CN102280626B - Composite lead dioxide electrode plate and manufacturing method thereof - Google Patents
Composite lead dioxide electrode plate and manufacturing method thereof Download PDFInfo
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- CN102280626B CN102280626B CN201010203738.XA CN201010203738A CN102280626B CN 102280626 B CN102280626 B CN 102280626B CN 201010203738 A CN201010203738 A CN 201010203738A CN 102280626 B CN102280626 B CN 102280626B
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Abstract
The invention discloses a composite lead dioxide electrode plate, which comprises a composite lead dioxide anode plate and a protective net covering the periphery of the composite lead dioxide anode plate, wherein the composite lead dioxide anode plate is arranged in a framework and comprises a plurality of small anode plates spliced and connected with one another; and each small anode plate comprises a titanium substrate, a transition layer coated on the titanium substrate, an alpha-PbO2 interlayer coated on the transition layer and a beta-PbO2 active layer coated on the alpha-PbO2 interlayer; and the transition layer comprises at least one component of Pt, IrO2, Ta and Ta2O5. Correspondingly, the invention also provides a method for manufacturing the composite lead dioxide electrode plate. The composite lead dioxide electrode plate prepared by the method has long service life, the passivation process is stable, and an excellent implementation effect is achieved.
Description
Technical field
The present invention relates to battery lead plate and manufacture method thereof, relate in particular to a kind of lead dioxide electrode plate and manufacture method thereof.
Background technology
Passivation Treatment is the important ring in electrotinning process, and object is the passivating film that generates one deck densification at the belt steel surface through zinc-plated, prevents that tin plate is oxidized in air, thereby strengthens the corrosion resistance of tin plate and covering with paint property.General paralysis facility is mainly made up of cell body, passivating solution, passivated electrodes plate, conductive rollers and rectifier etc., wherein passivated electrodes plate is connected with the positive pole of rectifier, for Passivation Treatment provides required electric current, electric current acts on band steel by passivating solution, forms passivating film at belt steel surface.
Conventional Electroplating Tin Set Passivation Treatment adopts mild steel as battery lead plate more, and such battery lead plate manufacture craft is simple, and cost is lower.But above-mentioned mild steel battery lead plate is the problem of following three aspects of ubiquity in use:
1. mild steel battery lead plate corrosion rate is fast, and corrosion product pollutes passivating solution.The pH value of passivating solution is generally between 4.5～5.5, and mild steel battery lead plate, in this acid solution, corrosion reaction can occur, and produces electrochemical reaction under the effect of passivation current, and corrosion rate is accelerated.While adopting mild steel battery lead plate as passivated electrodes plate, corrosion thickness is every year on average up to 15～30mm, and produce a large amount of free carbons after the corrosion of mild steel battery lead plate, free carbon does not produce and reacts with other material after entering passivating solution, is present in passivating solution with suspension, pollutes passivating solution, when being increased to after a certain amount of, carbon just starts enrichment, be easy to stick to belt steel surface, form the material of the highly dispersed shape of one deck grey black at belt steel surface, be called " grey black " defect.So while adopting mild steel as passivation positive electricity pole plate, within every about 6 months, to change one-time electrode plate, and tin plate sheet surface grey black degree weight, tin plate sheet surface quality and covering with paint property affected.
2. mild steel battery lead plate is oxidizable, causes passivation effect unstable.There is oxidation reaction after immersing passivating solution in mild steel battery lead plate, the product of oxidation reaction has FeO, Fe very soon
2o
3and Fe
3o
4these oxides constantly dissolve in again passivating solution in forming process, and the oxide components that plays discharge process in the different phase using at mild steel battery lead plate constantly changes, and causes passivation effect unstable, passivation film thickness changes greatly, causes tin plate unstable product quality.
3. mild steel battery lead plate is easily subject to being with steel drift to hit, and causes scratch and damages: in tinplating industry large-scale production process, carry out high-speed cruising with steel with the speed of 200～500m/min, the passivating solution in deactivation slot is also with 10～30m
3the flow velocity of/h circulates, and spacing with steel and battery lead plate is only 40mm left and right, therefore in the time that belt plate shape is not good, easy and battery lead plate produces to wipe and touches and short contact, now electric current is directly transferred to and is with steel to cause short circuit from positive electricity pole plate, thereby cause galled spots and the localized burn of positive electricity pole plate, when serious, can cause the damage of passivated electrodes plate and then cause whole piece unit to stop production, affect the steady production of unit.
The problem of above three aspects is technical barriers that Electroplating Tin Set cannot be avoided while using conventional mild steel passivated electrodes plate, therefore needs to invent a kind of novel passivated electrodes plate that is applicable to zinc-plated unit Passivation Treatment, addresses the above problem.
Summary of the invention
The object of this invention is to provide a kind of composite lead dioxide electrode plate and manufacture method thereof, this composite lead dioxide electrode plate has good corrosion resistance and discharging function, in addition the top layer of this composite lead dioxide electrode plate should not come off, can effectively avoid touching and short circuit with the wiping of steel and pole plate, thereby extend the useful life of battery lead plate, solve the various deficiencies that existing conventional mild steel passivation pole plate exists.
According to above-mentioned purpose of the present invention, a kind of composite lead dioxide electrode plate is proposed, comprising:
One dioxide composite chloride plate, is installed in a framework, comprises some blocks of primary anode plates of assembled connection each other, and described each primary anode plate includes: the transition zone, that a titanium-base, is overlying on titanium-base is overlying on the α-PbO on transition zone
2intermediate layer, and one be overlying on α-PbO
2β-PbO on intermediate layer
2active layer, the constituent of described transition zone is Pt, IrO
2, Ta, Ta
2o
5in at least one;
One anti-net, covers in described dioxide composite chloride plate periphery.
Transition zone in above-mentioned dioxide composite chloride plate can reduce the oxidation rate of titanium-base, β-PbO
2active layer is discharge layer, and its discharging function is cut and had good decay resistance well, but β-PbO
2enbrittle, inventor passes through at β-PbO
2between active layer and transition zone, α-PbO is set
2intermediate layer reduces β-PbO
2fragility, and the design of anti-net, can effectively avoid being with steel to wipe and touch composite lead dioxide electrode plate, causes galled spots and the short circuit scaling loss of pole plate.
Preferably, between described dioxide composite chloride plate and anti-net, be also provided with an insulation net.In energising situation, if band steel contacts with anti-net, can make power supply short circuit, the anti-net of scaling loss is therefore provided with insulation net between anti-net and lead dioxide electrode plate.
Preferably, the area of described primary anode plate is 0.2～0.4m
2.Inventor finds in invention process, because the phenomenon of expanding with heat and contract with cold of anode of lead dioxide is more serious, in the time that annode area is larger, easily cause coming off of top layer brown lead oxide coating, therefore monoblock composite lead dioxide electrode plate is divided into some fritters by inventor, and the area control of each piece is at 0.2～0.4m
2between, thereby the quality of assurance brown lead oxide coating.
Preferably, the constituent of described transition zone is Pt+IrO
2+ Ta
2o
5.
Inventor is by evidence, and the constituent of transition zone comprises Pt, IrO
2, Ta, Ta
2o
5in at least one all can realize the technical program, but its implementation result is slightly different, specifically in table 1:
Table 1
| Transition zone constituent | Pt | Pt+IrO 2 | IrO 2+Ta 2O 5 | Ta | Pt+IrO 2+Ta 2O 5 |
| Price | The highest | Higher | Lower | Higher | Higher |
| Manufacture craft difficulty | The easiest | Easier | Easier | The most difficult | Easier |
| Improve effect anode life | Larger | Larger | Larger | Larger | Maximum |
| Corrosion resistance | Better | Poor | The poorest | Better | Best |
Need to be appreciated that, in table 1, the evaluation of " poor ", " better " is the collocation of the each constituent described in the present invention and the comparison of choosing realized implementation result, but not technical solutions according to the invention compared with the prior art, even if be evaluated as " poor " in table 1, its performance index are also better than prior art.
Preferably, described anti-net is titanium net.Preferably the object of titanium net is its good toughness, and resistance to wear is high, is difficult in the course of the work being abraded by band steel.
Correspondingly, the present invention also provides a kind of manufacture method of above-mentioned composite lead dioxide electrode plate, and wherein, the manufacturing step of described primary anode plate comprises:
(1) pre-treatment of titanium-base: the titanium oxide of removing titanium-base surface according to the order of alkali cleaning → pickling → texturing;
(2) transition zone preparation: the titanium-base through pre-treatment is carried out to sintering in sintering solution, sintering temperature is controlled at 450～500 ℃, the solvent of described sintering solution is alcohol, and solute is at least one in platinum salt, iridium salt or tantalum salt, and the thickness of finally controlling transition zone is 3～5 μ m;
(3) α-PbO
2the preparation in intermediate layer: titanium-base prepared by process transition zone is at Pb
2+concentration is to electroplate in 120～145g/L, the NaOH concentration aqueous solution that is 4～8mol/L, and electroplating temperature is controlled at 40～50 ℃, and current density is controlled at 3～7A/dm
2, finally control α-PbO
2the thickness in intermediate layer is 10～20 μ m;
(4) β-PbO
2the preparation of active layer: will be through α-PbO
2titanium-base prepared by intermediate layer is at HNO
3concentration is 0.1～0.2mol/L, Pb
+concentration is to electroplate in the mixed aqueous solution of 0.3～0.8mol/L, and electroplating temperature is controlled at 60～80 ℃, and current density is controlled at 2～5A/dm
2, finally control β-PbO
2the thickness of active layer is 0.5～1.0mm.
Preferably, in described step (2), sintering solution is Pt
4+concentration be 10～20g/L, Ta
5+concentration be 30～70g/L, Ir
4+the concentration alcoholic solution that is 30～70g/L.
Make after above-mentioned primary anode plate, some blocks of primary anode plates are assembled into a bulk of anode of lead dioxide plate, be then installed in framework.Then at the forward and backward two sides of anode of lead dioxide plate installing insulating net, then in the outside of insulation net, anti-net is installed.
The present invention, owing to having adopted technique scheme, makes it compared to prior art, has following advantage:
(1) composite lead dioxide electrode plate is slow as anodic attack speed, has guaranteed the clean of passivating solution, can significantly alleviate the grey black degree of belt steel surface;
(2) use composite lead dioxide electrode plate, be increased dramatically with the stable of passivation effect index such as steel passivation film thickness, the maximum of lead dioxide electrode plate in passivating process use current density can be far above mild steel battery lead plate the current density in passivating process, can reach 50A/dm
2, this current density is about 5 times of ordinary low-carbon steel battery lead plate, therefore can increase strip speed, improves output;
(3) be much higher than existing mild steel battery lead plate the useful life of composite lead dioxide electrode plate, can reach 12 months its average life, and only have 6 months the useful life of ordinary low-carbon steel anode.
Accompanying drawing explanation
Fig. 1 is the structural scheme of mechanism of composite lead dioxide electrode plate in a kind of exemplary embodiment of the present invention.
Fig. 2 is the structural representation of a certain primary anode plate in composite lead dioxide electrode plate of the present invention.
Fig. 3 is composite lead dioxide electrode plate structural representation of the present invention.
Embodiment
Embodiment 1-5
In embodiment of the present invention 1-5, manufacture composite lead dioxide electrode plate by following step, first carry out the manufacture of primary anode plate, comprise the steps (the concrete technology parameter in each embodiment is referring to table 2):
(1) pre-treatment of titanium-base:
1. alkali cleaning: soak 20～40 minutes in the NaOH aqueous solution that is 3～7% at mass percent concentration by titanium-base, alkali cleaning temperature is 80～90 ℃;
2. pickling: by titanium-base at H
2sO
4and HNO
3pickling 5～15 minutes in the nitration mixture of composition, pickling temperature is 60～80 ℃, wherein H
2sO
4the mass percent concentration of solution is 5～15%, HNO
3the mass percent concentration of solution is 3～7%;
3. texturing: be 5～6Kg/cm at pressure
2compressed air in titanium-base is carried out to texturing processing with the carborundum of 100～500 order numbers, after texturing, titanium-base roughness is controlled at 5～7 μ m.
(2) transition zone preparation: the titanium-base through pre-treatment is carried out to sintering in sintering solution, and sintering temperature is controlled at 450～500 ℃, and sintering solution is Pt
4+concentration be 10～20g/L, Ta
5+concentration be 30～70g/L, Ir
4+the concentration alcoholic solution that is 30～70g/L.Need to be appreciated that, composite lead dioxide electrode plate manufacture method of the present invention is in the time preparing transition zone, the broad matter of sintering solution can be at least one in platinum salt, iridium salt or tantalum salt, but consider after the multiple factors such as manufacturing cost, performance index, inventor has all selected the combination of platinum salt, tantalic chloride and iridium chloride as solute in embodiment 1-5, and the thickness of finally controlling transition zone is 3～5 μ m.
(3) α-PbO
2the preparation in intermediate layer: titanium-base prepared by process transition zone is at Pb
2+concentration is to electroplate in 120～145g/L, the NaOH concentration aqueous solution that is 4～8mol/L, and electroplating temperature is controlled at 40～50 ℃, and current density is controlled at 3～7A/dm
2, finally control α-PbO
2the thickness in intermediate layer is 10～20 μ m;
(4) β-PbO
2the preparation of active layer: will be through α-PbO
2titanium-base prepared by intermediate layer is at HNO
3concentration is 0.1～0.2mol/L, Pb
+concentration is to electroplate in the mixed aqueous solution of 0.3～0.8mol/L, and electroplating temperature is controlled at 60～80 ℃, and current density is controlled at 2～5A/dm
2, finally control β-PbO
2the thickness of active layer is 0.5～1.0mm.
As shown in Figure 2, center is titanium-base 1 to the primary anode plate structure making through above-mentioned steps, is then followed successively by from the inside to surface transition zone 2, α-PbO
2 intermediate layer 3 and β-PbO
2active layer 4.As shown in figures 1 and 3, some primary anodes 5 plates are assembled into a bulk of anode of lead dioxide plate 9, are then installed in framework 8, then at the forward and backward two sides of anode of lead dioxide plate 9 installing insulating net 6, the material of insulation net 6 is polytetrafluoroethylene, and width of mesh is controlled at 2～6cm
2, then in the outside of insulation net 6, anti-friction titanium net 7 is installed, the Thickness Design of anti-net 7 is 1～3mm, mesh is 2～6cm
2 size.Insulation net 6, anti-net 9 realized with being connected by bolt of anode of lead dioxide plate 9, therefore at bolt connecting portion, were insulated with fluoroplastic plate and lining, thereby had guaranteed the insulation between anti-friction titanium net 7 and anode of lead dioxide plate 9.
Use the composite lead dioxide electrode plate making by said method to carry out passivation to band steel, the main technologic parameters of passivation still adopts existing technological parameter as follows.In use repeatedly check, do not find the phenomenons such as battery lead plate abrades, titanium net is pulled, brown lead oxide coating is intact, and mesh does not stop up, and can continue to use, and useful life was up to 14 months.
In whole use procedure, what passivation film thickness was stable is controlled at 0.3～0.9ug/cm
2, CPK value reaches more than 1.67, and surperficial grey black is brought up to average one-level level by average three grades.
As can be seen here, the use of composite lead dioxide electrode plate has improved band steel passivation technology, has reduced the replacing frequency of passivating solution, has reduced the defects such as tin plate sheet surface grey black, roll marks, the frequent discharge pollution on the environment that has reduced passivating solution, is applicable to zinc-plated unit Passivation Treatment completely.
Be noted that above enumerate only for specific embodiments of the invention, obviously the invention is not restricted to above embodiment, have many similar variations thereupon.If all distortion that those skilled in the art directly derives or associates from content disclosed by the invention, all should belong to protection scope of the present invention.
Claims (6)
1. a composite lead dioxide electrode plate, is characterized in that, comprising:
One dioxide composite chloride plate, is installed in a framework, comprises some blocks of primary anode plates of assembled connection each other, and described each primary anode plate includes: the transition zone, that a titanium-base, is overlying on titanium-base is overlying on the α-PbO on transition zone
2intermediate layer, and one be overlying on α-PbO
2β-PbO on intermediate layer
2active layer, the constituent of described transition zone is Pt+IrO
2+ Ta
2o
5;
One anti-net, covers in described dioxide composite chloride plate periphery.
2. composite lead dioxide electrode plate as claimed in claim 1, is characterized in that: between described dioxide composite chloride plate and anti-net, be also provided with an insulation net.
3. composite lead dioxide electrode plate as claimed in claim 2, is characterized in that: the area of described primary anode plate is 0.2～0.4m
2.
4. the composite lead dioxide electrode plate as described in claim 1 or 3, is characterized in that: described anti-net is titanium net.
5. the manufacture method of composite lead dioxide electrode plate as claimed in claim 1, is characterized in that: the manufacturing step of described primary anode plate comprises:
(1) pre-treatment of titanium-base: the titanium oxide of removing titanium-base surface according to the order of alkali cleaning → pickling → texturing;
(2) transition zone preparation: the titanium-base through pre-treatment is carried out to sintering in sintering solution, sintering temperature is controlled at 450～500 ℃, the solvent of described sintering solution is alcohol, and solute is platinum salt, iridium salt and tantalum salt, and the thickness of finally controlling transition zone is 3～5 μ m;
(3) α-PbO
2the preparation in intermediate layer: by the titanium-base that is covered with transition zone at Pb
2+concentration is to electroplate in 120～145g/L, the NaOH concentration aqueous solution that is 4～8mol/L, and electroplating temperature is controlled at 40～50 ℃, and current density is controlled at 3～7A/dm
2, finally control α-PbO
2the thickness in intermediate layer is 10～20 μ m;
(4) β-PbO
2the preparation of active layer: will be covered with α-PbO
2the titanium-base in intermediate layer is at HNO
3concentration is 0.1～0.2mol/L, Pb
2+concentration is to electroplate in the mixed aqueous solution of 0.3～0.8mol/L, and electroplating temperature is controlled at 60～80 ℃, and current density is controlled at 2～5A/dm
2, finally control β-PbO
2the thickness of active layer is 0.5～1.0mm.
6. the manufacture method of composite lead dioxide electrode plate as claimed in claim 5, is characterized in that: in described step (2), sintering solution is Pt
4+concentration be 10～20g/L, Ta
5+concentration be 30～70g/L, Ir
4+the concentration alcoholic solution that is 30～70g/L.
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| CN104362301A (en) * | 2014-10-14 | 2015-02-18 | 浙江南都电源动力股份有限公司 | Carbon coated titanium-based lead dioxide positive plate for lead-acid storage battery |
| CN104962977B (en) * | 2015-06-03 | 2017-03-22 | 昆明理工大学 | Preparation method of rod-shaped bimetallic-based composite anode material |
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| CN108914122B (en) * | 2018-07-30 | 2020-11-27 | 山东龙安泰环保科技有限公司 | Preparation method of titanium-based lead dioxide anode |
| CN110093633A (en) * | 2019-03-25 | 2019-08-06 | 厦门潼源科技有限公司 | A kind of anode of titanium-based-β type brown lead oxide, preparation method and applications |
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| CN114645293B (en) * | 2022-02-16 | 2024-03-22 | 浙江工业大学 | Preparation of conductive polymer @ lead dioxide/titanium composite electrode and application of conductive polymer @ lead dioxide/titanium composite electrode in electrolytic synthesis of succinic acid |
| CN117646270B (en) * | 2024-01-29 | 2024-04-12 | 宝鸡钛普锐斯钛阳极科技有限公司 | Titanium anode suitable for organic additive application system and manufacturing method thereof |
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| EP0262369B1 (en) * | 1986-08-29 | 1991-11-06 | The Agency of Industrial Science and Technology | Lead oxide-coated electrode for use in electrolysis and process for producing the same |
| CN1033657A (en) * | 1987-10-27 | 1989-07-05 | 福州大学化学工程系 | The modified anode of lead dioxide that electrolytic industry is used |
| CN2358560Y (en) * | 1999-04-05 | 2000-01-12 | 四川合邦电力投资有限责任公司 | Waveform curved surface storage battery grid and manufacture of lead-acid battery |
| CN100430528C (en) * | 2004-08-31 | 2008-11-05 | 宝山钢铁股份有限公司 | High-speed continuous electroplating non-soluble anode conducting surface ablation on-line identifying method |
| CN100580143C (en) * | 2007-02-07 | 2010-01-13 | 浙江工业大学 | Method of preparing fluorine-containing lead dioxide electrode on titanium basal body |
| CN100500585C (en) * | 2007-02-14 | 2009-06-17 | 浙江工业大学 | Electrooxidation treatment technique for wastewater of chlorobenzene-containing compound |
| CN101388479B (en) * | 2008-11-07 | 2010-09-22 | 莫绚宗 | Renovating method for lead-acid accumulator |
| CN101417831A (en) * | 2008-11-11 | 2009-04-29 | 北京师范大学 | Novel ti-supported lead dioxide electric pole and preparation method thereof |
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