CN102505126A - Low-Ag-content Pb-RE-Ag alloy electrode - Google Patents
Low-Ag-content Pb-RE-Ag alloy electrode Download PDFInfo
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Abstract
A low-Ag-content Pb-RE-Ag alloy electrode comprises (by weight percentage) rare earth (RE) 0.001-2.0, silver (Ag) 0.001-0.6 and lead in balance. RE is selected from at least one of La, Ce, Nd, Sm, Eu, Tb, Dy, Ho, Er, Dm, Yb, and Lu, and the total RE content is 0.001wt.%-2.0wt.%. With the invention, alloy has low cost, high mechanical strength, good corrosion resistance, and good electrochemical property, can find wide application in fields including metal electrodeposition, electroplating, wastewater treatment and organic electrosynthesis, and is suitable for industrial application.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of low silver content Pb-RE-Ag alloy electrode.
Background technology
The existing history that goes up a century of the use of the LY electrode utmost point.Have erosion resistance owing to it can form oxide film on the surface, be widely used in electrolytic deposition, electroplate wastewater treatment, fields such as organic electrosynthesis.
The LY electrode need have following performance, (1) good electrical conductivity; (2) erosion resistance is strong; (3) physical strength and good processability; (4) life-span is long; (5) the counter electrode reaction has good catalytic action.
Develop Pb-Ca, Pb-Sn, Pb-Sb, Pb-Ag, Pb-Ag-Co, Pb-Ca-Al-Sn, Pb-Ag-Ca-Sr, alloy electrodes such as Pb-Ag-Ca-Al-Sn-RE at present in succession.But there is following problem mostly in these electrodes: (1) poor mechanical property, and easy creep, deflection cause the moon, electrode short circuit, cause cathode efficiency to descend the electrode severe corrosion; (2) the electrode oxygen evolution potential is high, makes the electrolytic deposition process bath voltage high, and electric energy efficiency is low; (3) the electrode corrosion rate is big, and corrosion products is polluted the electrochemical process product.
In these electrodes, Pb-Ag alloy electrode over-all properties is best, yet the content of the precious metal silver in the plumbous silver electrode has generally reached 0.8～1.0wt.%, accounts for more than 80% of entire electrode raw materials cost, has increased investment in fixed assets.Polynary lead 2-base alloy electrodes such as serial ternary, quaternary even eight yuan have been invented in recent years in succession.These alloy electrodes are complicated component but also be compromise each other between mechanical property, corrosion resistance nature and chemical property mostly not only, and that over-all properties can't satisfy under industrial condition is long-time, the requirement of less energy-consumption military service.Therefore be badly in need of developing a kind of possess physical strength height, erosion resistance is strong, oxygen evolution potential is low and the electrode cost is low long lifetime Pb alloy electrode.
REE has the title of " industrial monosodium glutamate ", and a spot of adding can change the performance of alloy significantly.At present, there have been quilts such as following lead-rare earth metal alloy Pb-Al-Sn-RE, Pb-Sn-RE, Pb-Sn-Ce, Pb-Cd-Sb-Sn-RE, Pb-Ca-Al-Sn-Bi-RE, Pb-La-Ce-Sb-As-Sn-Se-S-Cu to apply for a patent and be used as the alloy grid of lead acid cell.Also have quilts such as Pb-Ag-Ca-RE, Pb-Ag-Ca-Al-Sn-RE, Pb-Ag-Ca-Sr-Ce, Pb-Sn-Co-RE to apply for a patent and be used as the non-ferrous metal galvanic deposit and use battery lead plate.Above-mentioned lead acid cell is used the Pb alloy grid; Owing to mainly play the effect of active ingredient carriers and collector, there were significant differences at Pb alloy electrode that aspect such as function, performance index, alloying constituent and ME and metal electrodeposition, wastewater treatment, plating, organic electrosynthesis are used.And above-mentioned galvanic deposit is with in the electrode; Used alloy all is to be the main body with the Pb-Ag alloy; In the basis of conventional P b-Ag alloy, add other alloying elements such as Ca, Al, Sn, Cr and Co; The performance or the part of attempting further to promote the Pb-Ag alloy electrode reduce Ag content, but have sacrificed other performances of Pb-Ag alloy when all existing partial properties to promote, and under low Ag content, are difficult to obtain the Pb alloy electrode that over-all properties meets the demands.As: though the adding of Ca has improved the intensity of alloy, in actual use, the anode sludge that electrode surface generates is prone to crust, causes problems such as anode potential rising regulating YIN and YANG utmost point short circuit.For this reason; Generally RE is added as a kind of assistant alloy element; Add caused problem or insoluble defective to solve other alloying element, the performance of alloy is promoted to some extent, because these alloying constituents are complicated though the result shows the interpolation of RE; Mutual restriction between the multiple alloying element, the RE of lower aq adds still can't solve the existing serial vice proper of these multicomponent alloys.Simultaneously, alloying constituent is many more, and the electroconductibility of alloy reduces, and alloy thing phase, structure are difficult to control, brings difficulty for the castingprocesses of alloy.In addition, the new thing of the formation that reacts to each other between the multicomponent alloy might reduce the improved performance ability of single-component mutually, finally causes the waste of RE.
Based on this, it is theoretical to need to use alloy designs, rationally adds alloying element according to actual needs, reaches and both reduces Ag content in the alloy, improves the purpose of the over-all properties of electrode again.This patent utilizes part RE element (La, Ce, Nd, Sm, Eu, Tb, Dy, Ho, Er, Dm, Yb, Lu and Y) that the mechanical property and the corrosion resistance nature of metal Pb are had significant improvement effect just as origin, the kind and the content of screening suitable R E element.Combine Ag can significantly improve the characteristics that the Pb alloy is analysed oxygen electro catalytic activity and conductivity on this basis; In the Pb-RE alloy, add a spot of Ag; Give full play to both synergies, develop a kind of Ag content lower and have concurrently excellent mechanical performances, good corrosion resistance can and the Pb-RE-Ag ternary alloy electrode of good electrochemical activity.This type alloy obtains than conventional P b-Ag alloy and the more excellent over-all properties of multicomponent alloy under the prerequisite of the content that reduces silver significantly (reducing the electrode cost).In addition, this patent according to the difference of applied environment, increases other alloying elements targetedly on the basis of preferred ternary Pb-RE-Ag alloy electrode, under the prerequisite that ensures basic over-all properties, further promotes some specified property.
Summary of the invention
The present invention is directed to the deficiency of existing LY electrode, proposed a kind of have high mechanical strength, highly corrosion resistant performance, good electrochemical, low silver content Pb-RE-Ag alloy electrode cheaply.
A kind of low silver content Pb-RE-Ag of the present invention alloy electrode comprises following compositions in weight percentage composition:
Rare earth 0.001～2.0, silver 0.001～0.6, surplus is plumbous;
Said rare earth is selected from La, Ce, Nd, Sm, Eu, Tb, Dy, Ho, Er, Dm, Yb, Lu, at least a among the Y.
In a kind of low silver content Pb-RE-Ag of the present invention alloy electrode, the content of said argent is 0.01～0.5wt.%.
In a kind of low silver content Pb-RE-Ag of the present invention alloy electrode, the content of said argent is 0.1～0.3wt.%.
In a kind of low silver content Pb-RE-Ag of the present invention alloy electrode, the content of said rare earth is 0.005～1.0wt.%.
In a kind of low silver content Pb-RE-Ag of the present invention alloy electrode, the content of said rare earth is 0.01～0.5wt.%.
In a kind of low silver content Pb-RE-Ag of the present invention alloy electrode, the component of said Pb-RE-Ag alloy electrode also comprises at least a among Pr, Gd, B, Ti, Co, Mn, Bi, Re, Se, the Mo, and its total content is less than 1.0wt.%.
In a kind of low silver content Pb-RE-Ag of the present invention alloy electrode, said rare earth is pure neodymium rare earth or contains the neodymium rare earth.
In a kind of low silver content Pb-RE-Ag of the present invention alloy electrode, the component of said Pb-RE-Ag alloy also comprises Ca, Al, and Sn, Sr, As, at least a among the Sb, its total content is less than 1.0wt.%.
In a kind of low silver content Pb-RE-Ag of the present invention alloy electrode, said low silver content Pb-RE-Ag alloy electrode is a kind of in plate, porous plate or the compound porous plate of cast sheet, calendering.
A kind of low silver content lead-rare earth-alloy silver electrode that the present invention proposes has following characteristics:
1, the adding of rare earth reduces content silver-colored in the alloy, when reducing the LY cost, can remedy the shortcoming that reduces the mis-behave that brings because of silver content.
2, REE and plumbous electronegativity differ greatly, and generate hard and crisp plumbous rare earth intermetallic compound in the tissue, can obtain the equally distributed plumbous sosoloid tissue of intermediate phase, thereby improve the mechanical property of lead electrode greatly.
3, rare earth can suppress the PbO generation of the low conductivity in the anodizing thing film, thereby reduces electropotential, and then reduces bath voltage, plays energy-saving and cost-reducing effect.Simultaneously, the low electrode current potential can reduce the corrosion at the bottom of the lead base.
4, owing under the electrochemical polarization condition, the REE generation oxidation in the alloy, the rare earth oxide of formation can promote oxygen to separate out, and reduces electropotential, reduces energy consumption, can reduce plumbous discharge corrosion simultaneously indirectly.
5, the calendering procedure of electrode can further be modified the crystal grain of alloy, thereby further improves the mechanical strength and the chemical property of electrode.
6, will be used for porous anode and compound porous anode than the Pb-RE-Ag alloy that conventional P b-Ag (0.8-1.0wt.%) anode has better mechanical property and a chemical property; Can further reduce the electrode cost, improve electrode performance, help the energy-saving and cost-reducing of actual application.
7, rare earth metal neodymium is a kind of oxygen-separating catalyst, can increase the oxygen activity of analysing of alloy electrode, simultaneously, but crystal grain thinning, the mechanical property and the corrosion resistance nature of raising alloy electrode.
In sum, a kind of low silver-colored Pb-RE-Ag alloy proposed by the invention, it is low to have a high mechanical strength, highly corrosion resistant performance, good electrochemical, cost; Be suitable for industrial applications.
Embodiment
Below in conjunction with embodiment content of the present invention is elaborated
Embodiment 1:
At first place the melting of vacuum electromagnetic induction melting furnace to prepare the plumbous rare earth intermediate alloy Pb-La (4wt.%) of high rare-earth content metallic lead and rare earth.Then Pb-La (4wt.%), Ag and Pb melt-casting are together become Pb-La (0.001wt.%)-Ag (0.6wt.%) alloy electrode; This alloy phase reduces 20mV for Pb-Ag (0.8wt.%) alloy electrode oxygen evolution potential in the zinc electrolytic deposition process; Erosion rate reduces by 18%, and tensile strength improves 30%.
Embodiment 2:
At first with metallic lead and corresponding rare earth place the vacuum electromagnetic induction melting furnace respectively melting prepare plumbous rare earth intermediate alloy Pb-Sm (2wt.%), Pb-Er (2wt.%) and Pb-Ce (2wt.%).With Pb-Sm (2wt.%), Pb-Er (2wt.%), Pb-Ce (2wt.%), Ag become Pb-Ce (0.9wt.%)-Er (0.5wt.%)-Sm (0.6wt.%)-Ag (0.001wt.%) to roll alloy electrode with pure Pb melt-casting together.This electrode is applied to handle and contains that the life-span can reach 3 years in the fragrant type organic matter waste water operation.
Embodiment 3:
At first metallic lead and corresponding rare earth are placed vacuum electromagnetic induction melting furnace melting preparation preparation Pb-Nd (1.0wt.%) and Pb-Gd (0.5wt.%) master alloy respectively.Above-mentioned alloy is become with Ag, Bi, Pb melt-casting together:
Pb-Nd (0.3wt.%)-Gd (0.05wt.%)-Bi (0.05wt.%)-Ag (0.4wt.%) alloy electrode.This closes and is applied to electro-galvanizing industry, reduces by 81% with respect to Pb-Ag (0.8wt.%) electrode corrosion rate, and anode potential reduces 60mV, and impurity content reduces by 51% in the plating piece coating.
Embodiment 4:
At first metallic lead and corresponding rare earth are placed vacuum electromagnetic induction melting furnace melting preparation preparation Pb-Nd (0.5wt.%) and Pb-Pr (2wt.%) master alloy respectively.Above-mentioned alloy and Ag, Pb are melted together, be cast as Pb-Nd (0.1wt.%)-Pr (0.9wt.%)-Ag (0.4wt.%) alloy electrode.This closes and is applied to electroplate Zn industry, reduces by 40% with respect to Pb-Ag (0.8wt.%) electrode corrosion rate, and anode potential reduces 80mV, and impurity content reduces by 18% in the plating piece coating.
Embodiment 5:
At first with metallic lead and corresponding rare earth place the vacuum electromagnetic induction melting furnace respectively melting prepare Pb-Nd (1.0wt.%), Pb-La (0.5wt.%) and Pb-Yb (0.5wt.%) master alloy.Then above-mentioned master alloy and Pb, Ag are melted together, process: Pb-Nd (0.3wt.%)-La (0.1wt.%)-Yb (0.2wt.%)-Ag (0.2wt.%) porous electrode plate.This alloy phase is for the tensile strength increase by 20% of zinc electrodeposition with Pb-Ag (1wt.%) alloy anode, and anode potential reduces 140mV, and corrosion rate reduces by 80%.
Embodiment 6:
At first place the melting of vacuum electromagnetic induction melting furnace to prepare Pb-nd-rich rare earths (1.0wt.%) master alloy metallic lead and nd-rich rare earths.Above-mentioned alloy and Pb, Ag melted together be prepared into Pb-nd-rich rare earths (0.003wt.%)-compound porous alloy electrode of Ag (0.25wt.%).This closes and is applied to electrodeposition Cu industry, reduces by 76% with respect to Pb-Ag (0.8wt.%) electrode corrosion rate, and impurity content reduces by 63% in the cathode copper, and anode potential reduces 124mV.
Embodiment 7:
At first place the melting of vacuum electromagnetic induction melting furnace to prepare Pb-nd-rich rare earths (1.0wt.%) and Pb-Ca (10wt.%) master alloy respectively metallic lead and nd-rich rare earths and metallic lead and calcium.Above-mentioned alloy, Pb, Ag are melted together, be cast as into Pb-nd-rich rare earths (2.0wt.%)-Ca (0.7wt.%)-Ag (0.15wt.%) alloy electrode plate.This closes and is applied to the relative Pb-Ag/RuO of Industrial Wastewater Treatment ton COD current consumption
2Composite anode reduces by 51%.
Embodiment 8:
After at first placing the melting of vacuum electromagnetic induction melting furnace to prepare Pb-Nd (1.0wt.%) master alloy metallic lead and rare earth, become with Pb, Sn, Ag, Co and Mo melt-casting: Pb-Nd (0.7wt.%)-Sn (0.7wt.%)-Co (0.01wt.%)-Mo (0.1wt.%)-Ag (0.55wt.%) alloy electrode plate.This alloy is applied to the electrolytic deposition of Cu, and prolong 67% than Pb-Ag (0.8wt.%)-Ca (0.3wt.%) anode work-ing life, and anode potential reduces 30mV, and tensile strength improves 45%.
Embodiment 9:
At first with metallic lead and rare earth and metallic lead and the silver-colored plumbous rare earth intermediate alloy Pb-Nd (1wt.%) that places the melting of vacuum electromagnetic induction melting furnace to prepare high rare-earth content respectively, plumbous silver-colored master alloy Pb-Ag (1.0wt.%).Then with Pb-Nd (1wt.%); Pb-Ag (1wt.%) becomes Pb-Nd (0.002wt.%)-Ag (0.6wt.%) alloy electrode with Pb melt-casting together; This alloy phase reduces 50mV for Pb-Ag (0.8wt.%) alloy electrode oxygen evolution potential, and erosion rate reduces by 30%, and tensile strength improves 50%.
Claims (9)
1. low silver content Pb-RE-Ag alloy electrode comprises that following compositions in weight percentage forms:
Rare earth 0.001～2.0, silver 0.001～0.6, surplus is plumbous;
Said rare earth is selected from La, Ce, Nd, Sm, Eu, Tb, Dy, Ho, Er, Dm, Yb, Lu, at least a among the Y.
2. a kind of low silver content Pb-RE-Ag alloy electrode according to claim 1, it is characterized in that: the weight percentage of said argent is 0.01～0.5wt.%.
3. a kind of low silver content Pb-RE-Ag alloy electrode according to claim 2, it is characterized in that: the weight percentage of said argent is 0.1～0.3wt.%.
4. a kind of low silver content Pb-RE-Ag alloy electrode according to claim 3 is characterized in that:
The weight percentage of said rare earth is 0.005～1.0wt.%.
5. a kind of low silver content Pb-RE-Ag alloy electrode according to claim 4, it is characterized in that: the weight percentage of said rare earth is 0.01～0.5wt.%.
6. a kind of low silver content Pb-RE-Ag alloy electrode according to claim 5; It is characterized in that: the component of said Pb-RE-Ag alloy electrode also comprises at least a among Pr, Gd, B, Ti, Co, Mn, Bi, Re, Se, the Mo, and its weight percent total content is less than 1.0wt.%.
7. a kind of low silver content Pb-RE-Ag electrode according to claim 1 is characterized in that: said rare earth is pure neodymium rare earth or contains the neodymium rare earth.
8. a kind of low silver content Pb-RE-Ag alloy electrode according to claim 7, it is characterized in that: the component of said Pb-RE-Ag alloy also comprises Ca, Al, Sn, Sr, As, at least a among the Sb, its total content is less than 1.0wt.%.
9. a kind of low silver content Pb-RE-Ag alloy electrode according to claim 1 is characterized in that: said low silver content Pb-RE-Ag alloy electrode is a kind of in plate, porous plate or the compound porous plate of cast sheet, calendering.
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Cited By (4)
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| CN104878409A (en) * | 2015-06-16 | 2015-09-02 | 中南大学 | Process of zinc electrodeposition by use of porous lead-based alloy anode |
| CN107732250A (en) * | 2017-08-30 | 2018-02-23 | 淄博火炬能源有限责任公司 | Charge type battery and preparation method thereof |
| CN108217850A (en) * | 2017-12-29 | 2018-06-29 | 苏州科技大学 | Er ions manganese oxide electro catalytic electrode, preparation method and the usage |
| CN110423917A (en) * | 2018-07-31 | 2019-11-08 | 荷贝克电池有限责任及两合公司 | Metal, electrode and battery |
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Application publication date: 20120620 |