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Titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and preparation method thereof

A technology of lead dioxide and composite electrodes, which is applied in the direction of electrodes, electrolytic processes, electrolytic components, etc., can solve the problems of affecting interface conductivity, small internal stress, and low porosity, so as to prolong service life, improve conductivity, and ease The effect of electrowinning distortion

Pending Publication Date: 2021-12-31
KUNMING UNIV OF SCI & TECH +2
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Problems solved by technology

[0010] The present invention aims at the problem that the traditional titanium-based lead dioxide electrode in the prior art is easily passivated and thus affects the interface conductivity, and provides a titanium-based gradient lead dioxide composite electrode material for copper electrowinning and a preparation method thereof. β-PbO 2 -Nano SnO 2 The middle layer is combined with pulse electrodeposition and composite plating technology. Pulse electrodeposition is used for anodic oxidation / cathode reduction of metal ions. The instantaneous high current density during current conduction makes metal ions oxidize / reduce at extremely high overpotentials. During the current shutdown period, the concentration polarization can be effectively eliminated, thereby improving the deep plating ability of the liquid, making the crystallization of the transition layer fine and uniform, with low porosity and internal stress, and even changing the preferred orientation of the crystal plane to obtain nanocrystalline grains, which can be effectively Improve the physical and chemical properties of the coating

Method used

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  • Titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and preparation method thereof
  • Titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and preparation method thereof
  • Titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and preparation method thereof

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Embodiment 1

[0070] Embodiment 1: the titanium-based gradient lead dioxide composite electrode material used for copper electrowinning in this embodiment, the molar ratio of metal Sn, Ru, Ta and Zr in the bottom layer Sn-Ru-Ta-ZrOx oxide is 70:5 respectively: 12:13; middle layer β-PbO 2 -Nano SnO 2 SnO in 2 The mass content is 1.0wt.%; transition layer α-PbO 2 -The mass content of copper-coated graphite powder in copper-coated graphite powder is 2.2wt.%; the active layer β-PbO 2 -nano-ZrN-cobalt-coated hollow glass microspheres have a mass content of 1.2wt.% of nano-ZrN particles, and the content of cobalt-coated hollow glass microspheres is 2.0wt.%;

[0071] Sn-Ru-Ta-ZrOx oxide layer thickness is 4μm, β-PbO 2 -Nano SnO 2 The thickness of the middle layer is 200μm, α-PbO 2 - Copper-coated graphite powder transition layer thickness is 300μm, β-PbO 2 - The thickness of the active layer of nano-ZrN-cobalt-coated hollow glass microspheres is 600 μm;

[0072] β-PbO 2 -Nano SnO 2 Nano-...

Embodiment 2

[0093] Embodiment 2: the titanium-based gradient lead dioxide composite electrode material used for copper electrowinning in this embodiment, the molar ratio of metal Sn, Ru, Ta and Zr in the bottom layer Sn-Ru-Ta-ZrOx oxide is 50:10 respectively: 20:20; middle layer β-PbO 2 -Nano SnO 2 SnO in 2 The mass content is 0.1wt.%; transition layer α-PbO 2 -The mass content of copper-coated graphite powder in copper-coated graphite powder is 1.0wt.%; the active layer β-PbO 2 -nano-ZrN-cobalt-coated hollow glass microspheres have a mass content of nano-ZrN particles of 0.6wt.%, and the content of cobalt-coated hollow glass microspheres is 0.5wt.%.

[0094] Sn-Ru-Ta-ZrOx oxide layer thickness is 0.5μm, β-PbO 2 -Nano SnO 2 The thickness of the intermediate layer is 100 μm, α-PbO 2 - Copper-coated graphite powder transition layer thickness is 100μm, β-PbO 2 - The thickness of the active layer of nano ZrN-cobalt-coated hollow glass microspheres is 100 μm;

[0095] β-PbO 2 -Nano Sn...

Embodiment 3

[0108] Embodiment 3: the titanium-based gradient lead dioxide composite electrode material used for copper electrowinning in this embodiment, the molar ratio of metal Sn, Ru, Ta and Zr in the bottom layer Sn-Ru-Ta-ZrOx oxide is 90:1 respectively: 5:4; middle layer β-PbO 2 -Nano SnO 2 SnO in 2 The mass content is 1.5wt.%; transition layer α-PbO 2 -The mass content of copper-coated graphite powder in copper-coated graphite powder is 3.2wt.%; the active layer β-PbO 2 - The nano-ZrN-cobalt-coated hollow glass microspheres have a mass content of 1.8wt.% of the nano-ZrN particles, and the content of the cobalt-coated hollow glass microspheres is 5.0wt.%;

[0109] Sn-Ru-Ta-ZrOx oxide layer thickness is 8μm, β-PbO 2 -Nano SnO 2 The thickness of the middle layer is 500μm, α-PbO 2 - Copper-coated graphite powder transition layer thickness is 400μm, β-PbO 2 - The thickness of the active layer of nano-ZrN-cobalt-coated hollow glass microspheres is 1000 μm;

[0110] β-PbO 2 -Nano ...

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Abstract

The invention relates to a titanium-based gradient lead dioxide composite electrode material for copper electrodeposition and a preparation method thereof, and belongs to the technical field of wet metallurgy anode plates. The titanium-based gradient lead dioxide composite electrode material for copper electrodeposition sequentially comprises a titanium substrate, a Sn-Ru-Ta-ZrOx oxide bottom layer, a beta-PbO2-nano SnO2 middle layer, an alpha-PbO2-copper coated graphite powder transition layer and a beta-PbO2-nano ZrN-cobalt coated hollow glass bead active layer from inside to outside. The invention further provides a preparation method of the titanium-based gradient lead dioxide composite electrode material for copper electrodeposition. The electrode material provided by the invention is applied to electrodeposited copper, and in an electrolytic copper solution which does not contain cobalt ions but contains manganese chloride ions, compared with a traditional Pb-0. 06wt% Ca-1.2wt% Sn anode, the cell voltage can be reduced by 480mV, the service life is prolonged by more than 3 times, the current efficiency is improved by more than 5%, and the current density can be increased to more than 2 times of the original current density.

Description

technical field [0001] The invention relates to a titanium-based gradient lead dioxide composite electrode material for copper electrowinning and a preparation method thereof, belonging to the technical field of hydrometallurgical anode plates. Background technique [0002] At present, copper resource mines with low ore grades account for more than half. With the increasing exploitation of high-grade copper mines by human beings and the distribution of copper mines with the characteristics of scattered deposits, many sites and small quantities, pyrometallurgical copper smelting technology High energy consumption, low output, and great environmental pollution can no longer meet the needs of people's production. Therefore, the hydrometallurgy process, which has advantages in processing oxidized ore and low-grade sulfide ore, is increasingly widely used. [0003] Wet production of copper requires a large amount of lead alloy anodes. At present, during wet electrodeposition of ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25D17/10C25D3/38C25C7/02C25C1/12
CPCC25D17/10C25D3/38C25C1/12C25C7/02Y02P10/20
Inventor 陈步明谢雄辉黄惠郭忠诚冷和
Owner KUNMING UNIV OF SCI & TECH
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