CN101841031A - Method for preparing positive electrode grid of lead storage battery - Google Patents
Method for preparing positive electrode grid of lead storage battery Download PDFInfo
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Abstract
The invention discloses a method for preparing a positive electrode grid of a lead storage battery, and belongs to the technical field of preparation of electrode materials. In the method, a lead alloy is used as a raw material, a lead-alloy positive electrode grid formed by fusion and casting is used as the positive electrode and is subjected to surface modification in rare earth sulfate and sulphuric acid solution by an anodic electrochemical oxidation process, and the surface performance of the lead-alloy positive electrode grid is improved by rare earth. The method avoids the difficulty in preparing the positive electrode grid from the lead-rare earth alloy, is easy to uniformly and quantitatively dope trace rare-earth elements on the surface of the lead-alloy positive electrode grid, and realizes the control of the surface performance of the electrode; and the electrochemical process for preparing rare earth oxides has the advantages of mild operating condition, simple operation, low preparation cost, high purity of prepared rare earth oxides, adjustable micro-area structure of the rare earth oxides, and the like. The method makes the lead-alloy positive electrode grid have the advantages of good electrochemical property and long service life, and is favorable for the production of low-cost lead-alloy positive electrode grids of the lead storage batteries.
Description
Technical field
The invention belongs to the preparing technical field of the anode plate grid of the preparing technical field of electrode material, particularly lead accumulator.
Background technology
Advantage such as that lead accumulator has is simple in structure, easy to use, dependable performance, price are lower, all departments are used widely in national economy, it is the product of big, the applied range of output in the chemical power source always, research and development and application along with new material and new technology, every performance of lead accumulator has had and has increased substantially, lead accumulator manifests more in the advantage of some special application fields, and as Moped Scooter, extraordinary electric motor car, new automobile power supply, the nearly stage is still the main flow power supply.But the characteristic of power-type lead accumulator heavy-current discharge under the characteristic, particularly low temperature of heavy-current discharge that existing market is used is far apart with alkaline battery.
The operation principle of lead accumulator is to utilize electrochemical principle to realize that matter and energy transforms, and the interfacial reaction characteristic between electrode and the electrolyte is core and the essential place that influences accumulator property.Therefore, for lead accumulator, the electrolytical use of the research and development of its functional electrode, function admirable and electrode and electrolytical matching optimization are extremely important technical problems in the lead accumulator research and development.
Positive electrode grid of lead storage battery is the important component of positive plate of lead storage battery, the two aspect effects that mainly contain of anode plate grid:
(1) colleeting comb skeleton: anode plate grid is anodal current collection skeleton, plays conduction, compiles electric current and make CURRENT DISTRIBUTION even, improves the utilance of positive active material;
(2) prop carrier of positive active material: anode plate grid plays support by frame and rib to positive active material.
Therefore, selecting for use of positive electrode grid of lead storage battery material needs to consider following principal element:
(1) high oxygen separated overpotential: the anode plate grid material should have high overpotential for oxygen evolution, can improve the charge-discharge performance and the efficient of battery, reduces the dehydration in the lead accumulator use simultaneously, makes battery have good maintenance-free performance;
(2) good anti-oxidant and corrosion resistance: anti-oxidant, the corrosion resistance of anode plate grid directly influences the life-span of lead accumulator, so anode plate grid must have good anti-oxidant and corrosion resistance, H in the electrolyte during can resisting charge and discharge process and shelving
2SO
4Corrosion;
(3) high conductivity: anode plate grid resistance is little, and the anode plate grid of high conductivity can make electric current be easier to be distributed to positive active material along anode plate grid, thereby has reduced the internal resistance of battery, plays afflux and electric action effectively;
(4) it is strong to wrap up in attached power: positive grid alloy can firmly contact with positive active material, and contact-making surface can have the good attached power of wrapping up in, and prevents coming off of positive active material;
(5) favorable mechanical performance: favorable mechanical performance and creep resistance are arranged, and anode plate grid will have certain intensity, hardness, tensile strength, is convenient to the manufacturing and the transportation of battery;
(6) but casting character and solderability: anode plate grid is generally made by fusion-cast, in the assembling process of battery, anodal group and negative pole group are welded respectively by positive plate and negative plate, so advantages of good casting and solderability, help casting processing and welding volt-ampere dress saving production equipment, reduce production costs;
(7) environment friendly: the material of anode plate grid itself has environment friendly, free from environmental pollution in production, use and removal process, not on the basis that human body is damaged, so should the least possible environmentally harmful element of introducing and impurity in the anode plate grid preparation process;
(8) source is wide, cost is low: the better economic characteristic is arranged, consider material cost, rare degree, cost performance height, reduce production costs.
Obviously, the material that can satisfy above condition is very difficult, and therefore, exploitation novel and efficient rare earth is modified the lead accumulator grid of lead alloy surface, improves performance of lead-acid battery and has very important application prospect.
Plante in 1859 has invented lead accumulator and has adopted two blocks of pure stereotypes as electrode, and pure stereotype both used as anode plate grid, also used as positive active material simultaneously.Because pure plumbous quality is soft, machinery and casting character are poor, are difficult to adapt to the every requirement in the lead accumulator use.
Sellon in 1881 adds metallic antimony and makes lead-antimony (Pb-Sb) alloy anode plate grid in the pure lead, the mechanical performance and the casting character of lead-antimony (Pb-Sb) alloy are superior, simultaneously positive active material there is good adhesive force power, the capacity and the life-span of storage battery have been improved, greatly improved the manufacturing process of lead accumulator, accepted extensively for The Storage Battery Industry in China always; Because antimony is a kind of low overpotential metal, meeting be dissolved from anode plate grid and be got off to move to the negative pole district, and deposits on the negative pole, thereby has reduced the overpotential of hydrogen evolution of negative pole, make storage battery increase the consumption of hydrogen amount of separating out and water in charging with when storing, destroyed the maintenance-free performance of storage battery.In addition, lead-antimony (Pb-Sb) alloy grid is bigger than pure stereotype gate resistance, easily crisp, and antimony also can be with SbH under the condition of overcharging
3Toxic gas separate out.In order further to improve the performance of lead-antimony (Pb-Sb) alloy, people have invented lead-antimony-arsenic (Pb-Sb-As) series alloy and low antimony alloy anode plate grid again, but no matter how low antimony content drop to, lead accumulator self-discharge phenomenon with lead-antimony (Pb-Sb) alloy anode plate grid is inevitable, so this type of storage battery will be accomplished non-maintaining comparatively difficulty.
Nineteen thirty-five, Haring and Thomas have invented lead-calcium (Pb-Ca) alloy anode plate grid, American Bell Incorporated at first formally used lead-calcium (Pb-Ca) alloy in the maintenance-free lead-acid battery in 1970, and plumbous calcium alloy begins to be used to non-maintaining series battery, was widely used and studied.Lead-calcium (Pb-Ca) alloy hydrogen separate out the overpotential height, hydrogen-separating quantity is few, damage by water consumption is few, has excellent maintenance-free performance, has been present maintenance-free lead-acid battery alloy commonly used.But during lead-calcium (Pb-Ca) alloy casting anode plate grid, pole plate charge and discharge cycles ability and retention of charge are all undesirable, charge acceptance neither be very strong, be easy to take place " early stage capacitance loss " phenomenon, moreover the binary lead calcium alloy is unsuitable for doing the anode plate grid material of dark circulation, because anodic solution when charging, the calcium on grid surface becomes CaSO
4, it is deposited in the micropore of corrosion product equably, is called PbSO
4The nucleus of crystallization causes and forms the fine and close PbSO that is difficult to permeate on the corrosive film
4Film, this film has increased impedance, makes to recharge ability to accept decline.
In order further to improve the performance of lead accumulator, element cadmium can well be improved the performance of lead-antimony (Pb-Sb) alloy to a great extent, and the hydrogen overpotential height of cadmium can reduce the evolving hydrogen reaction of alloy, reduces gassing reaction and process dehydration.Simultaneously, cadmium can improve PbSO between anode plate grid and the positive active material
4/ PbO
2Activity of conversion, improve the over-charging of battery, dark exoergic power and life-span, improve the corrosive nature of alloy, cadmium also can be used as the nuclearing centre of low antimony alloy in addition, crystallization is careful, owing to the superior performance of lead-antimony-cadmium (Pb-Sb-Cd) alloy, the good reputation of " ultra-calcium alloy " is arranged.But cadmium and compound thereof are a kind of extremely toxic substances, and environment is produced severe contamination, and this class battery is in the reclaiming process, and the part cadmium produces serious air pollution with toxic emission.
In addition, the anode plate grid that above-mentioned alloy is cast, in the charge and discharge process of lead acid accumulator, even in the process of shelving, can be oxidized to lead sulfate and brown lead oxide, finally cause its forfeiture to support the effect of active material and conduction, and make battery failure, perhaps, cause the large deformation of grid linear long because the formation of brown lead oxide corrosion layer makes alloy produce stress, will make the whole destruction of pole plate, cause active material and grid loose contact and come off,, finally make battery failure perhaps in the short circuit of bus-bar place.
In order to eliminate the problem that contains cadmium element in the existing alloy, reduce environmental pollution, remove the cadmium element in the alloy, solve the no antimony effect of battery, the premature capacity loss phenomenon of solution lead alloy.Therefore, the anode plate grid that processability is superior is a performance problem demanding prompt solution of further improving present lead accumulator.
The principle that adopts rare earth to improve anode plate grid is based on the method that the distinctive physics of rare earth, chemical property improve the anode plate grid performance of present lead accumulator.Rare earth element is arranged in periodic table of elements IIIB family, comprises the lanthanide series of scandium, yttrium and atomic number from 57 to 71, totally 17 metallic elements.The electron structure of rare earth element atom is (Xe) 4f
0-145d
0-16s
2, after losing two 6s and 5d or 4f electronics, formed modal Ln
3+, La wherein
3+, Gd
3+And Lu
3+The 4f subgrade be respectively full sky, half-full or full up state.According to Hund, these states all are the most stable, so these three elements+3 valencys are the most stable.Be positioned at the Ln of their both sides
3+All have and obtain or lose electronics to reach or near the trend of aforementioned stable state.This appraises at the current rate with regard to the lanthanide series that is positioned at La, Gd and Lu next door has been produced.As Ce
3+, Pr
3+, Tb
3+And Dy
3+Form tetravalence, and Sm
3+, Eu
3+, Tm
3+, Yb
3+Then formed divalence.
At present, the positive electrode grid of lead storage battery material adopts the method for formation lead-rare earth (Pb-RE) alloy more.Rare earth element and the plumbous Pb that generates
3RE, PbRE and Pb
3RE
2The type high melting compound is torn phenomenon with the lead alloy intergranular in the interpolation energy of rare earth, and can be improved the hot-workability of alloy, increases the toughness and the creep resistance of alloy, crystal grain thinning.Lanthanum La, cerium Ce, praseodymium Pr and neodymium Nd can both form good solid solution with Pb, and its alloy has very high hardness and good mechanical performance.Cerium-rich rare earth energy refinement lead-antimony alloy crystal grain, the thinning crystal boundary reduces the big crystal slight crack of harmfulness, reduces the harmfulness of general corrosion speed and corrosion; The adding of rare earth can suppress the PbO growth in the anode film, and the PbO of generation also is easy to reduction, has reduced the impedance of anode film, has improved the deep-circulating performance of positive grid alloy.
Prior art mainly adopts rare earth metal and lead or lead alloy to make rare-earth-lead alloy, uses as the anode grid then, and the subject matter that adopts this technology to exist has:
(1) difficulty of rare earth metal preparation: the preparation of rare earth metal is that employing rare earth oxide or rare-earth salts are raw material, adopt the fusion electrolysis method to make, specification requirement height, the preparation difficulty of rare earth metal, the preparation cost of fusion electrolysis reduction preparation rare earth metal are high;
(2) difficulty of rare-earth-lead alloy preparation: because rare earth elemental metals is big with the difference of the rerum natura (particularly fusing point and density) of lead, adopt traditional alloy molten casting forming technology, exist rare earth element to be difficult to add and add the uneven difficult problem of back rare-earth-lead alloy composition, must research and development solution treatment new technology rare earth element is difficult to add and adds difficult problems such as the back alloy composition is inhomogeneous to solve;
(3) be difficult to extensive use: because the preparation cost height of rare earth metal, rare-earth-lead alloy preparation, by in lead alloy, adding rare earth element, improved the method for the combination property of lead battery metal, cause rare earth high, be difficult to heavy industrialization and use at the production cost of modification lead or lead alloy.
The preparation method of the rare earth modified anode plate grid that therefore, research and development rare earth consumption is few, preparation technology is simple, production cost is low seems very important.
Summary of the invention
The purpose of this invention is to provide that a kind of performance is good, the preparation method of long service life, positive electrode grid of lead storage battery that production cost is low.
The present invention is a raw material with any one and lead at least in antimony, calcium, tin or the aluminium earlier, adopt the fusion-cast manufacturing process to make the lead alloy anode plate grid, be anode with the lead alloy anode plate grid again, with rare earth sulfate and aqueous sulfuric acid is electrolyte, adopt the anode electrochemical method for oxidation to carry out finishing, through washing, drying, make the positive electrode grid of lead storage battery of modifying lead alloy surface.
Know-why of the present invention: the operation principle of analyzing lead accumulator can find that the response characteristic of electrode and electrolyte interface is the key problem that influences battery performance.Traditional research and development thinking is to be H at electrolyte
2SO
4Prerequisite under, change the composition and the performance of electrode material.The present invention is by adding rare earth sulfate in electrolyte sulfuric acid solution, the Applied Electrochemistry oxidation technology, adopt rare earth to improve the performance on lead alloy anode plate grid surface, make the positive electrode grid of lead storage battery that rare earth is modified lead alloy surface, thereby obtain the novel and efficient positive electrode grid of lead storage battery.
Prepare in the rare earth oxide process in anodic oxidation, electrolyte middle rare earth metal ion reacts, and the rare earth oxide of generation is separated out and deposited to lead alloy anode plate grid electrode surface.
The present invention has following major advantage:
(1) fully use the characteristic of electrode surface in the anode plate grid use: the response characteristic of electrode surface and electrolyte interface is the key problem that influences battery performance.Improve the performance on anode plate grid surface by the anode plate grid surface modification, thereby obtain the novel and efficient positive electrode grid of lead storage battery;
(2) rare earth modified with electrochemical techniques: by in electrolyte sulfuric acid solution, adding different types of rare earth sulfate at electrode surface, by changing concentration and electrode material preconditioning technique in different electrolytes of rare earth sulfate, the Applied Electrochemistry oxidation technology improves the performance on anode plate grid surface;
(3) adopt electrochemical oxidation technology, utilize rare earth sulfate soluble in water, precipitation reaction takes place and generates rare-earth hydroxide or rare earth oxide in rare-earth salts under alkali condition, and rare-earth hydroxide or rare earth oxide are insoluble in the water characteristics.In the sulfuric acid character aqueous solution, prepare in the rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide that produces through peroxidating is separated out and is deposited to electrode surface;
(4) adopting electrochemical techniques at the electrode surface rare-earth modification technology, can be constant potential operation, constant current operation or cyclic voltammetric operation;
(5) method is simple, convenient operation and control: the difficulty of having avoided the preparation of lead-rare earth (Pb-RE) alloy; At some trace rare-earth elements that mix of electrode surface equal and quantitative, realize the regulation and control of electrode surface performance easily;
(6) equipment investment is low, and process modification is big: do not need complicated reaction reagent and special reaction condition, cost is low, and equipment is simple;
(7) convenient, flexible, can adapt to different electrodes (by changing electrolyte and operating condition); The consumption and the utilance that has improved rare earth of rare earth have been reduced significantly;
(8) electrochemical process prepares rare earth oxide and has operating condition gentleness, simple, advantage such as preparation cost is low and the domain structure of the rare earth oxide purity height that makes, rare earth oxide is adjustable;
(9) help heavy industrialization: preparation method of the present invention is simple, and is easy to prepare, and the process volt-ampere is reliable entirely.
The total mol concentration of electrolyte middle rare earth sulfate of the present invention is 0.02～0.16mol/L, and the molar concentration of sulfuric acid is 0.6～6.0mol/L in the aqueous sulfuric acid, and the temperature of electrolyte is 20～60 ℃.
Described anode electrochemical method for oxidation is a potentiostatic method, or galvanostatic method, perhaps cyclic voltammetry.
Described rare earth sulfate is the sulfate that any one rare earth element at least in cerium, lanthanum, praseodymium or the neodymium forms.
The ambient temperature of described drying is 90～140 ℃.
Description of drawings
Fig. 1 is a process chart of the present invention.
Embodiment
Main technique equipment: electrochemical reactor and lead alloy fusion, lead alloy grid former etc.
The operating procedure principle:
1, lead alloy anode plate grid preparation: with the lead alloy is raw material, adopts the fusion-cast forming technique to make the lead alloy anode plate grid;
2, lead alloy anode plate grid electrochemical surface is modified: with the lead alloy anode plate grid is anode, and the Applied Electrochemistry anodizing technology carries out finishing in rare earth sulfate and aqueous sulfuric acid, makes the anode plate grid that rare earth is modified lead alloy surface;
3, rare earth is modified the reprocessing of lead alloy surface anode plate grid: the rare earth that previous step obtains is modified the lead alloy surface anode plate grid through washing, drying, obtain rare earth modified rare earth and modify the lead alloy surface anode plate grid.
Wherein, lead alloy is any one in binary lead alloy, ternary lead alloy or the quaternary lead alloy of any one or any two kinds or any three kinds of formation in plumbous and antimony, calcium, tin or the aluminium.
Rare earth sulfate is the sulfate that any or two kinds in lanthanum, cerium, praseodymium or the neodymium or any three kinds of rare earth elements form.
The total mol concentration of lead alloy anode plate grid electrochemical surface modification middle rare earth sulfate is 0.02mol/L-0.16mol/L, the molar concentration concentration of sulfuric acid is 0.6mol/L-6.0mol/L in the aqueous sulfuric acid, the operating condition that lead alloy anode plate grid electrochemical surface is modified is that operating temperature is 20 ℃-60 ℃, can adopt potentiostatic method operation, galvanostatic method operation or cyclic voltammetry operation.
Modifying the anode plate grid reprocessing is 90 ℃-140 ℃ for the drying process temperature.
Operating procedure in the preparation of lead alloy anode plate grid is that lead alloy fusion, lead alloy grid are shaped, the operation of lead alloy grid cooling unit is formed.
The present invention is further detailed explanation below in conjunction with Fig. 1.
One, embodiment 1:
1, lead-antimony (Pb-Sb) alloy anode plate grid preparation: the antimony (pounding into fragment in advance) that in market pot, adds a certain amount of lead and 1/3rd quality earlier, 330 ℃～400 ℃ fusions, be warming up to 500 ℃～550 ℃ again, treat the whole fusions of solid phase, stir, pull scum silica frost out, take the dish out of the pot and cast lead-antimony (the being high antimony) alloy that contains antimony 25%.Add a certain amount of high antimony slab lattice alloy fusion and be mixed with and stipulate that plumbous antimony (Pb-Sb) alloy that contains the antimony amount makes the lead-antimony alloy anode plate grid with plumbous when being raw materials melt casting grid with lead-antimony (Pb-Sb) alloy;
2, lead alloy anode plate grid electrochemical surface is modified: lead-antimony (Pb-Sb) alloy anode plate grid that obtains with previous step is an anode, and lead-antimony (Pb-Sb) alloy is a negative electrode, at 0.02mol/L La
2(SO
4)
3With 6.0mol/L H
2SO
4In the aqueous solution, operating temperature is 60 ℃, is under the 2.0V vsSEC constant potential operating condition at electrode potential, carries out anodizing technology and carries out finishing, makes the anode plate grid that rare earth is modified lead alloy surface;
3, rare earth is modified the reprocessing of lead alloy surface anode plate grid: the rare earth that previous step obtains is modified the lead alloy surface anode plate grid through washing, 140 ℃ of dryings, obtain rare earth modified rare earth and modify the lead alloy surface anode plate grid.
Two, embodiment 2:
1, lead-calcium (Pb-Ca) alloy anode plate grid preparation: good with paper bag the calcium break into portions, gradation is incorporated with in the stainless steel corbeil of long handle, reaches the lead pan bottom and is stirred to the calcium fusion.Calcium and the plumbous reaction that generates grid alloy promptly obtain the high lead-calcium of calcium content (Pb-Ca) grid alloy with significantly sound and light, are that raw materials melt is cast into and makes lead-calcium (Pb-Ca) alloy anode plate grid with lead-calcium (Pb-Ca) grid alloy;
2, lead alloy anode plate grid electrochemical surface is modified: lead-calcium (Pb-Ca) alloy anode plate grid that obtains with previous step is an anode, and lead-calcium (Pb-Ca) alloy is a negative electrode, at 0.06mol/L Nd
2(SO
4)
3With 4.0mol/L H
2SO
4In the aqueous solution, operating temperature is 40 ℃, is 100mA/cm in apparent operating current density
2Galvanostatic conditions under carry out anodizing technology and carry out finishing, make the anode plate grid that rare earth is modified lead alloy surface;
3, rare earth is modified the reprocessing of lead alloy surface anode plate grid: the rare earth that previous step obtains is modified the lead alloy surface anode plate grid through washing, 120 ℃ of dryings, obtain rare earth modified rare earth and modify the lead alloy surface anode plate grid.
Three, embodiment 3:
1, lead-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy anode plate grid preparation: earlier with lead heating and melting in market pot, temperature is no more than 550 ℃, adds tin Sn and aluminium Al in regular turn and stirs evenly 550 ℃ of fusions; The calcium break into portions, good with paper bag, gradation is incorporated with in the stainless steel corbeil of long handle, reaches the lead pan bottom and is stirred to the calcium fusion.The reaction of calcium and plumbous generation grid alloy is with tangible sound and light.With lead-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy is that raw materials melt is cast plumbously-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy anode plate grid;
2, lead alloy anode plate grid electrochemical surface is modified: lead-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy anode plate grid that obtains with previous step is an anode, and lead-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy is a negative electrode, at 0.10mol/L Pr
2(SO
4)
3With 2.0mol/L H
2SO
4In the aqueous solution, operating temperature is 40 ℃, is 100mV/s in sweep speed, and scanning beginning current potential is 1.0V vs SEC, scanning stops current potential and carries out finishing for 2.0Vvs SEC carries out cycle potentials operation anodizing technology, makes the anode plate grid that rare earth is modified lead alloy surface;
3, rare earth is modified the reprocessing of lead alloy surface anode plate grid: the rare earth that previous step obtains is modified the lead alloy surface anode plate grid through washing, 100 ℃ of dryings, obtain rare earth modified lead alloy surface anode plate grid.
The invention is not restricted to the foregoing description, the technical scheme that all employings are equal to replacement or equivalence replacement formation all belongs to the scope of protection of present invention.Remove the various embodiments described above, embodiment of the present invention also have a lot, and the technical scheme that all employings are equal to or equivalence is replaced is all within protection scope of the present invention.
Four, embodiment 4:
1, lead-antimony (Pb-Sb) alloy anode plate grid preparation: earlier with lead heating and melting in market pot, temperature is no more than 550 ℃, adds tin Sn and aluminium Al in regular turn and stirs evenly 550 ℃ of fusions; The calcium break into portions, good with paper bag, gradation is incorporated with in the stainless steel corbeil of long handle, reaches the lead pan bottom and is stirred to the calcium fusion.The reaction of calcium and plumbous generation grid alloy is with tangible sound and light.Lead-antimony (Pb-Sb) alloy adds a certain amount of high antimony slab lattice alloy fusion and is mixed with lead-antimony (Pb-Sb) alloy that regulation contains the antimony amount and makes lead-antimony (Pb-Sb) alloy anode plate grid when being raw materials melt casting grid;
2, lead alloy anode plate grid electrochemical surface is modified: lead-antimony (Pb-Sb) alloy anode plate grid that obtains with previous step is an anode, and lead-antimony (Pb-Sb) alloy is a negative electrode, at 0.16mol/L Ce
2(SO
4)
3With 0.6mol/L H
2SO
4In the aqueous solution, operating temperature is 20 ℃, is 100mV/s in sweep speed, and scanning beginning current potential is 1.6V vs SEC, scanning stops current potential and carries out finishing for 2.2V vsSEC carries out cycle potentials operation anodizing technology, makes the anode plate grid that rare earth is modified lead alloy surface;
3, rare earth is modified the reprocessing of lead alloy surface anode plate grid: the rare earth that previous step obtains is modified the lead alloy surface anode plate grid through washing, 90 ℃ of dryings, obtain rare earth modified lead alloy surface anode plate grid.
The invention is not restricted to the foregoing description, the technical scheme that all employings are equal to replacement or equivalence replacement formation all belongs to the scope of protection of present invention.Remove the various embodiments described above, embodiment of the present invention also have a lot, and the technical scheme that all employings are equal to or equivalence is replaced is all within protection scope of the present invention.
Claims (5)
1. the preparation method of a positive electrode grid of lead storage battery, be raw material earlier with any one and lead at least in antimony, calcium, tin or the aluminium, adopt the fusion-cast manufacturing process to make the lead alloy anode plate grid, be anode with the lead alloy anode plate grid again, adopt the anode electrochemical method for oxidation to carry out finishing, through washing, drying, making the positive electrode grid of lead storage battery of modifying lead alloy surface, is electrolyte with rare earth sulfate and aqueous sulfuric acid when it is characterized in that described anode electrochemical method for oxidation carries out finishing.
2. the preparation method of positive electrode grid of lead storage battery according to claim 1, the total mol concentration that it is characterized in that described electrolyte middle rare earth sulfate is 0.02～0.16mol/L, the molar concentration of sulfuric acid is 0.6～6.0mol/L in the aqueous sulfuric acid, and the temperature of electrolyte is 20～60 ℃.
3. the preparation method of positive electrode grid of lead storage battery according to claim 1 is characterized in that described anode electrochemical method for oxidation is a potentiostatic method, or galvanostatic method, perhaps cyclic voltammetry.
4. according to the preparation method of claim 1 or 2 or 3 described positive electrode grid of lead storage battery, it is characterized in that described rare earth sulfate is the sulfate that any one rare earth element at least in cerium, lanthanum, praseodymium or the neodymium forms.
5. the preparation method of positive electrode grid of lead storage battery according to claim 1, the ambient temperature that it is characterized in that described drying is 90～140 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219522A (en) * | 2013-04-03 | 2013-07-24 | 江苏海德森能源有限公司 | Lead-acid battery grid doped with rare earth elements on surface layer and preparation method thereof |
| CN103219523A (en) * | 2013-04-03 | 2013-07-24 | 江苏海德森能源有限公司 | Negative plate of lead-acid storage battery and preparation method of negative plate |
| CN103227316A (en) * | 2013-04-03 | 2013-07-31 | 江苏海德森能源有限公司 | Positive electrode plate of lead-acid battery and preparation method thereof |
| CN104409783A (en) * | 2014-11-14 | 2015-03-11 | 江苏华富储能新技术股份有限公司 | Method using rare earth for modification of lead storage battery electrode plates |
| CN112086646A (en) * | 2020-10-12 | 2020-12-15 | 天能集团（河南）能源科技有限公司 | High-temperature-resistant lead-acid storage battery and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426122A (en) * | 2002-12-16 | 2003-06-25 | 武汉大学 | Method for preparing lead-acid battery negative pole |
-
2010
- 2010-05-27 CN CN2010101837034A patent/CN101841031B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426122A (en) * | 2002-12-16 | 2003-06-25 | 武汉大学 | Method for preparing lead-acid battery negative pole |
Non-Patent Citations (1)
| Title |
|---|
| 《电池工业》 20010831 朱松然 一种抑制正极活性物质软化的稀土化合物 171-173 1-5 第6卷, 第4期 2 * |
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| CN103219523A (en) * | 2013-04-03 | 2013-07-24 | 江苏海德森能源有限公司 | Negative plate of lead-acid storage battery and preparation method of negative plate |
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| CN103219523B (en) * | 2013-04-03 | 2015-07-01 | 江苏海德森能源有限公司 | Negative plate of lead-acid storage battery and preparation method of negative plate |
| CN103219522B (en) * | 2013-04-03 | 2015-08-05 | 江苏海德森能源有限公司 | Lead acid accumulator plate grid of a kind of top layer doped with rare-earth elements and preparation method thereof |
| CN104409783A (en) * | 2014-11-14 | 2015-03-11 | 江苏华富储能新技术股份有限公司 | Method using rare earth for modification of lead storage battery electrode plates |
| CN112086646A (en) * | 2020-10-12 | 2020-12-15 | 天能集团（河南）能源科技有限公司 | High-temperature-resistant lead-acid storage battery and preparation method thereof |
| CN112086646B (en) * | 2020-10-12 | 2022-01-07 | 天能集团（河南）能源科技有限公司 | High-temperature-resistant lead-acid storage battery and preparation method thereof |
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| CN101841031B (en) | 2012-07-11 |
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