CN1455025A - Method of preparing gradient function composite anode material - Google Patents
Method of preparing gradient function composite anode material Download PDFInfo
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- CN1455025A CN1455025A CN 03117908 CN03117908A CN1455025A CN 1455025 A CN1455025 A CN 1455025A CN 03117908 CN03117908 CN 03117908 CN 03117908 A CN03117908 A CN 03117908A CN 1455025 A CN1455025 A CN 1455025A
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Abstract
The preparation method of new-type functionally-gradient composite anode material adopts pulse electrodeposition method to prepare Pb/PbO2/RE-MnO2/RE-ZrO2-MnO2 or PbO2/RE-PbO2/Re-ZrO2-PbO2 composite anode material on the aluminium base body or stainless steel base, and when said composite cathode material is used for electrodepositing metal, a layer of compact film layer is formed on the anode surface to make anode be in non-dissolving state, and the use two composite anodes can obviously reduce voltage of electrolytic cell, can reduce electric consumption, at the same time the cost of plating liquor is low, when it is used for electrodepositing zinc, nickel, cobalt, manganese and chromium, the cell voltage can be reduced by 0.5-1V, the current efficiency can be raised by 1-3% so as to raise the quality of anode product.
Description
Technical field: the preparation method who the present invention relates to a kind of novel gradient function composite anode materials of using in the wet method electrodeposition process of metals such as non-ferrous metal metallurgy and field of metal surface treatment technology, particularly zinc, copper, nickel, cobalt, manganese, chromium.
Background technology: extract in wet method in the metal process such as zinc, copper, nickel, cobalt, manganese, chromium, anode material still uses lead and lead alloy at present, its shortcoming is: bath voltage height (3.4～3.8V), current efficiency low (75～88%), electrolytic deposition process energy consumption height (3400～4200 degree/ton metal), anode work-ing life short (0.5～1 year), anode lead easily dissolving enter in the negative electrode product, cause cathode product quality to descend.
For power consumption that reduces electrolytic deposition process such as zinc, copper, nickel, cobalt, manganese, chromium and the pollution that prevents anode lead anticathode product, both at home and abroad above-mentioned electrolytic deposition process of metal is furtherd investigate and developed with insoluble anode.Comprehensive present research and service condition both at home and abroad mainly contains following three class research work:
1, improved lead-Yin binary, multicomponent alloy anode: mainly comprise lead-Yin (Pb-Ag), lead-arsenic (Pb-As), lead-calcium (Pb-Ca), lead-mercury (Pb-Hg), lead-chromium (Pb-Cd), lead-titanium (Pb-Ti), lead-calcium-barium (Pb-Ca-Ba), lead-Yin-calcium (Pb-Ag-Ca), lead-Yin-strontium (Pb-Ag-Sr), lead-calcium-Xi (Pb-Ca-Sn) and lead-Yin-calcium-Xi (Pb-Ag-Ca-Sn) etc., but still exist work-ing life short, shortcomings such as the high and easy pollution negative electrode of energy consumption product.
2, titanium-based surface is coated with (plating) dimensionally stable anode: this type of anode is to be base with titanium (Ti), surface-coated precious metal or its oxide compound, but this anode has the following disadvantages: (1) adopts titanium matrix, electrode cost height; (2), cause the life-span of electrode short owing to the passivation of noble coatings dissolving and matrix titanium in the electrolysis production; (3) in electrodeposition solution, foreign ion as manganese, has reduced the effect of noble metal-coating layer in the anodic deposition with the oxidation states of matter after the oxidation.
3, titanium base oxide anode: this type of anode is a matrix with metal titanium (Ti), adopts the method for galvanic deposit at first to deposit plumbic oxide (PbO at titanium (Ti) primary surface
2), again at the thick Manganse Dioxide (MnO of 10 microns of plumbic oxide surface depositions (μ m)
2), form titanium-plumbic oxide-Manganse Dioxide (Ti/PbO
2/ MnO
2) electrode.This electrode is compared with lead-silver anode, the overpotential of oxygen has reduced by 0.344 volt, has certain application prospect, but this electrode have only 170-200 days the work-ing life in zinc electrodeposition solution (500 peaces/square metre current density under), await further raising, and this type of anode is body material with the titanium, and cost is higher, has limited and has applied.
Summary of the invention: at above-mentioned weak point of the prior art, the objective of the invention is to propose a kind of preparation method of novel gradient function composite anode materials, extract in wet method and adopt the method for pulse electrodeposition on aluminum substrate or stainless steel base, to prepare lead/plumbic oxide/rare earth-Manganse Dioxide/rare earth-zirconium dioxide-Manganse Dioxide (Pb/PbO in the metal process such as zinc, copper, nickel, cobalt, manganese, chromium
2/ RE-MnO
2/ RE-ZrO
2-MnO
2) or plumbic oxide/rare earth-plumbic oxide/rare earth-zirconium dioxide-plumbic oxide (PbO
2/ RE-PbO
2/ RE-ZrO
2-PbO
2) composite anode materials, use this composite anode materials when electrowinning, anode surface forms the rete of one deck densification, makes anode be in non-molten state, thereby improves the quality of negative electrode product.
The present invention adopts the pulse electrodeposition method to obtain Pb/PbO on aluminium matter matrix
2/ RE-MnO
2/ RE-ZrO
2-MnO
2The gradient function composite anode materials obtains PbO on stainless steel base
2/ RE-PbO
2/ RE-ZrO
2-PbO
2The gradient function composite anode materials,
(1) for aluminium matter matrix, the prescription and the processing condition of pulse electrodeposition Manganse Dioxide are: manganous sulfate (MnSO
4) 100～160g/L; Sulfuric acid (H
2SO
4) 20～60g/L; Rare earth 5～50g/L; Reactive electro catalytic specie 10～40g/L; 30～60 ℃ of temperature; Anodic current density 0.5～5A/dm
2
(2) for stainless steel base, pulse electrodeposition plumbic oxide (PbO
2) prescription and processing condition: lead nitrate Pb (NO
3)
2100～200g/L; Nitric acid (HNO
3) 1～10g/L; Rare earth 5～50g/L; Reactive electro catalytic specie 10～40g/L; Zirconium white (ZrO
2) 10～40g/L; Sodium Fluoride (NaF) 0.5～5g/L; Asccharin 0.5～5g/L; 10～40 ℃ of temperature; Anodic current density 1～8A/dm
2
The material of described aluminium matter matrix can be fine aluminium, duralumin and corrosion-resisting aluminium, and the material of stainless steel base can be 1Cr18Ni9Ti or 316L.
Described reactive electro catalytic specie is zirconium white (ZrO
2), wolfram varbide (WC), titanium dioxide (TiO
2), size range is 0.5～3 μ m; Rare earth is cerium oxide (CeO
2), lanthanum trioxide (La
2O
3), and Cerium II Chloride (CeCl
3), size range is 0.5～3 μ m.
The duty cycle range of described pulse electrodeposition is 1: 1～5: 1.
Advantage that the present invention is compared with prior art had and positively effect:
1, adopts plating bath of the present invention to form and the use of the gradient function composite anode materials that processing condition are produced on aluminum substrate and stainless steel base can significantly reduce bath voltage, reduce power consumption;
2, gradient function composite anode materials of the present invention can replace the lead anode of original technology, significantly reduces production costs;
3, plating bath nontoxicity of the present invention is polluted few to surrounding environment;
4, plating bath cost of the present invention is low, and facility investment is few, takes up an area of to lack instant effect;
5, in addition, zirconium dioxide, wolfram varbide, titanium dioxide etc. have electro catalytic activity, can significantly reduce the anodic overpotential, thereby capable of reducing energy consumption, further improve current efficiency.
Description of drawings:
Fig. 1 is the inventive method at the aluminum substrate sedimentary process flow sheet that powers on.
Fig. 2 is the inventive method at the stainless steel base sedimentary process flow sheet that powers on.
Embodiment is described in detail by the following examples.
Embodiment 1
At aluminium matter matrix, comprise pulse electrodeposition combination electrode material on fine aluminium, duralumin and the corrosion-resisting aluminium.
Technical process is: oil removing → soak zinc (Zn) → lead plating (Pb) → electrochemical oxidation → pulse electrodeposition Manganse Dioxide (MnO
2), prescription and processing condition are as follows
Dip galvanizing technique prescription and condition:
Sodium hydroxide (NaOH) 80～150g/L
Zinc oxide (ZnO) 10～40g/L
Seignette salt (NaKC
4H
4O
64H
2O) 20～80g/L
Iron(ic) chloride (FeCl
36H
2O) 1～5g/L
SODIUMNITRATE (NaNO
3) 1～5g/L
The temperature room temperature
Time 20～30s.
Lead plating technical recipe and condition:
Plumbic acetate (PbAC) 220～300g/L
Free fluorine boric acid (HBF
4) 100% 160～200g/L
Boric acid (H
3BO
3) 20～40g/L
Gelatin 1.0～5.0g/L.
Electrochemical oxidation prescription and processing condition:
Sulfuric acid (H
2SO
4) 140～200g/L
Temperature normal temperature
Time 40～60min
Current density 1～2A/dm
2
Pulse electrodeposition Manganse Dioxide prescription and processing condition:
Manganous sulfate (MnSO
4) 100～160g/L
Sulfuric acid (H
2SO
4) 20～60g/L
Rare earth (cerium oxide CeO
2, lanthanum trioxide La
2O
3, Cerium II Chloride CeCl
3) 5～50g/L
Reactive electro catalytic specie (zirconium white ZrO
2, tungsten carbide wc, titanium dioxide TiO
2) 10～40g/L
30～60 ℃ of temperature
Anodic current density 0.5～5A/dm
2
Adopt above-mentioned prescription and processing condition to obtain the gradient function composite anode materials of 20～100 micron thickness, enter as anode in the solution system of electrowinning zinc and use, bath voltage is 2.5～3.0V.
Embodiment 2
At stainless steel base, comprise that 316L and 1Cr18Ni9Ti go up the pulse electrodeposition combination electrode material.
Technical process is: sand face processing → oil removing → pulse electrodeposition plumbic oxide (PbO
2).
Pulse electrodeposition plumbic oxide (PbO
2) prescription and processing condition:
Lead nitrate Pb (NO
3)
2100～200g/L
Nitric acid (HNO
3) 1～10g/L
Rare earth (cerium oxide CeO
2, lanthanum trioxide La
2O
3, Cerium II Chloride CeCl
3) 5～50g/L
Reactive electro catalytic specie (zirconium white ZrO
2, tungsten carbide wc, titanium dioxide TiO
2)
10～40g/L
Zirconium white (ZrO
2) 10～40g/L
Sodium Fluoride (NaF) 0.5～5g/L
Asccharin 0.5～5g/L
10～40 ℃ of temperature
Anodic current density 1～8A/dm
2
Obtain the gradient function composite anode materials of 20～100 micron thickness according to above-mentioned prescription and processing condition, enter as anode in the solution system of electrowinning zinc and use, bath voltage is 2.6～3.1V.
Claims (5)
1. the preparation method of novel gradient function composite anode materials is characterized in that: adopt the pulse electrodeposition method to obtain Pb/PbO on aluminium matter matrix
2/ RE-MnO
2/ RE-ZrO
2-MnO
2The gradient function composite anode materials obtains PbO on stainless steel base
2/ RE-PbO
2/ RE-ZrO
2-PbO
2The gradient function composite anode materials,
(1) for aluminium matter matrix, the prescription and the processing condition of pulse electrodeposition Manganse Dioxide are: manganous sulfate (MnSO
4) 100～160g/L; Sulfuric acid (H
2SO
4) 20～60g/L; Rare earth 5～50g/L; Reactive electro catalytic specie 10～40g/L; 30～60 ℃ of temperature; Anodic current density 0.5～5A/dm
2
(2) for stainless steel base, pulse electrodeposition plumbic oxide (PbO
2) prescription and processing condition: lead nitrate Pb (NO
3)
2100～200g/L; Nitric acid (HNO
3) 1～10g/L; Rare earth 5～50g/L; Reactive electro catalytic specie 10～40g/L; Zirconium white (ZrO
2) 10～40g/L; Sodium Fluoride (NaF) 0.5～5g/L; Asccharin 0.5～5g/L; 10～40 ℃ of temperature; Anodic current density 1～8A/dm
2
2. preparation method according to claim 1 is characterized in that: the material of aluminium matter matrix is fine aluminium, duralumin and corrosion-resisting aluminium, and the material of stainless steel base is 1Cr18Ni9Ti and 316L.
3. preparation method according to claim 1 is characterized in that: the reactive electro catalytic specie is zirconium white (ZrO
2), wolfram varbide (WC), titanium dioxide (TiO
2), size range is 0.5～3 μ m.
4. preparation method according to claim 1 is characterized in that: rare earth is cerium oxide (CeO
2), lanthanum trioxide (La
2O
3), and Cerium II Chloride (CeCl
3), size range is 0.5～3 μ m.
5. preparation method according to claim 1 is characterized in that: the duty cycle range of pulse electrodeposition is 1: 1～5: 1.
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|---|---|---|---|
| CNB031179088A CN1184357C (en) | 2003-05-19 | 2003-05-19 | Method of preparing gradient function composite anode material |
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|---|---|---|---|
| CNB031179088A CN1184357C (en) | 2003-05-19 | 2003-05-19 | Method of preparing gradient function composite anode material |
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| CN1184357C CN1184357C (en) | 2005-01-12 |
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|---|---|---|---|
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|---|---|---|---|---|
| CN101665953B (en) * | 2009-09-21 | 2010-12-08 | 重庆大学 | Energy-saving method for electrolyzing metal manganese |
| CN101736369B (en) * | 2009-12-29 | 2011-08-17 | 昆明理工大学 | Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition |
| CN102409366A (en) * | 2011-12-05 | 2012-04-11 | 昆明理工大学 | Lead aluminium-base composite inert anode material for Zn electrodeposition and preparation method thereof |
| CN101775631B (en) * | 2009-12-29 | 2012-12-19 | 昆明理工大学 | Method for preparing lead dioxide based composite plating layer containing nano rare earth and nano zirconium dioxide |
| CN103060874A (en) * | 2013-01-30 | 2013-04-24 | 昆明理工大学 | Preparation method of stainless steel-based beta-PbO2-SnO2-CeO2-ZrO2 inertia composite anode material |
| CN103320832A (en) * | 2013-06-25 | 2013-09-25 | 北京航空航天大学 | Method for constructing wettability gradient surface by anodization |
| CN104064781A (en) * | 2014-06-18 | 2014-09-24 | 许昌学院 | Method for modifying carbon fibers by using beta-PbO2 particles and application of method |
| CN105132980A (en) * | 2015-09-21 | 2015-12-09 | 昆明理工恒达科技股份有限公司 | Film forming method for compounding ceramic film layer on surface of lead-silver alloy anode |
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| CN108004541A (en) * | 2017-12-14 | 2018-05-08 | 东北大学 | A kind of low stress gradient, the lead-based anode material preparation method of high life |
| CN110453244A (en) * | 2019-09-04 | 2019-11-15 | 西安建筑科技大学 | A kind of composite interlayer that ti-lead dioxide anode can be made to lengthen the life and its preparation and application |
| CN110791794A (en) * | 2019-11-27 | 2020-02-14 | 云南电网有限责任公司电力科学研究院 | Method and device for preparing converter valve thyristor by plating solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665953B (en) * | 2009-09-21 | 2010-12-08 | 重庆大学 | Energy-saving method for electrolyzing metal manganese |
| CN101736369B (en) * | 2009-12-29 | 2011-08-17 | 昆明理工大学 | Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition |
| CN101775631B (en) * | 2009-12-29 | 2012-12-19 | 昆明理工大学 | Method for preparing lead dioxide based composite plating layer containing nano rare earth and nano zirconium dioxide |
| CN102409366A (en) * | 2011-12-05 | 2012-04-11 | 昆明理工大学 | Lead aluminium-base composite inert anode material for Zn electrodeposition and preparation method thereof |
| CN102409366B (en) * | 2011-12-05 | 2015-05-20 | 昆明理工大学 | Lead aluminium-base composite inert anode material for Zn electrodeposition and preparation method thereof |
| CN103060874A (en) * | 2013-01-30 | 2013-04-24 | 昆明理工大学 | Preparation method of stainless steel-based beta-PbO2-SnO2-CeO2-ZrO2 inertia composite anode material |
| CN103320832B (en) * | 2013-06-25 | 2016-04-06 | 北京航空航天大学 | The method of wetting property gradient surface is constructed in anodic oxidation |
| CN103320832A (en) * | 2013-06-25 | 2013-09-25 | 北京航空航天大学 | Method for constructing wettability gradient surface by anodization |
| CN104064781A (en) * | 2014-06-18 | 2014-09-24 | 许昌学院 | Method for modifying carbon fibers by using beta-PbO2 particles and application of method |
| CN105132980A (en) * | 2015-09-21 | 2015-12-09 | 昆明理工恒达科技股份有限公司 | Film forming method for compounding ceramic film layer on surface of lead-silver alloy anode |
| CN105803513A (en) * | 2016-03-15 | 2016-07-27 | 昆明理工大学 | Preparation method for lead-coated copper-based inert composite anode material used for trivalent chromium plating |
| CN106835193A (en) * | 2017-03-15 | 2017-06-13 | 江西理工大学 | A kind of Pb bases/3D PbO2/MeOx composite anodes and preparation method thereof |
| CN108004541A (en) * | 2017-12-14 | 2018-05-08 | 东北大学 | A kind of low stress gradient, the lead-based anode material preparation method of high life |
| CN108004541B (en) * | 2017-12-14 | 2019-08-16 | 东北大学 | A kind of low stress gradient, the lead-based anode material preparation method of high life |
| CN110453244A (en) * | 2019-09-04 | 2019-11-15 | 西安建筑科技大学 | A kind of composite interlayer that ti-lead dioxide anode can be made to lengthen the life and its preparation and application |
| CN110791794A (en) * | 2019-11-27 | 2020-02-14 | 云南电网有限责任公司电力科学研究院 | Method and device for preparing converter valve thyristor by plating solution |
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