10 times, and then placing the frame at the temperature of 400-600 ℃ for sintering for 1-2 h to obtain the titanium-based oxide anode plate frame coated with a metal oxide interlayer;
(3) Immersing the titanium mesh formed by drawing into NaOH solution for 10-30 min, carrying out heat treatment after carrying out sand blasting surface treatment on the titanium mesh, then placing the titanium mesh in oxalic acid solution for activation for 0.5-2.0 h to obtain an activated titanium mesh, coating platinum-tin-antimony precursor solution or palladium-titanium-tin-antimony precursor solution on the surface of the activated titanium mesh, drying and sintering for 5-10 min, repeating the coating and sintering processes for 3-10 times, and then placing the titanium mesh at the temperature of 400-600 ℃ for sintering for 1-2 h to obtain the titanium mesh coated with Pt-Sn-SbOx or Pd-Ti-Sn-Sb; coating a tin-antimony precursor solution on the surface of a titanium net coated with Pt-Sn-SbOx or Pd-Ti-Sn-Sb, drying, sintering for 5-10 min, repeating the coating of the tin-antimony precursor solution for 3-5 times and the sintering process, and then sintering at 400-600 ℃ for 1-2 h to obtain the titanium net coated with a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer;
(4) Welding a titanium mesh coated with a Pt-Sn-SbOx/Sn-SbOx oxide intermediate layer or a Pd-Ti-Sn-SbOx/Sn-SbOx oxide intermediate layer on a titanium-based oxide anode plate frame coated with a metal oxide intermediate layer to form a titanium-based oxide anode plate blank, wherein the titanium mesh coated with the Pt-Sn-SbOx/Sn-SbOx intermediate layer or the Pd-Ti-Sn-SbOx/Sn-SbOx intermediate layer is positioned between adjacent titanium-aluminum-coated composite rods; placing the titanium-based oxide anode plate blank as an anode and the titanium plate as a cathode in manganese nitrate composite electroplating solution for composite electrodeposition, cleaning with deionized water, and blow-drying to obtain a titanium-based oxide anode plate;
(5) Welding the top end of a titanium plate of the titanium-based oxide anode plate at the bottom end of the titanium-clad aluminum conducting beam, and installing the insulator on the titanium-based oxide anode plate to obtain the titanium-based gradient composite manganese dioxide anode plate.
10. The preparation method of the titanium-based gradient composite manganese dioxide anode plate according to claim 9, characterized by comprising the following steps: in the step (1), the concentration of NaOH solution is 5-10 wt.%, the soaking temperature of the NaOH solution is 40-70 ℃, and HNO is added 3 The concentration of the solution is 10-40 wt.%, the concentration of the HF solution is 1-10 wt.%, the hot rolling temperature is 500-700 ℃, and the welding method is pulse argon protection aluminum-aluminum welding;
in the step (2), the concentration of NaOH solution is 10-20 wt.%, the soaking temperature of NaOH solution is 50-80 ℃, the heat treatment temperature is 400-700 ℃, the heat treatment time is 0.2-1.5 h, the concentration of oxalic acid solution is 5-30 wt.%, the activation temperature is 80-100 ℃, and the sintering pretreatment temperature is 400-700 ℃;
in the step (3), the concentration of NaOH solution is 10-20 wt.%, the soaking temperature of NaOH solution is 50-80 ℃, the heat treatment temperature is 400-700 ℃, the heat treatment time is 0.2-1.5 h, the concentration of oxalic acid solution is 5-30 wt.%, the activation temperature is 80-100 ℃, and the sintering pretreatment temperature is 400-700 ℃;
the temperature of the composite electrodeposition in the step (4) is 80-100 ℃, and the current density is 1-5A/dm 2 The stirring speed is 50-300 rpm, and the composite electrodeposition time is 4-20 h; the manganese nitrate composite electroplating solution contains 20-100 g/L of manganese nitrate, 2-30 g/L of nitric acid, 10-40 g/L of sodium tungstate and 10-30 g/L of Ag-doped carbon fiber-beta-PbO 2 4-30 g/L of Sn-Ru-TaOx coated hollow glass microspheres.
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