[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN109504987B - Titanium-based composite anode for electrolytic manganese and preparation method and application thereof - Google Patents

Titanium-based composite anode for electrolytic manganese and preparation method and application thereof Download PDF

Info

Publication number
CN109504987B
CN109504987B CN201811566952.4A CN201811566952A CN109504987B CN 109504987 B CN109504987 B CN 109504987B CN 201811566952 A CN201811566952 A CN 201811566952A CN 109504987 B CN109504987 B CN 109504987B
Authority
CN
China
Prior art keywords
titanium
anode
based composite
active oxygen
oxygen barrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811566952.4A
Other languages
Chinese (zh)
Other versions
CN109504987A (en
Inventor
郭华军
罗树亮
李新海
王志兴
彭文杰
胡启阳
王接喜
颜果春
张书恺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201811566952.4A priority Critical patent/CN109504987B/en
Publication of CN109504987A publication Critical patent/CN109504987A/en
Application granted granted Critical
Publication of CN109504987B publication Critical patent/CN109504987B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention discloses a titanium-based composite anode for electrolyzing manganese, which comprises a titanium substrate, an active oxygen barrier layer and a manganese dioxide deposition layer, wherein the active oxygen barrier layer is positioned on the surface of the titanium substrate, and the manganese dioxide deposition layer is deposited on the surface of the active oxygen barrier layer in situ. The invention also provides a preparation method of the titanium-based composite anode, which comprises the following steps: (1) cleaning the titanium substrate with the polished smooth surface, and then putting the titanium substrate into an acid solution for etching treatment to obtain a pretreated titanium substrate; (2) coating the mixed salt for forming the active oxygen barrier layer on the surface of the pretreated titanium substrate, and then roasting to obtain the titanium substrate containing the active oxygen barrier layer; (3) and (3) taking the titanium substrate containing the active oxygen barrier layer as an anode, and electrodepositing a manganese dioxide deposition layer on the surface of the anode to obtain the titanium-based composite anode. The invention also provides an application of the titanium-based composite anode in manganese electrolysis. The titanium-based composite anode has the advantages of long service life, no pollution to products and the like.

Description

Titanium-based composite anode for electrolytic manganese and preparation method and application thereof
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a titanium-based composite anode, and a preparation method and application thereof.
Background
In the process of electrolyzing metal manganese, a lead anode is used as a traditional anode, and a loose oxide film is generated on the surface of the anode in the process of electrolyzing the metal manganese, so that the area of the anode is increased, and the real current density is reduced, so that a large amount of manganese dioxide is generated by the anode, and the waste of resources and energy is caused. In addition, due to the porosity of the surface film of the lead anode, the attached manganese dioxide is easy to fall into the anolyte under the scouring of anode oxygen, so that the anolyte is deteriorated. Therefore, in the electrolytic manganese metal factory, production is stopped every half month or so, the electrolytic bath is cleaned, and the production efficiency is reduced.
Coated titanium anodes, also known as dimensionally stable anodes, DSA, invented by h.b. beer, were first produced industrially by the company De Nora, italy (titanium electrode engineering, beijing: metallurgical industry publishers, 2003). The metal matrix plays the role of electric conduction and skeleton, and the surface active coating participates in the electrochemical reaction of the anode. At present, DSA is widely applied to the fields of chlor-alkali industry, electroplating, wastewater treatment and the like. However, in the electrolytic manganese metal system, due to the low electrolysis temperature and the high current density, active oxygen generated by electrolysis on a common titanium anode is easy to migrate to a titanium substrate to form a titanium dioxide film with poor conductivity, so that the anode potential is too high, and the anode fails.
In order to solve this problem, many researchers in recent years mainly propose the following solutions: first, the use of thermal coating to add an intermediate layer, typically a tin dioxide intermediate layer, increases the bonding force between the substrate and the coating, makes the entire coating dense, and increases resistance to oxygen in solution. However, the addition of the intermediate layer only increases the physical bonding force between the coating layer and the substrate to a certain extent, and cannot fundamentally prevent the oxygen in the solution from permeating into the cracks of the coating layer to corrode the substrate. Secondly, titanium and other metals are formed into titanium alloy, such as titanium-manganese alloy which is widely applied in electrolytic manganese dioxide, and an oxide film on the surface of the titanium-manganese alloy is titanium-manganese composite oxide, so that the corrosion resistance of the titanium-manganese alloy is greatly improved. However, the method has complex manufacturing process and poor consistency. Third, a titanium dioxide nanotube interlayer is introduced to increase the corrosion resistance of the electrode. Although the method of introducing the thin and compact intermediate layer on the surface of the electrode in advance can greatly prolong the service life of the titanium anode, the preparation of the nano titanium dioxide layer is complex and difficult to be applied industrially.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and defects in the background technology and provides a titanium-based composite anode for electrolyzing manganese, a preparation method and application thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the titanium-based composite anode for electrolyzing manganese comprises a titanium substrate, an active oxygen barrier layer and a manganese dioxide deposition layer, wherein the active oxygen barrier layer is positioned on the surface of the titanium substrate, and the manganese dioxide deposition layer is deposited on the surface of the active oxygen barrier layer in situ. The manganese dioxide deposition layer is a dense manganese dioxide layer which grows in situ in an electrolytic manganese system, has good oxygen evolution activity and low anode overpotential, and provides a substrate and a template for subsequent deposition, so that the manganese dioxide layer which is tightly attached is formed.
In the above titanium-based composite anode, preferably, the active oxygen barrier layer is one or more layers, and each layer is made of Ca2Mn2O5、CoMn2O4、NiCo2O4And CoFe2O4Any one of the above.
In the titanium-based composite anode, preferably, the titanium substrate is a metal titanium plate or a titanium sheet.
As a general technical concept, the invention also provides a preparation method of the titanium-based composite anode for electrolyzing manganese, which comprises the following steps:
(1) cleaning the titanium substrate with the polished smooth surface (removing oil by alkali washing), and then putting the titanium substrate into an acid solution for etching treatment to obtain a pretreated titanium substrate;
(2) coating the mixed salt for forming the active oxygen barrier layer on the surface of the pretreated titanium substrate, and then roasting to obtain the titanium substrate containing the active oxygen barrier layer; when the active oxygen barrier layer is a plurality of layers, the coating-roasting process is repeated for a plurality of times, and when the active oxygen barrier layer is a plurality of layers, the next layer of coating is continued after one layer of coating is processed, and the processing method of each layer is the same;
(3) and (3) taking the titanium substrate containing the active oxygen barrier layer in the step (2) as an anode, and electrodepositing a manganese dioxide deposition layer on the surface of the titanium substrate (for example, electrodeposition is carried out for about 30 min) to obtain the titanium-based composite anode.
In the above production method, preferably, the mixed salt is any one of the following combinations:
calcium salt and manganese salt are mixed according to the molar ratio of calcium to manganese of 1: 1, mixing;
the molar ratio of cobalt to manganese of the cobalt salt to the manganese salt is 1: 2, mixing;
the molar ratio of nickel salt to cobalt salt is 1: 2, mixing;
the molar ratio of cobalt salt to iron salt is 1: 2, mixing the components.
In the above preparation method, more preferably, the active oxygen barrier layer has three layers, which are Ca in order from the surface of the titanium substrate2Mn2O5、NiCo2O4And CoMn2O4. Research shows that the active oxygen barrier layer is made of the specific material, and due to mutual influence among the material layers, the material layers are matched with the manganese dioxide layer, so that the performance of the titanium-based composite anode is optimal.
In the above preparation method, preferably, the salt solution of cobalt, nickel, manganese and calcium is chloride salt or acetate salt.
In the above preparation method, preferably, the roasting temperature is controlled to be 450-550 ℃ during the roasting treatment.
In the preparation method, preferably, when the manganese dioxide deposition layer is electrodeposited, the concentration of the divalent manganese in the electrolyte is controlled to be 10-20g/L, the concentration of the ammonium sulfate is controlled to be 100-120g/L, and the electrolysis pH is controlled to be 7-8. The manganese dioxide grown in the range has compatibility with manganese dioxide deposited in an electrolytic manganese system subsequently, and the obtained deposited layer is compact and is not easy to fall off.
In the above preparation method, preferably, the acid solution is HF and HNO3The mixed acid solution of (1).
As a general technical concept, the invention also provides an application of the titanium-based composite anode in manganese electrolysis.
Compared with the prior art, the invention has the advantages that:
1. in the titanium-based composite anode, the active oxygen barrier layer can effectively inhibit oxygen in the solution from directly eroding the titanium matrix, thereby preventing the titanium matrix from being passivated.
2. The service life of the titanium-based composite anode is far longer than that of a common composite electrode.
3. After the titanium-based composite anode is applied to the electrolysis of metal manganese, manganese dioxide generated by electrolysis is tightly attached and cannot fall into anolyte, the anolyte cannot be turbid, and a tank cleaning process is not needed.
4. The titanium-based composite anode adopts a structure of a titanium substrate, an active oxygen barrier layer and a manganese dioxide deposition layer, and the rate of generating manganese dioxide is only one third of that of a lead anode and is obviously less than that of the titanium anode.
5. The titanium-based composite anode can be directly applied to an electrolytic manganese anode, and after the electrolysis is finished, an electrodeposited manganese dioxide layer can be separated to be used as a basic chemical raw material. Particularly, compared with the traditional lead anode, the by-product does not contain lead, and can be used as a precursor to synthesize the lithium ion battery anode material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic view of a titanium-based composite anode according to the present invention.
FIG. 2 is a scanning electron micrograph of the titanium-based composite anodic active oxygen barrier prepared in example 1.
FIG. 3 is a scanning electron micrograph of the surface of the titanium-based composite anode prepared in example 1.
FIG. 4 is a graph comparing the 24h cell voltage of the titanium-based composite anode prepared in example 2 with that of a conventional lead anode in electrolytic manganese.
FIG. 5 is a graph comparing the 6h cell voltage of the titanium-based composite anode of example 3 with that of a conventional lead anode in electrolytic manganese.
FIG. 6 is a graph comparing the titanium-based composite anolyte and lead anolyte of example 3.
FIG. 7 is a graph showing the polarization curve of the anode in example 4.
FIG. 8 is a comparison of Tafel curves measured for titanium-based composite anodes and lead anodes with a three-electrode system as in example 5.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
as shown in fig. 1, the titanium-based composite anode of the present embodiment includes a titanium substrate, an active oxygen barrier layer, and a manganese dioxide deposition layer. Wherein the titanium substrate is pure titanium sheet, and the active oxygen barrier layer is Ca2Mn2O5And the manganese dioxide deposition layer is electrodeposited on the surface of the active oxygen barrier layer in situ.
The preparation method of the titanium-based composite anode comprises the following steps:
(1) titanium sheet pretreatment: the titanium sheet is sequentially polished by 360#, 600#, 800#, 1000# sand paper, then ultrasonically cleaned by acetone, ethanol and deionized water for 10min, and then the titanium sheet with the polished smooth surface is put into HF: HNO31: 2, activating for 30s in the mixed acid solution, cleaning and drying;
(2) preparation of an active oxygen barrier layer: calcium acetate and manganese acetate are mixed according to the atomic ratio of 1: 1 is dissolved in a mixed solution of glycol and citric acid solution, then the obtained solution is coated on the surface of the electrode, the electrode is placed in a muffle furnace for roasting for 15min at the temperature of 450 ℃, the process is repeated for 10 times, the roasting is carried out for 1h for the last time, the appearance is observed by a scanning electron microscope, and the appearance is shown in figure 2;
(3) preparing a manganese dioxide deposition layer: taking the titanium substrate containing the active oxygen barrier layer in the step (2) as an anode, and electrodepositing a manganese dioxide deposition layer on the surface of the anode to obtain the titanium-based composite anode in the embodiment; wherein:
A. preparation of an electrodeposition solution:
15g/L of manganese sulfate;
110g/L of ammonium sulfate;
pH 7.2；
B. electrodeposition conditions:
the temperature is 40 ℃;
anode current density 375mA/cm2；
The deposition time was 30 min.
The surface topography of the titanium-based composite anode fabricated in this example is shown in fig. 3, and the surface of the composite titanium anode is dense and flat (the cracks are caused by drying through a scanning electron microscope).
The titanium-based composite anode and the stainless steel cathode are adopted, the polar distance is 75mm, and the industrial electrolytic manganese electrolyte is adopted and is used at 375A/m at 40 DEG C2The electrolysis was carried out for 6 hours at an average anode potential of 2.2V and an average cell voltage of 4.26V. Lead and other impurity elements are not detected in the anode by-product, and the capacity of the lithium manganate is synthesized by taking the anode by-product as a precursor>115mAh/g, cycle life>500 times.
Example 2:
the titanium-based composite anode of this example was constructed in the same manner as in example 1, except that the active oxygen barrier layer was CoMn2O4And (3) a layer.
The preparation method of the titanium-based composite anode comprises the following steps:
(1) titanium sheet pretreatment: the titanium sheet is sequentially polished by 360#, 600#, 800#, 1000# sand paper, then ultrasonically cleaned by acetone, ethanol and deionized water for 10min, and then the titanium sheet with the polished smooth surface is put into HF: hNO31: 2, activating for 60s in the mixed acid solution, cleaning and drying;
(2) preparation of an active oxygen barrier layer: manganese acetate and cobalt acetate are mixed according to the atomic ratio of 2: 1 is dissolved in the mixed solution of glycol and citric acid solution, then the obtained solution is coated on the surface of the electrode, and the electrode is placed in a muffle furnace for roasting for 15min at 500 ℃, the process is repeated for 10 times, and the roasting is carried out for 1h for the last time;
(3) preparing a manganese dioxide deposition layer: taking the titanium substrate containing the active oxygen barrier layer in the step (2) as an anode, and electrodepositing a manganese dioxide deposition layer on the surface of the anode to obtain the titanium-based composite anode in the embodiment; wherein:
A. preparation of an electrodeposition solution:
17g/L of manganese sulfate;
110g/L of ammonium sulfate;
pH 7.2；
B. electrodeposition conditions:
the temperature is 45 ℃;
anode current density 375mA/cm2；
The deposition time was 20 min.
The titanium-based composite anode of the embodiment is applied to an electrolytic manganese system, electrolysis is carried out for 24 hours, the electrolytic manganese tank voltage is basically kept constant, as shown in fig. 4, the average tank voltage is 4.20V, the requirement of electrolytic manganese industry on the anode is met, and the titanium-based composite anode has a good energy-saving effect.
Example 3:
the titanium-based composite anode of this example was constructed in the same manner as in example 1 except that the active oxygen barrier layer was NiCo2O4And (3) a layer.
The preparation method of the titanium-based composite anode comprises the following steps:
(1) titanium sheet pretreatment: the titanium sheet is sequentially polished by 360#, 600#, 800#, 1000# sand paper, then ultrasonically cleaned by acetone, ethanol and deionized water for 20min, and then the titanium sheet with the polished smooth surface is put into HF: HNO31: 2, activating for 30s in the mixed acid solution, cleaning and drying;
(2) preparation of an active oxygen barrier layer: nickel acetate and cobalt acetate are mixed according to the atomic ratio of 1: 2, dissolving the solution in a mixed solution of glycol and citric acid solution, then coating the obtained solution on the surface of the electrode, roasting the electrode in a muffle furnace for 15min at 500 ℃, repeating the process for 10 times, and roasting the electrode for 1h for the last time;
(3) preparing a manganese dioxide deposition layer: taking the titanium substrate containing the active oxygen barrier layer in the step (2) as an anode, and electrodepositing a manganese dioxide deposition layer on the surface of the anode to obtain the titanium-based composite anode in the embodiment; wherein:
A. preparation of an electrodeposition solution:
15g/L of manganese sulfate;
110g/L of ammonium sulfate;
pH 7.2；
B. electrodeposition conditions:
the temperature is 45 ℃;
anode current density 400mA/cm2；
The deposition time was 18 min.
The titanium-based composite anode of this example was applied to an electrolytic manganese system, electrolysis was carried out for 6 hours, and compared with a lead anode. As can be seen from the graphs in FIGS. 5-6, the electrolytic manganese tank voltage is maintained to be basically constant, the average tank voltage is 4.28V, the average tank voltage is 260mV lower than that of a lead anode tank, and the electrolytic manganese tank has good energy-saving effect. In addition, as can be seen from the electrolyte after electrolysis, the titanium-based composite anolyte is clear and almost has no suspended matters in the solution, while the lead anode has a large amount of colloidal manganese dioxide, and the anolyte is seriously deteriorated. In addition, the anode by-product was collected, and the anode efficiency of the obtained titanium-based composite anode was calculated to be 1.5%, and the anode efficiency of the lead anode was calculated to be 4.5%, thereby showing that the use of the titanium-based composite anode can reduce the generation of anode side reactions.
Example 4:
the titanium-based composite anode of this example was constructed in the same manner as in example 1 except that the active oxygen barrier layer was CoFe2O4And (3) a layer.
The preparation method of the titanium-based composite anode comprises the following steps:
(1) titanium sheet pretreatment: sequentially grinding and polishing the titanium sheet by using 360#, 600#, 800#, 1000# sand paper, and then dividingRespectively ultrasonically cleaning the titanium plate by using acetone, ethanol and deionized water for 10min, and then putting the titanium plate with the polished smooth surface into an HF: HNO31: 2, activating for 60s in the mixed acid solution, cleaning and drying;
(2) preparation of an active oxygen barrier layer: mixing iron acetate and cobalt acetate according to an atomic ratio of 2: 1 is dissolved in the mixed solution of glycol and citric acid solution, then the obtained solution is coated on the surface of the electrode, and the electrode is placed in a muffle furnace for roasting for 10min at 500 ℃, the process is repeated for 10 times, and the roasting is carried out for 1h for the last time;
(3) preparing a manganese dioxide deposition layer: taking the titanium substrate containing the active oxygen barrier layer in the step (2) as an anode, and electrodepositing a manganese dioxide deposition layer on the surface of the anode to obtain the titanium-based composite anode in the embodiment; wherein:
A. preparation of an electrodeposition solution:
15g/L of manganese sulfate;
115g/L of ammonium sulfate;
pH 7.2；
B. electrodeposition conditions:
the temperature is 45 ℃;
anode current density 400mA/cm2；
The deposition time was 20 min.
When the titanium-based composite anode of this example was used in a three-electrode system to measure the polarization curve, it can be seen from FIG. 7 that the oxygen evolution potential of the titanium-based composite anode was 300mV lower than that of the lead anode, meaning that it was more suitable for use as an oxygen evolution anode.
Example 5:
the titanium-based composite anode of this example was the same as that of example 1 except that the active oxygen barrier layer was Ca2Mn2O5And CoFe2O4The composite layer of (1).
The preparation method of the titanium-based composite anode comprises the following steps:
(1) titanium sheet pretreatment: the titanium sheet is sequentially polished by 360#, 600#, 800#, 1000# sand paper, then ultrasonically cleaned by acetone, ethanol and deionized water for 10min, and then the titanium sheet with the polished smooth surface is put into HF: HNO3＝1：2, activating for 60s in the mixed acid solution, cleaning and drying;
(2) preparation of an active oxygen barrier layer: calcium acetate and manganese acetate are mixed according to the atomic ratio of 1: 1 is dissolved in a mixed solution of ethylene glycol and citric acid solution, then the obtained solution is coated on the surface of the electrode, and the electrode is placed under a muffle furnace for roasting for 15min at 450 ℃, and the process is repeated for 5 times. Then, mixing iron acetate and cobalt acetate according to the atomic ratio of 2: 1 is dissolved in the mixed solution of glycol and citric acid solution, then the obtained solution is coated on the surface of the electrode, and the electrode is placed in a muffle furnace for roasting for 10min at 500 ℃, the process is repeated for 5 times, and the roasting is carried out for 1h for the last time;
(3) preparing a manganese dioxide deposition layer: taking the titanium substrate containing the active oxygen barrier layer in the step (2) as an anode, and electrodepositing a manganese dioxide deposition layer on the surface of the anode to obtain the titanium-based composite anode in the embodiment; wherein:
A. preparation of an electrodeposition solution:
15g/L of manganese sulfate;
115g/L of ammonium sulfate;
pH 7.2；
B. electrodeposition conditions:
the temperature is 45 ℃;
anode current density 400mA/cm2；
The deposition time was 20 min.
The tafel curve of the titanium-based composite anode of this example was measured with a three-electrode system, as shown in fig. 8, and subjected to linear fitting, and the tafel slope of the obtained titanium-based composite anode was 196mV/dec, while the tafel slope on the lead anode was 234mV/dec, indicating that the titanium-based composite anode of this example is more suitable for use as an oxygen evolution anode.

Claims (6)

1. The titanium-based composite anode for electrolyzing manganese is characterized by comprising a titanium substrate, an active oxygen barrier layer and a manganese dioxide deposition layer, wherein the active oxygen barrier layer is positioned on the surface of the titanium substrate, and the manganese dioxide deposition layer is deposited on the surface of the active oxygen barrier layer in situ;
the active oxygen barrier layer is three layers, and Ca is sequentially arranged on the surface of the titanium substrate2Mn2O5、NiCo2O4And CoMn2O4；
When the manganese dioxide deposition layer is deposited in situ, the concentration of bivalent manganese in the electrolyte is controlled to be 10-20g/L, the concentration of ammonium sulfate is controlled to be 100-120g/L, and the electrolytic pH is controlled to be 7-8.
2. The titanium-based composite anode according to claim 1, wherein the titanium substrate is a metallic titanium plate or a titanium sheet.
3. A preparation method of a titanium-based composite anode for electrolyzing manganese is characterized by comprising the following steps:
(1) cleaning the titanium substrate with the polished smooth surface, and then putting the titanium substrate into an acid solution for etching treatment to obtain a pretreated titanium substrate;
(2) coating the mixed salt for forming the active oxygen barrier layer on the surface of the pretreated titanium substrate, and then roasting to obtain the titanium substrate containing the active oxygen barrier layer; controlling the active oxygen barrier layer to be three layers, wherein Ca is sequentially arranged on the surface of the titanium substrate2Mn2O5、NiCo2O4And CoMn2O4；
(3) Taking the titanium substrate containing the active oxygen barrier layer in the step (2) as an anode, and electrodepositing a manganese dioxide deposition layer on the surface of the anode to obtain a titanium-based composite anode; when the manganese dioxide deposition layer is electrodeposited, the concentration of divalent manganese in the electrolyte is controlled to be 10-20g/L, the concentration of ammonium sulfate is controlled to be 100-120g/L, and the electrolytic pH is controlled to be 7-8.
4. The method as claimed in claim 3, wherein the calcination temperature is controlled to be 450-550 ℃ during the calcination treatment.
5. The method according to claim 3, wherein the acid solution is HF and HNO3The mixed acid solution of (1).
6. Use of a titanium-based composite anode according to claim 1 or 2 or obtained by the preparation method according to any one of claims 3 to 5 in the electrolysis of manganese.
CN201811566952.4A 2018-12-20 2018-12-20 Titanium-based composite anode for electrolytic manganese and preparation method and application thereof Active CN109504987B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811566952.4A CN109504987B (en) 2018-12-20 2018-12-20 Titanium-based composite anode for electrolytic manganese and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811566952.4A CN109504987B (en) 2018-12-20 2018-12-20 Titanium-based composite anode for electrolytic manganese and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109504987A CN109504987A (en) 2019-03-22
CN109504987B true CN109504987B (en) 2020-09-11

Family

ID=65754058

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811566952.4A Active CN109504987B (en) 2018-12-20 2018-12-20 Titanium-based composite anode for electrolytic manganese and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109504987B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115125595B (en) * 2022-06-23 2023-11-24 中南大学 Preparation method of titanium-manganese alloy coating

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103668342B (en) * 2013-11-29 2016-03-09 中南大学 A kind of manganese electrolysis titanium based composite anode and preparation method
CN104593818B (en) * 2014-12-24 2017-04-26 中南大学 Titanium-based composite anode as well as preparation method and application thereof
CN105154915B (en) * 2015-08-18 2018-06-19 中南大学 A kind of titanium-based composite anode and its preparation method and application

Also Published As

Publication number Publication date
CN109504987A (en) 2019-03-22

Similar Documents

Publication Publication Date Title
US10975482B1 (en) Self-derivative iron-containing nickel anode for water electrolysis
US20200373586A1 (en) Highly corrosion-resistant porous metal body
CN103205780B (en) Grate type titanium-based PbO2 electrode for nonferrous metal electrodeposition and preparation method of grate type titanium-based PbO2 electrode
Zhang et al. Effect of CeO2 and graphite powder on the electrochemical performance of Ti/PbO2 anode for zinc electrowinning
Chen et al. Ag doping to boost the electrochemical performance and corrosion resistance of Ti/Sn–Sb-RuOx/α-PbO2/β-PbO2 electrode in zinc electrowinning
CN102888625B (en) Non-ferrous metal electrodeposition palisading type positive plate
CN104611731B (en) Preparation method of fence-type aluminum bar lead alloy anode plate for non-ferrous metal electrodeposition
WO2013038927A1 (en) Chlorine-generating positive electrode
CN106048690B (en) A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof
CN104313652B (en) Preparation method of aluminum-based multiphase inert composite anode material
CN106835193B (en) A kind of Pb bases/3D-PbO2/MeOx composite anodes and preparation method thereof
CN106086989A (en) A kind of titania modified by Argentine nanotube composite anode and preparation method thereof
CN109576733B (en) Preparation method of carbon fiber loaded chlorine evolution catalytic electrode
CN109504987B (en) Titanium-based composite anode for electrolytic manganese and preparation method and application thereof
CN101717950B (en) Method for preparing anode-catalyzed electrode for electrolyzing slurry coal
CN112195482B (en) Composite titanium anode plate and preparation method thereof
CN102433581A (en) Preparation method of novel anode material for non-ferrous metal electrodeposition
CN105040032A (en) Method of preparing transition metal and alloy thereof through low temperature molten salt electro-deposition
CN104846417A (en) Method for preparing Ni/CeO2 composite hydrogen evolution electrode
CN105132980B (en) A kind of lead silver alloy anode surface recombination ceramic film film build method
Zhang et al. Anodic behavior and microstructure of Al/Pb-Ag-Co anode during zinc electrowinning
CN114622238B (en) Preparation and application of transition metal-based hydrogen and oxygen evolution dual-functional electrode
CN114164419B (en) Method for preparing platinum active layer on anode plate by thermal decomposition method
Chen et al. Electrosynthesis and physicochemical properties of α–PbO2–CeO2–TiO2 composite electrodes
Valero-Vidal et al. Stability of 3D-porous Ni/Cu cathodes under real alkaline electrolyzer operating conditions and its effect on catalytic activity

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant