CN104562094B - A kind of preparation method of non-ferrous metal electrodeposition graded composite anode - Google Patents
A kind of preparation method of non-ferrous metal electrodeposition graded composite anode Download PDFInfo
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- CN104562094B CN104562094B CN201510027180.7A CN201510027180A CN104562094B CN 104562094 B CN104562094 B CN 104562094B CN 201510027180 A CN201510027180 A CN 201510027180A CN 104562094 B CN104562094 B CN 104562094B
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- nano polyaniline
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000010936 titanium Substances 0.000 claims abstract description 68
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 68
- 229920000767 polyaniline Polymers 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 51
- 238000001035 drying Methods 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 229910018316 SbOx Inorganic materials 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000007747 plating Methods 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000007772 electrode material Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 229910006531 α-PbO2 Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000010405 anode material Substances 0.000 claims description 13
- 241000292525 Titanio Species 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 229910000464 lead oxide Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229910006654 β-PbO2 Inorganic materials 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 2
- 239000011733 molybdenum Substances 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 1
- 238000009713 electroplating Methods 0.000 claims 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000003466 welding Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 abstract 1
- 238000005253 cladding Methods 0.000 abstract 1
- 238000003717 electrochemical co-deposition Methods 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 238000002604 ultrasonography Methods 0.000 description 10
- 230000005611 electricity Effects 0.000 description 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000010981 drying operation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910006529 α-PbO Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010033546 Pallor Diseases 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000007788 roughening Methods 0.000 description 1
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- Paints Or Removers (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
A kind of preparation method of non-ferrous metal electrodeposition graded composite anode, drawing extrusion process is used to prepare titanium rod, one group of titanium rod sidewards is erected rod with three titanium copper-clads and assembles into palisading type titanium board substrate, after matrix chemically oil removing activation processing, dopen Nano polyaniline tin-antimony oxide is prepared again with cladding process, then the titanium plate of palisading type is prepared the α PbO of dopen Nano polyaniline with titanium copper-clad conducting beam respectively by argon arc welding, the further method using electrochemical co-deposition2Intermediate layer and mix molybdenum oxide β PbO2Active layer.Anode electro catalytic activity prepared by the present invention is good, tank voltage in electrodeposition is low, length in service life, energy consumption are low.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to the insoluble sun of non-ferrous metal electrodeposition in a kind of hydrometallurgy
The preparation method of pole.
Background technology
In whole commercial production, metallurgical industry remains big power consumer, and energy consumption is high, in the smelting of non-ferrous metal
Cheng Zhong, the zinc of about more than 90% and the copper of about 30% are extracted by hydrometallurgical technology.Especially in Zinc Hydrometallurgy Process,
Electrodeposition operation consumes whole zinc and extracts the energy consumption of process 2/3.And extract process at non-ferrous metal (zinc, copper, manganese, nickel etc.) electrodeposition
In, anode material character directly affects ionic discharge current potential, the change of overpotential, current efficiency size, power consumption, sun
The indexs such as pole life-span and cathode product quality.
Currently used insoluble anode is lead based alloy anodes, lead based alloy anodes low price, stable performance, but lead
In use there is overpotential for oxygen evolution height, energy consumption greatly in base alloy anode, quality is heavy, it is inconvenient, yielding to operate, and facial pallor easily exists
Negative electrode separates out and pollutes cathode product, and electrolyte needs periodically except shortcomings such as lead.
The preparation of the inertia anode of lead dioxide of prior art, generally selects titanium, graphite, plastics and pottery etc. for matrix material
Material, by matrix surface roughening treatment, coating bottom, α-PbO2Intermediate layer and plating β-PbO2Etc. basic process, it is coated with and obtains
PbO2Electrode.Its advantage can operate at higher current densities for (1)；(2) generation of mud can be suppressed；(3) oxidation effect can be improved
Rate；(4) good corrosion resistance and long-life；(5) in Zinc electrolysis, chemical conversion treatment need not be carried out, and the amount that lead is mixed in zinc subtracts
Lack, good to the corrosion resistance of chlorine, and chlorine can be removed (it is demonstrated experimentally that electrolyte is chloride more than 1000mg/L, chloride ion general's corrosion
Anode, anode is oxidized to chlorate, and pole plate is thinning, perforation, and the life-span is greatly shortened), manganese slag will not be produced, extract the electric current of zinc
Efficiency is high.But the PbO that so plating prepares2Electrode, as insoluble anode, in use occur the problem that (1) PbO2Heavy
Lamination is combined not tight with electrode surface or sedimentary is uneven；(2) PbO2Sedimentary porous and coarse, internal stress is big；(3)
PbO2Sedimentary is easily peeled off or corrodes, and the life-span is the longest.For this reason, it may be necessary to find a kind of lightweight high intensity, corrosion-resistant, conduct electricity,
The composite of low cost, to improve the electric conductivity of insoluble anode in hydrometallurgy, reduces tank voltage, saves energy consumption, increase
Add intensity and corrosion resistance.
Summary of the invention
The invention aims to the shortcoming overcoming the existence of above-mentioned prior art, it is provided that a kind of electro catalytic activity is good,
The preparation method of the non-ferrous metal electrodeposition graded composite anode that the tank voltage in electrodeposition is low, length in service life, energy consumption are low.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of a kind of non-ferrous metal electrodeposition graded composite anode, the method sequentially includes the following steps:
Use drawing extrusion process to prepare titanium rod, one group of titanium rod sidewards is erected rod with three titanium copper-clads and assembles into
Palisading type titanium board substrate, then puts into this matrix in the sodium hydroxide boiling liquid that mass volume ratio is 10% and boils 0.5h, use clear water
After flushing, put into HCl:HF:HNO3Volume ratio be 5:1:2 mixed acid liquid in soak 3～5min, then with clear water rinse after put into body
The long-pending HCl solution than 20% boils 0.5h, after cleaning with deionized water, hot blast drying, standby；
By stepThe substrate material surface processed uniformly coats precursor liquid, dries in 110 DEG C of drying baker
10min, puts into roasting 20min at resistance furnace 500 DEG C after above coating precursor liquid the step 4 time dried repeatedly；Weigh again
Putting into the step 4 time of resistance furnace roasting after coating precursor liquid more than multiple and drying four times, other technic index is constant, simply
Last roasting 0.5h, naturally cools to room temperature, obtains titanio and mix the Sn-SbOx coating pole plate of nano polyaniline；Before described
Drive body fluid and be configured that weighing gross mass is 100g and mass ratio is the SnCl of 9:14.5H2O and SbCl3Be dissolved in n-butyl alcohol with
In the 2L mixed liquor of hydrochloric acid 5:1 by volume, add the nano polyaniline that mass percent is 5～15%, then rotating steaming
Send out device seals after evaporating water stand-by；The preparation method of described nano polyaniline is: by oxidant Ammonium persulfate. and aniline list
After the mol ratio of body is the amount mixing of 1～1.5, adding concentration is the aqueous oxidizing agent solution of 1mol/L, by adulterant sulfosalisylic
Acid and the amount that mol ratio is 1～2.5 of aniline monomer, dripping in emulsion as adulterant sulfosalisylic acid concentration is 0.5
～the aqueous sulfuric acid of 1mol/L, magnetic force is sufficiently stirred for afterwards, keeps less than 10 DEG C to react 10～20 hours, then pickling and steaming
Distilled water is washed, the polyaniline particle of drying to obtain 200～500nm；
By stepThe titanio of preparation is mixed the Sn-SbOx coating pole plate of nano polyaniline and is carried out argon with titanium copper-clad conducting beam
Arc-welding is connected into electrode material, is then placed in electroplate liquid by electrode material, and at 20～50 DEG C, anodic current density is 1～4A/
dm2, electroplate 4～8 hours under conditions of mechanical agitation 120～200r/min, by the electrode after plating through washing, dried and get final product
The Sn-SbOx/ of titanium/mix nano polyaniline mixes nano polyaniline α-PbO2Composite anode materials；Wherein plating solution formula is: oxidation
After the mixing of lead 30～50g/L, nano polyaniline 5～20g/L, sodium hydroxide 120～180 g/L, antioxidant 1～5g/L, warp
Ultrasound wave disperses electro-deposition after 30 minutes；
By stepThe Sn-SbOx/ of titanium/the mix nano polyaniline of preparation mixes nano polyaniline α-PbO2Composite anode material
Material is placed in electroplate liquid, and at 40～80 DEG C, anodic current density is 4～8A/dm2, the condition of mechanical agitation 250～400r/min
Lower plating 4～8 hours, the electrode material after plating through washing, i.e. obtain the Sn-SbOx/ of titanium/mix nano polyaniline after drying and mix and receive
Rice polyaniline α-PbO2/ mix molybdenum oxide β-PbO2Composite anode；Wherein plating solution formula is: plumbi nitras 200～350g/L, nanometer
After the mixing of molybdenum oxide 5～20g/L, nitric acid 5～10 g/L, NaF 0.5g/L, surfactant 0.1～0.5g/L, through ultrasound wave
Electro-deposition after disperseing 30 minutes.
Titanium prepared by employing drawing extrusion process of the present invention rod, the cylinder of titanium rod is profile of tooth cylinder, including but do not limit
In round zigzag cylinder, ellipse zigzag cylinder, round isomery flute profile cylinder, ellipse isomery flute profile cylinder.Described titanium
The maximum outside diameter of rod is 5～12mm, and material is TA1.The titanium copper-clad conducting beam used is pole or cuboid, its titanium bag
Coating wall thickness is 2～4mm.The perpendicular rod a diameter of 8～14mm of the three titanium copper-clads being connected with titanium rod sidewards, its titanium clad wall thickness
2～5mm.Described antioxidant is one or more in ascorbic acid, EDTA or formaldehyde.Described nanoscale molybdenum oxide
Average diameter be 100nm～800nm.Described surfactant is the one in PVP, OP emulsifying agent or polyethylene glycol 6000
Or more than one.
The present invention has the advantage that compared to existing technology
1, use palisading type positive plate to substitute traditional planar anode plate, compared with classic flat-plate type positive plate, can change
The mobility of kind electrolyte, reduces the concentration polarization on cathode chamber metal ion (copper, zinc, nickel), improves the deposition of cathodic metal,
Thus improve cathode efficiency.
2, titanium rod is carried out drawing process, drastically increase the adhesion of Lead oxide brown and matrix, it is to avoid because of coating
Internal stress that Lead oxide brown is intrinsic and the obscission that produces, extend electrode life.
3, one group of titanium rod sidewards is used to assemble palisading type positive plate, it is to avoid coating Lead oxide brown is because of longitudinal internal stress
The seminess produced, extends electrode life.
The perpendicular rod of 4 three be connected with titanium rod sidewards introduces titanium copper-clad rod, improves the electric conductivity of whole positive plate, fall
Low tank voltage.
5, Sn-SbOx coating introduces nano polyaniline particle, decrease the crackle of coating, it is to avoid solution penetrates into base
Body, improves electrode life.
6, introducing has the nanoscale molybdenum oxide (MoO of catalysis activity3), it will be apparent that improve the analysis oxygen catalysis activity of electrode, press down
System analysis chlorine so that the tank voltage that electrode is used in non-ferrous metal electrodeposition significantly reduces.
7, increasingly stricter along with the requirement of environmental protection, ti-based coating will not produce during using and pollute cathode product
Lead, positive plate can secondary resource comprehensive reutilization, enjoy the favor of vast researcher, be the material of a kind of sustainable development.
Accompanying drawing explanation
Fig. 1 is the structural representation of electrode material of the present invention；
Fig. 2 is the A-A section enlarged diagram of Fig. 1；
Fig. 3 is the B-B section enlarged diagram of Fig. 1；
Fig. 4 is the enlarged section of the round isomery flute profile cylinder titanium rod of drawing extruding；
Fig. 5 is the enlarged section of the ellipse isomery flute profile cylinder titanium rod of drawing extruding；
Fig. 6 is the enlarged section of the round zigzag cylinder titanium rod of drawing extruding；
Fig. 7 is the enlarged section of the ellipse zigzag cylinder titanium rod of drawing extruding.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, but scope is not limited to described interior
Hold.
Embodiment 1: the preparation method of a kind of non-ferrous metal electrodeposition graded composite anode, the method is entered according to the following steps
OK:
Use drawing extrusion process to prepare titanium rod 1, one group of rod 2 perpendicular with three titanium copper-clads of titanium rod sidewards is assembled
Become palisading type titanium board substrate as shown in Figure 1, then this matrix is put in the sodium hydroxide boiling liquid that mass volume ratio is 10%
Boil 0.5h, after rinsing with clear water, put into HCl:HF:HNO3Volume ratio be 5:1:2 mixed acid liquid in soak 3～5min, then with clearly
Put into after water flushing in the HCl solution of volume ratio 20% and boil 0.5h, after cleaning with deionized water, hot blast drying, standby；Titanium rod
For round isomery flute profile cylinder titanium rod, its shape of cross section is round isomery flute profile as shown in Figure 4, maximum outside diameter i.e. tooth
A diameter of 5mm of tip circle, material is TA1；A diameter of 8mm, the wall thickness 2mm of its titanium clad of three perpendicular rods of titanium copper-clad；
First preparing nano polyaniline, concrete grammar is to be 1 by the mol ratio of oxidant Ammonium persulfate. Yu aniline monomer
After amount mixing, adding concentration is the aqueous oxidizing agent solution of 1mol/L, by the mol ratio of adulterant sulfosalicylic acid Yu aniline monomer
Being the amount of 1.5, dripping in emulsion as adulterant sulfosalisylic acid concentration is the aqueous sulfuric acid of 1mol/L, afterwards magnetic force
It is sufficiently stirred for, keeps less than 10 DEG C to react 15 hours, then pickling and distilled water wash, the polyaniline of drying to obtain 280nm
Particle；Preparing precursor liquid again, concrete grammar is that to weigh gross mass be 100g and mass ratio is the SnCl of 9:14.5H2O and SbCl3
It is dissolved in the 2L mixed liquor with n-butyl alcohol and hydrochloric acid 5:1 by volume, adds the nanometer polyphenyl that mass percent is 10%
Amine, seals stand-by the most in a rotary evaporator after evaporating water；Finally by stepOn the substrate material surface processed all
In 110 DEG C of drying baker, dry 10min evenly after coating precursor liquid, be coated with precursor liquid and then dry in 110 DEG C of drying baker
10min, is placed in chamber type electric resistance furnace roasting 20min at 500 DEG C after such repeatable operation four times；Again at substrate material surface
On be evenly coated with after precursor liquid drying 10min in 110 DEG C of drying baker, be placed in box resistance after such repeatable operation four times
Roasting 20min at 500 DEG C in stove；Resistance furnace roasting is put into again after repeating above coating precursor liquid drying operation four times
Step 4 time, other technic index is constant, the most last roasting 0.5h, naturally cools to room temperature, obtains titanio and mix nanometer
The Sn-SbOx coating pole plate of polyaniline；
By stepThe titanio of preparation is mixed the Sn-SbOx coating pole plate of nano polyaniline and is carried out with titanium copper-clad conducting beam 3
Argon arc welding obtains the palisading type anode electrode material such as Fig. 1, is then placed in electroplate liquid by electrode material at 40 DEG C, anode electricity
Current density is 3A/dm2, electroplate 6 hours under conditions of mechanical agitation 200r/min, by the electrode material after plating through washing, dry
The Sn-SbOx/ i.e. obtaining titanium/mix nano polyaniline after dry mixes polyaniline α-PbO2Composite anode materials, wherein plating solution formula is:
Lead oxide 36g/L, nano polyaniline 10g/L, sodium hydroxide 120 g/L, ascorbic acid 2g/L, after mixing, disperse through ultrasound wave
Electro-deposition after 30 minutes；Titanium copper-clad conducting beam is pole, and its titanium clad 3a wall thickness is 2mm；
By stepThe Sn-SbOx/ of titanium/the mix nano polyaniline of preparation mixes nano polyaniline α-PbO2Composite anode material
Material is placed in electroplate liquid, and at 60 DEG C, anodic current density is 5A/dm2, electroplate 6 hours under conditions of mechanical agitation 260r/min,
Electrode material after plating mixes nano polyaniline α-PbO through washing, the Sn-SbOx/ that i.e. obtains after drying titanium/mix nano polyaniline2/
Mix molybdenum oxide β-PbO2Composite anode；Wherein plating solution formula: plumbi nitras 280g/L, 200nm nanoscale molybdenum oxide 15g/L, nitric acid
10 g/L, NaF 0.5g/L, OP emulsifying agent 0.2g/L, after mixing, electro-deposition after ultrasound wave disperses 30 minutes.
Novel gradient composite anode prepared by the present embodiment is at zinc electrolyte (60g/L Zn2+、160 g/L H2SO4, be less than
100mg/L fluoride, 600mg/L C1-Ion, 35 DEG C, i=500A/m2) use, its electricity effect improves than traditional alloy lead anode plate
6%, lead tolerance≤0.003% in zinc metal sheet.(180 g/L H are tested by poled lifetime2SO4, 900mg/L C1-Ion, i=
5000A/m2) reach 4 years service life.
Embodiment 2: the preparation method of a kind of non-ferrous metal electrodeposition graded composite anode, concrete operations are as follows:
Use drawing extrusion process to prepare titanium rod 1, one group of rod 2 perpendicular with three titanium copper-clads of titanium rod sidewards is assembled
Become palisading type titanium board substrate as shown in Figure 1, then this matrix is put in the sodium hydroxide boiling liquid that mass volume ratio is 10%
Boil 0.5h, after rinsing with clear water, put into HCl:HF:HNO3Volume ratio be 5:1:2 mixed acid liquid in soak 3～5min, then with clearly
Put into after water flushing in the HCl solution of volume ratio 20% and boil 0.5h, after cleaning with deionized water, hot blast drying, standby；Titanium rod
For round isomery flute profile cylinder titanium rod, its shape of cross section is ellipse isomery flute profile as shown in Figure 5, its maximum outside diameter
I.e. a diameter of 8mm of major axis outside circle；A diameter of 12mm, the wall thickness 3mm of its titanium clad of the perpendicular rod of titanium copper-clad；
First preparing nano polyaniline, concrete grammar is to be 1 by the mol ratio of oxidant Ammonium persulfate. Yu aniline monomer
After amount mixing, adding concentration is the aqueous oxidizing agent solution of 1mol/L, by the mol ratio of adulterant sulfosalicylic acid Yu aniline monomer
Being the amount of 1.5, dripping in emulsion as adulterant sulfosalisylic acid concentration is the aqueous sulfuric acid of 1mol/L, afterwards magnetic force
It is sufficiently stirred for, keeps less than 10 DEG C to react 15 hours, then pickling and distilled water wash, the polyaniline of drying to obtain 280nm
Particle；Preparing precursor liquid again, concrete grammar is that to weigh gross mass be 100g and mass ratio is the SnCl of 9:14.5H2O and SbCl3
It is dissolved in the 2L mixed liquor with n-butyl alcohol and hydrochloric acid 5:1 by volume, adds the nanometer polyphenyl that mass percent is 15%
Amine, seals stand-by the most in a rotary evaporator after evaporating water；Finally by stepOn the substrate material surface processed all
In 110 DEG C of drying baker, dry 10min evenly after coating precursor liquid, be coated with precursor liquid and then dry in 110 DEG C of drying baker
10min, is placed in chamber type electric resistance furnace roasting 20min at 500 DEG C after such repeatable operation four times；Again at substrate material surface
On be evenly coated with after precursor liquid drying 10min in 110 DEG C of drying baker, be placed in box resistance after such repeatable operation four times
Roasting 20min at 500 DEG C in stove；Resistance furnace roasting is put into again after repeating above coating precursor liquid drying operation four times
Step 4 time, other technic index is constant, the most last roasting 0.5h, naturally cools to room temperature, obtains titanio and mix nanometer
The Sn-SbOx coating pole plate of polyaniline；
By stepThe titanio of preparation is mixed the Sn-SbOx coating pole plate of nano polyaniline and is carried out with titanium copper-clad conducting beam 3
Argon arc welding obtains the palisading type anode electrode material such as Fig. 1, is then placed in electroplate liquid by electrode material at 40 DEG C, anode electricity
Current density is 3A/dm2, electroplate 6 hours under conditions of mechanical agitation 200r/min, by the electrode material after plating through washing, dry
The Sn-SbOx/ i.e. obtaining titanium/mix nano polyaniline after dry mixes polyaniline α-PbO2Composite anode materials, wherein plating solution formula is:
Lead oxide 36g/L, nano polyaniline 10g/L, sodium hydroxide 120 g/L, EDTA 4g/L, after mixing, disperses 30 points through ultrasound wave
Electro-deposition after clock；Titanium copper-clad conducting beam is cuboid, and its titanium clad wall thickness is 4mm；
By stepThe Sn-SbOx/ of titanium/the mix nano polyaniline of preparation mixes nano polyaniline α-PbO2Composite anode material
Material is placed in electroplate liquid, and at 60 DEG C, anodic current density is 4A/dm2, electroplate 6 hours under conditions of mechanical agitation 260r/min,
Electrode material after plating mixes nano polyaniline α-PbO through washing, the Sn-SbOx/ that i.e. obtains after drying titanium/mix nano polyaniline2/
Mix molybdenum oxide β-PbO2Composite anode；Wherein plating solution formula: plumbi nitras 280g/L, 200nm nanoscale molybdenum oxide 15g/L, nitric acid
10 g/L, NaF 0.5g/L, polyethylene glycol 6000 0.2g/L, after mixing, electro-deposition after ultrasound wave disperses 30 minutes.
Novel gradient composite anode prepared by the present embodiment is at copper electrolyte (45g/L Cu2+、180 g/L H2SO4, be less than
100mg/L fluoride, 50 DEG C) use during, the output capacity of high purity copper reaches more than 96%.(180 are tested by poled lifetime
g/L H2SO4, 40g/L Cu2+, i=5000A/m2) reach 8 years service life.
Embodiment 3: the preparation method of a kind of non-ferrous metal electrodeposition graded composite anode, concrete grammar is as follows:
Use drawing extrusion process to prepare titanium rod 1, one group of rod 2 perpendicular with three titanium copper-clads of titanium rod sidewards is assembled
Become palisading type titanium board substrate as shown in Figure 1, then this matrix is put in the sodium hydroxide boiling liquid that mass volume ratio is 10%
Boil 0.5h, after rinsing with clear water, put into HCl:HF:HNO3Volume ratio be 5:1:2 mixed acid liquid in soak 3～4min, then with clearly
Put into after water flushing in the HCl solution of volume ratio 20% and boil 0.5h, after cleaning with deionized water, hot blast drying, standby；Titanium rod
For round zigzag cylinder titanium rod, its shape of cross section is round zigzag as shown in Figure 6, and titanium rod maximum outside diameter is
12mm, material is TA1；A diameter of 14mm, titanium clad wall thickness 5mm of the perpendicular rod of titanium copper-clad；
First preparing nano polyaniline, concrete grammar is to be 1 by the mol ratio of oxidant Ammonium persulfate. Yu aniline monomer
After amount mixing, adding concentration is the aqueous oxidizing agent solution of 1.5mol/L, by adulterant sulfosalicylic acid and aniline monomer mole
Ratio is the amount of 2.5, and dripping in emulsion as adulterant sulfosalisylic acid concentration is the aqueous sulfuric acid of 0.8mol/L, afterwards
Magnetic force is sufficiently stirred for, and keeps less than 10 DEG C to react 20 hours, then pickling and distilled water wash, and drying to obtain 200nm's is poly-
Aniline particle；Preparing precursor liquid again, concrete grammar is that to weigh gross mass be 100g and mass ratio is the SnCl of 9:14.5H2O and
SbCl3It is dissolved in the 2L mixed liquor with n-butyl alcohol and hydrochloric acid 5:1 by volume, adds the nanometer that mass percent is 5% and gather
Aniline, seals stand-by the most in a rotary evaporator after evaporating water；Finally by stepOn the substrate material surface processed
In 110 DEG C of drying baker, dry 10min after being evenly coated with precursor liquid, be coated with precursor liquid then in 110 DEG C of drying baker
Roasting 20min at 500 DEG C it is placed in chamber type electric resistance furnace after drying 10min, such repeatable operation four times；Again at matrix material table
It is evenly coated with after precursor liquid drying 10min on face in 110 DEG C of drying baker, after such repeatable operation four times, is placed in box electricity
Roasting 20min at 500 DEG C in resistance stove；Resistance furnace roasting is put into again after repeating above coating precursor liquid drying operation four times
Step 4 time, other technic index is constant, the most last roasting 0.5h, naturally cools to room temperature, obtains titanio and mixes and receive
The Sn-SbOx coating pole plate of rice polyaniline；
By stepThe titanio of preparation is mixed the Sn-SbOx coating pole plate of nano polyaniline and is carried out with titanium copper-clad conducting beam 3
Argon arc welding obtains the palisading type anode electrode material such as Fig. 1, is then placed in electroplate liquid by electrode material at 20 DEG C, anode electricity
Current density is 1A/dm2, electroplate 4 hours under conditions of mechanical agitation 150r/min, by the electrode material after plating through washing, dry
The Sn-SbOx/ i.e. obtaining titanium/mix nano polyaniline after dry mixes polyaniline α-PbO2Composite anode materials, wherein plating solution formula is:
Lead oxide 30g/L, nano polyaniline 20g/L, sodium hydroxide 150 g/L, formaldehyde 5g/L, after mixing, disperse 30 points through ultrasound wave
Electro-deposition after clock；Titanium copper-clad conducting beam is pole, and its titanium clad wall thickness is 3mm；
By stepThe Sn-SbOx/ of titanium/the mix nano polyaniline of preparation mixes nano polyaniline α-PbO2Composite anode material
Material is placed in electroplate liquid, and at 80 DEG C, anodic current density is 8A/dm2, electroplate 8 hours under conditions of mechanical agitation 250r/min,
Electrode material after plating mixes nano polyaniline α-PbO through washing, the Sn-SbOx/ that i.e. obtains after drying titanium/mix nano polyaniline2/
Mix molybdenum oxide β-PbO2Composite anode；Wherein plating solution formula: plumbi nitras 200g/L, 200nm nanoscale molybdenum oxide 20g/L, nitric acid
8 g/L, NaF 0.5g/L, PVP 0.5g/L, after mixing, electro-deposition after ultrasound wave disperses 30 minutes.
Novel gradient composite anode prepared by the present embodiment is at zinc electrolyte (50g/L Zn2+、150 g/L H2SO4, be less than
100mg/L fluoride, 800mg/L C1-Ion, 30-40 DEG C, i=500A/m2) use, the electricity effect of this Novel anode is than traditional lead
Alloy anode plate improves 4%, lead tolerance≤0.003% in zinc metal sheet.(180 g/L H are tested by poled lifetime2SO4, 1000mg/L
C1-Ion, i=5000A/m2) reach 3 years service life.
Embodiment 4: the preparation method of a kind of non-ferrous metal electrodeposition graded composite anode, concrete grammar is as follows:
Use drawing extrusion process to prepare titanium rod 1, one group of rod 2 perpendicular with three titanium copper-clads of titanium rod sidewards is assembled
Become palisading type titanium board substrate as shown in Figure 1, then this matrix is put in the sodium hydroxide boiling liquid that mass volume ratio is 10%
Boil 0.5h, after rinsing with clear water, put into HCl:HF:HNO3Volume ratio be 5:1:2 mixed acid liquid in soak 3～5min, then with clearly
Put into after water flushing in the HCl solution of volume ratio 20% and boil 0.5h, after cleaning with deionized water, hot blast drying, standby；Titanium rod
For ellipse zigzag cylinder titanium rod, its shape of cross section is ellipse zigzag as shown in Figure 7, maximum major axis outside diameter
For 10mm；A diameter of 10mm, the wall thickness 4mm of its titanium clad of the perpendicular rod of titanium copper-clad；
First preparing nano polyaniline, concrete grammar is to be 1.2 by the mol ratio of oxidant Ammonium persulfate. Yu aniline monomer
Amount mixing after, adding concentration is the aqueous oxidizing agent solution of 1mol/L, by adulterant sulfosalicylic acid and aniline monomer mole
Ratio is the amount of 1, and dripping in emulsion as adulterant sulfosalisylic acid concentration is the aqueous sulfuric acid of 0.5mol/L, afterwards magnetic
Power is sufficiently stirred for, and keeps less than 10 DEG C to react 10 hours, then pickling and distilled water wash, the polyphenyl of drying to obtain 500nm
Amine particle；Preparing precursor liquid again, concrete grammar is that to weigh gross mass be 100g and mass ratio is the SnCl of 9:14.5H2O and
SbCl3It is dissolved in the 2L mixed liquor with n-butyl alcohol and hydrochloric acid 5:1 by volume, adds the nanometer that mass percent is 15%
Polyaniline, seals stand-by the most in a rotary evaporator after evaporating water；Finally by stepThe substrate material surface processed
On be evenly coated with after precursor liquid drying 10min in 110 DEG C of drying baker, be coated with precursor liquid then at 110 DEG C of drying baker
Middle baking 10min, is placed in chamber type electric resistance furnace roasting 20min at 500 DEG C after such repeatable operation four times；Again at matrix material
It is placed in box after drying 10min, such repeatable operation four times in 110 DEG C of drying baker after coating precursor liquid uniformly over the surface
Roasting 20min at 500 DEG C in resistance furnace；Put into again resistance furnace after repeating above coating precursor liquid drying operation four times to roast
The step 4 time burnt, other technic index is constant, the most last roasting 0.5h, naturally cools to room temperature, obtains titanio and mix
The Sn-SbOx coating pole plate of nano polyaniline；
By stepThe titanio of preparation is mixed the Sn-SbOx coating pole plate of nano polyaniline and is carried out with titanium copper-clad conducting beam 3
Argon arc welding obtains the palisading type anode electrode material such as Fig. 1, is then placed in electroplate liquid by electrode material at 50 DEG C, anode electricity
Current density is 4A/dm2, electroplate 8 hours under conditions of mechanical agitation 120r/min, by the electrode material after plating through washing, dry
The Sn-SbOx/ i.e. obtaining titanium/mix nano polyaniline after dry mixes polyaniline α-PbO2Composite anode materials, wherein plating solution formula is:
Lead oxide 50g/L, nano polyaniline 5g/L, sodium hydroxide 180 g/L, EDTA14g/L, after mixing, disperse 30 points through ultrasound wave
Electro-deposition after clock；Titanium copper-clad conducting beam is cuboid, and its titanium clad 3a wall thickness is 4mm；
By stepThe Sn-SbOx/ of titanium/the mix nano polyaniline of preparation mixes nano polyaniline α-PbO2Composite anode material
Material is placed in electroplate liquid, and at 40 DEG C, anodic current density is 5A/dm2, electroplate 4 hours under conditions of mechanical agitation 400r/min,
Electrode material after plating mixes nano polyaniline α-PbO through washing, the Sn-SbOx/ that i.e. obtains after drying titanium/mix nano polyaniline2/
Mix molybdenum oxide β-PbO2Composite anode；Wherein plating solution formula: plumbi nitras 350g/L, 200nm nanoscale molybdenum oxide 5g/L, nitric acid 5
G/L, NaF 0.5g/L, polyethylene glycol 6000 0.1g/L, after mixing, electro-deposition after ultrasound wave disperses 30 minutes.
Novel gradient composite anode prepared by the present embodiment is at copper electrolyte (45g/L Cu2+、180 g/L H2SO4, be less than
100mg/L fluoride, 60 DEG C) use during, the output capacity of high purity copper reaches more than 97%.(180 are tested by poled lifetime
g/L H2SO4, i=5000A/m2) reach more than 10 years service life.
Claims (8)
1. the non-ferrous metal electrodeposition preparation method of graded composite anode, it is characterised in that the method is entered according to the following steps
OK:
(1) use drawing extrusion process to prepare titanium rod, one group of titanium rod sidewards is erected rod with three titanium copper-clads and assembles into grid
Hurdle type titanium board substrate, then puts into this matrix in the sodium hydroxide boiling liquid that mass volume ratio is 10% and boils 0.5h, rush with clear water
After washing, put into HCl:HF:HNO3Volume ratio be 5:1:2 mixed acid liquid in soak 3～5min, then with clear water rinse after put into volume
0.5h is boiled than in the HCl solution of 20%, after cleaning with deionized water, hot blast drying, standby；
(2) substrate material surface that step (1) processed uniformly is coated precursor liquid, 110 DEG C of drying baker dries 10min,
Repeatedly put into roasting 20min at resistance furnace 500 DEG C after above coating precursor liquid the step 4 time dried；Repeat above
Putting into the step 4 time of resistance furnace roasting after coating precursor liquid and drying four times, other technic index is constant, is last
Secondary roasting 0.5h, naturally cools to room temperature, obtains titanio and mixes the Sn-SbOx coating pole plate of nano polyaniline；Described precursor liquid
It is configured that weighing gross mass is 100g and mass ratio is the SnCl of 9:14.5H2O and SbCl3Be dissolved in n-butyl alcohol and hydrochloric acid by
In the 2L mixed liquor of volume ratio 5:1, add the nano polyaniline that mass percent is 5～15%, the most in a rotary evaporator
Seal stand-by after evaporating water；The preparation method of described nano polyaniline is: by rubbing of oxidant Ammonium persulfate. and aniline monomer
After you mix than the amount being 1～1.5, adding concentration is the aqueous oxidizing agent solution of 1mol/L, by adulterant sulfosalicylic acid and benzene
The mol ratio of amine monomers is the amount of 1～2.5, and dripping in emulsion as adulterant sulfosalisylic acid concentration is 0.5～1mol/
The aqueous sulfuric acid of L, magnetic force is sufficiently stirred for afterwards, keeps less than 10 DEG C to react 10～20 hours, then pickling and distillation washing
Wash, the polyaniline particle of drying to obtain 200～500nm；
(3) the Sn-SbOx coating pole plate that titanio prepared by step (2) is mixed nano polyaniline carries out argon arc with titanium copper-clad conducting beam
Being welded into electrode material, be then placed in electroplate liquid by electrode material, at 20～50 DEG C, anodic current density is 1～4A/dm2、
Electroplate 4～8 hours under conditions of mechanical agitation 120～200r/min, by the electrode after plating through washing, after drying i.e. obtain titanium/
The Sn-SbOx/ mixing nano polyaniline mixes nano polyaniline α-PbO2Composite anode materials；Wherein plating solution formula is: lead oxide
30～50g/L, after nano polyaniline 5～20g/L, sodium hydroxide 120～180 g/L, antioxidant 1～5g/L mixing, through super
Sound wave disperses electro-deposition after 30 minutes；
(4) Sn-SbOx/ of titanium step (3) prepared/mix nano polyaniline mixes nano polyaniline α-PbO2Composite anode materials
Being placed in electroplate liquid, at 40～80 DEG C, anodic current density is 4～8A/dm2, under conditions of mechanical agitation 250～400r/min
Electroplating 4～8 hours, the electrode material after plating mixes nanometer through washing, the Sn-SbOx/ that i.e. obtains after drying titanium/mix nano polyaniline
Polyaniline α-PbO2/ mix molybdenum oxide β-PbO2Composite anode；Wherein plating solution formula is: plumbi nitras 200～350g/L, nano oxygen
After changing molybdenum 5～20g/L, nitric acid 5～10 g/L, NaF 0.5g/L, surfactant 0.1～0.5g/L mixing, through ultrasonic wavelength-division
Electro-deposition after dissipating 30 minutes.
The preparation method of a kind of non-ferrous metal electrodeposition graded composite anode, it is characterised in that institute
Stating the titanium rod using drawing extrusion process to prepare, the cylinder of titanium rod is profile of tooth cylinder, includes round zigzag cylinder, ellipse
Zigzag cylinder, round isomery flute profile cylinder, ellipse isomery flute profile cylinder.
The preparation method of a kind of non-ferrous metal electrodeposition graded composite anode the most according to claim 1 or claim 2, its feature exists
In, described titanium rod maximum outside diameter is 5～12mm, and material is TA1.
The preparation method of a kind of non-ferrous metal electrodeposition graded composite anode the most according to claim 1 or claim 2, its feature exists
In: the titanium copper-clad conducting beam of employing is pole or cuboid, and its titanium clad wall thickness is 2～4mm.
The preparation method of a kind of non-ferrous metal electrodeposition graded composite anode the most according to claim 1 or claim 2, its feature exists
In, the perpendicular rod a diameter of 8～14mm of the three titanium copper-clads being connected with titanium rod sidewards, its titanium clad wall thickness 2～5mm.
The preparation method of a kind of non-ferrous metal electrodeposition graded composite anode the most according to claim 1 or claim 2, described antioxygen
Agent is one or more in ascorbic acid, EDTA or formaldehyde.
The preparation method of a kind of non-ferrous metal electrodeposition graded composite anode the most according to claim 1 or claim 2, described nano oxygen
The average diameter changing molybdenum is 100nm～800nm.
The preparation method of a kind of non-ferrous metal electrodeposition graded composite anode the most according to claim 1 or claim 2, lives in described surface
Property agent is the one or more than one in PVP, OP emulsifying agent or polyethylene glycol 6000.
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| CN114318469B (en) * | 2021-12-30 | 2023-08-04 | 中国科学院合肥物质科学研究院 | Preparation method and application of polyaniline nanofiber/carbon cloth composite electrode material |
| CN115287737B (en) * | 2022-08-03 | 2024-07-02 | 昆明理工大学 | Titanium-based gradient composite manganese dioxide anode plate and preparation method thereof |
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