CN101705500A - Composite anode and preparation method thereof - Google Patents
Composite anode and preparation method thereof Download PDFInfo
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- CN101705500A CN101705500A CN200910237560A CN200910237560A CN101705500A CN 101705500 A CN101705500 A CN 101705500A CN 200910237560 A CN200910237560 A CN 200910237560A CN 200910237560 A CN200910237560 A CN 200910237560A CN 101705500 A CN101705500 A CN 101705500A
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Abstract
The invention discloses a composite anode and a preparation method thereof, belonging to the technical field of electrochemistry. The composite anode is prepared by tabletting of lead dioxide powder, modified metal oxide powder and binding agent powder, wherein according to the mass percentage, content of the lead dioxide powder is more than or equal to 65 percent, the content of the modified metal oxide powder is less than or equal to 30 percent and more than or equal to 5 percent, and the content of the binding agent powder is less than or equal to 5 percent. The composite anode has more advantages on saving power consumption and prolonging the service life compared with the common base body PbO2 anode. The preparation method belongs to a preparation method without base body and avoids the problems that the coating falls off, the oxygen evolution potential is high and the like. The added modified metal oxide with excellent electro-catalysis performance plays a role of reducing the oxygen evolution potential. The added polytetrafluoroethylene powder with extremely high stability plays a role of bonding, thus not only solving the defect that the traditional lead dioxide anode without the base body has poor mechanical strength, but also having no influence on the working of the whole electrolysis system due to the introduction of impurities.
Description
Technical field
The invention belongs to technical field of electrochemistry, particularly a kind of composite anode and preparation method thereof.
Background technology
Anode of lead dioxide can be divided into matrix and no matrix anode two classes.Traditional no matrix anode of lead dioxide is because bad mechanical strength is unsuitable for industrial application.That uses at present is generally the matrix anode of lead dioxide, and wherein studying more is ti-lead dioxide anode.Titanium is the valve shaped metal, is good carriers to many electro catalytic activity materials, shows good anode performance behind titanium matrix surface plating one deck conduction, the anti-corrosion plumbic oxide; But there are two shortcomings in this coating anode: the one, no matter coating is α-PbO
2Or β-PbO
2, all have the high shortcoming of oxygen evolution potential; The 2nd, some crystal boundary slits can appear in lead dioxide plating coat, and the oxygen that produces during electrolysis sees through the crystal boundary slit titanium oxide matrix of coating, form the titanium dioxide of poorly conductive, worsen anode performance.Above-mentioned two shortcomings are restricted the application of anode of lead dioxide in the metallurgical industry of non-ferrous metal electrification.
In recent years, in order to reach the purpose that reduces the plumbic oxide oxygen evolution potential, generally adopt the technology of mixing a small amount of electrocatalysis material at the electrode activity layer both at home and abroad.The existing report that in the ti-supported lead dioxide electric pole active coating, mixes catalyzer such as palladous oxide, Manganse Dioxide, cobalt nickel spinel, tricobalt tetroxide, ruthenium dioxide on the document.But still there is the shortcoming of the easy passivation of titanium matrix in this anode in operational process.
In order to overcome the passivation of titanium in the long-time electrolysis production process, improve the job stability and the work-ing life of anode of lead dioxide, people are at titanium matrix and PbO
2Add the middle layer between the coating, to suppress the passivation of titanium.But this technology has increased anodic cost of manufacture and process complexity, and can not fundamentally solve the problem of passivation of titanium matrix.After this, people manufacture experimently out ceramic matrix PbO again
2Anode.Though ceramic base PbO
2Do not have the matrix problem of passivation, yet ceramic physical strength own is low, easily broken, can only make the pole shape, can not make plate (sheet) shape, this makes troubles for the design of electrolysis cells of scale operation.Because the tube wall of vitrified pipe need have certain thickness, this just makes the ceramic matrix deadweight increase, and the high-temperature firing Production of Ceramics cycle is long simultaneously, and yield rate is low, causes ceramic matrix PbO
2The anode cost is higher.Therefore, people are progressive to consider to adopt satisfactory mechanical property, stable chemical performance, surface can plate with the matrix of the low ABS plastic of light weight, cost as anode of lead dioxide, but its application does not appear in the newspapers as yet.In addition, be that the preparation research of matrix also has report with graphite, epoxy plastics, iron plate etc.But these technology all are to be basic skills with electrochemical plating or electroless plating method, what material to be matrix with no matter, all can not fundamentally avoid the etching problem that is caused by the coating slit.
Summary of the invention
The purpose of this invention is to provide a kind of composite anode and preparation method thereof.
A kind of composite anode, it is characterized in that, this composite anode is made through compressing tablet by lead dioxide powder, modified metal-oxide powder and binder powders, the mass percent of each component is: lead dioxide powder 〉=65%, 5%≤modified metal-oxide powder≤30%, binder powders≤5%, wherein, the median size of binder powders is less than 300 microns.
Described modified metal-oxide powder is V
2O
5, TiO
2, ZrO
2, MoO
3, WO
3, Nb
2O
5, Ta
2O
5, MnO
2, Sb
2O
3, CrO
2, Co
3O
4In at least a.
Described binder powders is a kind of in tetrafluoroethylene, polyethylene and the polypropylene powder.
A kind of preparation method of composite anode, it is characterized in that, with lead dioxide powder, modified metal-oxide powder and binder powders are raw material, the mass percent of each component is: lead dioxide powder 〉=65%, 5%≤modified metal-oxide powder≤30%, binder powders≤5%, uniform mixing according to the above ratio, depress to pellet electrode at 10～50MPa pressure, adopt hyperthermia drying or preelectrolysis ageing method to stablize and modification to shaped electrode, wherein, the temperature of hyperthermia drying is 80～350 ℃, time is 1～6 hour, to improve anode stability; Preelectrolysis in target electrolytic non-ferrous metal liquid, preelectrolysis digestion time are 8～32 hours, to improve the anodic electrocatalysis characteristic.
In the aforesaid method, can under 250～550 ℃ of conditions, carry out pyroprocessing,, thereby change the anodic microtexture with the form of change tackiness agent to the composite anode progress.
In the aforesaid method, plumbic oxide and modified metal-oxide powder source are commercially available or chemical method preparation.
Beneficial effect of the present invention is: with the composite anode of the present invention preparation anode as the electrolytic non-ferrous metal process, saving power consumption and improving on work-ing life all than common base body PbO
2Anode has more advantage.
Composite anode by the present invention's preparation belongs to no matrix preparation method, has fundamentally avoided problems such as coating comes off, oxygen evolution potential height.Play the effect that reduces the anode oxygen evolution potential by the modified metal-oxide powder that adds the electrocatalysis characteristic excellence.Add the high polytetrafluoroethylene powder of stability and play adhesive effect, both solved the shortcoming of traditional no matrix anode of lead dioxide bad mechanical strength, can not influence the work of whole electrolysis system again because of introducing impurity.
Composite anode preparation process of the present invention is very simple, helps industrial applications.Anode erosion resistance with this method preparation is good, and oxygen evolution potential is low, as the electrolytic non-ferrous metal anode, has a significant effect with the work-ing life of improving insoluble anode to reducing the metallurgical power consumption of non-ferrous metal electrification.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
Is 85: 10: 5 uniform mixing with the lead dioxide powder of chemical precipitation method preparation, commercially available tricobalt tetroxide and technical grade polytetrafluorethylepowder powder (the polytetrafluorethylepowder powder median size is less than 100 microns) with mass ratio, depresses to the rectangular plate of 300mm * 260mm * 6mm at 35MPa pressure.In baking under 180～220 ℃ of conditions after 2 hours, anode surface is smooth, firmly compact with this positive plate.Composite anode after the oven dry is 120g/L at sulfuric acid concentration, Cu
2+Concentration is 50g/L, and current density is 300A/cm
2, the 316L stainless steel is as negative electrode, and spacing is that a ton copper power consumption is 1620KWh (titanium base PbO after working 6 months under the condition of 60mm between the anode and cathode
2Anode is 1860KWh), anodic corrosion speed is 0.02mg/m
2H (titanium base PbO
2Anode is 5.6mg/m
2H).
Embodiment 2
The polytetrafluorethylepowder powder (the polytetrafluorethylepowder powder median size is 5 microns) that commercially available lead dioxide powder, Manganse Dioxide and the Shanghai rich novel material of three love company limited are provided is 80: 15: 5 uniform mixing with mass ratio, depresses to the rectangular plate of 300mm * 260mm * 6mm at 40MPa pressure.In baking under 260～320 ℃ of conditions after 1 hour, anode surface is smooth, firmly compact with this positive plate.Composite anode after the oven dry is 180g/L at sulfuric acid concentration, Zn
2+Concentration is 55g/L, Mn
2+Concentration is 5g/L, and current density is 600A/cm
2, aluminium sheet is as negative electrode, and spacing is that a ton zinc power consumption is 2880KWh (titanium base PbO after working 2 months under the condition of 60mm between the anode and cathode
2Anode is 3210KWh), anodic corrosion speed is 0.05mg/m
2H (titanium base PbO
2Anode is 38mg/m
2H).
Embodiment 3
The polytetrafluorethylepowder powder (the polytetrafluorethylepowder powder median size is 25 microns) that commercially available lead dioxide powder, zirconium dioxide and Tianjin City Jingying Organic Polymer Co., Ltd are provided is 70: 17: 3 uniform mixing with mass ratio, depress to the rectangular plate of 300mm * 260mm * 6mm at 30MPa pressure. with this positive plate under 150～180 ℃ of conditions the baking 3 hours after, anode surface is smooth, firmly compact. and the composite anode after the oven dry is 180g/L at sulfuric acid concentration, Zn
2+Concentration is 55g/L, Mn
2+Concentration is 10g/L, and current density is 500A/cm
2, aluminium sheet is as negative electrode, and spacing is that a ton zinc power consumption is 2960KWh (titanium base PbO after working 5 months under the condition of 60mm between the anode and cathode
2Anode is 3210KWh), anodic corrosion speed is 0.03mg/m
2H (titanium base PbO
2Anode is 38mg/m
2H).
Embodiment 4
The polytetrafluorethylepowder powder (the polytetrafluorethylepowder powder median size is 25 microns) that the lead dioxide powder of chemical precipitation method preparation, commercially available antimonous oxide and Tianjin City Jingying Organic Polymer Co., Ltd are provided is 90: 8: 2 uniform mixing with mass ratio, depresses to the rectangular plate of 300mm * 260mm * 6mm at 30MPa pressure.In baking under 200～230 ℃ of conditions after 1.5 hours, anode surface is smooth, firmly compact with this positive plate.Composite anode after the oven dry is 120g/L at sulfuric acid concentration, and negative electrode is the 316L stainless steel, and current density is 250A/cm
2Condition under, preelectrolysis 2 hours is 180g/L at sulfuric acid concentration then, Zn
2+Concentration is 55g/L, Mn
2+Concentration is 10g/L, and current density is 500A/cm
2, aluminium sheet is as negative electrode, and spacing is that a ton zinc power consumption is 2820KWh (titanium base PbO after working 6 months under the condition of 60mm between the anode and cathode
2Anode is 3210KWh), anodic corrosion speed is 0.04mg/m
2H (titanium base PbO
2Anode is 38mg/m
2H).
Claims (5)
1. composite anode, it is characterized in that, this composite anode is made through compressing tablet by lead dioxide powder, modified metal-oxide powder and binder powders, the mass percent of each component is: lead dioxide powder 〉=65%, 5%≤modified metal-oxide powder≤30%, binder powders≤5%, wherein, the median size of binder powders is less than 300 microns.
2. a kind of composite anode according to claim 1 is characterized in that, described modified metal-oxide powder is V
2O
5, TiO
2, ZrO
2, MoO
3, WO
3, Nb
2O
5, Ta
2O
5, MnO
2, Sb
2O
3, CrO
2, Co
3O
4In at least a.
3. a kind of composite anode according to claim 1 is characterized in that, described binder powders is a kind of in tetrafluoroethylene, polyethylene and the polypropylene powder.
4. the preparation method of a composite anode, it is characterized in that, with lead dioxide powder, modified metal-oxide powder and binder powders is raw material, the mass percent of each component is: lead dioxide powder 〉=65%, 5%≤modified metal-oxide powder≤30%, binder powders≤5%, uniform mixing according to the above ratio, depress to pellet electrode at 10～50MPa pressure, adopt hyperthermia drying or preelectrolysis ageing method to stablize and modification to shaped electrode, wherein, the temperature of hyperthermia drying is 80～350 ℃, and the time is 1～6 hour; The preelectrolysis digestion time is 8～32 hours.
5. the preparation method of a kind of composite anode according to claim 4 is characterized in that, composite anode is further carried out pyroprocessing under 250～550 ℃ of conditions.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677093A (en) * | 2012-05-30 | 2012-09-19 | 合肥工业大学 | Lead dioxide powder porous electrode and preparation method thereof |
| CN102838191A (en) * | 2012-09-27 | 2012-12-26 | 昆明理工大学 | Method for preparing composite anode material |
| CN104562094A (en) * | 2015-01-20 | 2015-04-29 | 昆明理工恒达科技股份有限公司 | Preparation method of gradient composite anode for nonferrous metals electrodeposition |
| CN106206071A (en) * | 2016-09-08 | 2016-12-07 | 江苏科技大学 | A kind of WO3 H2O/PbO2 combination electrode of height ratio capacity and preparation method and application |
| 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 |
| CN107841768A (en) * | 2017-12-01 | 2018-03-27 | 昆明理工大学 | A kind of Al-matrixcomposites and its preparation method and application |
| CN108677221A (en) * | 2018-06-13 | 2018-10-19 | 昆明理工大学 | A kind of titanium-based β-MnO2Composite coating anode and preparation method thereof |
| CN109763021A (en) * | 2019-03-27 | 2019-05-17 | 贵州省过程工业技术研究中心 | A kind of low Ag metal composite anode materials preparation method |
| CN112158919A (en) * | 2020-09-03 | 2021-01-01 | 广东臻鼎环境科技有限公司 | Sandwich structure composite lead dioxide anode and preparation method thereof |
| CN114772684A (en) * | 2022-04-26 | 2022-07-22 | 南京理工大学 | Microporous titanium-based iridium tantalum whole body electrode applied to deep treatment of chemical tail water and preparation method and application thereof |
-
2009
- 2009-11-12 CN CN200910237560A patent/CN101705500A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677093B (en) * | 2012-05-30 | 2015-04-22 | 合肥工业大学 | Lead dioxide powder porous electrode and preparation method thereof |
| CN102677093A (en) * | 2012-05-30 | 2012-09-19 | 合肥工业大学 | Lead dioxide powder porous electrode and preparation method thereof |
| CN102838191A (en) * | 2012-09-27 | 2012-12-26 | 昆明理工大学 | Method for preparing composite anode material |
| CN104562094A (en) * | 2015-01-20 | 2015-04-29 | 昆明理工恒达科技股份有限公司 | Preparation method of gradient composite anode for nonferrous metals electrodeposition |
| CN104562094B (en) * | 2015-01-20 | 2016-11-16 | 昆明理工恒达科技股份有限公司 | A kind of preparation method of non-ferrous metal electrodeposition graded composite anode |
| CN106206071B (en) * | 2016-09-08 | 2018-08-31 | 江苏科技大学 | A kind of WO3H2O/PbO2 combination electrodes of height ratio capacity and the preparation method and application thereof |
| CN106206071A (en) * | 2016-09-08 | 2016-12-07 | 江苏科技大学 | A kind of WO3 H2O/PbO2 combination electrode of height ratio capacity and preparation method and application |
| 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 |
| CN107841768A (en) * | 2017-12-01 | 2018-03-27 | 昆明理工大学 | A kind of Al-matrixcomposites and its preparation method and application |
| CN108677221A (en) * | 2018-06-13 | 2018-10-19 | 昆明理工大学 | A kind of titanium-based β-MnO2Composite coating anode and preparation method thereof |
| CN109763021A (en) * | 2019-03-27 | 2019-05-17 | 贵州省过程工业技术研究中心 | A kind of low Ag metal composite anode materials preparation method |
| CN112158919A (en) * | 2020-09-03 | 2021-01-01 | 广东臻鼎环境科技有限公司 | Sandwich structure composite lead dioxide anode and preparation method thereof |
| CN114772684A (en) * | 2022-04-26 | 2022-07-22 | 南京理工大学 | Microporous titanium-based iridium tantalum whole body electrode applied to deep treatment of chemical tail water and preparation method and application thereof |
| CN114772684B (en) * | 2022-04-26 | 2023-08-11 | 南京理工大学 | Microporous titanium-based iridium tantalum-doped whole electrode applied to chemical tail water advanced treatment and preparation method and application thereof |
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Open date: 20100512 |