CN101705499B - Method for preparing positive plate for electrolyzing manganese dioxide - Google Patents
Method for preparing positive plate for electrolyzing manganese dioxide Download PDFInfo
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- CN101705499B CN101705499B CN2009102422789A CN200910242278A CN101705499B CN 101705499 B CN101705499 B CN 101705499B CN 2009102422789 A CN2009102422789 A CN 2009102422789A CN 200910242278 A CN200910242278 A CN 200910242278A CN 101705499 B CN101705499 B CN 101705499B
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Abstract
The invention discloses a method for preparing positive plates for electrolyzing manganese dioxide, which belongs to the technical field of preparation of positive plates for electrolysis. The preparation method comprises the steps of coating a layer of metal powder on the surface of a titanium plate; conducting high-temperature vacuum pulling-sintering to the titanium plate coated with metal powder to form a compound positive strip with metal coating on the surface and titanium in the center; and conducting welding assembly and aluminum-casting assembly to a plurality of compound positive strips to obtain the positive plates, wherein the high-temperature vacuum pulling-sintering is carried out at the temperature of 1000 to 1400 DEG C; and the pulling speed is controlled to ensure that the effective heating time of each part of work pieces is between 5 and 120 minutes. The positive plate prepared by the method for electrolyzing manganese dioxide has high anti-passivation property, and bath voltage of the positive plate is lower than that of the pure titanium positive plate by more than 0.5 to 1 volt; after being discharged from a trough by electrolysis, the positive plates can be directly put in the trough to continue the electrolysis of the next cycle, without depassivation processes such as sand-blasting or anti-electrolysis and the like; therefore, the production efficiency is high and the manufacturing cost is low; and the positive plates are ideal positive plates for electrolyzing manganese dioxide.
Description
Technical field
The invention belongs to the positive plate preparing technical field that electrolysis is used, particularly a kind of preparation method of positive plate for electrolyzing manganese dioxide.
Background technology
Producing materials such as Manganse Dioxide, manganese, copper, cobalt, nickel, zinc with electrolytic method is a kind of method that generally adopts in the industry.Owing in electrolytic process, have oxygen or chlorine to separate out, therefore employed anode had higher requirement at anode.
Since Manganse Dioxide adopted electrolytic process to carry out industrial production, employed anode had passed through the development course of graphite, pb-ag alloy, pure titanium, titanium manganese ferrochrome quad alloy and titanium manganese coated anode.At present, graphite and pb-ag alloy anode are superseded by fully.
Pure titanium has its special advantages as replacing graphite and pb-ag alloy anode; But its inherent passivation tendency is arranged but; Under the low slightly situation of high slightly current density or electrolysis temperature and after using certain hour, passivation very easily takes place, cause bath voltage to raise; Power consumption increases, even can't continue electrolysis; These people have also been taked the whole bag of tricks, like suspension electrolysis, surface sand-blasting, chemical conversion treatment etc. are improved to a great extent, but still the phenomenon of passivation often occurs, need adopt the measure of sandblast again or back-electrolysis could continue to use.
Titanium manganese ferrochrome quad alloy also is the more successful anode of industrial application; Yet still there is the defective that is difficult to overcome in this anode; The welding property that is alloy is bad, can not carry out large-scale anodic welding assembly, again because plate rolling process is difficult to control; The trend that behind life-time service, still exists simultaneously bath voltage to rise stops production for many years at present.
Titanium manganese alloy coated anode (Chinese utility model patent 87216402) begins sizable application in industrial production from nineteen ninety, and anti-inactivating performance is superior, and the life-span is long, and the anode major part that came into operation in present 1991 still under arms.In current density is 50～100A/m
2The time bath voltage be merely 2.2～3.2 volts, even use for many years, bath voltage is also seldom above 3.5 volts.The purer titanium anode of power consumption obviously reduces, and is also lower than titanium manganese ferrochrome quad alloy.But adopt common vacuum sintering technology, facility investment is big, and production efficiency is low; Preparation cost is high, and the titanium manganese anode of production adopts bolted, and it is not firm to electrically contact; Need re-assembly every now and then, also influence the maximization of positive plate thus, thereby limit its range of application.
Summary of the invention
The present invention is directed to the problem that titanium base titanium manganese alloy coated anode exists, adopt and dynamically lift sintering process, and welding and cast aluminium assembling mode solve the problems referred to above, and further reduce the power consumption of electrolytic manganese dioxide.
The preparation method who the purpose of this invention is to provide a kind of positive plate for electrolyzing manganese dioxide; It is characterized in that; The preparation method is following for this positive plate: at the surface-coated layer of metal powder of titanium plate, surface-coated the titanium plate of metal powder after high-temperature vacuum lifts sintering, be titanium in the middle of forming, surperficially is the composite anode bar of metallic coating; A plurality of composite anode bars through welding assembly, cast aluminium assembling, obtain positive plate again; Wherein, it is to carry out under 1000～1400 ℃ in temperature that high-temperature vacuum lifts sintering, is that 5～120 minutes pull rate is carried out with the effective heating time that guarantees each part of workpiece when lifting.High-temperature vacuum lifts sintering in temperature preferred 1250～1350 ℃, and it is 5～15 minutes that pull rate preferably makes the effective heating time of each part of workpiece.
It is following that said high-temperature vacuum lifts the sintering concrete steps: surface-coated the titanium plate of metal powder be placed in the vacuum storage tanks of normal temperature, be evacuated to 10
-5～10
-3Applying argon gas protection behind the Pa; Continue then to lift make surface-coated the titanium plate of metal powder heat through the constant temperature vacuum furnace that is positioned at directly over the vacuum storage tanks; Lift rapidly after the heating in the cold well of vacuum to the constant temperature vacuum furnace and cool off, cooled off 5～10 minutes, make it pass through the constant temperature vacuum furnace after the cooling rapidly downwards and place back storage tank; Thereby completion vacuum sintering is that titanium, surface are the composite anode bar of metallic coating in the middle of forming.
Said metal powder component is titanium and manganese, and each weight percentages of components is following: titanium: 10～90%, and manganese: 10～90%.
Said metal powder component is titanium, manganese, chromium and iron, and each weight percentages of components is following: titanium: 20～50%, and manganese: 35～50%, chromium: 7～15%, iron: 8～15%.
Said composite anode bar be shaped as trapezoidal waveform, waviness, zig-zag, wherein, zig-zag comprises that mainly W type, NW are combined.
Said welding assembly is the lower end and vertical welding of pure titanium gusset with the composite anode bar, and the back side is with argon shield cover argon-filled protection during welding, and weld with argon arc welding in the front.
Said composite anode bar stays not applying coating of 5～15mm at an end of welding.
Said cast aluminium assembling is after the upper end of composite anode bar is riveted with rivet and conducting copper; Standing upside down wraps conducting copper and riveting portion with cast aluminium alloy, form the cast aluminium cross-arm, exposes to connect electric ear or the conduction bayonet socket is used for being connected with power supply;, said rivet is copper rivet or steel rivet.
Said cast aluminium alloy is 6063 duraluminums.
Hanger in the cast aluminium cross-arm replaces with the suspension hook shape.
At the surface-coated layer of metal powder of titanium plate, operate as follows among the present invention: metal powder or alloy powder are proportionally mixed, and stirring in water, alcohol or organic solvent with sticker afterwards is coated in the pure titanium plate surface of compression moulding with spray gun.Organic solvent can be selected from acetone etc., and sticker can be selected from dextrin, Z 150PH etc.
Beneficial effect of the present invention is: present method preparation be used for the electrolytic anode of Manganse Dioxide, have extremely strong anti-passivation property, under normal industrial electrolysis condition, when current density is 50～100A/m
2The time bath voltage be 1.8～3 volts, purer titanium anode is low more than 0.5～1 volt, after electrolysis goes out the groove discharging; Need not sandblast or depassivation such as back-electrolysis processing handle, can continue the electrolysis of next cycle directly into groove, so production efficiency is high; Production cost is low, is the ideal positive plate for electrolyzing manganese dioxide.
Adopt the titanium manganese positive plate of such scheme preparation can reduce sintering time on the one hand; Realized the semicontinuous production of technology on the other hand; Improve production efficiency greatly, reduced production cost, adopted the method for welding and cast aluminium assembling simultaneously; Solve maximization and electrically contacted illusive problem, further reduced the power consumption of electrolytic manganese dioxide.
Description of drawings
Fig. 1 is the positive plate for electrolyzing manganese dioxide synoptic diagram of present method preparation;
Fig. 2 is an A-A ' sectional view among Fig. 1;
Label among the figure: 1-composite anode bar; The 2-rivet; The 3-conducting copper; 4-connects electric ear; The pure titanium gusset of 5-; 6-cast aluminium cross-arm; The 7-hanger.
Embodiment
Below in conjunction with accompanying drawing the present invention is described further:
Embodiment 1
The metal powder component is titanium and manganese, and each weight percentages of components is following: titanium: 50%, and manganese: 50%.The Vilaterm alcohol and water is prepared into the aqueous solution of sticker in 1: 100 ratio of mass ratio; Then metal powder being joined the back that stirs in the aqueous solution of sticker of 5 times of metal powder weight is coated in spray gun and is pressed into the pure titanium plate of the combined 1350mm * 84mm of NW * 1.5mm surface; The lower end stays 10mm not to be coated with application layer; Be placed on after drying in the vacuum storage tanks of normal temperature, be evacuated to 10
-5Applying argon gas protection behind the Pa; Continue then to lift make surface-coated the titanium plate of metal powder heat through the constant temperature vacuum furnace that is positioned at directly over the vacuum storage tanks; Wherein, constant temperature vacuum furnace thermostat temperature is 1350 ℃, is that 10 minutes pull rate is carried out with the effective heating time that guarantees each part of workpiece when lifting; Lifted in the cold well of vacuum to the constant temperature vacuum furnace cooling after the heating rapidly 5 minutes; Making it in 10 seconds, place back storage tank through the constant temperature vacuum furnace after the cooling rapidly downwards, thereby accomplish vacuum sintering, is that pure titanium, surface are the composite anode bar 1 of titanium manganese alloy coating in the middle of forming.
Adopt 14 composite anode bars to be evenly distributed in the 1400mm again; Rivet tightly with four copper rivets 2 and 1500mm * 30mm * 3mm conducting copper 3 in every composite anode bar top; The electric ear 4 usefulness brazings that connect of conducting copper and copper are welded; Vertical welding is adopted with the pure titanium gusset (titanium bar) 5 of 1400mm * 20mm * 6mm in every composite anode bar bottom, and the back side is with argon shield cover argon-filled protection during welding, and weld with argon arc welding in the front; Standing upside down again conducting copper and riveting portion are being wrapped with 6063 cast aluminium alloys; Form cast aluminium cross-arm 6; Connect electric ear and can be connected with power supply but expose, be assembled into composite anode plate (as shown in Figure 1) through welding and cast aluminium, the cast aluminium cross-arm is of a size of 1650mm * 70mm * 30mm; Titanium connects electric ear and is of a size of 70mm * 50mm * 5mm, from top 25mm bore one
the hole; The outside radius of hanger 7 is 70mm, and internal diameter is 40mm.A-A ' sectional view is as shown in Figure 2 among Fig. 1.
By under the normal industrial electrolysis condition, current density is 60A/m
2The time, bath voltage is stabilized between 1.8～2.2 volts; The electrolytic manganese dioxide quality product reaches mercury-free alkaline manganese dioxide battery level level, can supply battery producer to use.
Embodiment 2
Other processing condition are with embodiment 1, and thermostat temperature is 1300 ℃, the confirming of pull rate: the effective heating time that guarantees each part of workpiece is 15 minutes.By under the normal industrial electrolysis condition, current density is 100A/m
2The time, bath voltage is stabilized between 2.5～2.8 volts; The electrolytic manganese dioxide product appearance is good.
Embodiment 3
Other processing condition are with embodiment 1, and thermostat temperature is 1200 ℃, the confirming of pull rate: the effective heating time that guarantees each part of workpiece is 30 minutes.By under the normal industrial electrolysis condition, current density is 100A/m
2The time, bath voltage is stabilized between 2.6～2.9 volts; The electrolytic manganese dioxide product appearance is good.
Embodiment 4
Other processing condition are with embodiment 1, and each component of metal powder and weight percent thereof are manganese: 90%, and titanium: 10%.By under the normal industrial electrolysis condition, current density is 100A/m
2The time, bath voltage is stabilized between 2.8～3 volts; The electrolytic manganese dioxide product appearance is good.
Embodiment 5
Other processing condition are with embodiment 1, and each component of metal powder and weight percent thereof are manganese: 50%, and chromium: 10%, iron: 10%, titanium: 30%.By under the normal industrial electrolysis condition, current density is 100A/m
2The time, bath voltage is stabilized between 2.8～3 volts; The electrolytic manganese dioxide product appearance is good.
Other processing condition are with embodiment 1.The titanium plate is pressed into circular arc, and development size is 1400mm * 160mm * 1.5mm, is of a size of 1400mm * 120mm * 1.5mm after the moulding, and every block of plate adopts 11 composite anode bars, hanger change bit hook-shaped.By under the normal industrial electrolysis condition, current density is 70A/m
2The time, bath voltage is stabilized between 2.2～2.7 volts; The electrolytic manganese dioxide product appearance is good.
Embodiment 7
Other processing condition are with embodiment 1.The titanium plate is pressed into trapezoidal, and development size is 1400mm * 160mm * 1.5mm, is of a size of 1400mm * 120mm * 1.5mm after the moulding, and every block of plate adopts 11 anode straps, hanger change bit hook-shaped.By under the normal industrial electrolysis condition, current density is 100A/m
2The time, bath voltage is stabilized between 2.8～3 volts; The electrolytic manganese dioxide product appearance is good.
Embodiment 8
Other processing condition are with embodiment 1.The titanium plate is pressed into trapezoidal, and development size is 1400mm * 160mm * 1.5mm, is of a size of 1400mm * 120mm * 1.5mm after the moulding, and every block of plate adopts 11 anode straps, and hanger is replaced by hook-shaped.By under the suspension industrial electrolysis condition, suspension agent is ultra-fine electrolytic manganese dioxide, and current density is 100A/m
2The time, bath voltage is stabilized between 2.4～2.6 volts; The electrolytic manganese dioxide product appearance is good.
Claims (10)
1. the preparation method of a positive plate for electrolyzing manganese dioxide; It is characterized in that; The preparation method is following for this positive plate: at the surface-coated layer of metal powder of titanium bar, surface-coated the titanium bar of metal powder after high-temperature vacuum lifts sintering, be titanium in the middle of forming, surperficially is the composite anode bar of metallic coating; A plurality of composite anode bars through welding assembly, cast aluminium assembling, obtain positive plate again; Wherein, it is to carry out under 1000～1400 ℃ in temperature that high-temperature vacuum lifts sintering, is that 5～120 minutes pull rate is carried out with the effective heating time that guarantees each part of workpiece when lifting; Said welding assembly is the lower end and vertical welding of pure titanium gusset with the composite anode bar; The assembling of said cast aluminium be with the upper end of composite anode bar with after rivet and the conducting copper riveted joint, standing upside down wraps conducting copper and riveting portion with cast aluminium alloy, formation cast aluminium cross-arm exposes to connect electric ear or conduct electricity bayonet socket and is used for being connected with power supply.
2. the preparation method of a kind of positive plate for electrolyzing manganese dioxide according to claim 1 is characterized in that, it is following that said high-temperature vacuum lifts the sintering concrete steps: surface-coated the titanium bar of metal powder be placed in the vacuum storage tanks of normal temperature, be evacuated to 10
-5～10
-3Applying argon gas protection behind the Pa; Continue then to lift make surface-coated the titanium bar of metal powder heat through the constant temperature vacuum furnace that is positioned at directly over the vacuum storage tanks; Lift rapidly after the heating in the cold well of vacuum to the constant temperature vacuum furnace and cool off; Making it pass through the constant temperature vacuum furnace after the cooling rapidly downwards and place back storage tank, thereby accomplish vacuum sintering, is that titanium, surface are the composite anode bar of metallic coating in the middle of forming.
3. the preparation method of a kind of positive plate for electrolyzing manganese dioxide according to claim 1 and 2 is characterized in that, said metal powder component is titanium and manganese, and each weight percentages of components is following: titanium: 10～90%, and manganese: 10～90%.
4. the preparation method of a kind of positive plate for electrolyzing manganese dioxide according to claim 1 and 2 is characterized in that, said metal powder component is titanium, manganese, chromium and iron; Each weight percentages of components is following: titanium: 20～50%; Manganese: 35～50%, chromium: 7～15%, iron: 8～15%.
5. the preparation method of a kind of positive plate for electrolyzing manganese dioxide according to claim 1 and 2 is characterized in that, said composite anode bar be shaped as trapezoidal waveform, waviness, zig-zag.
6. the preparation method of a kind of positive plate for electrolyzing manganese dioxide according to claim 1 and 2 is characterized in that, the back side is with argon shield cover argon-filled protection during welding, and weld with argon arc welding in the front.
7. the preparation method of a kind of positive plate for electrolyzing manganese dioxide according to claim 6 is characterized in that, said composite anode bar stays not applying coating of 5～15mm at an end of welding.
8. the preparation method of a kind of positive plate for electrolyzing manganese dioxide according to claim 1 and 2 is characterized in that, said rivet is copper rivet or steel rivet.
9. the preparation method of a kind of positive plate for electrolyzing manganese dioxide according to claim 8 is characterized in that, said cast aluminium alloy is 6063 duraluminums.
10. the preparation method of a kind of positive plate for electrolyzing manganese dioxide according to claim 8 is characterized in that, the hanger in the cast aluminium cross-arm replaces with the suspension hook shape.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102422789A CN101705499B (en) | 2009-12-08 | 2009-12-08 | Method for preparing positive plate for electrolyzing manganese dioxide |
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| CN2009102422789A CN101705499B (en) | 2009-12-08 | 2009-12-08 | Method for preparing positive plate for electrolyzing manganese dioxide |
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| CN103173784A (en) * | 2011-12-20 | 2013-06-26 | 北京有色金属研究总院 | Large full-immersion Ti-Mn alloy coat anode plate for manganese dioxide electrolysis, and its making method |
| CN109468657B (en) * | 2018-12-18 | 2020-07-03 | 有研工程技术研究院有限公司 | Preparation method of anode plate for electrolyzing manganese dioxide |
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Effective date of registration: 20190401 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals |
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Effective date of registration: 20210414 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Youyan resources and Environment Technology Research Institute (Beijing) Co.,Ltd. Address before: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: YOUYAN ENGINEERING TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. |
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