CN105406143A - Method for preparing lead storage battery electrode plate from lead-bearing compound in waste lead storage battery as raw material - Google Patents
Method for preparing lead storage battery electrode plate from lead-bearing compound in waste lead storage battery as raw material Download PDFInfo
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- CN105406143A CN105406143A CN201510733810.2A CN201510733810A CN105406143A CN 105406143 A CN105406143 A CN 105406143A CN 201510733810 A CN201510733810 A CN 201510733810A CN 105406143 A CN105406143 A CN 105406143A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention discloses a preparation method of a lead storage battery electrode plate, and belongs to the technical field of comprehensive utilization of solid wastes and preparation of a lead storage battery electrode material. Particularly, the method comprises the following steps: with PbSO4, PbO and PbO2, which are obtained by separating and refining a waste lead storage battery, as raw materials for preparing active materials of the lead storage battery directly, respectively carrying out coating and filling on a positive grid and a negative grid to obtain a green electrode plate by a technology of preparing the lead storage battery electrode plate by a formation method; carrying out PbSO4 oxidation on a positive electrode to prepare PbO2 by an electrochemical formation technology, and preparing a positive electrode plate from the obtained PbO2 as a positive active material directly; and carrying out PbSO4 reduction on a negative electrode to prepare Pb, and preparing a negative electrode plate from the obtained Pb as a negative active material directly. The method disclosed by the invention is simple, safe and reliable in process and beneficial to large-scale industrialization; and regulation and control of the electrode properties are easy to achieve.
Description
Technical field
The present invention relates to a kind of preparation method of lead-acid battery electrode plate, belong to technical field of material, especially the preparing technical field of electrode material technical field and lead-acid battery electrode plate; Also three-protection design and application technology as the second resource field is belonged to, especially Comprehensive Utilization of Waste Lead Accumulator technical field.
Background technology
Lead accumulator has the advantages such as structure is simple, easy to use, dependable performance, price are lower, is the product of large, the applied range of output in chemical power source.Along with the application of new material and new technology, the properties of lead accumulator has had and has increased substantially, and application is more extensive, and as Moped Scooter, extraordinary electric motor car, new automobile power supply, the lead accumulator nearly stage is still main flow power supply.
The operation principle of lead accumulator is the conversion utilizing electrochemical principle to realize matter and energy, and electrode and electrolytical interfacial reaction characteristic affect the core of accumulator property and essential place.Therefore, for lead accumulator, the research and development of its functional electrode, the electrolytical use of function admirable and electrode and electrolytical matching optimization are extremely important problems during lead accumulator is researched and developed.
The basic element of character and the material that form monomer lead accumulator comprise: positive plate, negative plate, sulfuric acid solution, dividing plate, cell jar etc.
The positive and negative pole plate of lead accumulator is the vitals forming monomer lead accumulator.Pole plate is made up of grid and active material, the characteristic of pole plate/electrolyte interface, and particularly grid/electrolyte interface and active material/electrolyte interface characteristic are the key factors affecting battery performance.The microstructure of active material and pattern are also affect cell active materials utilance, electrode conductivuty and the key factor in useful life.
Lead accumulator grid Main Function has:
(1) colleeting comb skeleton: grid is the current collection skeleton of electrode, conducts, collects electric current and make homogeneous current distribution, improves the utilance of plate active material;
(2) prop carrier of active material: grid is played a supportive role to the active material on pole plate by frame and rib.
Active material mainly contains two kinds of functions:
(1) electrochemical reaction is participated in, the PbO of conductivity on interdischarge interval positive pole
2and conductivity Pb is converted into non-conductive PbSO on negative pole
4;
(2) active material is porous mass, and realization response point provides conductive path to grid.
Therefore, it is high that the active material of positive plate should have high oxygen evolution potential, and corrosion resistance is good, good conductivity, by big current.The active material of negative plate should have higher hydrogen-evolution overpotential, good conductivity, by big current.At present, positive electode of lead battery active material is PbO
2, negative electrode active material is Pb.
The structure of waste lead accumulator is substantially identical with lead accumulator with composition.As forming the main composition material-lead of lead accumulator, be one of conventional metal, its output, after iron, copper, aluminium, zinc metal, occupies the 5th.At present, about about 70% metallic lead produced is for the preparation of lead accumulator, and lead plaster is actually the PbSO that the painting cream in lead accumulator is formed after changing into and using
4, PbO, PbO
2in the mixture of composition, its composition and content are determined because of the cycle-index of waste lead accumulator and life-span length.
Therefore, from waste lead accumulator, recycle lead is extremely important lead source.Sufficiently and reasonably utilize the lead resource of waste lead accumulator, not only can alleviate the situation that lead resource now falls sharply day by day, can preparation cost be reduced simultaneously, reduce environmental pollution.So, realize the recycling of the lead of waste lead accumulator, not only there is the strategic importance of sustainable development, and there is important economy and social value.
The lead plaster that waste lead accumulator obtains after sorting and preliminary treatment is important lead-containing compounds, and in lead plaster, main component is roughly: 45%-65%PbSO
4, 10%-30%PbO, 10%-20%PbO
2with the mixture of 2%-3% metallic lead, wherein PbSO in lead plaster
4content is generally more than 50%.
At present, mainly contain from the technique of waste lead battery lead recovery and technology: pyrogenic process, wet method, pyrogenic process-wet method coupled processing method etc.Recycling waste lead batteries treatment technology mainly reclaims and obtains metallic lead, and the active material of pole plate prepared again by metallic lead for the production of lead accumulator as raw material, has to pass through the complicated production technological process of multiple working procedure.If by the direct Application and preparation of the lead plaster of waste lead accumulator in the electrode material of battery production, significantly operating unit can be reduced, reduce energy consumption, reduce accessory substance, improve Atom economy.Obvious optimal production model is the closed circulation of " manufacturing-reclaim-production ".In the production process of lead accumulator, the demand of lead is mainly concentrated in the preparation process of grid and lead plaster.The material of grid is lead-antimony alloy or slicker solder calcium alloy, by after the remelting of waste lead accumulator grid and adjusting component, during the circulation that can enter grid well manufactures.Lead plaster is generally obtain with lead monoxide, lead monoxide then by pure lead in grinding in ball grinder, simultaneously surface is oxidized, or pure lead is melted in a bar pot, is then oxidized in atmosphere to make.Lead sulfate is obtained after lead monoxide and effect of sulfuric acid.
Therefore, the recycling of waste lead accumulator is prepared with lead-acid battery electrode and is coupled, recycling of lead resource can be realized, solve recycling waste lead batteries and utilize process Problems existing, adopt the pole plate of Modified by Rare Earth Elements technology processability excellence can improve the performance of lead accumulator further simultaneously.
Summary of the invention
The object of this invention is to provide one and obtain PbSO with waste lead accumulator through separation and purification
4, PbO, PbO
2the direct raw material as preparing positive electode of lead battery active material and negative electrode active material, adopts forming method to prepare the technology of positive plate of lead storage battery and negative plate, through filling the green plate that pole plate obtains, adopts electrochemistry forming technology PbSO on anode
4oxidation prepares PbO
2, the PbO obtained
2directly as positive active material; Adopt electrochemistry forming technology PbSO on negative electrode
4reduction prepares Pb, and the Pb obtained is directly as negative pole positive active material.
Realizing above-mentioned purpose technical scheme is:
A preparation method for lead-acid battery electrode plate is the PbSO obtained through separation and purification with waste lead accumulator
4, PbO, PbO
2the direct raw material as preparing positive electode of lead battery active material and negative electrode active material, the painting filler of positive active material and negative electrode active material is obtained respectively through batching mixing, fill on anode plate grid and negative electrode grid respectively and obtain positive pole green plate and negative pole green plate, then carry out lead accumulator assembling, fill with liquid, finally adopt electrochemistry forming technology PbSO on anode
4oxidation obtains PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction obtains spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery, also achieves the utilization of waste lead accumulator lead resource while obtaining lead-acid battery electrode plate.
Method concrete steps of the present invention are as follows:
(1) batching mixing: respectively in positive pole, cathode blending mixing apparatus, by refining PbO, PbSO of obtaining
4, PbO carries out batching with positive pole, negative electrode active material additive respectively and mixes, be mixed to get positive pole through batching and be coated with filler and negative pole and be coated with filler and enter next step;
(2) fill pole plate: the positive pole that is mixed to get of previous step being prepared burden respectively is coated with filler, negative pole is coated with filler as preparing positive electode of lead battery active material, on positive pole that the raw material of negative electrode active material fills electrode and negative electrode grid, prepare positive pole green plate and negative pole green plate enters next step;
(3) dry: previous step to be prepared positive pole green plate and negative pole green plate carries out drying, enter next step through the positive pole green plate of super-dry and negative pole green plate;
(4) assemble: positive pole green plate previous step prepared and negative pole green plate are assembled into lead accumulator according to the requirement of lead accumulator;
(5) liquid is filled with: the sulfuric acid electrolyte of preparation is poured into previous step and assemble in the lead accumulator obtained;
(6) electrochemistry changes into: adopt electrochemistry forming technology, PbSO on anode
4oxidation prepares PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction prepares spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery.
Further, in first step batching mixed process, positive pole is coated with PbSO in filler ingredients mixture
4, PbO, PbO
2mol ratio be 1.0:(0.0-1.0): (0.0-1.0), anode activity substance additive be graphite, Graphene, charcoal any one, any one or combination in any, be added to the 0.1-1.0% of mixture quality.，
Further, in first step batching mixed process, PbSO in ingredients mixture
4, PbO, PbO
2mol ratio be 1.0:(0.0-1.0): (0.0-1.0), negative electrode active material additive is swelling agent and retardant, and swelling agent is BaSO
4to add in graphite, Graphene, carbon black and charcoal any one multiple, the addition of swelling agent is the 0.1-1.0% of mixture quality, and retardant is any one or combination in any of humic acid, lignosulphonates, and humic acid addition is 0-2.5%.
Further, fill in pole plate process at second step, it is characterized in that any one of the grid of the Titanium base material matter that described anode plate grid is metallic lead, lead alloy or Titanium, surface scribbles metal oxide, the lead alloy in the preparation of lead alloy anode plate grid is any one in plumbous any one or any two with antimony, calcium, tin or aluminium or any three kinds of the binary lead alloys formed, ternary lead alloy or quaternary lead alloys.
Further, fill in pole plate process at second step, described negative electrode grid metallic lead, lead alloy or Titanium, surface scribble any one of the grid of the Titanium base material matter of metal oxide, and described lead alloy is any one in plumbous any one or two kinds or any three kinds the binary lead alloys formed, ternary lead alloy or quaternary lead alloys with antimony, calcium, tin or aluminium.
Further, described 6th one-step electrochemistry chemical synthesizing method is potentiostatic method, or galvanostatic method, or cyclic voltammetry or based on any one method in the pulse current charge scheme of Maas theorem or combination, the operating temperature changed into is 10 DEG C-60 DEG C, and operating current density is 5mA/cm
2-20mA/cm
2, when the cell tank voltage of electrolytic bath is stabilized in 2.6V-2.8V, electrochemistry formation process terminates.
Further, in described 3rd step dry run, baking temperature is 10 DEG C-120 DEG C.
Further, the 5th step fills with the concentration of sulfuric acid in sulfuric acid electrolyte described in liquid process is 0.6mol/L-6.0mol/L.
Further, the 5th step is filled with in sulfuric acid electrolyte described in liquid process can add rare earth, and the total mol concentration of rare earth ion is less than 0.20mol/L.Described rare earth element is the combination of any one or more rare earth in cerium, praseodymium, terbium, europium, samarium, yttrium, neodymium, praseodymium.
Further, the 5th described step is filled with in liquid process, it is characterized in that described Battery formation liquid dosing apparatus is stirred tank or tubular-mix equipment.
Further, the preparation method of lead-acid battery electrode plate according to claim 1, it is characterized in that the geometry of described electrode matrix metal can be plate, silk, rod, draw in the net any one.
The main technical principle that the present invention adopts:
(1) PbSO is utilized
4/ H
2sO
4the characteristic of interfacial reaction
At PbSO
4/ H
2sO
4interface, PbSO
4oxidation reaction can be there is and generate PbO
2.With waste lead accumulator through physical separation obtain by PbSO
4fill on positive plate of lead storage battery grid, PbSO
4as the raw material preparing positive electode of lead battery active material, electrochemical techniques are adopted to prepare PbO in anodic oxidation
2, the PbO obtained
2directly as positive active material.Reaction equation is:
PbSO
4→PbO
2+2e
At PbSO
4/ H
2sO
4interface, PbSO
4reduction reaction can be there is and generate spongy Pb.With waste lead accumulator through physical separation obtain by PbSO
4fill on negative plate of lead storage battery grid, PbSO
4as the raw material preparing lead accumulator negative electrode active material, the Pb obtained is directly as negative electrode active material.
Reaction equation is:
PbSO
4→Pb-2e
(2) response characteristic of electrode and electrolyte interface is utilized
PbSO
4, Pb, PbO
2all be insoluble in the characteristic in water and aqueous sulfuric acid, in electrochemistry formation process, in electrochemistry formation process, reaction only occurs in electrode/electrolyte interface, the PbSO on anode
4be oxidized the PbO prepared
2directly as positive electode of lead battery active material; PbSO on negative electrode
4reduction prepares spongiform Pb directly as lead accumulator negative electrode active material.
(3) lead-acid battery electrode active material is rare earth modified
By adding rare earth oxide or rare earth sulfuric acid salt additives in electrode active material, the rare earth element oxygenate particularly added at electrode active material or sulfuric acid rare earth sulfate material, further improve the performance of electrode active material, improve the conductive capability of electrode, active material utilization and charge-discharge performance.Particularly in positive active material, add the light rare earth such as cerium, lanthanum oxide or light rare earth oxide concentration thing; In negative electrode active material, add the light rare earth such as europium, yttrium oxide or light rare earth oxide concentration thing, the utilization rate of active material can be improved, reach under equal-wattage, reduce the use amount of active material, realize lead accumulator unit capacity and consume plumbous minimizing.
Technology of the present invention has taken into full account following characteristic:
(1) particularity of waste lead accumulator lead plaster: waste lead accumulator lead plaster is primarily of lead sulfate, lead oxide, brown lead oxide composition, about wherein the content of lead sulfate accounts for the half of recoverable lead resource in lead plaster, lead oxide and lead sulfate account for more than 80% of recoverable lead resource in lead plaster, and the stable chemical nature of lead sulfate and brown lead oxide, the solubility in solvent most is absolutely little.Therefore, first lead oxide and nitric acid reaction generate the plumbi nitras aqueous solution of solubility, and the plumbi nitras aqueous solution obtained is the important source material reclaiming lead resource further; Through selecting suitable leaching agent to enter in solution by the lead sulfate in lead plaster, through further removal of impurities separation and purification, the lead sulfate obtaining refining uses as product; Last separation and purification obtains refining brown lead oxide.
(2) particularity of positive electode of lead battery active material: lead accumulator is typical secondary chemical cell, must meet that electrode reaction is reversible, electrolyte solution is simple, product indissoluble three conditions.1. electrode reaction is reversible: whole battery system reaction is reversible, and the two poles of the earth of battery become electric energy when discharging by chemical energy; After electric discharge, product by means of the method for logical reverse current, can revert to the active material that can discharge, and this is one and is converted to the charging process of chemical energy by electric energy.2. electrolyte solution is simple: only adopt a kind of electrolyte, there is not extending influence between electrolyte solution.3. product indissoluble: after battery discharge, the active material at the two poles of the earth is all converted into the lead sulfate of indissoluble.Obviously, lead sulfate meets the condition as lead accumulator positive and negative electrode active material.
(3) the electrochemical reaction characteristic of plumbous electric power storage chemistry formation process is utilized: its essence of plate formation of lead accumulator process is exactly charge to the first time of battery pole plates, so the quality changed into will directly have influence on the performance and used life of lead accumulator.Electric current uneven on pole plate and Potential distribution obviously can affect the utilance of active material, especially positive plate.Traditional plate formation of lead accumulator technique is placed in dilute sulfuric acid electrolyte by the green plate of bone dry to change into, green plate carries out being oxidized and reduction reaction respectively, make the lead monoxide of positive plate be changed to brown lead oxide, the lead monoxide of negative plate is changed to biscuit lead.Electrochemistry changes into charging/discharging thereof and meets green plate charge-discharge characteristic, and charging current all the time in the acceptable scope of lead accumulator, and is discharged in good time, eliminates polarizing voltage rapidly and effectively, and charging rate is fast, changes into the time short.
(4) pulse current charge based on Maas theorem is adopted to change into scheme: Mas law is pointed out, in charging process, when the intrinsic charging curve current value of lead accumulator is down near the value of charging current, lead accumulator is carried out the electric discharge in short-term of appropriateness, the intrinsic charging curve of lead accumulator can be made to move to right, improve the value of lead accumulator acceptable charging current, thus lead accumulator can be made to keep large current charge, improve charge efficiency.Meanwhile, electric discharge in short-term, can remove electrochemical polarization and concentration polarization that lead accumulator produces in charging process, the temperature of lead accumulator inside also can reduce, thus promotes charge efficiency further, shortens the charging interval.
(5) electrochemical process electrode surface rare-earth modification technology: add rare earth sulfate or rare earth oxide in forming liquid, in electrochemistry formation process, makes the variable valency rare earth ion (RE in forming liquid
3+) generate RE in anode generation oxidation reaction
4+modify positive plate of lead storage battery, generate RE in negative electrode generation reduction reaction
2+modify negative plate of lead storage battery.While battery lead plate changes into, realize rare earth modified electrode plate, improve the performance of lead accumulator.
Main outstanding advantages of the present invention:
(1) PbSO is made full use of
4the PbO of conductivity is easily generated in anode generation oxidation reaction
2, generate the Pb of conductivity in negative electrode generation reduction reaction, adopt electrochemical method, directly by PbSO
4pbO is prepared respectively through electrochemical oxidation and reduction
2and Pb.
(2) PbSO is achieved
4direct utilization, avoid with PbSO
4for raw material, need through de-SO
4 2-, the unit operations such as carbonization just can the defect of reuse lead resource.The PbSO that recycling waste lead batteries can directly obtain by this technique
4as the raw material preparing lead-acid battery electrode active material, significantly reduce the unit process that waste lead accumulator lead resourceization utilizes, can improve the utilance of process, the process that avoids consumes secondary alkali compounds and the sulphate cpd of by-product because removing sulfate ion.
(3) PbSO is avoided
4middle SO
4 2-remove, formed sulfate by-products, atom utilization is high.
(4) problem that in waste lead accumulator, lead resource reclaims is efficiently solved.
(5) carry out rare earth modified by electrochemical techniques to electrode surface, realize the regulation and control of electrode performance.By adding different types of rare earth compound in electrolyte sulfuric acid solution, changing concentration and the operating condition of rare earth ion, can regulate and control and improve the performance of electrode.This method avoid difficulty prepared by Lead-Rare Earth alloy, also can reduce the consumption of rare earth significantly, improve the utilance of rare earth.
(6) adopt electrochemical method to carry out changing into and electrode rare earth modified, can constant potential operation, constant current operation or the operation of circulation peace, method is simple, convenient operation and control, and process safety is reliable, is conducive to heavy industrialization.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention.Below in conjunction with Fig. 1 and embodiment, the present invention is further detailed explanation.
Embodiment
Major process unit is: stirred tank or tubular-mix electrochemical reduction liquid dosing apparatus, electrochemical reactor, lead alloy fusion apparatus, lead alloy grid former and cream equipment, pole plate electrochemistry formation device etc.
Embodiment 1:
As shown in Figure 1, a kind of preparation method of lead-acid battery electrode plate, particularly with the PbSO that waste lead accumulator obtains through separation and purification
4, PbO, PbO
2the direct raw material as preparing positive electode of lead battery active material and negative electrode active material, the painting filler of positive active material and negative electrode active material is obtained respectively through batching mixing, fill on anode plate grid and negative electrode grid respectively and obtain positive pole green plate and negative pole green plate, then carry out lead accumulator assembling, fill with liquid, finally adopt electrochemistry forming technology PbSO on anode
4oxidation obtains PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction obtains spongy Pb, the Pb obtained is directly as lead accumulator negative electrode active material, prepare negative plate of lead storage battery, while obtaining lead-acid battery electrode plate, also achieve the utilization of waste lead accumulator lead resource, it is characterized in that described method step is as follows:
(1) batching mixing: respectively in the autoclave Mix and dosing mixing apparatus of positive pole, negative pole, by the refining PbSO obtained
4carry out batching with positive pole, negative electrode active material additive respectively to mix.Anode activity substance additive is graphite, and addition is 0.1 of mixture quality; By the refining PbSO obtained
4carry out batching mixing with negative electrode active material additive, negative electrode active material additive is swelling agent and retardant, and swelling agent is BaSO
4and graphite, the addition of swelling agent is 0.1% of mixture quality, and retardant is humic acid, and humic acid addition is 2.5%, is mixed to get positive pole is coated with filler and negative pole and is coated with filler and enters next step through batching;
(2) pole plate is filled: the positive pole that is mixed to get of previous step being prepared burden respectively is coated with filler, negative pole is coated with on the positive pole and negative electrode grid that filler fills electrode as the raw material preparing lead accumulator positive and negative electrode active material.Positive and negative electrode grid material is metallic lead, and shape is tabular, prepares positive pole green plate and negative pole green plate enters next step;
(3) dry: previous step to be prepared positive pole green plate and negative pole green plate carries out drying, baking temperature is 10 DEG C, enters next step through the positive pole green plate of super-dry and negative pole green plate;
(4) assemble: positive pole green plate previous step prepared and negative pole green plate are assembled into lead accumulator according to the requirement of lead accumulator;
(5) liquid is filled with: the sulfuric acid electrolyte of preparation is poured into previous step and assemble in the lead accumulator obtained, in electrolyte, the concentration of sulfuric acid is 0.6mol/L;
(6) electrochemistry changes into: adopt electrochemistry forming technology, the operating temperature changed into is 10 DEG C, and operating current density is 5mA/cm
2-20mA/cm
2, when the cell tank voltage of electrolytic bath is stabilized in 2.6V-2.8V, electrochemistry changes into complete, PbSO on anode
4oxidation prepares PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction prepares spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery, also achieves the utilization of waste lead accumulator lead resource while obtaining lead-acid battery electrode plate.
Embodiment 2:
As shown in Figure 1, a kind of preparation method of lead-acid battery electrode plate, particularly with the PbSO that waste lead accumulator obtains through separation and purification
4, PbO, PbO
2the direct raw material as preparing positive electode of lead battery active material and negative electrode active material, the painting filler of positive active material and negative electrode active material is obtained respectively through batching mixing, fill on anode plate grid and negative electrode grid respectively and obtain positive pole green plate and negative pole green plate, then carry out lead accumulator assembling, fill with liquid, finally adopt electrochemistry forming technology PbSO on anode
4oxidation obtains PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction obtains spongy Pb, the Pb obtained is directly as lead accumulator negative electrode active material, prepare negative plate of lead storage battery, while obtaining lead-acid battery electrode plate, also achieve the utilization of waste lead accumulator lead resource, it is characterized in that described method step is as follows::
(1) batching mixing: respectively in the tubular type batching mixing apparatus of positive pole, negative pole, by refining PbO, PbSO of obtaining
4, PbO carries out batching with positive pole, negative electrode active material additive respectively and mixes, PbSO in ingredients mixture
4, PbO, PbO
2mol ratio be 1.0:1.0:1.0, anode activity substance additive is graphite, Graphene, charcoal, and addition is 1.0% of mixture quality; Negative electrode active material additive is swelling agent and retardant, and swelling agent is BaSO
4with graphite, Graphene, carbon black, charcoal, the addition of swelling agent is 1.0% of mixture quality, and retardant is humic acid and lignosulphonates, and retardant addition is 2.5%, is mixed to get positive pole is coated with filler and negative pole and is coated with filler and enters next step through batching;
(2) pole plate is filled: the positive pole that is mixed to get of previous step being prepared burden respectively is coated with filler, negative pole is coated with filler as preparing positive electode of lead battery active material, on positive pole that the raw material of negative electrode active material fills electrode and negative electrode grid, positive and negative electrode grid is plumbous and antimony alloy, grid shape is mesh-like, prepares positive pole green plate and negative pole green plate enters next step;
(3) dry: previous step to be prepared positive pole green plate and negative pole green plate carries out drying, baking temperature 120 DEG C, enter next step through the positive pole green plate of super-dry and negative pole green plate;
(4) assemble: positive pole green plate previous step prepared and negative pole green plate are assembled into lead accumulator according to the requirement of lead accumulator;
(5) fill with liquid: the sulfuric acid electrolyte of preparation is poured into previous step and assemble in the lead accumulator obtained, in electrolyte, the concentration of sulfuric acid is 8.0mol/L, sulfuric acid electrolyte adds rare earth sulfate, and rare earth element is cerium, europium, lanthanum, yttrium, changeable valence rare earth ion Ce
3+and Eu
3+0.001mol/L is respectively, rare earth ion RE in the concentration of Battery formation liquid
3+be 0.20mol/L in the total concentration of Battery formation liquid;
(6) electrochemistry changes into: adopt electrochemistry forming technology, electrochemistry chemical synthesizing method is galvanostatic method, and operating temperature is 60 DEG C, and operating current density is 20mA/cm
2, PbSO on anode
4oxidation prepares PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction prepares spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery, also achieves the utilization of waste lead accumulator lead resource while obtaining lead-acid battery electrode plate.
Embodiment 3:
As shown in Figure 1, a kind of preparation method of lead-acid battery electrode plate, particularly with the PbSO that waste lead accumulator obtains through separation and purification
4, PbO, PbO
2the direct raw material as preparing positive electode of lead battery active material and negative electrode active material, the painting filler of positive active material and negative electrode active material is obtained respectively through batching mixing, fill on anode plate grid and negative electrode grid respectively and obtain positive pole green plate and negative pole green plate, then carry out lead accumulator assembling, fill with liquid, finally adopt electrochemistry forming technology PbSO on anode
4oxidation obtains PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction obtains spongy Pb, the Pb obtained is directly as lead accumulator negative electrode active material, prepare negative plate of lead storage battery, while obtaining lead-acid battery electrode plate, also achieve the utilization of waste lead accumulator lead resource, it is characterized in that described method step is as follows:
(1) batching mixing: respectively in the tubular type batching mixing apparatus of positive pole, negative pole, by refining PbO, PbSO of obtaining
4, PbO carries out batching with positive pole, negative electrode active material additive respectively and mixes, PbSO in ingredients mixture
4, PbO, PbO
2mol ratio be 1.0:0.5:0.5, anode activity substance additive is graphite, Graphene, charcoal, and addition is 0.5% of mixture quality; Negative electrode active material additive is swelling agent, and swelling agent is BaSO
4with any one or combination in any of graphite, Graphene, carbon black, charcoal etc., the addition of swelling agent is 1.0% of mixture quality, is mixed to get positive pole is coated with filler and negative pole and is coated with filler and enters next step through batching;
(2) pole plate is filled: the positive pole that is mixed to get of previous step being prepared burden respectively is coated with filler, negative pole is coated with filler as preparing positive electode of lead battery active material, on positive pole that the raw material of negative electrode active material fills electrode and negative electrode grid, positive and negative electrode grid is Titanium, grid shape, for drawing in the net shape, prepares positive pole green plate and negative pole green plate enters next step;
(3) dry: previous step to be prepared positive pole green plate and negative pole green plate carries out drying, baking temperature is 120 DEG C, enters next step through the positive pole green plate of super-dry and negative pole green plate;
(4) assemble: positive pole green plate previous step prepared and negative pole green plate are assembled into lead accumulator according to the requirement of lead accumulator;
(5) fill with liquid: the sulfuric acid electrolyte of preparation is poured into previous step and assemble in the lead accumulator obtained, in electrolyte, the concentration of sulfuric acid is 4.0mol/L, fill with in liquid process and add rare earth sulfate, rare earth element is cerium, praseodymium, yttrium, samarium, changeable valence rare earth ion Pr
3+and Sm
3+the concentration of Battery formation liquid is 0.001mol/L respectively, rare earth ion RE
3+be 0.004mol/L in the total concentration of Battery formation liquid;
(6) electrochemistry changes into: adopt electrochemistry forming technology, electrochemistry chemical synthesizing method is cyclic voltammetry, and operating temperature is 40 DEG C, and operating current density is 5mA/cm
2-20mA/cm
2, PbSO on anode
4oxidation prepares PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction prepares spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery, also achieves the utilization of waste lead accumulator lead resource while obtaining lead-acid battery electrode plate.
Embodiment 4:
As shown in Figure 1, a kind of preparation method of lead-acid battery electrode plate, particularly with the PbSO that waste lead accumulator obtains through separation and purification
4, PbO, PbO
2the direct raw material as preparing positive electode of lead battery active material and negative electrode active material, the painting filler of positive active material and negative electrode active material is obtained respectively through batching mixing, fill on anode plate grid and negative electrode grid respectively and obtain positive pole green plate and negative pole green plate, then carry out lead accumulator assembling, fill with liquid, finally adopt electrochemistry forming technology PbSO on anode
4oxidation obtains PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction obtains spongy Pb, the Pb obtained is directly as lead accumulator negative electrode active material, prepare negative plate of lead storage battery, while obtaining lead-acid battery electrode plate, also achieve the utilization of waste lead accumulator lead resource, it is characterized in that described method step is as follows:
(1) batching mixing: respectively in the autoclave batching mixing apparatus of positive pole, negative pole, by the refining PbSO obtained
4, PbO
2carry out batching with positive pole, negative electrode active material additive respectively to mix, PbSO in ingredients mixture
4, PbO
2mol ratio be 1.0:0.2, anode activity substance additive is Graphene, and addition is 0.1% of mixture quality; Negative electrode active material additive is swelling agent and retardant, and swelling agent is BaSO
4with any one or combination in any of graphite, Graphene, carbon black, charcoal etc., the addition of swelling agent is 0.6% of mixture quality, retardant is any one or combination in any of humic acid, lignosulphonates, humic acid addition is 1.5%, is mixed to get positive pole is coated with filler and negative pole and is coated with filler and enters next step through batching;
(2) pole plate is filled: the positive pole that is mixed to get of previous step being prepared burden respectively is coated with filler, negative pole is coated with filler as preparing positive electode of lead battery active material, on positive pole that the raw material of negative electrode active material fills electrode and negative electrode grid, positive and negative electrode grid is the grid that surface scribbles the Titanium base material matter of metal oxide, grid shape is tabular, prepares positive pole green plate and negative pole green plate enters next step;
(3) dry: previous step to be prepared positive pole green plate and negative pole green plate carries out drying, baking temperature is 100 DEG C, enters next step through the positive pole green plate of super-dry and negative pole green plate;
(4) assemble: positive pole green plate previous step prepared and negative pole green plate are assembled into lead accumulator according to the requirement of lead accumulator;
(5) liquid is filled with: the sulfuric acid electrolyte of preparation is poured into previous step and assemble in the lead accumulator obtained, in electrolyte, the concentration of sulfuric acid is 6.0mol/L;
(6) electrochemistry changes into: adopt electrochemistry forming technology, electrochemistry chemical synthesizing method is the pulse current charge scheme based on Maas theorem, and operating temperature is 60 DEG C, when the cell tank voltage of electrolytic bath is stabilized in 2.6V-2.8V, electrochemistry changes into complete, PbSO on anode
4oxidation prepares PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction prepares spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery, also achieves the utilization of waste lead accumulator lead resource while obtaining lead-acid battery electrode plate.
Embodiment 5:
As shown in Figure 1, a kind of preparation method of lead-acid battery electrode plate, particularly with the PbSO that waste lead accumulator obtains through separation and purification
4, PbO, PbO
2the direct raw material as preparing positive electode of lead battery active material and negative electrode active material, the painting filler of positive active material and negative electrode active material is obtained respectively through batching mixing, fill on anode plate grid and negative electrode grid respectively and obtain positive pole green plate and negative pole green plate, then carry out lead accumulator assembling, fill with liquid, finally adopt electrochemistry forming technology PbSO on anode
4oxidation obtains PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction obtains spongy Pb, the Pb obtained is directly as lead accumulator negative electrode active material, prepare negative plate of lead storage battery, while obtaining lead-acid battery electrode plate, also achieve the utilization of waste lead accumulator lead resource, it is characterized in that described method step is as follows:
(1) batching mixing: respectively in the batching mixing apparatus of positive pole, negative pole, by the refining PbSO obtained
4, PbO, PbO carry out batching with positive pole, negative electrode active material additive respectively and mix, PbSO in ingredients mixture
4, PbO, PbO
2mol ratio be 1.0:1.0:1.0, anode activity substance additive is graphite, Graphene, charcoal, and addition is 1.0% of mixture quality; Negative electrode active material additive is swelling agent and retardant, and swelling agent is BaSO
4with any one or combination in any of graphite, Graphene, carbon black, charcoal etc., the addition of swelling agent is 0.8% of mixture quality, retardant is humic acid, lignosulphonates, humic acid addition is 1.0%, is mixed to get positive pole is coated with filler and negative pole and is coated with filler and enters next step through batching;
(2) pole plate is filled: the positive pole that is mixed to get of previous step being prepared burden respectively is coated with filler, negative pole is coated with filler as preparing positive electode of lead battery active material, on positive pole that the raw material of negative electrode active material fills electrode and negative electrode grid, positive and negative electrode grid is metallic antimony, calcium, tin and the plumbous alloy formed, the shape of grid, for drawing in the net shape, prepares positive pole green plate and negative pole green plate enters next step;
(3) dry: previous step to be prepared positive pole green plate and negative pole green plate carries out drying, baking temperature is 120 DEG C, enters next step through the positive pole green plate of super-dry and negative pole green plate;
(4) assemble: positive pole green plate previous step prepared and negative pole green plate are assembled into lead accumulator according to the requirement of lead accumulator;
(5) liquid is filled with: the sulfuric acid electrolyte of preparation is poured into previous step and assemble in the lead accumulator obtained, in electrolyte, the concentration of sulfuric acid is 4.0mol/L, adds rare earth sulfate terbium, lanthanum and yttrium, changeable valence rare earth ion Tb
3+and Eu
3+0.001mol/L is respectively, rare earth ion RE in the concentration of Battery formation liquid
3+be 0.20mol/L in the total concentration of Battery formation liquid;
(6) electrochemistry changes into: adopt electrochemistry forming technology, electrochemistry chemical synthesizing method is galvanostatic method, and operating temperature is 40 DEG C, and operating current density is 20mA/cm
2, PbSO on anode
4oxidation prepares PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction prepares spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery, also achieves the utilization of waste lead accumulator lead resource while obtaining lead-acid battery electrode plate.
Embodiment 6:
As shown in Figure 1, a kind of preparation method of lead-acid battery electrode plate, particularly with the PbSO that waste lead accumulator obtains through separation and purification
4, PbO, PbO
2the direct raw material as preparing positive electode of lead battery active material and negative electrode active material, the painting filler of positive active material and negative electrode active material is obtained respectively through batching mixing, fill on anode plate grid and negative electrode grid respectively and obtain positive pole green plate and negative pole green plate, then carry out lead accumulator assembling, fill with liquid, finally adopt electrochemistry forming technology PbSO on anode
4oxidation obtains PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction obtains spongy Pb, the Pb obtained is directly as lead accumulator negative electrode active material, prepare negative plate of lead storage battery, while obtaining lead-acid battery electrode plate, also achieve the utilization of waste lead accumulator lead resource, it is characterized in that described method step is as follows:
(1) batching mixing: respectively in the batching mixing apparatus of positive pole, negative pole, by refining PbO, PbSO of obtaining
4, PbO carries out batching with positive pole, negative electrode active material additive respectively and mixes, PbSO in ingredients mixture
4, PbO, PbO
2mol ratio be 1.0:0.2:0.2, anode activity substance additive is graphite, Graphene, charcoal, and addition is 1.0% of mixture quality; Negative electrode active material additive is swelling agent and retardant, and swelling agent is BaSO
4and charcoal, the addition of swelling agent is 0.8% of mixture quality, retardant is any one or combination in any of humic acid, lignosulphonates, and humic acid addition is 2.0%, is mixed to get positive pole is coated with filler and negative pole and is coated with filler and enters next step through batching;
(2) pole plate is filled: the positive pole that is mixed to get of previous step being prepared burden respectively is coated with filler, negative pole is coated with filler as preparing positive electode of lead battery active material, on positive pole that the raw material of negative electrode active material fills electrode and negative electrode grid, positive and negative electrode grid is the plumbous quaternary lead alloy formed with antimony, calcium, aluminium, grid shape, for drawing in the net shape, prepares positive pole green plate and negative pole green plate enters next step;
(3) dry: previous step to be prepared positive pole green plate and negative pole green plate carries out drying, baking temperature is 100 DEG C, enters next step through the positive pole green plate of super-dry and negative pole green plate;
(4) assemble: positive pole green plate previous step prepared and negative pole green plate are assembled into lead accumulator according to the requirement of lead accumulator;
(5) liquid is filled with: the sulfuric acid electrolyte of preparation is poured into previous step and assemble in the lead accumulator obtained, in electrolyte, the concentration of sulfuric acid is 6.0mol/L;
(6) electrochemistry changes into: adopt electrochemistry forming technology, electrochemistry chemical synthesizing method is galvanostatic method, and operating temperature is 10 DEG C-60 DEG C, and operating current density is 10mA/cm
2, PbSO on anode
4oxidation prepares PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction prepares spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery, also achieves the utilization of waste lead accumulator lead resource while obtaining lead-acid battery electrode plate.
The invention is not restricted to above-described embodiment, the technical scheme that all employings are equal to replacement or equivalence replacement formation all belongs to the scope of protection of present invention.Except 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, all within protection scope of the present invention.
Claims (10)
1. a preparation method for lead-acid battery electrode plate, is characterized in that, the PbSO obtained through separation and purification with waste lead accumulator
4, PbO, PbO
2the direct raw material as preparing positive electode of lead battery active material and negative electrode active material, the painting filler of positive active material and negative electrode active material is obtained respectively through batching mixing, fill on anode plate grid and negative electrode grid respectively and obtain positive pole green plate and negative pole green plate, then carry out lead accumulator assembling, fill with liquid, finally adopt electrochemistry chemical synthesizing method PbSO on anode
4oxidation obtains PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction obtains spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery.
2. the preparation method of lead-acid battery electrode plate according to claim 1, is characterized in that comprising the following steps:
(1) batching mixing: respectively in positive pole, cathode blending mixing apparatus, by the refining PbSO obtained
4, PbO, PbO
2carry out batching with positive pole, negative electrode active material additive respectively to mix, be mixed to get positive pole through batching and be coated with filler and negative pole and be coated with filler and enter next step;
(2) fill pole plate: the positive pole that is mixed to get of previous step being prepared burden respectively is coated with filler, negative pole is coated with filler as preparing positive electode of lead battery active material, on positive pole that the raw material of negative electrode active material fills electrode and negative electrode grid, prepare positive pole green plate and negative pole green plate enters next step;
(3) dry: previous step to be prepared positive pole green plate and negative pole green plate carries out drying, enter next step through the positive pole green plate of super-dry and negative pole green plate;
(4) assemble: positive pole green plate previous step prepared and negative pole green plate are assembled into lead accumulator according to the requirement of lead accumulator;
(5) liquid is filled with: the sulfuric acid electrolyte of preparation is poured into previous step and assemble in the lead accumulator obtained;
(6) electrochemistry changes into: adopt electrochemistry chemical synthesizing method, PbSO on anode
4oxidation prepares PbO
2, the PbO obtained
2directly as positive active material, prepare positive plate; PbSO on negative electrode
4reduction prepares spongy Pb, and the Pb obtained directly as lead accumulator negative electrode active material, prepares negative plate of lead storage battery.
3. the preparation method of lead-acid battery electrode plate according to claim 2, is characterized in that, in (1) step batching mixed process, positive pole is coated with PbSO in filler ingredients mixture
4, PbO, PbO
2mol ratio be 1.0:(0.0-1.0): (0.0-1.0), anode activity substance additive is the combination in any of any one or they of graphite, Graphene, charcoal, and addition is the 0.1%-1.0% of mixture quality.
4. the preparation method of lead-acid battery electrode plate according to claim 2, is characterized in that, in (1) step batching mixed process, negative pole is coated with PbSO in filler ingredients mixture
4, PbO, PbO
2mol ratio be 1.0:(0.0-1.0): (0.0-1.0), negative electrode active material additive is swelling agent and retardant, and swelling agent is BaSO
4add any one in graphite, Graphene, carbon black and charcoal multiple, the addition of swelling agent is the 0.1%-1.0% of mixture quality, for any one or combination in any of humic acid, lignosulphonates, retardant addition is less than 2.5% of mixture quality.
5. the preparation method of lead-acid battery electrode plate according to claim 2, it is characterized in that, fill in pole plate process in (2) step, any one of the grid of the Titanium base material matter that described anode plate grid is metallic lead, lead alloy or Titanium, surface scribbles metal oxide, described lead alloy is any one in plumbous any one or any two with antimony, calcium, tin or aluminium or any three kinds of the binary lead alloys formed, ternary lead alloy or quaternary lead alloys.
6. the preparation method of lead-acid battery electrode plate according to claim 2, it is characterized in that, fill in pole plate process in (2) step, any one of the grid of the Titanium base material matter that described negative electrode grid is metallic lead, lead alloy or Titanium, surface scribbles metal oxide, described lead alloy is any one in plumbous any one or two kinds or any three kinds the binary lead alloys formed, ternary lead alloy or quaternary lead alloys with antimony, calcium, tin or aluminium.
7. the preparation method of lead-acid battery electrode plate according to claim 2, it is characterized in that described (6) one-step electrochemistry chemical synthesizing method is potentiostatic method, or galvanostatic method, or cyclic voltammetry or based on any one method in the pulse current charge scheme of Maas theorem or combination, the operating temperature changed into is 10 DEG C-60 DEG C, and operating current density is 5mA/cm
2-20mA/cm
2, when the cell tank voltage of electrolytic bath is stabilized in 2.6V-2.8V, electrochemistry formation process terminates.
8. the preparation method of lead-acid battery electrode plate according to claim 2, is characterized in that the concentration that the 5th step fills with sulfuric acid in sulfuric acid electrolyte described in liquid process is 0.6mol/L-6.0mol/L.
9. the preparation method of lead-acid battery electrode plate according to claim 2, it is characterized in that (5) step is filled with in sulfuric acid electrolyte described in liquid process and add rare earth, the total mol concentration of rare earth ion is less than 0.20mol/L.
10. the preparation method of negative plate of lead storage battery according to claim 9, is characterized in that described rare earth element is the combination of any one or more rare earth in cerium, praseodymium, terbium, europium, samarium, yttrium, neodymium, praseodymium.
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| CN107302118A (en) * | 2016-04-15 | 2017-10-27 | 北京化工大学 | A kind of lead oxide that reclaims is as the high-performance lead-acid accumulator of active material |
| CN108461831A (en) * | 2018-03-20 | 2018-08-28 | 朱玉法 | A kind of novel storage battery manufacturing method |
| CN110656352A (en) * | 2019-11-01 | 2020-01-07 | 巨江电源科技有限公司 | Recycling method of solid-phase electrolytic secondary lead of waste lead-acid storage battery |
| CN112420996A (en) * | 2020-10-29 | 2021-02-26 | 天能电池集团股份有限公司 | Method for preparing power battery by utilizing recycled lead powder, positive plate and power battery |
| CN112736254A (en) * | 2021-01-06 | 2021-04-30 | 天能电池集团股份有限公司 | Preparation method of negative grid of lead storage battery and negative grid |
| CN113046788A (en) * | 2021-03-17 | 2021-06-29 | 扬州大学 | Electrolyte and method for preparing lead and lead dioxide by electrochemical deposition |
| CN114188531A (en) * | 2021-10-21 | 2022-03-15 | 超威电源集团有限公司 | Battery cathode powder and preparation method and application thereof |
| CN114566724A (en) * | 2022-01-27 | 2022-05-31 | 淄博火炬能源有限责任公司 | Method for repairing positive active material of lead-acid battery |
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| CN116247170A (en) * | 2023-02-28 | 2023-06-09 | 昆明理工大学 | Method for preparing negative plate of formation-free lead-acid storage battery by using waste lead paste as raw material |
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| CN114583116A (en) * | 2022-01-27 | 2022-06-03 | 淄博火炬能源有限责任公司 | Starting forming lead accumulator |
| CN114566724B (en) * | 2022-01-27 | 2023-09-15 | 淄博火炬能源有限责任公司 | Method for repairing positive electrode active material of lead-acid battery |
| CN116247170A (en) * | 2023-02-28 | 2023-06-09 | 昆明理工大学 | Method for preparing negative plate of formation-free lead-acid storage battery by using waste lead paste as raw material |
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Application publication date: 20160316 |