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Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition

A lead dioxide and manganese dioxide technology, used in electrodes, electrolytic processes, electrolytic components, etc., can solve the problems of large internal stress, easy peeling of the deposited layer, poor electrical conductivity, etc., and achieve strong acid and alkali corrosion resistance. , The electrode price is low, the effect of superior acid and alkali resistance

Inactive Publication Date: 2010-06-16
KUNMING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] In the process of wet extraction of zinc, copper, nickel, cobalt, manganese, chromium and other metals, lead and lead alloys are still used as anode materials at present. The disadvantages are: high cell voltage (3.4-3.8V), low current efficiency (75- 88%), high energy consumption in the electrowinning process (3400-4200 degrees / ton of zinc), short service life of the anode (0.5-1 year), easy dissolution of anode lead into the cathode product, resulting in a decline in the quality of the cathode product
[0003] 1. Improved lead-silver binary and multi-component alloy anodes: mainly including lead-silver (Pb-Ag), lead-arsenic (Pb-As), lead-calcium (Pb-Ca), lead-mercury (Pb-Hg) , lead-cadmium (Pb Pb-Cd), lead-titanium (Pb-Ti), lead-calcium-barium (Pb-Ca-Ba), lead-silver-calcium (Pb-Ag-Ca), lead-silver- Strontium (Pb-Ag-Sr), lead-calcium-tin (Pb-Ca-Sn) and lead-silver-calcium-tin (Pb-Ag-Ca-Sn), etc., but still have short service life and high energy consumption and easy to pollute cathode products and other shortcomings
[0004] 2. Titanium-based surface-coated (plated) dimensionally stable anode: This type of anode is based on titanium (Ti) and coated with noble metal or its oxide on the surface, but this anode has the following shortcomings: (1) using titanium substrate, The cost of the electrode is high; (2) due to the dissolution of the noble metal coating and the passivation of the matrix titanium in the electrolytic production, the life of the electrode is short; (3) in the electrowinning solution, impurity ions, such as manganese, are oxidized in the oxide state Deposition of the anode reduces the effect of coating the precious metal layer
But the PbO produced by electroplating in this way 2 As an insoluble anode, the electrode will have the following problems in use: (1) PbO 2 The deposition layer is not tightly combined with the electrode surface or the deposition layer is uneven; (2) PbO 2 The deposited layer is porous and rough, with large internal stress; (3) PbO 2 The deposited layer is easy to peel off or corrode, and the service life is not long
But its disadvantages are low strength, poor conductivity and short life.

Method used

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  • Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition
  • Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition
  • Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] The lead dioxide-manganese dioxide anode is compounded on the aluminum substrate, and the aluminum plate is processed into a small sample of 50mm×20mm×2mm. The process flow is: aluminum plate→quenching→degreasing→sandblasting→spraying conductive coating→electrodepositing α-PbO 2 -CeO 2 -TiO 2 →Electrodeposited β-PbO 2 -MnO 2 -WC-ZrO 2 , the alkaline composite plating α-PbO 2 -CeO 2 -TiO 2 Formula and process conditions: lead monoxide (PbO) 30g / L, sodium hydroxide (NaOH) 200g / L, particle size 30nm cerium dioxide (CeO 2 ) 10g / L, particle size 50nm titanium dioxide (TiO 2 )30g / L, temperature is 40℃, anode current density is 1~3A / dm 2 , and plated for 4 h under magnetic stirring. The thickness of this intermediate layer is approximately equal to 200 μm.

[0037] The acid composite plating β-PbO 2 -MnO 2 -WC-ZrO 2 Formula and process conditions: lead nitrate Pb(NO 3 ) 2 200g / L, nitric acid (HNO 3 )2~15g / L, sodium fluoride (NaF)3~10g / L, manganese nitrate Mn(N...

Embodiment 2

[0039] The lead dioxide-manganese dioxide anode is compounded on the aluminum substrate, and the aluminum plate is processed into a small sample of 50mm×20mm×2mm. The process flow is: aluminum plate→quenching→degreasing→sandblasting→spraying conductive coating→electrodepositing α-PbO 2 -CeO 2 -TiO 2 →Electrodeposited β-PbO 2 -MnO 2 -WC-ZrO 2 , the alkaline composite plating α-PbO 2 -CeO 2 -TiO 2 Formula and process conditions: lead monoxide (PbO) 30g / L, sodium hydroxide (NaOH) 200g / L, particle size 30nm cerium dioxide (CeO 2 ) 20g / L, particle size 50nm titanium dioxide (TiO 2 )20g / L, temperature is 40℃, anode current density is 1~3A / dm 2 , and plated for 2 h under magnetic stirring. The thickness of this intermediate layer is approximately equal to 100 μm.

[0040] The acid composite plating β-PbO 2 -MnO 2 -WC-ZrO 2 Formula and process conditions: lead nitrate Pb(NO 3 ) 2 250g / L, nitric acid (HNO 3 )2~15g / L, sodium fluoride (NaF)3~10g / L, manganese nitrate Mn(N...

Embodiment 3

[0042] The preparation method and process parameters are as described in Example 1. The acid composite plating β-PbO 2 -MnO 2 -WC-ZrO 2 Formula and process conditions: lead nitrate Pb(NO 3 ) 2 280g / L, nitric acid (HNO 3 )2~15g / L, sodium fluoride (NaF)3~10g / L, manganese nitrate Mn(NO 3 ) 2 80g / L, particle size 50nm zirconia (ZrO 2 ) 40g / L, 0.02~1 anode tungsten carbide (WC) 10g / L, use pure lead plate as cathode, temperature is 50~60℃, current density is 3~4A / dm 2 , and plated for 3 h under magnetic stirring. Thus, about 250 μm thick β-PbO 2 (61wt%)-MnO 2 (32wt%)-WC(5.9wt%)-ZrO 2 (1.1wt%) coating, the surface morphology of its coating is as attached Figure 4 . The coating is used as an anode in the electrolytic zinc plating solution system, the cell voltage is 2.7-2.8V; the current density at 40°C is 2A / cm 2 150g / L H 2 SO 4 Electrolysis is carried out in the solution, and the time elapsed when the voltage of the electrolytic cell rises (about 10V) is the expecte...

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Abstract

The invention discloses a method for preparing a novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition, which is characterized by sequentially plating conductive coating, an alpha-PbO2-CeO2-TiO2 layer and a beta-PbO2-MnO2-WC-ZrO2 layer outside an aluminum matrix of a composite lead dioxide-manganese dioxide anode from inside to outside. The method comprises the following steps of: carrying out quenching, oil removal and sand blasting processing on the aluminum matrix; spraying the conductive coating on a matrix material; then carrying out alkaline composite plating on the alpha-PbO2-CeO2-TiO2 layer and carrying out acidic composite plating on the beta-PbO2-MnO2-WC-ZrO2 layer to obtain the composite lead dioxide-manganese dioxide anode. The aluminum-based composite lead dioxide-manganese dioxide anode manufactured by the process and method of the invention can obviously reduce the voltage of an electrode bath and energy consumption; and meanwhile, a plating layer and a matrix have strong binding force and small internal stress, and the service life of an electrode is long.

Description

technical field [0001] The invention relates to a composite anode material used in the field of metal surface treatment, in particular to a preparation method of a novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrowinning. Background technique [0002] In the process of wet extraction of zinc, copper, nickel, cobalt, manganese, chromium and other metals, lead and lead alloys are still used as anode materials at present. The disadvantages are: high cell voltage (3.4-3.8V), low current efficiency (75- 88%), high energy consumption in the electrowinning process (3400-4200 degrees / ton of zinc), short service life of the anode (0.5-1 year), easy dissolution of anode lead into the cathode product, resulting in a decline in the quality of the cathode product. In order to reduce the energy consumption of electrowinning zinc, copper, nickel, cobalt, manganese, chromium, etc. and prevent the pollution of cathode products by anode lead, in-depth resear...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25C7/02C25C1/16C25D9/04
Inventor 郭忠诚陈步明
Owner KUNMING UNIV OF SCI & TECH
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