CN104313652B - Preparation method of aluminum-based multiphase inert composite anode material - Google Patents
Preparation method of aluminum-based multiphase inert composite anode material Download PDFInfo
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Abstract
The invention relates to a preparation method of an aluminum-based multiphase inert composite anode material, and belongs to the technical field of metal surface treatment. The aluminum-based PbO2-MnO2-CeO2-WC multiphase inert composite anode material doped by nanometer cerium oxide and micrometer tungsten carbide is prepared through an anodization technology, a coating layer of the material has a dark-black compact crystallization surface, has a thickness of 90-180[mu]m, and has good adhesion with a substrate. When the composite anode material is used as an anode in zinc electrowinning, the surface of the anode is in a non-soluble state as a conductive multiphase composite material, so the pollution of the dissolving of traditional lead and a lead-based alloy anode to a cathode zinc is avoided, and the quality of the cathode product is improved; the addition of tungsten carbide (WC) with good electrocatalytic activity and electrical conductivity enhances the electrocatalytic activity of electrode materials, and the bath voltage of the anode of the invention is 0.2-0.5V lower than that of traditional lead and silver alloy anodes, and is stable, so the power consumption is effectively reduced; and the addition of a rare earth oxide CeO2 makes the grains of the coating refined and the coating compact and flattened, so the corrosion resistance of the material is effectively improved.
Description
Technical field
The present invention relates to a kind of preparation method of multiphase inertia composite anode materials, belong to metal surface treatment technology neck
Domain.
Background technology
In Zinc hydrometallurgy process, Pb-Ag alloy anode is widely used, and such anode material can meet electrowinning zinc life
The fundamental need producing, but there is also many inherent shortcomings being difficult to and improving, such as：Pliable deformation causes short circuit, weight to lead to greatly
Assembling difficulty, electrolytic deposition process high energy consumption, anode electro catalytic activity are more low.Meanwhile, anode lead is easily with Pb2+Ionic speciess dissolve into
Enter solution, and in negative electrode deposition, so that cathode zinc product hierarchy is declined.In order to solve the above problems, scientist is on the one hand right
Traditional Pb based alloy anode is modified, and on the one hand continues to explore and researches and develops new inertia energy-conserving anode, such as PbO2And MnO2Anode
Deng.For the research of Pb based alloy anode, it is concentrated mainly on the alloy materials such as Pb-Ag, Pb-Ca, Pb-Ag-Ti, Pb-Ca-Sn
Research and development, the PbO in terms of the research of new inertia energy-conserving anode, mainly with Ti as matrix2Or MnO2Deng metal-oxide conduct
The anode material of outer layer, though the latter has relatively low overpotential for oxygen evolution, its high cost makes it difficult to take with defects such as low life-spans
Generation traditional lead based alloy anodes.Therefore, research and develop the weight that new inertia energy-conserving anode material is still zinc hydrometallurgy field at present
Want problem.
Content of the invention
It is an object of the invention to provide a kind of preparation method of multiphase inertia composite anode materials, specifically include following step
Suddenly：
（1）Aluminum substrate is carried out the pre-treatment of physics polishing and oil removing；
（2）To step（1）The aluminum substrate processing carries out two step leaching zinc successively；
（3）Carry out quick electronickelling by soaking the aluminum substrate after zinc is processed through two steps；
（4）By step（3）In the aluminum substrate that obtains make anode, with corrosion resistant plate for negative electrode in 60 ~ 80 DEG C of temperature, anode electricity
Current density 20-40mA/cm2, electroplate 1～2 hour under conditions of mechanical agitation 200-250r/min, the anode after plating is through water
Wash, dry up after aluminium base PbO2-MnO2-CeO2- WC inertia composite anode materials.
Step（1）Described physics polishing can be polished using 120 mesh sand paper, with industrial alkaline degreaser oil removing.
Step（1）Described polishing and oil removal treatment are conventional handling process, specifically include following steps：Polishing → washing
→ oil removing（Na3PO440g/L, Na2SiO315g/L, 1-3min）→ washing → alkali soaks（NaOH 20 g/L, Na2CO32 g/L,
1min）→ washing → acidleach（HF 10ml·L-1, HNO3250 ml·L-1, H3PO4250 ml·L-1, 3min）→ washing.
Step（2）Described in two steps to soak zinc be conventional method：Al matrix → washing after pre-treatment → once plate
Zinc (60 seconds) → wash → move back zinc（20 seconds, use 1:1 HNO3Zinc is moved back in solution dissolving）→ secondary galvanization (40 seconds), temperature control exists
Room temperature；Wherein, zinc-plated formula of liquid is：Sodium hydroxide 500g/L, sodium potassium tartrate tetrahydrate 50g/L, zinc oxide 50g/L, ferric chloride 3g/
L, sodium nitrate 2g/L.
Step of the present invention（3）Described in quick electronickelling：Al matrix after electroless zinc plating twice after washing, will be through two
Al matrix after secondary electroless zinc plating does negative electrode, and graphite cake of the same area makees anode, is 50 DEG C in temperature, and electric current density is
1.5A·dm-2, electroplating time is to carry out quick electronickelling under conditions of 5 minutes；Wherein, nickel plating formula of liquid：NiSO480 g·L-1,
Two citric acid monohydrate trisodiums（Na3C6H5O7·2H2O）90 g·L-1, H3BO310g·L-1, NaCl10 g L-1, Na2SO4
.10H2O 35g·L-1, additive（Gelatin）0.4 g·L-1.
Step of the present invention（4）The area of middle cathode material is 1.5 ~ 2 times of sheet material area to be plated.
Step of the present invention（4）In before plating adopt ultrasound wave by mixed electrolyte disperse 30 ~ 40 minutes.
Step of the present invention（4）Described in electroplating process the composition of electroplate liquid be plumbi nitrass 190-250g/L, manganese nitrate molten
Liquid 40-70g/L, sodium fluoride 1-2g/L, ceria 10-20g/L, tungsten carbide 20-50g/L.
Step of the present invention（4）The granularity of middle ceria is 10 ~ 30nm, and the granularity of tungsten carbide is 1 ~ 3 μm, ceria
Particle diameter is 10 ~ 30nm, and the particle diameter of tungsten carbide is 1 ~ 3 μm.
This composite anode materials surface is in furvous, and surface crystallization is fine and close, and thickness of coating is 90-180 μm, coating and substrate
Adhesion is excellent.
The present invention prepares doped micron-size tungsten carbide using anodizing（WC）With nanoscale ceria（CeO2）'s
Aluminium base β-PbO2-MnO2-CeO2- WC multiphase inertia composite anode materials, when making anode in Zinc electrolysis, multiple as conductive multiphase
Condensation material, its surface is in non-molten state, it is to avoid the pollution to cathode zinc of traditional lead and lead based alloy anodes dissolving, improves
Cathode product quality；There is the tungsten carbide of satisfactory electrical conductivity（WC）The addition of granule improve electrode material electro catalytic activity and
Corrosion resistance, reduces overpotential for oxygen evolution, tank voltage can be made to reduce 0.2-0.5V, and tank voltage is stable, effectively reduces power consumption；Rare earth
Oxide CeO2Addition, can crystal grain thinning, make coating more fine and close smooth, the corrosion resistance of anode material can be effectively improved.
Beneficial effects of the present invention are：
（1）Prepared Zinc electrolysis multiphase inertia composite anode materials, it is to avoid traditional lead and lead based alloy anodes are molten
The pollution to cathode zinc for the solution, can effectively improve the grade of negative electrode zinc product；
（2）This anode material has good electro catalytic activity, effectively can reduce oxygen overpotential on anode, thus reducing groove
Voltage, reaches energy-saving purpose；
（3）The addition of rare earth oxide, makes electrode surface more fine and close smooth, can effectively improve its corrosion resistance, extends
Service life.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, but protection scope of the present invention does not limit
In described content.
Embodiment 1
（1）Aluminum substrate is carried out the pre-treatment of physics polishing and oil removing：
Polished using 120 mesh sand paper, with industrial alkaline degreaser oil removing.Concretely comprise the following steps：Polish → wash → remove
Oil（Degreaser consists of：Na3PO440g/L, Na2SiO315g/L, 1-3min）→ washing → alkali soaks（NaOH 20 g/L,
Na2CO32 g/L, 1min）→ washing → acidleach（HF 10ml·L-1, HNO3250 ml·L-1, H3PO4250 ml·L-1,
3min）→ washing.
（2）To step（1）The aluminum substrate processing carries out two step leaching zinc successively：
Two step leaching zinc, two step dip galvanizing technique formula are carried out to the aluminum substrate of pre-treatment：Al matrix after pre-treatment →
Washing → once zinc-plated (60 seconds) → wash → move back zinc（20 seconds, use 1:1 HNO3Zinc is moved back in solution dissolving）→ secondary galvanization (40
Second), temperature control is in room temperature；Wherein, zinc-plated formula of liquid is：Sodium hydroxide 500g/L, sodium potassium tartrate tetrahydrate 50g/L, zinc oxide
50g/L, ferric chloride 3g/L, sodium nitrate 2g/L.
（3）Carry out quick electronickelling by soaking the aluminum substrate after zinc is processed through two steps：Al matrix after electroless zinc plating twice
After washing, the Al matrix after electroless zinc plating twice is done negative electrode, graphite cake of the same area makees anode, be 50 in temperature
DEG C, electric current density is 1.5A dm-2, electroplating time is to carry out quick electronickelling under conditions of 5 minutes；Wherein, nickel plating formula of liquid：
NiSO480 g·L-1, two citric acid monohydrate trisodiums（Na3C6H5O7·2H2O）90g·L-1, H3BO310g·L-1, NaCl10
g·L-1, Na2SO4.10H2O 35g·L-1, additive（Gelatin）0.4 g·L-1.
（4）Aluminium base β-PbO is prepared in electro-deposition2-MnO2-CeO2- WC multiphase inertia composite anode materials：With corrosion resistant plate it is
Negative electrode is in temperature 70 C, anodic current density 30mA/cm2, electroplate 1.5 hours under conditions of mechanical agitation 230r/min, plating
Anode afterwards obtains aluminium base PbO after washing, drying up2-MnO2-CeO2- WC inertia composite anode materials；Wherein, electroplate liquid formulation is：
Plumbi nitrass（Pb(NO3)2）190g/L, 50% manganese nitrate solution（Mn(NO3)2）40g/L, sodium fluoride（NaF）1g/L, ceria
（CeO2Granularity is：15nm）10g/L, tungsten carbide（Wc grain size is 2 μm）20g/L；Before plating, electroplate liquid is carried out ultrasound wave dispersion
35 minutes.
The thickness of multiple plating that the present embodiment prepares be 90 ~ 120 μm, in coating Ce constituent content be 5.26 ~
6.78%, content of element W is 1.48 ~ 3.91%.
Embodiment 2
Step in the present embodiment（1）~（3）Same as Example 1；Difference is step（4）In with corrosion resistant plate as negative electrode
In 80 DEG C of temperature, anodic current density 40mA/cm2, electroplate 2 hours under conditions of mechanical agitation 250r/min, the sun after plating
Pole obtains aluminium base PbO after washing, drying up2-MnO2-CeO2- WC inertia composite anode materials；Wherein, electroplate liquid formulation is：Plumbi nitrass
（Pb(NO3)2）220g/L, 50% manganese nitrate solution（Mn(NO3)2）50g/L, sodium fluoride（NaF）1.5g/L, ceria（CeO2Grain
Spend and be：10~30nm）15g/L, tungsten carbide（Wc grain size is 3 μm）30g/L；Before plating, electroplate liquid is carried out ultrasound wave and disperse 40 points
Clock.
Aluminium base β-the PbO that the present embodiment prepares2-MnO2-CeO2- WC thickness of multiple plating is 130 ~ 160 μm, coating
Middle Ce constituent content is 8.75 ~ 9.67%, and content of element W is 3.61 ~ 4.59%.
Embodiment 3
Step in the present embodiment（1）~（3）Same as Example 1；Difference is step（4）In with corrosion resistant plate as negative electrode
In temperature 60 C, anodic current density 20mA/cm2, electroplate 1 hour under conditions of mechanical agitation 200r/min, the sun after plating
Pole obtains aluminium base PbO after washing, drying up2-MnO2-CeO2- WC inertia composite anode materials；Wherein, electroplate liquid formulation is：Plumbi nitrass
（Pb(NO3)2）250g/L, 50% manganese nitrate solution（Mn(NO3)2）70g/L, sodium fluoride（NaF）2g/L, ceria（CeO2Granularity
For：20~30nm）20g/L, tungsten carbide（Wc grain size is 1 μm）40g/L；Before plating, electroplate liquid is carried out ultrasound wave to disperse 30 minutes.
Aluminium base β-the PbO that the present embodiment prepares2-MnO2-CeO2- WC thickness of multiple plating is 140 ~ 180 μm, coating
Middle Ce constituent content is 9.01 ~ 12.38%, and content of element W is 5.64 ~ 7.89%.
Claims (3)
1. a kind of preparation method of multiphase inertia composite anode materials is it is characterised in that specifically include following steps：
（1）Aluminum substrate is carried out the pre-treatment of physics polishing and oil removing；
（2）To step（1）The aluminum substrate processing carries out two step leaching zinc successively；
（3）Carry out quick electronickelling by soaking the aluminum substrate after zinc is processed through two steps；
（4）By step（3）In the aluminum substrate that obtains make anode, close in 60 ~ 80 DEG C of temperature, anode current for negative electrode with corrosion resistant plate
Degree 20-40mA/cm2, electroplate 1～2 hour under conditions of mechanical agitation 200-250r/min, the anode after plating through washing, blow
Aluminium base PbO is obtained after dry2-MnO2-CeO2- WC inertia composite anode materials；
Step（4）Described in electroplating process the composition of electroplate liquid be plumbi nitrass 190-250g/L, manganese nitrate solution 40-70 g/
L, sodium fluoride 1-2 g/L, ceria 10-20 g/L, tungsten carbide 20-50 g/L；
The granularity of ceria is 10 ~ 30nm, and the granularity of tungsten carbide is 1 ~ 3 μm, and the particle diameter of ceria is 10 ~ 30nm, carbonization
The particle diameter of tungsten is 1 ~ 3 μm.
2. multiphase inertia composite anode materials according to claim 1 preparation method it is characterised in that：Cathode material
Area is 1.5 ~ 2 times of sheet material area to be plated.
3. multiphase inertia composite anode materials according to claim 1 preparation method it is characterised in that：Adopt before plating
With ultrasound wave, mixed electrolyte is disperseed 30 ~ 40 minutes.
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| CN104762639B (en) * | 2015-03-09 | 2017-03-15 | 中南大学 | Hydrometallurgy electro-deposition operation porous aluminum based composite anode and preparation method |
| CN105568340B (en) * | 2015-12-30 | 2021-03-05 | 河北工业大学 | Preparation method of manganese ion-doped lead dioxide positive electrode material for supercapacitor |
| CN107841765B (en) * | 2017-09-29 | 2019-08-16 | 中南大学 | A kind of Zinc electrolysis anode material and preparation method thereof |
| CN108774737B (en) * | 2018-06-13 | 2020-02-14 | 昆明理工恒达科技股份有限公司 | Preparation method of foam metal-based lead alloy composite anode material |
| CN109537000B (en) * | 2018-11-27 | 2020-12-08 | 昆明理工大学 | Stainless steel based beta-PbO2-MnO2-CeO2-ZrO2Preparation method of inert composite anode material |
| CN110904463A (en) * | 2019-12-04 | 2020-03-24 | 安徽铜冠有色金属（池州）有限责任公司 | Cleaning method for removing oil stains on cathode and anode plate surfaces in zinc hydrometallurgy |
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| US5632872A (en) * | 1995-06-21 | 1997-05-27 | Marion Dattilo | Composite electrical electrode and a method for forming the same |
| 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 |
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| CN103060875B (en) * | 2013-01-30 | 2015-06-03 | 昆明理工大学 | Preparation method of copper-based SnO2-Sb2O5-CeO2-TiO2 inert composite anode material |
| CN103060874B (en) * | 2013-01-30 | 2015-09-30 | 昆明理工大学 | A kind of stainless steel-based β-PbO 2-SnO 2-CeO 2-ZrO 2the preparation method of inertia composite anode materials |
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Effective date of registration: 20210310 Address after: 650106, No. 1299 Chang Yuan North Road, Kunming hi tech Development Zone, Yunnan Patentee after: KUNMING HENDERA SCIENCE AND TECHNOLOGY Co.,Ltd. Address before: 650093 No. 253, Xuefu Road, Wuhua District, Yunnan, Kunming Patentee before: Kunming University of Science and Technology |