CN114411206A - Composite anode for zinc electrodeposition and preparation method thereof - Google Patents

Composite anode for zinc electrodeposition and preparation method thereof Download PDF

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Publication number
CN114411206A
CN114411206A CN202210148038.8A CN202210148038A CN114411206A CN 114411206 A CN114411206 A CN 114411206A CN 202210148038 A CN202210148038 A CN 202210148038A CN 114411206 A CN114411206 A CN 114411206A
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mno
znfe
composite anode
solution
particles
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CN114411206B (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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

The invention discloses Pb-ZnFe for zinc electrodeposition2O4@MnO2A composite anode and a preparation method. The method comprises the following steps: ZnFe is mixed with water2O4Particles dispersed in Mn-containing2+Soaking in the solution for 12 h; will adsorb Mn2+ZnFe (b)2O4The particles are transferred to a solution of MnO4 ‑In solution of (2), MnO is obtained by neutralization reaction2A housing; lead powder and ZnFe are mixed by a mixer2O4@MnO2Mixing uniformly; pressing and molding the uniformly mixed powder sample, and then adopting a sintering furnace to lead Pb-ZnFe to be formed2O4@MnO2And sintering the green body, and cooling to room temperature along with the furnace. In the sintering process, Pb powder is melted to form a liquid phase, and after cooling, the liquid phase forms ZnFe taking lead as a continuous phase2O4@MnO2Is a composite anode of a dispersed phase. Using MnO2Wrapped ZnFe2O4The particles can inhibit ZnFe2O4Dissolving.

Description

Composite anode for zinc electrodeposition and preparation method thereof
Technical Field
The invention relates to the field of material preparation, in particular to Pb-ZnFe for zinc electrodeposition2O4@MnO2A composite anode and a method for preparing the same.
Background
During zinc electrodeposition, Zn is generated at the cathode2+While the anode primarily functions to conduct the electrical circuit. Therefore, zinc electrodeposition generally employs lead-based inert anodes. Currently, Pb-Ag alloys are standard anodes for zinc electrodeposition. However, Pb-Ag anodes have the disadvantages of large Ag consumption, high cost, undesirable corrosion resistance, and the like. In recent years, lead-ceramic composite anodes have received much attention. The lead-ceramic composite anode is formed by uniformly mixing, pressing and sintering lead powder and ceramic particles with oxygen evolution catalytic activity, and has good oxygen evolution activity. However, the electrolyte for electrodeposition generally contains sulfuric acid at about 150 g/L. Under the acidic condition, the ceramic particles are easy to dissolve, and the stability of the composite anode is not ideal. ZL201910040251.5 provides a lead-zinc ferrite composite anode for zinc electrodeposition, and due to the existence of zinc ferrite particles, the anode has good oxygen evolution activity and low anode potential, and can play a role in reducing the energy consumption of zinc electrodeposition. However, during service, ZnFe2O4The Pb around the particles is electrochemically oxidized into PbO2Or PbSO4. Due to Pb and oxidation product PbO2Or PbSO4The molar volumes are different, resulting in ZnFe2O4Bare, thereby inducing ZnFe2O4Dissolving.
Disclosure of Invention
For Pb-ZnFe2O4ZnFe exists in the composite anode2O4The invention provides Pb-ZnFe with the defects of easy dissolution and low stability of particles2O4@MnO2A composite anode and a method for preparing the same.
The invention provides Pb-ZnFe for zinc electrodeposition2O4@MnO2A composite anode made of Pb and ZnFe2O4@MnO2The composition is that Pb is a continuous phase and is wrapped by MnO2ZnFe of the shell2O4As a disperse phase, Pb and ZnFe2O4@MnO2The metallurgical bonding is achieved by pressing-sintering.
Preferably, Pb-ZnFe2O4@MnO2ZnFe in composite anode2O4@MnO2The mass percentage of (B) is 0.50-10.00 wt.%.
The invention provides Pb-ZnFe for zinc electrodeposition2O4@MnO2The preparation method of the composite anode comprises the following steps:
ZnFe is mixed with water2O4Particles dispersed in Mn-containing2+Soaking in the solution for 12 h;
will adsorb Mn2+ZnFe (b)2O4The particles are transferred to a solution of MnO4 -In solution of (2), MnO is obtained by neutralization reaction2A housing;
lead powder and ZnFe are mixed by a mixer2O4@MnO2Mixing uniformly;
pressing and molding the uniformly mixed powder sample, and then adopting a sintering furnace to lead Pb-ZnFe to be formed2O4@MnO2And sintering the green body, and cooling to room temperature along with the furnace.
Preferably, the particle size of the lead powder is 100 nm-1000 μm; ZnFe2O4The particle size of the particles is 50 nm-1000 μm.
Preferably, containing Mn2+Mn in solution2+The concentration is 0.05-1.50 mol/L.
Preferably, containing MnO4 -MnO in solution4 -The concentration is 0.01-0.05 mol/L.
Preferably, the compression molding pressure is 10-30 MPa, and the sintering temperature is 327-337 ℃.
The invention concept and technical principle of the invention are as follows:
MnO2the composite material has good chemical stability and high electrochemical stability in an acid solution. By neutralization reaction on ZnFe2O4MnO is formed on the surface2A coating shell layer for inhibiting ZnFe in the electrolytic process2O4The stability and service life of the anode are improved. Notably, MnO2The thickness of the layer needs to be regulated below 1 μm, otherwise ZnFe2O4The oxygen evolution activity of (A) cannot be exerted. However, Mn2+And MnO with MnO4 -The reaction is fast and individual MnO is easily formed2Particles or too thick MnO2And (4) shell layer. Thus, in the preparation of MnO2When the shell is formed, ZnFe is firstly needed2O4Adsorb some Mn2+Then transferring the particles to a solid support containing MnO4 -In solution, by optimizing Mn2+Concentration, soaking time, MnO4 -At a concentration such that MnO of a suitable thickness can be obtained2And (4) shell layer. In conclusion, the invention provides Pb-ZnFe2O4@MnO2The composite anode has the advantages of good corrosion resistance and low energy consumption, and has great industrial application value.
Detailed Description
The present invention will be described in detail with reference to the following examples.
Example 1
ZnFe having an average particle diameter of 220nm2O4The particles were dispersed in a dispersion containing 0.05mol/L Mn2+Soaking in the solution for 12 h; will adsorb Mn2+ZnFe (b)2O4The particles were transferred to a solution of 0.05mol/L MnO4 -In solution of (2), MnO is obtained by neutralization reaction2A shell, the thickness of the shell is 0.52 μm; mixing 200nm lead powder and ZnFe with a mixer2O4@MnO2Uniformly mixed, ZnFe2O4@MnO2The mass fraction was 1.0 wt%. Pressing the uniformly mixed powder sample under 30Mpa to form a mould, then carrying out heat preservation sintering at 327 ℃ for 2h, and carrying out furnace cooling to room temperature. The composite anode is polarized in a simulated zinc electrodeposition electrolyte in a constant current mode (500A m)-2) After 72hAnd the ICP-MASS detection of the electrolyte does not detect Fe2+And Fe3+The anode potential is 72mV lower than that of the traditional Pb-Ag plate.
Example 2
ZnFe having an average particle diameter of 1.96 μm2O4The particles were dispersed in a dispersion containing 0.10mol/L Mn2+Soaking in the solution for 12 h; will adsorb Mn2+ZnFe (b)2O4The particles were transferred to a solution of 0.03mol/L MnO4 -In solution of (2), MnO is obtained by neutralization reaction2A shell, the thickness of the shell is 0.91 μm; mixing 200nm lead powder and ZnFe with a mixer2O4@MnO2Uniformly mixed, ZnFe2O4@MnO2The mass fraction was 1.0 wt%. Pressing the uniformly mixed powder sample under 25Mpa to form a mould, then carrying out heat preservation sintering at 327 ℃ for 2h, and carrying out furnace cooling to room temperature. The composite anode is polarized in a simulated zinc electrodeposition electrolyte in a constant current mode (500A m)-2) After 72h, the electrolyte ICP-MASS detects that Fe is not detected2+And Fe3+The anode potential is 25mV lower than that of the traditional Pb-Ag plate.
Comparative example 1
ZnFe having an average particle diameter of 1.96 μm2O4The particles are dispersed in a dispersion containing 1.00mol/L Mn2+Soaking in the solution for 12 h; will adsorb Mn2+ZnFe (b)2O4The particles were transferred to a solution of 0.05mol/L MnO4 -In solution of (2), MnO is obtained by neutralization reaction2A shell, the thickness of the shell is 2.30 μm; mixing 200nm lead powder and ZnFe with a mixer2O4@MnO2Uniformly mixed, ZnFe2O4@MnO2The mass fraction was 1.0 wt%. Pressing the uniformly mixed powder sample under 25Mpa to form a mould, then carrying out heat preservation sintering at 327 ℃ for 2h, and carrying out furnace cooling to room temperature. The composite anode is polarized in a simulated zinc electrodeposition electrolyte in a constant current mode (500A m)-2) After 72h, the electrolyte ICP-MASS detects that Fe is not detected2+And Fe3+The anode potential is 50mV higher than that of the traditional Pb-Ag anode.
Comparative example 2
ZnFe having an average particle diameter of 18.5 μm2O4The particles are dispersed in a solvent containing 1.5mol/L Mn2+Soaking in the solution for 12 h; will adsorb Mn2+ZnFe (b)2O4The particles were transferred to a solution of 0.08mol/L MnO4 -In solution of (2), ZnFe2O4MnO was not obtained on the surface of the particles2A housing; 200nm lead powder and treated ZnFe are mixed by a mixer2O4Uniformly mixing the particles, and treating the ZnFe2O4The mass fraction was 1.0 wt%. Pressing the uniformly mixed powder sample under 30Mpa to form a mould, then carrying out heat preservation sintering at 327 ℃ for 2h, and carrying out furnace cooling to room temperature. The composite anode is polarized in a simulated zinc electrodeposition electrolyte in a constant current mode (500A m)-2) After 72h, the electrolyte is detected to be 0.28mg/L Fe by adopting ICP-MASS3+The anode potential is equivalent to that of the traditional Pb-Ag anode.

Claims (7)

1. Pb-ZnFe for zinc electrodeposition2O4@MnO2Composite anode, characterized in that it consists of Pb and ZnFe2O4@MnO2The composition is that Pb is a continuous phase and is wrapped by MnO2ZnFe of the shell2O4As a disperse phase, Pb and ZnFe2O4@MnO2Metallurgical bonding is achieved by pressing-sintering, wherein MnO is2The thickness of the shell layer is 1 μm or less.
2. The Pb-ZnFe electrolyte of claim 12O4@MnO2Composite anode, characterized in that Pb-ZnFe2O4@MnO2ZnFe in composite anode2O4@MnO2The mass percentage of (B) is 0.50-10.00 wt.%.
3. Pb-ZnFe for zinc electrodeposition according to claim 1 or 22O4@MnO2The preparation method of the composite anode is characterized by comprising the following steps of:
ZnFe is mixed with water2O4Particles dispersed in Mn-containing2+Soaking in the solution for 12 h;
will adsorb Mn2+ZnFe (b)2O4The particles are transferred to a solution of MnO4 -In solution of (2), MnO is obtained by neutralization reaction2A housing;
lead powder and ZnFe are mixed by a mixer2O4@MnO2Mixing uniformly;
pressing and molding the uniformly mixed powder sample, and then adopting a sintering furnace to lead Pb-ZnFe to be formed2O4@MnO2And sintering the green body, and cooling to room temperature along with the furnace.
4. The Pb-ZnFe for zinc electrodeposition as claimed in claim 32O4@MnO2The preparation method of the composite anode is characterized in that the particle size of lead powder particles is 100 nm-1000 mu m; ZnFe2O4The particle size of the particles is 50 nm-1000 μm.
5. The Pb-ZnFe for zinc electrodeposition as claimed in claim 32O4@MnO2The preparation method of the composite anode is characterized in that the composite anode contains Mn2+Mn in solution2+The concentration is 0.05-1.50 mol/L.
6. The Pb-ZnFe for zinc electrodeposition as claimed in claim 32O4@MnO2A method for producing a composite anode, characterized in that it contains MnO4 -MnO in solution4 -The concentration is 0.01-0.05 mol/L.
7. The Pb-ZnFe for zinc electrodeposition as claimed in claim 32O4@MnO2The preparation method of the composite anode is characterized in that the press forming pressure is 10-30 MPa, and the sintering temperature is 327-337 ℃.
CN202210148038.8A 2022-02-17 2022-02-17 Composite anode for zinc electrodeposition and preparation method thereof Active CN114411206B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009293117A (en) * 2008-06-09 2009-12-17 Doshisha Anode for use in electrowinning zinc, and electrowinning method
JP2013234384A (en) * 2012-04-13 2013-11-21 Dowa Holdings Co Ltd Electrowinning method of nonferrous metal and method of manufacturing anode used for the same
JP2016060917A (en) * 2014-09-16 2016-04-25 Ｄｏｗａホールディングス株式会社 Electroextraction method of non-ferrous metals and method for producing anode used therefor
CN106011468A (en) * 2016-06-13 2016-10-12 云南祥云飞龙再生科技股份有限公司 Method for removing ferrous ions from iron-containing zinc sulfate solution by using industrial enriched oxygen
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
CN107675212A (en) * 2017-10-18 2018-02-09 江西理工大学 A kind of Zinc electrolysis fluorine-resistant lead base composite anode and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009293117A (en) * 2008-06-09 2009-12-17 Doshisha Anode for use in electrowinning zinc, and electrowinning method
JP2013234384A (en) * 2012-04-13 2013-11-21 Dowa Holdings Co Ltd Electrowinning method of nonferrous metal and method of manufacturing anode used for the same
JP2016060917A (en) * 2014-09-16 2016-04-25 Ｄｏｗａホールディングス株式会社 Electroextraction method of non-ferrous metals and method for producing anode used therefor
CN106011468A (en) * 2016-06-13 2016-10-12 云南祥云飞龙再生科技股份有限公司 Method for removing ferrous ions from iron-containing zinc sulfate solution by using industrial enriched oxygen
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
CN107675212A (en) * 2017-10-18 2018-02-09 江西理工大学 A kind of Zinc electrolysis fluorine-resistant lead base composite anode and preparation method thereof

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