CN101834295B - Method for preparing negative grid of lead storage battery - Google Patents
Method for preparing negative grid of lead storage battery Download PDFInfo
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- CN101834295B CN101834295B CN2010101837180A CN201010183718A CN101834295B CN 101834295 B CN101834295 B CN 101834295B CN 2010101837180 A CN2010101837180 A CN 2010101837180A CN 201010183718 A CN201010183718 A CN 201010183718A CN 101834295 B CN101834295 B CN 101834295B
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Abstract
The invention discloses a method for preparing a negative grid of a lead storage battery, which belongs to the technical field of electrode material preparation. In the method, a lead alloy is used as a raw material, a negative grid formed by pouring molten lead alloy serves as a cathode, a cathodic electrochemical reduction technology is used to perform surface modification in aqueous solution of a rare earth sulfate and sulfuric acid, rare earth is used to improve the performance of the surface of the lead alloy negative grid, and thus, the lead storage battery negative grid with a rare earth-modified lead alloy surface is formed. The method avoids the difficulty in the preparation of a rare earth-lead (Pb-Re) alloy, can dope some trace rare earth elements on the surface of an electrodeeasily, uniformly and quantitatively and realize the adjustment of the surface performance of the electrode. The preparation of a rare earth oxide by an electrochemical method has the advantages of ensuring the high purity of the prepared rare earth oxide, making the domain structure of the rare earth oxide adjustable, along with mild operation conditions, simple operation, low preparation cost and the like, and thus, conditions are provided for process industrialization. In the invention, the preparation method is simple, the preparation is convenient and the process is safe and reliable.
Description
Technical field
The present invention relates to the preparation method of the negative electrode grid of the preparing technical field of electrode material, particularly lead accumulator.
Background technology
The operation principle of lead accumulator is to utilize electrochemical principle to realize that matter and energy transforms, and electrode and electrolytical interfacial reaction characteristic are core and the essential places 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 key issues in the lead accumulator research and development.
The basic element of character and the material that constitute lead accumulator comprise: positive plate, negative plate, sulfuric acid solution (be electrolyte or be commonly called as electric liquid), dividing plate, cell jar (comprising fill cap).Positive and negative pole plate is welded into utmost point group respectively, comprises bus-bar and pole.Negative grid of lead storage battery is the important component of lead accumulator, the two aspect effects that mainly contain of negative electrode grid:
1, colleeting comb skeleton: negative electrode grid is the current collection skeleton of electrode, plays conduction, compiles electric current and make CURRENT DISTRIBUTION even, improves the utilance of negative electrode active material;
2, the prop carrier of negative electrode active material: negative electrode grid plays support by frame and rib anticathode active material.
Therefore, the needs that are suitable as the negative grid of lead storage battery material are considered with principal element:
1, high overpotential of hydrogen evolution: negative electrode grid has high overpotential of hydrogen 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 corrosion resistance: the corrosion resistance of negative electrode grid directly influences the life-span of lead accumulator, so negative electrode grid must have good corrosion resistance, can resist charge and discharge process and shelve during H in the electrolyte
2SO
4Corrosion;
3, high conductivity: negative electrode grid resistance is little, and the negative electrode grid of high conductivity can make electric current be easier to be distributed to negative electrode active material along negative electrode grid, thereby has reduced the internal resistance of battery;
4, it is strong to wrap up in attached power: negative plate grid alloy can firmly contact with negative electrode active material, and contact-making surface can have the good attached power of wrapping up in, and prevents coming off of negative electrode active material;
5, favorable mechanical performance: favorable mechanical performance and creep resistance are arranged, and negative electrode grid will have certain intensity, hardness, tensile strength, is convenient to the manufacturing and the transportation of battery;
But 6 casting characters and solderability: negative electrode 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 welded and installed and save production equipment, reduce production costs;
7, environment friendly: the material of negative electrode 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 negative electrode grid preparation process;
8, the source is wide, cost is low: the better economic characteristic is arranged, consider material cost, rare degree, cost performance height, reduce production costs.
The prior art of negative electrode grid mainly adopts lead-antimony (Pb-Sb), the lead-containing alloy material preparations such as (Pb-Ca) of lead-calcium, by in lead-antimony (Pb-Sb) and lead-calcium alloys such as (Pb-Ca), mixing the performance that metallic addition improves alloy, improve the corrosion resistance of negative electrode grid, improve the mechanical strength of negative electrode grid, improve the age-hardening rate of alloy, delay the expansion of negative electrode grid and coming off of negative electrode active material, prolong the life-span of storage battery.
Element cadmium can well be improved the performance of lead-antimony (Pb-Sb) alloy to a great extent, and the overpotential of hydrogen evolution height of cadmium can reduce the evolving hydrogen reaction of alloy, reduces gassing reaction and process dehydration.Cadmium also can be used as the nuclearing centre of low antimony alloy in addition, and 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 order to eliminate the problem that contains cadmium element in the existing alloy, reduce environmental pollution, remove the cadmium element in the alloy, and the approximate premature capacity loss phenomenon that cadmium alloy, the approximate no antimony effect that cadmium alloy is arranged, solve battery of deep discharge performance is arranged, solve lead-calcium (Pb-Ca) alloy of novel alloy heavy-current discharge performance, adding superior lead-calcium (Pb-Ca) alloy etc. of one or more metallic addition processabilities in lead-calcium (Pb-Ca) alloy is present research focus.
The performance that adopts rare earth material to improve negative electrode grid and negative electrode active material is present important R﹠D direction.Rare earth is called as new material " treasure-house ".Rare earth element is typical metallic element, the two-layer electron configuration of their outermosts is similar substantially, in chemical reaction, show typical metalline, easily lose three electronics, be positive trivalent, rare earth element is more active element, their metal activity is only second to alkali metal and alkali earth metal, and it is more active than other metal, proper amount of rare-earth can be improved the mechanical property and the conductivity of alloy, they can form chemically stable oxide, hydride, sulfide etc., also can and fluorine, hydrogen, phosphorus etc. react, and are soluble in hydrochloric acid, in sulfuric acid and the nitric acid.
Rare earth element is arranged in periodic table of elements IIIB family, comprises the lanthanide series of scandium (Sc), yttrium (Y) 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.
Meeting of lead-acid battery negative pole plate grid and sulfuric acid reaction, discharge forms hydrogen on negative pole, the liberation of hydrogen overpotential is directly measuring of electrochemistry liberation of hydrogen process, with respect to other metal, the liberation of hydrogen overpotential of rare earth is all than higher, after adding these metals, the overpotential of hydrogen evolution of lead electrode can improve, and reduces the separating out of hydrogen, dehydration.
Storage battery is when low-temperature high-current discharge, and the resistivity of pole plate increases with the speed of geometric progression, and at this moment, the resistivity size of grid is the important factor in order that can the decision electric energy make full use of.Studies show that some rare earth metal that mixes can reduce the resistance of alloy effectively, improves conductivity in alloy.
The negative grid of lead storage battery alloy all can generate negative electrode passivating film, particularly lead-calcium (Pb-Ca) alloy under the condition of filling deeply, putting deeply, lead-calcium (Pb-Ca) alloy anode grid calcium metal and sulphation in carrying out anodic solution, deposition process synthesize CaSO
4, it has PbSO
4The class quasi-lattice, served as PbSO
4Nucleus, make PbSO
4Generate equably with very fast speed, original like this lattice dimensions diminishes, and finally forms the fine and close passivating film of one deck poor permeability.That passivating film generates is PbSO
4And PbO, it is more much bigger than the volume of lead, and the variation of volume can cause the dilatancy of grid, causes that the generation loose and passivating film that comes off of active material causes the energy content of battery depleted phenomenon to occur, and this phenomenon is called the PCL phenomenon.The adding that studies show that rare earth can suppress the PbO growth in the negative electrode passivating film, and the PbO of generation also is easy to reduction, the PbSO of refinement simultaneously
4Crystal grain, the PbSO that forms when making discharge
4Crystallization is loose, and crystal grain is thick, helps the diffusion of the electrolysis concentrated sulfuric acid, has improved the deep-circulating performance of negative plate grid alloy, avoids the generation of PCL phenomenon.
Prior art mainly adopts the metal of rare earth element and lead or lead alloy to make rare earth lead (Pb-Re) alloy, uses as battery cathode grid or electrode material then.The subject matter that adopts this technology to exist has:
1, the difficulty of rare earth metal preparation: the preparation of rare earth metal is that employing rare earth reduzate or rare-earth salts are raw material, adopts the fusion electrolysis method to make, the specification requirement height of fusion electrolysis reduction preparation rare earth metal, the preparation cost height of rare earth metal;
2, the 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 technique, have that rare earth element is 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, the preparation of rare earth lead (Pb-Re) alloy, 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 negative electrode 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 a kind ofly conduct electricity very well, preparation method that long service life, lead accumulator rare earth that production cost is low are modified the lead alloy surface negative electrode grid.
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 negative electrode grid, be negative electrode with the lead alloy negative electrode grid again, with rare earth sulfate and aqueous sulfuric acid is electrolyte, adopt the electrochemical cathode method of reducing to carry out finishing, through washing, drying, make the negative grid of lead storage battery of modifying lead alloy surface.
Main technical principle of the present invention:
Analyze the operation principle of lead accumulator and can find that the response characteristic of electrode and electrolyte interface is the key problem that influences battery performance.Traditional research 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 different types of rare earth sulfate in electrolyte sulfuric acid solution, by changing concentration and electrode material preconditioning technique in different electrolytes of rare earth sulfate, the Applied Electrochemistry reduction technique, improve the performance on negative electrode grid surface, thereby obtain the novel and efficient negative grid of lead storage battery.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, adopt rare earth to improve the performance on lead alloy negative electrode grid surface, make the negative grid of lead storage battery that rare earth is modified lead alloy surface.
Prepare in the rare earth oxide process in the cathodic reduction method, hydrogen ion or water are in negative electrode generation reduction reaction, releasing hydrogen gas, separate near interface at electrode/electro simultaneously and generate one deck alkaline solution, rare earth ion generates rare-earth hydroxide or rare earth oxide under alkali condition, generate rare-earth hydroxide or rare-earth oxidation deposits yields precipitation, separate out and deposit to cathode electrode surface.
Major advantage of the present invention:
(1) fully use the characteristic of electrode surface in the negative electrode grid use: the response characteristic of electrode surface and electrolyte interface is the key problem that influences battery performance.Improve the performance on negative electrode grid surface by the negative electrode grid surface modification, thereby obtain the novel and efficient negative grid of lead storage battery;
(2) rare earth modified with electrochemical techniques at electrode surface; The present invention is by adding different types of rare earth sulfate in electrolyte sulfuric acid solution, by changing concentration and electrode material preconditioning technique in different electrolytes of rare earth sulfate, the Applied Electrochemistry reduction technique, improve the performance on negative electrode grid surface, thereby obtain the novel and efficient negative grid of lead storage battery;
(3) can use the electrochemical reduction technology, also can be constant potential operation, constant current operation or cyclic voltammetric operation;
(4) difficulty of having avoided rare earth lead (Pb-Re) alloy to prepare;
(5) reduced the consumption of rare earth and improved the utilance of rare earth significantly;
(6) method is simple, convenient operation and control: easily equal and quantitative mix some trace elements, realize the regulation and control of electrode performance;
(7) 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;
(8) convenient, flexible, can adapt to different electrodes (by changing electrolyte and operating condition); Adopt electrochemistry to help preparing difformity and electrodes sized material easily by process for modifying surface.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 process is safe and reliable.
The concentration of electrolyte middle rare earth sulfate of the present invention is 0.02mol/L～0.16mol/L, and the concentration of sulfuric acid is 0.6mol/L～6.0mol/L in the aqueous sulfuric acid, and the operating temperature in the electrochemical cathode method of reducing is 20 ℃～60 ℃.
Described electrochemical cathode method of reducing is potentiostatic method or galvanostatic method or cyclic voltammetry.
Described rare earth sulfate is the sulfate that any one element at least among europium Eu, samarium Sm, yttrium Y, neodymium Nd, the praseodymium Pr forms.
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.
As shown in Figure 1, production stage of the present invention:
1, lead alloy negative electrode grid preparation: with the lead alloy is raw material, adopts the fusion-cast technology to make the lead alloy negative electrode grid; Wherein, lead alloy is in negative any one of binary lead alloy, ternary lead alloy or the quaternary lead alloy of any one or two kinds in plumbous and antimony, calcium, tin or the aluminium or any three kinds of formation.
2, lead alloy negative electrode grid electrochemical surface is modified: the lead alloy negative electrode grid that obtains with previous step is a negative electrode, Applied Electrochemistry cathodic reduction technology is carried out finishing in rare earth sulfate and aqueous sulfuric acid, makes the negative electrode grid that rare earth is modified lead alloy surface; Wherein, rare earth sulfate is the sulfate that any or two kinds in europium (Eu), samarium (Sm), yttrium (Y), neodymium (Nd), the praseodymium (Pr) or any three kinds of rare earth elements form.The total mol concentration of 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 negative electrode grid electrochemical surface is modified is that operating temperature is 20 ℃～60 ℃, and can adopt is potentiostatic method operation, galvanostatic method operation or cyclic voltammetry operation.
3, rare earth is modified the reprocessing of lead alloy surface negative electrode grid: the rare earth that previous step obtains is modified the lead alloy surface negative electrode grid through washing, 90 ℃～140 ℃ dryings, obtain rare earth and modify the lead alloy surface negative electrode grid.
The present invention is further detailed explanation below in conjunction with accompanying drawing.
One, embodiment 1:
1, lead-antimony (Pb-Sb) alloy anode 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 ℃ of 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 (Pb-Sb) alloy that contains antimony 25%.Add a certain amount of high antimony slab lattice alloy fusion and be mixed with and stipulate that lead-antimony (Pb-Sb) alloy that contains the antimony amount makes lead-antimony (Pb-Sb) alloy anode grid with plumbous when being raw materials melt casting grid with lead-antimony (Pb-Sb) alloy;
2, lead alloy negative electrode grid electrochemical surface is modified: lead-antimony (Pb-Sb) alloy anode grid that obtains with previous step is a negative electrode, and lead-antimony (Pb-Sb) alloy is an anode, at 0.02mol/LEu
2(SO
4)
3With 6.0mol/L H
2SO
4In the aqueous solution, operating temperature is 20 ℃, at electrode potential be-1.2V vs SEC potentiostatic method operating condition under, adopt the cathodic reduction technology to carry out finishing, make the negative electrode grid that rare earth is modified lead alloy surface;
3, rare earth is modified the reprocessing of lead alloy surface negative electrode grid: the rare earth that previous step obtains is modified the lead alloy surface negative electrode grid through washing, 140 ℃ of dryings, obtain rare earth modified rare earth and modify the lead alloy surface negative electrode grid.
Two, embodiment 2:
1, lead-calcium (Pb-Ca) alloy anode 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 grid with lead-calcium (Pb-Ca) grid alloy;
2, lead alloy negative electrode grid electrochemical surface is modified: lead-calcium (Pb-Ca) alloy anode grid that obtains with previous step is a negative electrode, and lead-calcium (Pb-Ca) alloy is an anode, at 0.06mol/LSm
2(SO
4)
3With 4.0mol/L H
2SO
4In the aqueous solution, operating temperature is 40 ℃, is 10mA/cm in apparent operating current density
2Galvanostatic conditions under the cathodic reduction technology carry out finishing, make the negative electrode grid that rare earth is modified lead alloy surface;
3, rare earth is modified the reprocessing of lead alloy surface negative electrode grid: the rare earth that previous step obtains is modified the lead alloy surface negative electrode grid through washing, 120 ℃ of dryings, obtain rare earth modified rare earth and modify the lead alloy surface negative electrode grid.
Three, embodiment 3:
1, lead-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy anode grid preparation: earlier with lead heating and melting in market pot, temperature is no more than 550 ℃, adds tin (Sn) in regular turn and aluminium (Al) stirs evenly 550 ℃ of fusions; Calcium (Ca) 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 into lead-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy anode grid;
2, lead alloy negative electrode grid electrochemical surface is modified: lead-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy anode grid that obtains with previous step is a negative electrode, and lead-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy is an anode, at 0.10mol/L Y
2(SO
4)
3With 2.0mol/L H
2SO
4In the aqueous solution, operating temperature is 60 ℃, is 100mV/s in sweep speed, and scanning beginning current potential be-0.6V vs SEC, and scanning stops current potential and carries out the negative electrode grid that cyclic voltammetry operation cathodic reduction makes rare earth modification lead alloy surface for-1.6V vs SEC;
3, rare earth is modified the reprocessing of lead alloy surface negative electrode grid: the rare earth that previous step obtains is modified the lead alloy surface negative electrode grid through washing, 90 ℃ of dryings, obtain rare earth modified rare earth and modify the lead alloy surface negative electrode grid.
Four, embodiment 4:
1, lead-Xi (Pb-Sn) alloy anode 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 ℃ of 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-Xi (Pb-Sn) alloy that contains antimony 25%.Add a certain amount of high antimony slab lattice alloy fusion and be mixed with and stipulate that lead-Xi (Pb-Sn) alloy that contains the antimony amount makes lead-Xi (Pb-Sn) alloy anode grid with plumbous when being raw materials melt casting grid with lead-Xi (Pb-Sn) alloy;
2, lead alloy negative electrode grid electrochemical surface is modified: lead-Xi (Pb-Sn) alloy anode grid that obtains with previous step is a negative electrode, and lead-Xi (Pb-Sn) alloy is an anode, at 0.12mol/LPr
2(SO
4)
3With 1.0mol/L H
2SO
4In the aqueous solution, operating temperature is 20 ℃, at electrode potential be-1.2V vs SEC constant potential operating condition under, adopt the cathodic reduction technology to carry out finishing, make the negative electrode grid that rare earth is modified lead alloy surface;
3, rare earth is modified the reprocessing of lead alloy surface negative electrode grid: the rare earth that previous step obtains is modified the lead alloy surface negative electrode grid through washing, 140 ℃ of dryings, obtain rare earth modified rare earth and modify the lead alloy surface negative electrode grid.
Five, embodiment 5:
1, lead-calcium (Pb-Ca) alloy anode 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 grid with lead-calcium (Pb-Ca) grid alloy;
2, lead alloy negative electrode grid electrochemical surface is modified: lead-calcium (Pb-Ca) alloy anode grid that obtains with previous step is a negative electrode, and lead-calcium (Pb-Ca) alloy is an anode, at 0.16mol/LNd
2(SO
4)
3With 0.6mol/L H
2SO
4In the aqueous solution, operating temperature is 20 ℃, is 100mA/cm in apparent operating current density
2Galvanostatic conditions under the cathodic reduction technology carry out finishing, make the negative electrode grid that rare earth is modified lead alloy surface;
3, rare earth is modified the reprocessing of lead alloy surface negative electrode grid: the rare earth that previous step obtains is modified the lead alloy surface negative electrode grid through washing, 120 ℃ of dryings, obtain rare earth modified rare earth and modify the lead alloy surface negative electrode 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 (3)
1. the preparation method of a negative 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 negative electrode grid, be negative electrode with the lead alloy negative electrode grid again, adopt the electrochemical cathode method of reducing to carry out finishing, through washing, drying, making the negative 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 electrochemical cathode method of reducing carries out finishing; The concentration of described electrolyte middle rare earth sulfate is 0.02mol/L～0.16mol/L, and the concentration of sulfuric acid is 0.6mol/L～6.0mol/L in the aqueous sulfuric acid, and the operating temperature in the electrochemical cathode method of reducing is 20 ℃～60 ℃.
2. the preparation method of negative grid of lead storage battery according to claim 1 is characterized in that described electrochemical cathode method of reducing is potentiostatic method or galvanostatic method or cyclic voltammetry.
3. the preparation method of negative grid of lead storage battery according to claim 1 and 2 is characterized in that described rare earth sulfate is the sulfate that any one element at least among europium Eu, samarium Sm, yttrium Y, neodymium Nd, the praseodymium Pr forms.
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| CN102610829B (en) * | 2012-03-23 | 2015-01-21 | 江苏华富储能新技术股份有限公司 | Cadmium-free copper, aluminum and rare earth alloy grid of power type lead-acid battery and preparation method of cadmium-free copper, aluminum and rare earth alloy grid |
| CN102856533B (en) * | 2012-09-29 | 2015-03-04 | 浙江南都电源动力股份有限公司 | Negative plate of lead-carbon battery |
| CN104409783B (en) * | 2014-11-14 | 2016-06-29 | 江苏华富储能新技术股份有限公司 | A kind of rare earth modifies the method for lead-acid battery electrode plate |
| CN104409691B (en) * | 2014-11-14 | 2017-01-25 | 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 negative electrode plate |
| EP3598539A4 (en) * | 2017-12-11 | 2021-03-24 | Takasaki Denka Kougyousho Co., Ltd. | Lead storage battery electrode body and lead storage battery using same |
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| CN1426122A (en) * | 2002-12-16 | 2003-06-25 | 武汉大学 | Method for preparing lead-acid battery negative pole |
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| CN1426122A (en) * | 2002-12-16 | 2003-06-25 | 武汉大学 | Method for preparing lead-acid battery negative pole |
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