CN101841030A - Method for preparing positive plate of lead storage battery - Google Patents
Method for preparing positive plate of lead storage battery Download PDFInfo
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- CN101841030A CN101841030A CN201010183692A CN201010183692A CN101841030A CN 101841030 A CN101841030 A CN 101841030A CN 201010183692 A CN201010183692 A CN 201010183692A CN 201010183692 A CN201010183692 A CN 201010183692A CN 101841030 A CN101841030 A CN 101841030A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing a positive plate of a lead storage battery, and belongs to the technical field of preparation of electrode materials, in particular to a process for a preparation method for the lead storage battery. 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 to prepare a positive plate of the lead storage battery that the surface of the lead alloy is modified by the rare earth; and lead powder, water, sulfuric acid and rare earth oxides or rare earth sulfate and additives are mixed into a lead plaster, and the lead plaster is subjected to plate coating, solidification, drying and formation to prepare the rear-earth modified positive electrode grid of the lead storage battery. The method is simple, reduces the using amount of the rear earth and improves the utilization ratio of the rear earth, 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 electrode, and realizes the control of the surface performance of the electrode.
Description
Technical field
The invention belongs to the preparing technical field of electrode material, particularly a kind of preparation method's of positive plate of lead storage battery technology.
Background technology
Advantage such as that lead accumulator has is simple in structure, easy to use, dependable performance, price are lower, therefore be used widely in national economy all departments, 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, 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 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 plate is the vitals that constitutes lead accumulator.Positive plate of lead storage battery is made up of anode plate grid and positive active material.
Positive electrode grid of lead storage battery mainly contains two aspect effects:
1, colleeting comb skeleton: anode plate grid is the current collection skeleton of electrode, plays conduction, compiles electric current and make CURRENT DISTRIBUTION even, improves the utilance of positive active material;
2, the prop carrier of positive active material: anode plate grid plays support by frame and rib to positive active material.
Therefore, the positive electrode grid of lead storage battery material require is considered 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;
But 6 casting characters 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 welded and installed and save 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, the source is wide, cost is low: the better economic characteristic is arranged, consider material cost, rare degree, cost performance height, reduce production costs.
Positive active material mainly contains two kinds of functions:
(1) participates in electrochemical reaction, interdischarge interval conductivity PbO
2Be converted into non-conductive PbSO
4
(2) provide conductive path for reflecting point in the porous active material to grid.The PbO of back one some conductivity of functional requirement
2Active material is not participated in electrochemical reaction, and only is used for keeping structural integrity and electric conductivity is good.
Therefore, the active material of positive plate of lead storage battery has following requirement: the oxygen evolution potential height, and corrosion resistance is good, and good conductivity can be passed through big electric current.The lead accumulator positive active material is PbO at present
2
The positive plate of lead storage battery of prior art exists subject matter to have:
1, anode plate grid in use exists corrosion and electricity to lead ability reduction problem: in the anode plate grid use, particularly under the operating condition of overcharging, oxidation reaction easily takes place in grid, corrosion and electricity takes place lead ability reduction property;
2, positive active material mis-behave problem: along with the increase of charge and discharge cycles number of times, discharge capacity reduces gradually.Subject matter is that the particle adhesion reduces, and electrically contacts destroyedly, and resistance increases thereupon.In addition, in the later stage of each charging, aerobic is separated out on positive pole, under the impact of analysing oxygen, has more promoted weakening of active material adhesion, and it is bad to cause the grid that comes off of active material to combine with active material, the easy softening and shedding of positive active material; Electrode reaction is preferentially carried out at electrode surface, product PbSO
4Be non-conductor, the internal resistance of battery is increased with discharge, simultaneously PbSO
4With PbO
2Encase, molal volume is greater than PbO
2PbSO
4Stopped up the aperture of porous electrode, made reactant H
2SO
4Can not be diffused into the electrode depths smoothly, cause residual more unreacting substance, cause positive electrode active material utilization to reduce.
3, the matching problem of the active material of positive plate of lead storage battery and anode plate grid: it is attached that prior art exists anode plate grid and positive active material to be that machinery is wrapped up in substantially, exists contact to wrap up in the problem that comes off that attached power is not enough, have positive active material in the lead accumulator use.
Therefore, research and develop novel anode grid and positive active material and improve anode plate grid and the technology of positive active material coupling, the positive plate that processability is superior is a performance of further improving present lead accumulator, and the lead accumulator that needs to be resolved hurrily is the problem of existence at present.
Summary of the invention
The purpose of this invention is to provide a kind ofly conduct electricity very well, the preparation method of long service life, positive plate 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; Be coated with the mixing lead plaster in the positive electrode grid of lead storage battery surface of modifying lead alloy surface again, mix lead plaster and comprise lead powder, water, sulfuric acid and rare earth oxide or rare earth sulfate, the addition of rare earth oxide or rare earth sulfate is 1%～5% of a lead powder quality, again through solidify and dry, change into and obtain rare earth modified positive plate of lead storage battery.
The technology of the present invention principle is:
1, makes full use of the characteristic of rare earth element: adopt rare earth material to improve anode plate grid and rare-earth oxide modified positive plate active material, improve performance of lead-acid battery, it is low to solve traditional lead accumulator specific energy, significantly improves problems such as power characteristic, consistency and the cryogenic property of lead accumulator be relatively poor.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 a kind of additive of monosodium glutamate formula, because the special 4f electron structure of lanthanide series, determine it that performance and many-sided specific performances such as special light, electricity, magnetic are arranged, be widely used in field of new such as magnetic, electricity, luminous, metallurgical, catalysis, nuclear energy, metal material.
2, make full use of the response characteristic of electrode and electrolyte interface: 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 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, Applied Electrochemistry OR technology, improve the performance on anode plate grid surface, thereby obtain the novel and efficient positive electrode grid of lead storage battery.With the lead alloy is raw material, the lead alloy anode plate grid that is shaped through fusion-cast is an anode, in rare earth sulfate and aqueous sulfuric acid, use the anode electrochemical oxidation technology and carry out finishing, 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.
3, the rare-earth oxide modified of lead accumulator positive active material: by in positive active material, adding rare earth oxide or rare earth sulfuric acid salt additives, particularly at PbO
2The rare earth oxide material that positive electrode active materials adds has significantly improved PbO
2The performance of positive electrode active materials.As La
2O
3, Ce
2O
3, Pr
2O
3, Nd
2O
3Deng, improved anodal conductive capability, active material utilization and charge-discharge performance, reduced circulate the deeply deterioration of being connected of anode plate grid and positive active material in the discharge process of battery.
Advantage of the present invention:
(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 at electrode surface with electrochemical techniques: 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 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, reduced the consumption and the utilance that has improved rare earth of rare earth significantly, can be that constant potential operation, constant current operation or circulation peace are operated;
(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 process is safe and reliable.
In addition, described rare earth oxide or rare earth sulfate middle rare earth be in cerium, lanthanum, praseodymium or the neodymium at least any one.
The total mol concentration of described electrolyte middle rare earth sulfate 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 can be potentiostatic method, or galvanostatic method, perhaps cyclic voltammetry.
The ambient temperature of described drying is 90～140 ℃.
The operating temperature that changes into of the present invention is 25～45 ℃, electrolyte sulfuric acid density 1.050～1.150g/cm
3, as operating current density 5～20mA/cm
2, when electrolytic bath voltage is stabilized in 2.6～2.8V, changes into and finish.
Description of drawings
Fig. 1 is a process chart of the present invention.
Embodiment
Main technique equipment is: electrochemical reactor and lead alloy fusion, lead alloy grid former and and cream equipment etc.
As shown in Figure 1, production stage principle of the present invention:
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.
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.
2, lead alloy anode plate grid electrochemical surface is modified: the lead alloy anode plate grid that obtains with previous step is an anode, 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.
Wherein, 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 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 ℃, and can adopt is constant potential operation, constant current operation or the operation of circulation peace.
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.
4, positive electrode active materials and cream: lead powder, water, sulfuric acid and rare earth oxide or rare earth sulfate be added to mix in the container be mixed into compliant lead plaster.
Wherein, rare earth oxide or rare earth sulfate are rare earth oxide or the sulfate that any or two kinds in cerium, lanthanum, praseodymium or the neodymium or any three kinds or any four kinds of rare earth elements form.The addition of rare earth oxide or sulfate is 1%～5% of a lead powder quality.
5, coated plate: the even full-filling of lead plaster that previous step is prepared goes on foot on the anode plate grid for preparing the 3rd, obtains the good positive plate of full-filling, takes out behind 1s～2s in the sulfuric acid that the pole plate that full-filling is good immerses rapidly, and drip-dry sulfuric acid, standby.
6, curing and dry: the pole plate that full-filling is good is placed on and solidifies drying under the room temperature, obtains anodal green plate.
7, pole plate changes into: the anodal green plate that will obtain is formed electrolytic cell as anodal and negative electrode green plate and is carried out pole plate and change into and make positive plate of lead storage battery.
Wherein, changing into operating temperature is 25 ℃～45 ℃, electrolyte sulfuric acid density 1.050g/cm
3～1.150g/cm
3, as operating current density 5mA/cm
2～20mA/cm
2, the electrolytic bath tank voltage has been stabilized in 2.6V～2.8V, changes into to finish.
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 ℃ of-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 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: the lead-antimony alloy anode plate grid that obtains with previous step is an anode, and lead-antimony 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 2.6VvsSEC 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;
4, positive electrode active materials and cream: lead powder, water, sulfuric acid and rare earth oxide are mixed into compliant lead plaster.
Rare earth oxide is the rare earth oxide that any or two kinds in cerium, lanthanum, praseodymium or the neodymium or any three kinds or any four kinds of rare earth elements form.The addition of rare earth oxide is 1% of a lead powder adding quality.
5, coated plate: the lead plaster for preparing is placed in the container that has lid, prevents water evaporates, when treating that the lead plaster temperature drops near room temperature, evenly full-filling is on grid, and the grid part must fill up and wipe off and make the surface evenly smooth; Get the shield that a deionized water soaks again and cover on the good pole plate of full-filling, grid is inverted the shield that takes off in the previous covering, repetitive operation, the pole plate of the good another side of full-filling, the two sides firmly must be consistent when it should be noted that coated plate; The two sides covers shield, with weight grid is applied certain pressure, removes shield, obtains the good pole plate of full-filling; It is 1.050-1.150g/cm that the pole plate that full-filling is good immerses density rapidly
3Sulfuric acid in 1-2s, drip-dry sulfuric acid, standby;
6, curing and dry: adopt the method for cold curing, the pole plate that full-filling is good is placed on indoor shady and cool place and dries in the shade, and generally solidifies dry 48h, obtains green plate;
7, pole plate changes into: the negative pole green plate that obtains is formed electrolytic cell as negative electrode and anodal green plate, and logical upward direct current carries out pole plate and changes into, and the condition of changing into is: 25 ℃-45 ℃ of temperature, electrolyte sulfuric acid density 1.050-1.150g/cm
3, as operating current density 10mA/cm
2, positive and negative electrode produces bubble in the battery case, the no white lead sulfate spot in both positive and negative polarity surface, and positive plate all is sepia, and negative plate all is cinerous, when electrolytic bath voltage has been stabilized in 2.6-2.8V, just can think to change into to finish.
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 0.050mol/L Nd
2(SO
4)
3With 4.0mol/L H
2SO
4In the aqueous solution, operating temperature is 50 ℃, 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;
4, positive electrode active materials and cream: lead powder, water, sulfuric acid and rare earth oxide are mixed into compliant lead plaster; Subsequently sulfuric acid is slowly added lead plaster at 10-15min in the time, continuous stirring 30-40min stops after the lead plaster apparent density reaches certain requirement, and whole and cream process needs to reduce with water-cooling method the temperature of lead plaster;
Rare earth oxide is the rare earth oxide that any or two kinds in cerium, lanthanum, praseodymium or the neodymium or any three kinds or any four kinds of rare earth elements form.The addition of rare earth oxide is 5% of a lead powder adding quality.
5, coated plate: the lead plaster for preparing is placed in the container that has lid, prevents water evaporates, when treating that the lead plaster temperature drops near room temperature, evenly full-filling is on grid, and the grid part must fill up and wipe off and make the surface evenly smooth; Get the shield that a deionized water soaks again and cover on the good pole plate of full-filling, grid is inverted the shield that takes off in the previous covering, repetitive operation, the pole plate of the good another side of full-filling, the two sides firmly must be consistent when it should be noted that coated plate; The two sides covers shield, with weight grid is applied certain pressure, removes shield, obtains the good pole plate of full-filling; It is 1.050-1.150g/cm that the pole plate that full-filling is good immerses density rapidly
3Sulfuric acid in 1-2s, drip-dry sulfuric acid, standby;
6, curing and dry: adopt the method for room temperature weekization, the pole plate that full-filling is good is placed on indoor shady and cool place and dries in the shade, and generally solidifies dry 48h, obtains green plate;
7, pole plate changes into: the negative pole green plate that obtains is formed electrolytic cell as negative electrode and anodal green plate, and logical upward direct current carries out pole plate and changes into, and the condition of changing into is: 25 ℃-45 ℃ of temperature, electrolyte sulfuric acid density 1.050-1.150g/cm
3, as operating current density 5mA/cm
2, positive and negative electrode produces bubble in the battery case, the no white lead sulfate spot in both positive and negative polarity surface, and positive plate all is sepia, and negative plate all is cinerous, when electrolytic bath voltage has been stabilized in 2.6-2.8V, changes into and finishes.
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 Sn and 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 casting grid makes lead-calcium-Xi-aluminium (Pb-Ca-Sn-Al) alloy anode plate grid;
2, lead alloy anode plate grid electrochemical surface is modified: the lead-antimony alloy anode plate grid that obtains with previous step is an anode, and lead-antimony alloy is a negative electrode, at 0.10mol/L Pr
2(SO
4)
3And 2.0mol/LH
2SO
4In the aqueous solution, operating temperature is 40 ℃, is 100mV/s in sweep speed, and scanning beginning current potential is 1.6V vsSEC, it is that 2.6V vs SEC carries out cycle potentials operation anodizing technology and carries out finishing that scanning stops current potential, 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;
4, positive electrode active materials and cream: lead powder, water, sulfuric acid and sulfate are mixed into compliant lead plaster, the deionized water that under condition of stirring, adds a certain amount of organic expander that is scattered here and there, lead plaster is carried out oxidation, and oxidization time is generally 5-10min; The sulfuric acid of will filling a prescription subsequently slowly adds lead plaster at 10-15min in the time, continuous stirring 30-40min stops after the lead plaster apparent density reaches certain requirement, and whole and cream process needs to reduce with water-cooling method the temperature of lead plaster;
Wherein, the addition of rare earth sulfate is 2% of a lead powder quality.Rare earth sulfate is the rare earth sulfate that any or two kinds in cerium, lanthanum, praseodymium or the neodymium or any three kinds or any four kinds of rare earth elements form.
5, coated plate: the lead plaster for preparing is placed in the container that has lid, prevents water evaporates, when treating that the lead plaster temperature drops near room temperature, evenly full-filling is on grid, and the grid part must fill up and wipe off and make the surface evenly smooth; Get the shield that a deionized water soaks again and cover on the good pole plate of full-filling, grid is inverted the shield that takes off in the previous covering, repetitive operation, the pole plate of the good another side of full-filling, the two sides firmly must be consistent when it should be noted that coated plate; The two sides covers shield, with weight grid is applied certain pressure, removes shield, obtains the good pole plate of full-filling; It is 1.050-1.150g/cm that the pole plate that full-filling is good immerses density rapidly
3Sulfuric acid in 1-2s, drip-dry sulfuric acid, standby;
6, curing and dry: adopt the method for cold curing, the pole plate that full-filling is good is placed on indoor shady and cool place and dries in the shade, and generally solidifies dry 48h, obtains green plate;
7, pole plate changes into: the negative pole green plate that obtains is formed electrolytic cell as negative electrode and anodal green plate, and logical upward direct current carries out pole plate and changes into, and the condition of changing into is: 25 ℃-45 ℃ of temperature, electrolyte sulfuric acid density 1.050-1.150g/cm
3, as operating current density 10mA/cm
2, positive and negative electrode produces a large amount of bubbles in the battery case, the no white lead sulfate spot in both positive and negative polarity surface, and positive plate all is sepia, and negative plate all is cinerous, and electrolytic bath voltage has been stabilized in 2.6-2.8V, changes into to finish.
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 Sn and 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.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 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: the lead-antimony alloy anode plate grid that obtains with previous step is an anode, and lead-antimony 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 1.0V vsSEC, it is that 2.2V vs SEC carries out cycle potentials operation anodizing technology and carries out finishing that scanning stops current potential, 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;
4, positive electrode active materials and cream: lead powder, water, sulfuric acid and rare earth sulfate are mixed into compliant lead plaster, the deionized water that under condition of stirring, adds a certain amount of organic expander that is scattered here and there, lead plaster is carried out oxidation, and oxidization time is generally 5-10min; The sulfuric acid of will filling a prescription subsequently slowly adds lead plaster at 10-15min in the time, continuous stirring 30-40min stops after the lead plaster apparent density reaches certain requirement, and whole and cream process needs to reduce with water-cooling method the temperature of lead plaster;
Wherein, the addition of rare earth sulfate is 5% of a lead powder quality.Rare earth sulfate is the rare earth sulfate that any or two kinds in cerium, lanthanum, praseodymium or the neodymium or any three kinds or any four kinds of rare earth elements form.
5, coated plate: the lead plaster for preparing is placed in the container that has lid, prevents water evaporates, when treating that the lead plaster temperature drops near room temperature, evenly full-filling is on grid, and the grid part must fill up and wipe off and make the surface evenly smooth; Get the shield that a deionized water soaks again and cover on the good pole plate of full-filling, grid is inverted the shield that takes off in the previous covering, repetitive operation, the pole plate of the good another side of full-filling, the two sides firmly must be consistent when it should be noted that coated plate; The two sides covers shield, with weight grid is applied certain pressure, removes shield, obtains the good pole plate of full-filling; It is 1.050-1.150g/cm that the pole plate that full-filling is good immerses density rapidly
3Sulfuric acid in 1-2s, drip-dry sulfuric acid, standby;
6, curing and dry: adopt the method for cold curing, the pole plate that full-filling is good is placed on indoor shady and cool place and dries in the shade, and generally solidifies dry 48h, obtains green plate;
7, pole plate changes into: the negative pole green plate that obtains is formed electrolytic cell as negative electrode and anodal green plate, and logical upward direct current carries out pole plate and changes into, and the condition of changing into is: 25 ℃-45 ℃ of temperature, electrolyte sulfuric acid density 1.050-1.150g/cm
3, as operating current density 20mA/cm
2, positive and negative electrode produces a large amount of bubbles in the battery case, the no white lead sulfate spot in both positive and negative polarity surface, and positive plate all is sepia, and negative plate all is cinerous, and electrolytic bath voltage has been stabilized in 2.6-2.8V, changes into to finish.
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 (6)
1. the preparation method of a positive plate of lead storage battery, earlier with antimony, calcium, any one and lead at least in tin or the aluminium are raw material, 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, dry, make the positive electrode grid of lead storage battery of modifying lead alloy surface, be coated with the mixing lead plaster in the positive electrode grid of lead storage battery surface of modifying lead alloy surface again, again through solidifying and drying, change into and obtain rare earth modified positive plate of lead storage battery, be electrolyte with rare earth sulfate and aqueous sulfuric acid when it is characterized in that described anode electrochemical method for oxidation carries out finishing, described mixing lead plaster comprises lead powder, water, sulfuric acid and rare earth oxide or rare earth sulfate, the addition of described rare earth oxide or rare earth sulfate are 1%～5% of lead powder quality.
2. the preparation method of positive plate of lead storage battery according to claim 1, it is characterized in that described rare earth oxide or rare earth sulfate middle rare earth be in cerium, lanthanum, praseodymium or the neodymium at least any one.
3. the preparation method of positive plate 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 ℃.
4. according to the preparation method of claim 1 or 3 described positive plate of lead storage battery, it is characterized in that described anode electrochemical method for oxidation is a potentiostatic method, or galvanostatic method, perhaps cyclic voltammetry.
5. the preparation method of positive plate of lead storage battery according to claim 1, the ambient temperature that it is characterized in that described drying is 90～140 ℃.
6. the preparation method of positive plate of lead storage battery according to claim 1 is characterized in that the described operating temperature that changes into is 25～45 ℃, electrolyte sulfuric acid density 1.050～1.150g/cm
3, as operating current density 5～20mA/cm
2, when electrolytic bath voltage is stabilized in 2.6～2.8V, changes into and finish.
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