CN114411201B - Pb/Pb-Mn anode for zinc electrodeposition and preparation method thereof - Google Patents

Pb/Pb-Mn anode for zinc electrodeposition and preparation method thereof Download PDF

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CN114411201B
CN114411201B CN202210139106.4A CN202210139106A CN114411201B CN 114411201 B CN114411201 B CN 114411201B CN 202210139106 A CN202210139106 A CN 202210139106A CN 114411201 B CN114411201 B CN 114411201B
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anode
electrolyte
alloy
matrix
preparation
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CN114411201A (en
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钟晓聪
徐志峰
王瑞祥
朱茂兰
衷水平
曹才放
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Jiangxi University of Science and Technology
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Jiangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a Pb/Pb-Mn anode for zinc electrodeposition and a preparation method thereof. The anode consists of a Pb matrix and a Pb-Mn alloy coating. The preparation method of the anode comprises the following steps: in the first step, pbO and MnO are mixed 2 Dissolving in a eutectic solvent consisting of choline chloride and urea in a molar ratio of 1:2; and secondly, electrodepositing a Pb-Mn alloy layer on the Pb matrix by adopting the solution as electrolyte and adopting a constant-current polarization method. When the anode is applied to the zinc electrodeposition process, pb and Mn in the plating layer are oxidized to form PbO 2 、PbSO 4 And MnO 2 An oxide film layer is formed. The oxide film layer generated in the service process of the Pb/Pb-Mn anode has uniform structure, compact structure and high stability. Thanks to this, the service life of Pb/Pb-Mn anodes is longer than that of conventional lead alloy anodes.

Description

Pb/Pb-Mn anode for zinc electrodeposition and preparation method thereof
Technical Field
The invention relates to the field of material preparation, in particular to a Pb/Pb-Mn anode for zinc electrodeposition and a preparation method thereof.
Background
The lead alloy anode has the advantages of simple preparation and lower cost, and has been applied to the zinc electrowinning industry for hundreds of years. In the zinc electrodeposition process, an oxide film layer is gradually formed on the surface of the lead alloy anode. The oxide film layer is not only a physical barrier between the lead alloy substrate and the electrolyte, but also a place where oxygen evolution reaction occurs. Thus, the composition and structure of the oxide film layer is a key factor in determining the performance of the lead alloy anode. However, it is notable that the electrolyte contains 2-10g/L Mn during zinc electrodeposition 2+ The oxide film layer grown on the surface of the anode of the traditional lead alloy consists of a plurality of layers of MnO 2 With loose porous PbSO 4 -PbO 2 Stacked, the structure causes the membrane layer to be easy to fall off, and the service life of the anode is not ideal.
Disclosure of Invention
Aiming at the defects of low stability of an oxide film layer and non-ideal service life of the anode of the traditional lead alloy anode, the invention provides a Pb/Pb-Mn anode for zinc electrodeposition and a preparation method thereof.
The invention provides a Pb/Pb-Mn anode for zinc electrowinning, which consists of a Pb matrix and a Pb-Mn alloy coating.
Preferably, the mass percentage of Mn in the Pb-Mn alloy plating layer is 0.50-5.00 wt.%, and the thickness of the Pb-Mn alloy plating layer is 50 nm-2000 μm.
The invention provides a preparation method of a Pb/Pb-Mn anode for zinc electrodeposition, which comprises the following steps:
in the first step, pbO and MnO are mixed 2 Dissolved in a solution consisting of choline chloride in a molar ratio of 1:2: the eutectic solvent composed of urea;
and secondly, electrodepositing a Pb-Mn alloy layer on the Pb matrix by adopting the solution as electrolyte and adopting a constant-current polarization method.
Preferably, the concentration of Pb in the eutectic solvent is 0.01 to 0.04mol/L and the concentration of Mn is 0.005 to 0.02mol/L.
Preferably, the Pb concentration in the eutectic solvent is 0.04mol/L and the Mn concentration is 0.015mol/L.
Preferably, the temperature of the electrolyte is 50-80 ℃ and the cathode current density is 0.1-3 mA/cm 2 The deposition time is 10-120 min.
Preferably, the electrolyte temperature is 70 ℃ and the cathode current density is 0.5mA/cm 2 The deposition time was 100min.
The invention concept and the technical principle of the invention are as follows:
to suppress MnO 2 |PbSO 4 -PbO 2 The multilayer stacked structure improves the stability of the lead anode oxide film layer, and a plurality of lead-based coating anodes are developed by researchers in the field through prefabricating the oxide film layer on the surface of lead or lead alloy. However, the lead matrix and the coating respectively belong to a metal phase and a ceramic phase, and the chemical potential difference is large, the compatibility of the two-phase interface is poor, and the chemical stability is low. Once the defects such as cracks and holes appear in the coating, the acidic electrolyte can permeate and destroy the combination of the metal matrix and the coating, so that the coating is detached and the service life is terminated in advance.
Thus, mohammadi M. Et al, states,compared with lead-based coating anode, the bulk composite anode (also called lead-ceramic composite anode) is more suitable for the service environment with severe electrodeposition of nonferrous metals. The lead-ceramic composite anode is generally prepared from metallic lead powder and ceramic particles with oxygen evolution catalytic activity by a powder metallurgy method. The metal Pb has a low melting point, and can be used as a binding phase to fix active particles in the sintering process and form a conductive framework. Therefore, the lead-ceramic anode has both Pb stability and oxygen evolution activity of the ceramic particles. In this type of anode, pb-MnO is prepared by powder compacting-sintering 2 The anode is widely concerned, however, the lead-ceramic anode matrix prepared by the method has larger porosity, low density and poor mechanical strength due to the limitation of a powder metallurgy preparation method. Pb-MnO during long-time service 2 The composite anode needs to overcome the problems of discrete falling of matrix particles and the like.
Is subjected to Pb-MnO 2 Inspiring the composite anode to overcome Pb-MnO 2 The invention provides a lead anode with Mn introduced in alloy element form, which improves the density and mechanical strength of the matrix, simultaneously makes use of electrochemical oxidation of alloy Mn and MnO 2 Embedding the film layer to further influence Mn 2+ Regulating and controlling the growth process of lead anodic oxide film layer, inhibiting MnO 2 |PbO 2 -PbSO 4 And the multilayer stacking structure improves the stability of the lead anode oxide film layer and prolongs the service life of the anode.
Notably, mn has low solid solubility in Pb, and Mn properties are active and easy to burn, so that Pb-Mn alloy with high Mn content and uniform composition is difficult to obtain by a casting method. In addition, in an aqueous system Pb 2+ /Pb、Mn 2+ The potential difference of the Mn standard electrode is more than 1.0V, and Mn 2+ The deposition needs to be performed in a near neutral system, and thus, co-deposition of Pb and Mn is also difficult to achieve in an aqueous system. In view of the above, the invention proposes to construct Pb-Mn alloy plating layers by adopting eutectic solvent system constant current deposition.
Detailed Description
The present invention will be described in detail with reference to the following examples.
Example 1
Choline chloride containing 0.04mol/L Pb and 0.015mol/L Mn was prepared: urea (molar ratio 1:2) eutectic solvent; the solution is taken as electrolyte, the temperature is set to be 70 ℃, pb is taken as a cathode, graphite is taken as an anode, and the temperature is set to be 0.5mA/cm 2 The deposition was carried out at a current density for 100 minutes to obtain a Pb-Mn plating layer having a thickness of 10 μm on the Pb surface, the Mn content in the plating layer being 2.5wt.%.
The Pb/Pb-Mn anode was prepared in a simulated zinc electrowinning electrolyte (160 g/L H 2 SO 4 +5g/L Mn 2+ ) Medium constant current polarization (500A m) -2 ) After 72 hours, the anode slime formation amount was 0.287g, and under the same conditions, the anode slime formation amount using the conventional Pb anode was 0.723g.
Example 2
Preparing a eutectic solvent of choline chloride containing 0.01mol/L Pb and 0.005mol/L Mn and urea (molar ratio 1:2); the solution is taken as electrolyte, the temperature is set to 65 ℃, pb is taken as cathode, graphite is taken as anode, and the temperature is set to 2.5mA/cm 2 The deposition was carried out at a current density for 120 minutes to obtain a Pb-Mn plating layer having a thickness of 20 μm on the Pb surface, the Mn content in the plating layer being 3.1wt.%.
The Pb/Pb-Mn anode was prepared in a simulated zinc electrowinning electrolyte (160 g/L H 2 SO 4 +5g/L Mn 2+ ) Medium constant current polarization (500A m) -2 ) After 72 hours, the anode slime formation amount was 0.356g, and under the same conditions, the anode slime formation amount using the conventional Pb anode was 0.723g.
Example 3
Choline chloride containing 0.01mol/L Pb and 0.005mol/L Mn was prepared: urea (molar ratio 1:2) eutectic solvent; the solution is taken as electrolyte, the temperature is set to 65 ℃, pb is taken as cathode, graphite is taken as anode, and the temperature is set to 0.2mA/cm 2 The deposition was carried out at a current density for 50 minutes to obtain a Pb-Mn plating layer having a thickness of 1 μm on the Pb surface, the Mn content in the plating layer being 3.0wt.%.
The Pb/Pb-Mn anode was prepared in a simulated zinc electrowinning electrolyte (160 g/L H 2 SO 4 +5g/L Mn 2+ ) Medium constant current polarization (500A m) -2 ) After 72 hours, the anode slime formation amount was 0.456g, and under the same conditions, the anode slime formation amount using the conventional Pb anode was 0.723g.
Example 4
Preparing a eutectic solvent of choline chloride containing 0.04mol/L Pb and 0.01mol/L Mn and urea (molar ratio 1:2); the solution is taken as electrolyte, the temperature is set to 65 ℃, pb is taken as cathode, graphite is taken as anode, and the temperature is set to 2.5mA/cm 2 The deposition was carried out at a current density for 100 minutes to obtain a Pb-Mn plating layer having a thickness of 40 μm on the Pb surface, the Mn content in the plating layer being 1.4wt.%.
The Pb/Pb-Mn anode was prepared in a simulated zinc electrowinning electrolyte (160 g/L H 2 SO 4 +5g/L Mn 2+ ) Medium constant current polarization (500A m) -2 ) After 72 hours, the anode slime formation amount was 0.510g, and under the same conditions, the anode slime formation amount using the conventional Pb anode was 0.723g.
Comparative example 1
Preparing a eutectic solvent of choline chloride containing 0.01mol/L Pb and 0.005mol/L Mn and urea (molar ratio 1:2); the solution is taken as electrolyte, the temperature is set to 65 ℃, pb is taken as cathode, graphite is taken as anode, and the temperature is set to 5mA/cm 2 And (3) depositing for 50min under the current density, wherein no alloy coating is obtained on the Pb surface, and Pb is deposited in a powder form and enters the electrolyte.

Claims (3)

1. A method for preparing a Pb/Pb-Mn anode for zinc electrodeposition, which is characterized in that the anode consists of a Pb matrix and a Pb-Mn alloy coating, wherein the mass percent of Mn in the Pb-Mn alloy coating is 0.50-5.00 wt%, and the thickness of the Pb-Mn alloy coating is 50 nm-2000 mu m, and the method comprises the following steps:
in the first step, pbO and MnO are mixed 2 Dissolving in a eutectic solvent consisting of choline chloride and urea in a molar ratio of 1:2, wherein the concentration of Pb in the eutectic solvent is 0.01-0.04 mol/L, and the concentration of Mn is 0.005-0.02 mol/L;
secondly, electrodepositing a Pb-Mn alloy layer on a Pb matrix by adopting a constant-current polarization method by taking the solution as electrolyte, wherein the temperature of the electrolyte is 50-80 ℃ and the current density of a cathode is 0.1-3 mA/cm 2 The deposition time is 10-120 min.
2. The method for preparing a Pb/Pb-Mn anode for zinc electrodeposition according to claim 1, wherein the concentration of Pb in the eutectic solvent is 0.04mol/L and the concentration of Mn is 0.015mol/L.
3. The method for producing Pb/Pb-Mn anode for zinc electrodeposition according to claim 1, wherein the electrolyte temperature is 70℃and the cathode current density is 0.5mA/cm 2 The deposition time was 100min.
CN202210139106.4A 2022-02-15 2022-02-15 Pb/Pb-Mn anode for zinc electrodeposition and preparation method thereof Active CN114411201B (en)

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GB0023708D0 (en) * 2000-09-27 2000-11-08 Scionix Ltd Hydrated salt mixtures
CN101235521B (en) * 2007-01-29 2010-07-14 中南大学 Energy-saving anode for non-ferrous metal electrodeposition
CN103173795B (en) * 2012-03-27 2016-08-03 上海域高环境技术有限公司 A kind of electric plating method
CN104878409B (en) * 2015-06-16 2017-07-21 中南大学 The technique that a kind of porous lead based alloy anodes are used for Zinc electrolysis
TWI662162B (en) * 2016-11-15 2019-06-11 財團法人工業技術研究院 Electroplating method and system thereof
CN107675212B (en) * 2017-10-18 2019-05-21 江西理工大学 A kind of Zinc electrolysis fluorine-resistant lead base composite anode and preparation method thereof
CN109680301B (en) * 2019-02-19 2020-06-12 湘西土家族苗族自治州产商品质量监督检验所 Anode plate for zinc electrolysis and preparation method thereof

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