CN103668342B - A kind of manganese electrolysis titanium based composite anode and preparation method - Google Patents
A kind of manganese electrolysis titanium based composite anode and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of manganese electrolysis titanium based composite anode and preparation method thereof.What titanium based composite anode of the present invention adopted is is that skeleton is combined titanium foam that the titanium wire network that formed strengthens as matrix with titanium foam with titanium wire network, after described matrix surface applies one or more noble metal oxide layer, then obtain through preelectrolysis coating manganese dioxide layer.Preparation technology of the present invention is simple, and the titanium based composite anode of preparation solves that anode potential existing for traditional lead silver alloy anode is high, anode by product is leaded and is difficult to the difficult problem that reuses, in addition, also solve the problem of traditional titanium base modified anode easy passivation in electrolytic manganese system simultaneously.
Description
Technical field
The present invention relates to a kind of manganese electrolysis titanium based composite anode and preparation method, belong to electrochemical field.
Background technology
China is the production and supplyment big country of electrolytic metal Mn, and improving resource utilization, reducing energy consumption is the significant problem that manganese electrolytic industry faces.
Adopt pb-ag alloy as anode in the industry of traditional electrolyte manganese, mainly oxygen evolution reaction occurs at anode, and the oxidation of adjoint part manganese, can Manganse Dioxide be generated.Because the facial pallor in pb-ag alloy easily enters in anode solid product, usually mass ratio with manganese plumbous containing 10%(in gained anode Manganse Dioxide) lead, there is no economy, effective means is removed, cause manganese electrolytic anode slag to be difficult to recycling, reduce the utilization ratio of promoter manganese.
For reducing the generation of anode Manganse Dioxide, usually need to improve anodic current density, wherein cathode current density is generally 350-400A/m2, and anodic current density is generally 600-700A/m
2, but the increase of current density correspondingly can increase anodic polarization, makes the corresponding rising of bath voltage, thus adds the energy consumption of electrolytic process.
In addition, titanium base modified anode is being applied in electrolytic manganese dioxide industry, but in hydrosulphate system, is easy to passivation by the coated titanium anode that traditional method obtains, can only at low current density (as 50A/m
2), could steady operation under high temperature, when current density increases, the rapid passivation of electrolytic manganese system, causes bath voltage significantly to rise, and electrolytic process cannot carry out.
Therefore, high performance electrolytic manganese anode is researched and developed significant for the development of electrolytic manganese industry.
Summary of the invention
The present invention is directed to the great demand that current electrolysis manganese industry is saved energy and reduce the cost and improved resource utilization, a kind of manganese electrolysis titanium based composite anode and preparation method are provided.To the invention solves in traditional lead silver alloy anode that existing anode potential is high, anode by product is leaded and be difficult to the difficult problem that reuses, solving the problem of traditional titanium base modified anode easy passivation in electrolytic manganese system simultaneously.
Concrete technical scheme
A kind of manganese electrolysis titanium based composite anode, adopting take titanium wire network as skeleton is combined the titanium wire network that formed and strengthens titanium foam matrix with titanium foam, after described titanium foam matrix surface applies one or more noble metal oxide layer, again through preelectrolysis coating manganese dioxide layer, obtain the composite anode with metal oxide containing precious metals and Manganse Dioxide compound coating.
Wherein, the string diameter of titanium wire network is preferably 0.15-0.50mm, and aperture is preferably 60-16 order.
A kind of preparation method of manganese electrolysis titanium based composite anode, adopting take titanium wire network as skeleton is combined the titanium wire network that formed and strengthens titanium foam matrix with titanium foam, after described titanium foam matrix surface applies one or more noble metal oxide layer, then through preelectrolysis coating manganese dioxide layer.
In the present invention, described titanium foam matrix is by being coated on titanium wire network for 1:0.05-0.2:0.1-0.3:0.5-1 is made into slurry in mass ratio by the pure titanium valve of-320 object, polyvinyl alcohol, hydrogen peroxide and deionized water, foam at 40-60 DEG C, drying, then at 1250-1300 DEG C, high temperature sintering obtains in a vacuum furnace.
In the present invention, the forming process of described noble metal oxide layer is, adopts oxalic acid solution to be heated to by titanium foam matrix after boiling slightly etches, by RuCl
33H
2o, H
2irCl
66H
2o, TaCl
5in one or more masking liquids made be coated on titanium foam matrix surface, at 450-550 DEG C, be oxidized 5-15min after drying, cooling, then remove surface porosity thing, then repetitive coatings be repeatedly, finally at 450-550 DEG C of calcining 1-2h.
In the present invention, described preelectrolysis has the titanium foam matrix of one or more noble metal oxide layer for anode with surface-coated, and graphite is negative electrode, at the MnSO containing 60-75g/L
4and 25-30g/LH
2sO
4electrolytic solution in, with 30-50A/m
2anodic current density preelectrolysis coating manganese dioxide layer.
The preferred embodiment of preparation method of the present invention is, first the pure titanium valve of-320 object, polyvinyl alcohol, hydrogen peroxide and deionized water are coated on titanium wire network for 1:0.05-0.2:0.1-0.3:0.5-1 is made into slurry in mass ratio, foam at 40-60 DEG C, drying, at 1250-1300 DEG C, high temperature sintering obtains titanium foam matrix in a vacuum furnace; Then adopt oxalic acid solution that the titanium foam matrix obtained is heated to boiling slightly to etch, and by RuCl
33H
2o, H
2irCl
66H
2o, TaCl
5or their mixture is mixed with masking liquid, is coated on the titanium foam matrix surface after etching, after drying, at 450-550 DEG C, is oxidized 5-15min, remove surface porosity thing after cooling, then repetitive coatings repeatedly, and sample is calcined 1-2h at 450-550 DEG C; Then, with the titanium foam matrix after noble metal-coating oxide skin for anode, graphite is negative electrode, at the MnSO containing 60-75g/L
4and 25-30g/LH
2sO
4electrolytic solution in, with 30-50A/m
2anodic current density preelectrolysis 10-20h apply Manganse Dioxide, obtain the composite anode with metal oxide containing precious metals and electrolytic manganese dioxide compound coating.
Beneficial effect of the present invention
Compared with traditional lead silver alloy anode, not leaded in manganese electrolysis titanium based composite anode of the present invention, make anode by product Manganse Dioxide can realize recycling, such as, can be used as the presoma of synthesis of anode material of lithium-ion battery lithium manganate, thus realize the efficiency utilization of anode by product.In addition, the titanium foam that the present invention adopts titanium wire network to strengthen, as matrix, significantly improves the intensity of titanium foam matrix, solves the problem adopting pure foam titanium to be out of shape due to attachment electrolytic manganese dioxide in electrolytic process as the anode of matrix.Further, compared with dull and stereotyped titanium base modified anode, in the present invention, adopt titanium foam matrix, thus good electrochemical activity can be kept under larger apparent anodic current density, not easily passivation occurs.In addition, by electrode surface noble metal-coating oxide compound, can realize the good covering of Titanium base and improve anode to the catalytic activity of oxygen evolution reaction.Meanwhile, adopt preelectrolysis method to modify electrode surface, the electrolytic manganese dioxide tectum that electrode forming property under suitable electrolytic solution and operational condition is good, stable can be made, be conducive to electrode in electrolytic process and stablize, work efficiently.With chemical method obtain manganese bioxide coated compared with, there is better electro catalytic activity, and better with the consistency of electrolysis system.Such as, at 400A/m
2current density under electrolysis time, the current potential of dull and stereotyped titanium base modified anode rises to more than 7V very soon, the average potential of traditional lead silver alloy anode is about 1.95V, and the anode potential of titanium based composite anode in the present invention is only 1.2-1.3V, illustrate that the cycle life of titanium based composite anode of the present invention is high, capacity is large, and capability retention is high.The present invention is by choosing suitable matrix and by suitable preparation method, had the composite anode of metal oxide containing precious metals and electrolytic manganese dioxide compound coating simultaneously.The titanium based composite anode adopting the technology of the present invention to prepare effectively can reduce the bath voltage of electrolytic metal Mn, realize the recycling of anode by product, and this anode can work in manganese electrolysis system for a long time, stably.
Accompanying drawing explanation
Fig. 1 is manganese electrolysis titanium based composite anode surface topography;
As can be seen from the figure titanium based composite anode have evenly, abundant pore structure, make its surface-area much larger than ordinary flat electrode, contribute to the real current density reducing Titanium base, prevent Titanium base passivation, and improve the catalytic activity of electrode.
Embodiment
Below in conjunction with concrete comparative example and embodiment, the present invention is described further.Following examples can not be considered as limitation of the present invention.
Comparative example 1
Adopt lead silver alloy anode and stainless steel cathode, pole span is 75mm, adopts industrial electrolysis manganese electrolyte, with 400A/m at 40 DEG C
2current electroanalysis 20 hours, anode average potential is 1.95V, average cell voltage is 5.1V, in anode by product Manganse Dioxide, lead content is 5.1%, with the lithium manganate capacity for precursor synthesis for 95mAh/g, cycle life <50 time (capability retention after 50 times that circulates is only 55%).
Comparative example 2
Adopt titanium base modified anode of the prior art and stainless steel cathode, pole span is 75mm, adopts industrial electrolysis manganese electrolyte, at 40 DEG C, carries out electrolysis with the electric current of 400A/m2, bath voltage rises to more than 10V (anode potential reaches more than 7V) very soon, and electrolysis can not normally be carried out.
Embodiment 1
By the pure titanium valve of-320 object and polyvinyl alcohol, hydrogen peroxide, deionized water in mass ratio for 1:0.1:0.2:0.7 is made into slurry, be coated on the 60 order titanium wire networks of 0.15mm, foaming at 60 DEG C is also dry, then sinter 2h at 1300 DEG C in a vacuum furnace, obtain the titanium foam matrix that titanium wire network strengthens.Adopt massfraction be 15% oxalic acid solution titanium foam matrix that titanium wire network the is strengthened 2h that is heated to seethe with excitement slightly etch, by RuCl
33H
2o, H
2irCl
66H
2o is mixed with masking liquid by amount of substance than for 3:1 is dissolved in hydrochloric acid and ethanol, be applied to titanium foam matrix surface, dry 15min at 100 DEG C, then 10min is oxidized at 500 DEG C, surface porosity thing is removed after cooling, repetitive coatings 10 times, finally calcines 2h by sample at 500 DEG C again, makes muriate be converted into corresponding oxide compound.Then with the matrix material of above-mentioned noble metal-coating oxide coating for anode, graphite is negative electrode, containing the MnSO of 75g/L
4and 30g/LH
2sO
4electrolytic solution in, with 50A/m
2anodic current density preelectrolysis 10h apply Manganse Dioxide, obtain the titanium foam based composite anode with metal oxide containing precious metals and electrolytic manganese dioxide compound coating.
Adopt above-mentioned titanium based composite anode and stainless steel cathode, pole span is 75mm, adopt industrial electrolysis manganese electrolyte, electrolysis is carried out 20 hours with the electric current of 400A/m2 at 40 DEG C, anode average potential is 1.3V, and average cell voltage is 4.2V, lead do not detected in anode by product Manganse Dioxide, with the lithium manganate capacity for precursor synthesis for >112mAh/g, cycle life >500 time.
Embodiment 2
By the pure titanium valve of-320 object and polyvinyl alcohol, hydrogen peroxide, deionized water in mass ratio for 1:0.05:0.3:0.5 is made into slurry, be coated on 40 order titanium wire networks that string diameter is 0.25mm, foaming at 50 DEG C is also dry, then sinter 2h at 1250 DEG C in a vacuum furnace, obtain the titanium foam matrix that titanium wire network strengthens.Adopt massfraction be 15% oxalic acid solution titanium foam matrix that titanium wire network the is strengthened 2h that is heated to seethe with excitement slightly etch, by H
2irCl
66H
2o, TaCl
5masking liquid is mixed with than for 2:1 is dissolved in hydrochloric acid and ethanol by amount of substance, be applied to titanium foam matrix surface, dry 15min at 100 DEG C, then 10min is oxidized at 500 DEG C, surface porosity thing is removed after cooling, repetitive coatings 15 times, finally calcines 1h by sample at 500 DEG C again, makes muriate be converted into corresponding oxide compound.Then with the matrix material of above-mentioned noble metal-coating oxide coating for anode, graphite is negative electrode, containing the MnSO of 60g/L
4and 25g/LH
2sO
4electrolytic solution in, with 30A/m
2anodic current density preelectrolysis 15h apply Manganse Dioxide, obtain the titanium foam based composite anode with metal oxide containing precious metals and electrolytic manganese dioxide compound coating.
Adopt above-mentioned titanium based composite anode and stainless steel cathode, pole span is 75mm, adopt industrial electrolysis manganese electrolyte, electrolysis is carried out 20 hours with the electric current of 400A/m2 at 40 DEG C, anode average potential is 1.2V, and average cell voltage is 4.1V, lead do not detected in anode by product Manganse Dioxide, with the lithium manganate capacity for precursor synthesis for >112mAh/g, cycle life >500 time.
Embodiment 3
By the pure titanium valve of-320 object and polyvinyl alcohol, hydrogen peroxide, deionized water in mass ratio for 1:0.2:0.2:0.6 is made into slurry, be coated on the 30 order titanium wire networks of 0.29mm, foaming at 45 DEG C is also dry, then sinter 2h at 1300 DEG C in a vacuum furnace, obtain the titanium foam matrix that titanium wire network strengthens.Adopt massfraction be 15% oxalic acid solution titanium foam matrix that titanium wire network the is strengthened 2h that is heated to seethe with excitement slightly etch, by RuCl
33H
2o is dissolved in hydrochloric acid and ethanol and is mixed with masking liquid, is applied to titanium foam matrix surface, 100 DEG C of dry 15min, then at 500 DEG C, be oxidized 10min, after cooling, remove surface porosity thing, then repetitive coatings 5 times, finally sample is calcined 1-2h at 500 DEG C, make muriate be converted into corresponding oxide compound.Then with the matrix material of above-mentioned noble metal-coating oxide coating for anode, graphite is negative electrode, containing the MnSO of 70g/L
4and 28g/LH
2sO
4electrolytic solution in, with 50A/m
2anodic current density preelectrolysis 10h apply Manganse Dioxide, obtain the titanium foam base modified anode with metal oxide containing precious metals and electrolytic manganese dioxide compound coating.
Adopt above-mentioned titanium base modified anode and stainless steel cathode, pole span is 75mm, adopts industrial electrolysis manganese electrolyte, with 400A/m at 40 DEG C
2electric current carry out electrolysis 20 hours, anode average potential is 1.3V, and average cell voltage is 4.3V, lead do not detected in anode by product Manganse Dioxide, with the lithium manganate capacity for precursor synthesis for >112mAh/g, cycle life >500 time.
Embodiment 4
By the pure titanium valve of-320 object and polyvinyl alcohol, hydrogen peroxide, deionized water in mass ratio for 1:0.1:0.1:1 is made into slurry, be coated on the 16 order titanium wire networks of 0.50mm, foaming at 60 DEG C is also dry, then sinter 2h at 1300 DEG C in a vacuum furnace, obtain the titanium foam matrix that titanium wire network strengthens.Adopt massfraction be 15% oxalic acid solution titanium foam matrix that titanium wire network the is strengthened 2h that is heated to seethe with excitement slightly etch, by RuCl
33H
2o, H
2irCl
66H
2o, TaCl
5masking liquid is mixed with than for 1:1:1 is dissolved in hydrochloric acid and ethanol by amount of substance, be applied to titanium foam matrix surface, dry 15min at 100 DEG C, then 10min is oxidized at 500 DEG C, surface porosity thing is removed after cooling, repetitive coatings 10 times, finally calcines 1.5h by sample at 500 DEG C again, makes muriate be converted into corresponding oxide compound.Then with the matrix material of above-mentioned noble metal-coating oxide coating for anode, graphite is negative electrode, containing the MnSO of 75g/L
4and 30g/LH
2sO
4electrolytic solution in, with 50A/m
2anodic current density preelectrolysis 10h apply Manganse Dioxide, obtain the titanium foam base modified anode with metal oxide containing precious metals and electrolytic manganese dioxide compound coating.
Adopt above-mentioned titanium base modified anode and stainless steel cathode, pole span is 75mm, adopts industrial electrolysis manganese electrolyte, with 400A/m at 40 DEG C
2electric current carry out electrolysis 20 hours, anode average potential is 1.2V, and average cell voltage is 4.1V, lead do not detected in anode by product Manganse Dioxide, with the lithium manganate capacity for precursor synthesis for >112mAh/g, cycle life >500 time.
Claims (11)
1. a manganese electrolysis titanium based composite anode, it is characterized in that, adopting take titanium wire network as skeleton is combined the titanium wire network that formed and strengthens titanium foam matrix with titanium foam, after described titanium foam matrix surface applies one or more noble metal oxide layer, again through preelectrolysis coating manganese dioxide layer, obtain the composite anode with metal oxide containing precious metals and Manganse Dioxide compound coating.
2. composite anode according to claim 1, is characterized in that, the string diameter of titanium wire network is 0.15-0.50mm, and aperture is 60-16 order.
3. composite anode according to claim 1 and 2, it is characterized in that, described titanium foam matrix is by being coated on titanium wire network for 1:0.05-0.2:0.1-0.3:0.5-1 is made into slurry in mass ratio by pure titanium valve, polyvinyl alcohol, hydrogen peroxide and deionized water, foam at 40-60 DEG C, drying, then at 1250-1300 DEG C, high temperature sintering obtains in a vacuum furnace.
4. composite anode according to claim 1 and 2, is characterized in that, the forming process of described noble metal oxide layer is, adopts oxalic acid solution that titanium foam matrix is heated to boiling and slightly etches, by RuCl
33H
2o, H
2irCl
66H
2o, TaCl
5in one or more masking liquids made be coated on the titanium foam matrix surface after etching, at 450-550 DEG C, be oxidized 5-15min after drying, cooling, then remove surface porosity thing, then repetitive coatings be repeatedly, finally at 450-550 DEG C of calcining 1-2h.
5. composite anode according to claim 1 and 2, is characterized in that, described preelectrolysis has the titanium foam matrix of one or more noble metal oxide layer for anode with surface-coated, and graphite is negative electrode, at the MnSO containing 60-75g/L
4and 25-30g/LH
2sO
4electrolytic solution in, with 30-50A/m
2anodic current density preelectrolysis coating manganese dioxide layer.
6. composite anode according to claim 3, is characterized in that, described preelectrolysis has the titanium foam matrix of one or more noble metal oxide layer for anode with surface-coated, and graphite is negative electrode, at the MnSO containing 60-75g/L
4and 25-30g/LH
2sO
4electrolytic solution in, with 30-50A/m
2anodic current density preelectrolysis coating manganese dioxide layer.
7. the manganese electrolysis preparation method of titanium based composite anode, it is characterized in that, adopting take titanium wire network as skeleton is combined the titanium wire network that formed and strengthens titanium foam matrix with titanium foam, after described titanium foam matrix surface applies one or more noble metal oxide layer, then through preelectrolysis coating manganese dioxide layer.
8. preparation method according to claim 7, it is characterized in that, described titanium foam matrix is by being coated on titanium wire network for 1:0.05-0.2:0.1-0.3:0.5-1 is made into slurry in mass ratio by the pure titanium valve of-320 object, polyvinyl alcohol, hydrogen peroxide and deionized water, foam at 40-60 DEG C, drying, then at 1250-1300 DEG C, high temperature sintering obtains in a vacuum furnace.
9. preparation method according to claim 7, is characterized in that, the forming process of described noble metal oxide layer is, adopts oxalic acid solution to be heated to by titanium foam matrix after boiling slightly etches, by RuCl
33H
2o, H
2irCl
66H
2o, TaCl
5in one or more masking liquids made be coated on titanium foam matrix surface, at 450-550 DEG C, be oxidized 5-15min after drying, cooling, then remove surface porosity thing, then repetitive coatings be repeatedly, finally at 450-550 DEG C of calcining 1-2h.
10. preparation method according to claim 7, is characterized in that, described preelectrolysis has the titanium foam matrix of one or more noble metal oxide layer for anode with surface-coated, and graphite is negative electrode, at the MnSO containing 60-75g/L
4and 25-30g/LH
2sO
4electrolytic solution in, with 30-50A/m
2anodic current density preelectrolysis coating manganese dioxide layer.
11. preparation methods according to claim 7, first the pure titanium valve of-320 object, polyvinyl alcohol, hydrogen peroxide and deionized water are coated on titanium wire network for 1:0.05-0.2:0.1-0.3:0.5-1 is made into slurry in mass ratio, foam at 40-60 DEG C, drying, at 1250-1300 DEG C, high temperature sintering obtains titanium foam matrix in a vacuum furnace; Then adopt oxalic acid solution that the titanium foam matrix obtained is heated to boiling slightly to etch, and by RuCl
33H
2o, H
2irCl
66H
2o, TaCl
5or their mixture is mixed with masking liquid, is coated on the titanium foam matrix surface after etching, after drying, at 450-550 DEG C, is oxidized 5-15min, remove surface porosity thing after cooling, then repetitive coatings repeatedly, and sample is calcined 1-2h at 450-550 DEG C; Then, with the titanium foam matrix after noble metal-coating oxide skin for anode, graphite is negative electrode, at the MnSO containing 60-75g/L
4and 25-30g/LH
2sO
4electrolytic solution in, with 30-50A/m
2anodic current density preelectrolysis 10-20h apply Manganse Dioxide, obtain the composite anode with metal oxide containing precious metals and electrolytic manganese dioxide compound coating.
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| CN105332008A (en) * | 2014-08-08 | 2016-02-17 | 施军锐 | Dsa honeycomb anode |
| CN105603455B (en) * | 2016-02-26 | 2018-03-16 | 武汉大学 | A kind of electrolytic manganese production-scale cell |
| CN107768673B (en) * | 2016-08-23 | 2021-01-01 | 宁德新能源科技有限公司 | Modified foam metal, electrode plate and secondary battery |
| CN106835192B (en) * | 2017-02-02 | 2018-12-21 | 桂林理工大学 | A kind of preparation method of electrolytic manganese dioxide titanium substrate anode surface composite coating |
| CN106929878A (en) * | 2017-04-06 | 2017-07-07 | 宁夏天元锰业有限公司 | A kind of anode of electrolytic manganese metal |
| CN109504987B (en) * | 2018-12-20 | 2020-09-11 | 中南大学 | Titanium-based composite anode for electrolytic manganese and preparation method and application thereof |
| CN111926349B (en) * | 2020-09-09 | 2021-10-15 | 中南大学 | Composite anode for hydrometallurgy and preparation method and application thereof |
| CN113755902B (en) * | 2021-09-30 | 2023-04-07 | 宁波创致超纯新材料有限公司 | Titanium anode plate and preparation method and application thereof |
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