CN107302118B - High-performance lead-acid storage battery with recovered lead oxide as active substance - Google Patents
High-performance lead-acid storage battery with recovered lead oxide as active substance Download PDFInfo
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- CN107302118B CN107302118B CN201610237712.4A CN201610237712A CN107302118B CN 107302118 B CN107302118 B CN 107302118B CN 201610237712 A CN201610237712 A CN 201610237712A CN 107302118 B CN107302118 B CN 107302118B
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Abstract
A high-performance lead-acid storage battery with recovered lead oxide as an active substance belongs to the technical field of lead-acid storage batteries. Additives such as tetrabasic lead sulfate, metallic lead, binder and the like are added into the positive electrode of the battery. High-apparent density lead plaster is prepared by adopting high-temperature paste mixing and a high-temperature curing process. The recovered lead powder is high-purity lead oxide powder prepared by the waste lead-acid storage battery based on a novel atomic economic method, and the process overcomes the defects that the secondary lead is smelted by a pyrogenic method or electrolyzed by a wet method to be metal lead, a large amount of energy is consumed, and the environment is polluted. The lead powder is directly used as an electrode made of active substances, so that the process of producing the lead powder by a lead ingot is omitted, and the production cost and the pollution to the environment are reduced. By adding metallic lead, tetrabasic lead sulfate, a binder and the like in an electrode formula, and adopting a high-temperature paste mixing process to prepare high apparent density lead paste and a high-temperature curing process, the battery performance is further improved, so that the assembled lead-acid storage battery has high initial capacity, long cycle life, high multiplying power, large current and excellent low-temperature performance.
Description
Technical Field
The invention relates to a high-performance lead-acid storage battery with recovered lead oxide as an active substance, and belongs to the field of lead-acid storage battery manufacturing and waste battery recycling.
Background
Lead acid batteries were invented in 1859 by the French Press (Plante) and have been in history for over a hundred years to date. The lead-acid storage battery has absolute advantages in chemical power supplies after the lead-acid storage battery is invented. The lead-acid storage battery has the advantages of low price, easily obtained raw materials, sufficient reliability in use, suitability for heavy-current discharge, wide environmental temperature range and the like, so that the lead-acid storage battery is widely applied, and meanwhile, the automobile consumption market in China is rapidly developed in recent years, so that the production of the lead-acid storage battery is kept on a continuous growth trend for a long time in the future.
With the increasing scarcity of primary lead ore resources, the waste lead storage battery becomes a main raw material in the secondary lead industry. The modern industry for recovering lead is always to obtain crude lead by using the traditional pyrometallurgical lead-smelting process and then obtain refined lead by electrolytic refining or pyrometallurgical refining. However, the active material of the lead-acid battery is lead oxide, so three main links of melting refined lead, casting lead balls and oxidizing are also needed to be used for producing the lead-acid battery. The whole process involves high-temperature pyrometallurgical smelting, which not only consumes a large amount of energy, but also generates a large amount of lead-containing waste residues and lead-containing dust, and causes serious secondary lead pollution in partial areas. Also, the refining of lead bullion and the ball milling oxidation of refined lead consume a large amount of electric energy and generate lead-containing dust. Therefore, the clean low-energy-consumption recycling of the waste lead-acid storage battery for the production of the lead-acid storage battery is an urgent task for realizing the sustainable development of the secondary lead industry.
The method comprises the steps of converting waste lead-acid storage battery waste lead paste to obtain lead oxide powder and using the lead oxide powder for the technology of manufacturing lead-acid storage batteries, wherein the Yankee broad subject group publication patent CN201210121636.2 of Huazhong university of science and technology utilizes raw materials such as sodium carbonate and the like to perform a desulfurization reaction with the waste lead paste, then utilizes the desulfurization lead paste to react with a citric acid solution and dry to obtain lead citrate, and the lead citrate is roasted to finally obtain superfine lead oxide powder. Although the lead-acid battery meets the characteristics of clean production, chemical reagents such as sodium carbonate, hydrogen peroxide and citric acid are consumed in a large amount, and meanwhile, the subject group reports that the lead-acid battery prepared from the lead oxide powder (Yandanni. lead-acid battery preparation based on novel lead powder and electrochemical performance research [ D ] Huazhong university of science and technology, 2013) has good initial performance, but the cycle life is short, the capacity retention rate is only 70% after 40 cycles, and the use requirement cannot be met at all.
Patent CN201310665446.1 disclosed in the task group of lei lixu university in southeast 2014, in which a lead-containing solution obtained by reacting a positive electrode waste lead paste mixture with a reducing agent in an acidic medium or a negative electrode lead paste mixture with acetic acid or nitric acid is reacted with a soluble sulfate to obtain lead sulfate; or reacting the positive waste lead paste mixture with a reducing agent, or reacting the negative lead paste mixture with soluble carbonate to obtain aqueous dispersion containing lead insoluble substances, mixing and reacting the aqueous dispersion with a sulfuric acid aqueous solution in a collision flow reactor, centrifuging and drying to obtain lead sulfate, and preparing the lead-acid storage battery by using the lead sulfate. The invention has simple process route, but consumes a large amount of acid reagent and carbonate. Meanwhile, when the lead-acid storage battery prepared by using lead sulfate is used, only data which are used as a negative electrode active material and stably circulated for 50 times are reported.
The group of lei lixu subjects, university in southeast 2015, discloses patent 201510513062.7, which prepares a lead acid battery using lead sulfate as a positive electrode active material. Wherein, lead dioxide and lead tetroxide are added in lead sulfate, the lead dioxide is obtained by reacting anode waste lead plaster with soluble alkali, the obtained precipitate is reacted with acid reagents such as dilute nitric acid, and the like, and the lead dioxide is obtained after filtering, and the lead tetroxide is obtained by reacting the anode waste lead plaster with the soluble alkali, and the precipitate is roasted to obtain the lead tetroxide. Although the method has a simple process route, a large amount of soluble alkali, dilute nitric acid and other acidic reagents can be consumed, and particularly, a large amount of lead-containing solution is wasted in the process of preparing lead dioxide, so that lead resources are wasted. The patent reports that the lead-acid storage battery prepared by using lead sulfate as the positive active material has cycle data which is only stable for more than 50 times and has much shorter cycle life than the common lead-acid storage battery.
The Pan army professor group of Beijing chemical university does a great deal of work in the aspect of waste lead-acid storage battery recovery, and patents CN104520240A and CN104789776A respectively disclose a novel method for efficiently, cleanly and low-cost recovery of lead paste of waste lead-acid storage batteries to produce lead oxide.
We have found that lead oxide powder or lead sulfate recovered from waste lead paste is unsatisfactory in battery life when used for the preparation of lead-acid storage batteries, particularly as a positive electrode active material. The preparation of high-performance lead-acid storage batteries by recovering lead powder from waste lead plaster is a task to be solved urgently. Further research was carried out to this end, leading to the present invention.
Disclosure of Invention
The invention provides a novel method for producing a high-performance lead-acid storage battery by using lead oxide recovered based on an atomic economy method, aiming at the problems that the lead powder produced and recovered by the existing waste lead-acid storage battery is directly used for the lead-acid storage battery and the cycle life of the manufactured lead-acid storage battery is poor. It is therefore an object of the present invention to produce a high performance lead acid battery using lead oxide recovered based on an atomic economic process.
A high-performance lead-acid storage battery for recovering lead oxide as an active substance comprises the following raw materials in a positive electrode of the lead-acid storage battery: recovering lead oxide, metallic lead, tetrabasic lead sulfate, a battery additive, a binder, paste acid and water; the mass and dosage of the solid material recovered lead oxide, the metallic lead, the tetrabasic lead sulfate and the battery additive are 100 percent, wherein the metallic lead accounts for 1 to 20 percent, the tetrabasic lead sulfate accounts for 1 to 8 percent, and the battery additive accounts for 0 to 2 percent.
The invention relates to a high-performance lead-acid storage battery with recovered lead oxide as an active substance, wherein the recovered lead oxide powder is pure lead oxide powder produced by a process for recovering waste lead storage batteries based on an atom economy method, and the high-performance lead-acid storage battery mainly comprises the following components in percentage by weight:
the recycled lead oxide is α -PbO of red tetragonal crystal or/and β -PbO of yellow orthorhombic crystal, the oxidation degree of the recycled lead oxide is 100%, the recycled lead oxide is single-component pure lead oxide, the particle size is 1-20 mu m, the apparent density is 0.6-1.5g/mL, and when the recycled lead oxide powder is applied to the anode of a lead-acid storage battery, α -PbO of red tetragonal crystal is selected, because experiments prove that the recycled lead oxide powder is superior to β -PbO of yellow orthorhombic crystal in capacity and cycle life.
The metal lead is simple substance lead powder with the grain diameter of 1-10 mu m. Because the recovered lead powder is pure lead oxide, the anode is added with simple substance lead, and lead paste is free from lead oxidation in the curing process, so that better binding force is formed between active substances and between the active substances and a grid, the active substances are not easy to fall off, and the effect of prolonging the service life of the lead-acid storage battery is achieved.
The particle size of the tetrabasic lead sulfate is 10-100 mu m, the tetrabasic lead sulfate plays a role of crystal seeds in the lead paste, and meanwhile, the tetrabasic lead sulfate crystals grow in the lead paste by further combining high-temperature paste mixing and high-temperature curing processes, so that the conversion rate of the tetrabasic lead sulfate to the tetrabasic lead sulfate is greatly improved, the tetrabasic lead sulfate in the polar plate plays a role of a framework, and active substances are not easy to soften and fall off, so that the cycle life of the lead-acid storage battery is prolonged.
Other additives are conventional in the art, such as stannous sulfate, antimony trioxide, graphite, fibers, and the like.
The binder is selected from at least one of PTFE emulsion, CMC and PVDF emulsion. The structure of the active substance in the charging and discharging process, especially in the positive electrode, is ensured by adding the binder emulsion, and the softening and falling-off of the active substance caused by volume expansion in the charging and discharging process are reduced. The invention creatively mixes the binder with the cream acid, but not with the deionized water, in order to prevent caking caused by adding the binder into the water and incomplete reaction.
The invention relates to a high-performance lead-acid storage battery with recovered lead oxide as an active substance, which is characterized in that the positive electrode of the lead-acid storage battery adopts high apparent density lead plaster prepared by a high-temperature plaster mixing process, and the process comprises the following steps:
(1) adding the recovered lead oxide powder, the metallic lead, the tetrabasic lead sulfate and the electrolytic cell additive into a paste mixer at the temperature of 50-95 ℃ and uniformly mixing;
(2) adding boiled deionized water accounting for 10-11.5% of the total material mass in the step (1) into the step (1), and stirring for 8-15min to obtain a lead mixture;
(3) adding the binder into the cream acid, uniformly mixing, slowly adding the mixed cream acid solution into the lead mixture obtained in the step (2), and adding the cream acid solution within 15-20 min; wherein the mixed paste acid is sulfuric acid solution, preferably mixed paste acid with density of 1.4g/cm3The adding mass of the cream-mixing acid is 4-8% of the total amount of the materials in the step (1), and the binder is 0.1-1% of the total amount of the materials in the step (1);
(4) after the cream acid solution is added and the stirring is continued for 5-10min, measuring the apparent density, wherein the apparent density is required to be more than 4.45g/mL, otherwise, continuing stirring until the standard is reached; finally, coating the standard-reaching lead plaster on a positive grid, and then curing by adopting a high-temperature curing process;
(5) and finally, polishing the solidified positive plate electrode lugs to be clean, assembling the positive plate electrode lug and the negative plate electrode lug into a battery in a matching way, and carrying out internal formation after acid filling, namely completing the manufacture of the lead-acid storage battery.
The apparent density of the lead paste can be effectively improved by utilizing a high-temperature paste mixing process. Experiments prove that the higher the apparent density of the lead paste is in a certain range, the longer the cycle life of the battery is. According to research, the water adding amount and the acid adding amount are in a negative correlation with the apparent density of the lead paste, so that the water adding amount and the acid adding amount of the process are both less than those of a conventional battery, and the evaporation of water is accelerated by using boiling water and a high-temperature paste mixing mode. The process effectively enhances the binding force between active substances, and simultaneously generates tetrabasic lead sulfate crystals, thereby greatly prolonging the cycle life of the lead-acid storage battery.
The high-performance lead-acid storage battery with the recycled lead oxide as the active substance is characterized in that the positive electrode of the lead-acid storage battery adopts a high-temperature curing process. The process comprises the following stages:
(1) a high-temperature high-humidity curing stage, wherein the temperature is 80-90 ℃, the humidity is 95-100%, and the time of the stage is 10-15 h.
(2) A medium-temperature curing stage, wherein the temperature is 60-70 ℃, the humidity is 80-90%, and the time of the stage is 3-5 h.
(3) A constant speed drying stage, wherein the temperature is 80-90 ℃, the humidity is 0-20%, and the time of the stage is 5 h.
(4) A high-temperature drying stage, wherein the temperature is 80-90 ℃, the humidity is 0, and the time of the high-temperature drying stage is 5 hours.
Because the oxidation degree of the recovered lead powder is 100 percent, although a small amount of metallic lead is added in the paste mixing process, the curing time is greatly shortened and the curing can be completed within 24 hours, thereby improving the production efficiency and shortening the production period. The basic skeleton (strong and hard porous substance) of the solidified lead plaster is formed by utilizing a high-temperature solidification process, and the temperature is higher than 85 ℃, so that tribasic lead sulfate generated in the plaster combining process and the solidification process is more easily converted into tetrabasic lead sulfate. The high humidity can dissolve small crystal particles in the lead paste and grow large crystal particles. Meanwhile, a small amount of metal lead is added into the lead plaster, so that the lead plaster is tightly connected with crystal particles in the lead plaster in the oxidation process, the strength of the green sheet can be enhanced, heat is released in the process, and the generation of tetrabasic lead sulfate is promoted, so that the aim of prolonging the cycle life of the lead-acid storage battery is fulfilled.
The pure lead oxide powder produced by the process for recovering the waste lead storage battery based on the atomic economy method is different from the traditional Shimadzu powder or Buton powder, and the high-energy-consumption process of producing the lead powder by pyrometallurgy, crude lead refining and fine lead oxidation is omitted, so that the production cost and the pollution to the environment are greatly reduced, and meanwhile, the curing time of the green plate of the lead-acid storage battery can be effectively reduced, the energy consumption is saved, and the production period is shortened by utilizing the pure lead oxide powder.
The lead-acid storage battery using the recycled lead oxide as the active substance has excellent electrochemical performance and high initial capacity, and the strength of the green plate is improved, the binding force between the active substances is enhanced, the softening and falling of the active substances are relieved, and the cycle life is prolonged by adding the metallic lead, the tetrabasic lead sulfate and the binding agent and simultaneously adopting the high-temperature paste mixing and high-temperature curing processes.
Drawings
FIG. 1 Battery cycling profile of example 1;
fig. 2 example 2 battery cycling curves;
fig. 3 example 3 battery cycling curves;
fig. 4 example 4 battery cycling curves;
fig. 5 example 5 cell cycling profile.
Detailed Description
The high-performance lead-acid battery of the present invention, which is a recovered lead oxide as an active material, will be further explained with reference to specific examples, but the present invention is not limited to the following examples.
Example 1
The lead oxide powder is α -PbO which is recovered from waste lead paste of a certain company based on an atom economy method, and is red tetragonal crystal, and the stacking mode is lamellar stacking.
The specific implementation process is as follows:
(1) accurately weighing 5kg of recovered lead oxide, 125g of metallic lead, 125g of red lead, 100g of tetrabasic lead sulfate and 50g of CMC binder emulsion.
(2) Adding the recovered lead oxide powder and other additives except the binder into a paste mixer at the temperature of 90 ℃ and carrying out dry stirring for 5 min.
(3) Add 590g of boiled deionized water and stir for 8-15 min.
(4) Adding the binder into the mixed sulfuric acid solution of the cream acid, uniformly mixing, slowly adding the mixed cream acid solution into the lead mixture obtained in the step (2), and adding the mixed cream acid solution within 15-20 min. Wherein the cream acid is sulfuric acid solution with density of 1.4g/cm3, and the addition amount is 400 g.
(5) After the cream acid mixed solution is added, stirring is continued for 5min, and the apparent density of the lead cream is measured and is required to reach more than 4.45g/mL, otherwise, stirring is continued until the standard is reached. And finally, coating the standard-reaching lead plaster on the positive grid, and performing a high-temperature curing process. The cathode adopts the traditional paste mixing and curing mode.
Wherein the positive electrode of the lead-acid storage battery adopts a high-temperature curing process. The process comprises the following steps:
(1) a high-temperature high-humidity curing stage, wherein the temperature is 90 ℃, the humidity is 99%, and the time of the stage is 10-15 h.
(2) A medium-temperature curing stage at 60 ℃ and 80% humidity for 3-5 h.
(3) A constant speed drying stage, the temperature is 85 ℃, the humidity is 20%, and the time of the stage is 5 h.
(4) A high temperature drying stage at 90 ℃ and humidity of 0, the time of the stage being 5 h.
And finally, polishing the solidified green plate lugs to be clean, assembling the positive plate lug and the negative plate lug into a battery in a matching way, and carrying out internal formation after acid filling, namely completing the manufacture of the lead-acid storage battery.
Through detection, the 12Ah battery has excellent performance, the initial capacity reaches 13.2Ah, and the 100% DOD discharge cycle life reaches more than 350 times (see figure 1).
Example 2
The lead oxide powder is the lead oxide powder recovered from waste lead paste of a certain company based on an atom economy method, wherein the positive electrode is α -PbO, the negative electrode is β -PbO, and the stacking mode is lamellar stacking.
The specific implementation process is as follows:
(1) accurately weighing 5kg of recovered lead oxide, 150g of metallic lead, 125g of red lead, 100g of tetrabasic lead sulfate and 50g of PTFE emulsion.
(2) Adding the recovered lead oxide powder and other additives except the binder into a paste mixer at the temperature of 90 ℃ and carrying out dry stirring for 5 min.
(3) Add 550g of boiled deionized water and stir for 8-15 min.
(4) Adding the binder into the cream acid, uniformly mixing, slowly adding the mixed cream acid solution into the lead mixture obtained in the step (2), and adding the cream acid mixed solution within 15-20 min. Wherein the mixed cream acid has a density of 1.4g/cm3The amount of the sulfuric acid solution added was 250 g.
(5) After the cream acid mixed solution is added, stirring is continued for 5min, and the apparent density of the lead cream is measured and is required to reach more than 4.45g/mL, otherwise, stirring is continued until the standard is reached. And finally, coating the standard-reaching lead plaster on the positive grid, and performing a high-temperature curing process. The cathode adopts the traditional paste mixing and curing mode.
Wherein the positive electrode of the lead-acid storage battery adopts a high-temperature curing process. The process comprises the following steps:
(1) a high-temperature high-humidity curing stage, wherein the temperature is 86 ℃, the humidity is 99%, and the stage time is 10-15 h.
(2) A medium-temperature curing stage at 70 ℃ and 80% humidity for 3-5 h.
(3) A constant speed drying stage, the temperature is 85 ℃, the humidity is 20%, and the time of the stage is 5 h.
(4) A high temperature drying stage at 90 ℃ and humidity of 0, the time of the stage being 5 h.
And finally, polishing the solidified green plate lugs to be clean, assembling the positive plate lug and the negative plate lug into a battery in a matching way, and carrying out internal formation after acid filling, namely completing the manufacture of the lead-acid storage battery.
Through detection, the 12Ah battery has excellent performance, the initial capacity reaches 13.5Ah, and the 100% DOD discharge cycle life reaches more than 380 times (see figure 2).
Example 3
The lead oxide powder is α -PbO which is recovered from waste lead paste of a certain company based on an atom economy method, and is red tetragonal crystal, and the stacking mode is lamellar stacking.
The specific implementation process is as follows:
(1) accurately weighing 10kg of recovered lead oxide, 300g of metallic lead, 200g of tetrabasic lead sulfate and 80g of mixed emulsion of PVDF and PTFE.
(2) Adding the recovered lead oxide powder and other additives except the binder into a paste mixer at the temperature of 90 ℃ and carrying out dry stirring for 5 min.
(3) Add 1050g of boiled deionized water and stir for 8-15 min.
(4) Adding the binder into the cream acid, uniformly mixing, slowly adding the mixed cream acid solution into the lead mixture obtained in the step (2), and adding the cream acid mixed solution within 15-20 min. Wherein the mixed cream acid has a density of 1.4g/cm3670g of sulfuric acid solution.
(5) After the cream acid mixed solution is added, stirring is continued for 5min, and the apparent density of the lead cream is measured and is required to reach more than 4.45g/mL, otherwise, stirring is continued until the standard is reached. And finally, coating the standard-reaching lead plaster on the positive grid, and performing a high-temperature curing process. The cathode adopts the traditional paste mixing and curing mode.
Wherein the positive electrode of the lead-acid storage battery adopts a high-temperature curing process. The process comprises the following steps:
(1) a high-temperature high-humidity curing stage, wherein the temperature is 86 ℃, the humidity is 99%, and the stage time is 10-15 h.
(2) A medium-temperature curing stage at 70 ℃ and 80% humidity for 3-5 h.
(3) A constant speed drying stage, the temperature is 85 ℃, the humidity is 20%, and the time of the stage is 5 h.
(4) A high temperature drying stage at 90 ℃ and humidity of 0, the time of the stage being 5 h.
And finally, polishing the solidified green plate lugs to be clean, assembling the positive plate lug and the negative plate lug into a battery in a matching way, and carrying out internal formation after acid filling, namely completing the manufacture of the lead-acid storage battery.
Through detection, the 12Ah battery has excellent performance, the initial capacity can reach 13Ah, and the 100% DOD discharge cycle life reaches more than 400 times (see figure 3).
Example 4
The lead oxide powder is the lead oxide powder recovered by waste lead paste of a certain company based on an atom economy method, the positive electrode is α -PbO, red tetragonal crystals, the negative electrode is α -PbO and β -PbO which are 50 wt% respectively, and the stacking mode is lamellar stacking.
The specific implementation process is as follows:
(1) accurately weighing 20kg of recovered lead oxide, 550g of metallic lead, 500g of tetrabasic lead sulfate and 200g of PTFE emulsion.
(2) Adding the recovered lead oxide powder and other additives except the binder into a paste mixer at the temperature of 90 ℃ and carrying out dry stirring for 5 min.
(3) Adding 2200g of boiled deionized water and stirring for 8-15 min.
(4) Adding the binder into the cream acid, uniformly mixing, slowly adding the mixed cream acid solution into the lead mixture obtained in the step (2), and adding the cream acid mixed solution within 15-20 min. Wherein the mixed cream acid has a density of 1.4g/cm3Sulfuric acid solution of (2), addedThe amount was 1500 g.
(5) After the cream acid mixed solution is added, stirring is continued for 5min, and the apparent density of the lead cream is measured and is required to reach more than 4.45g/mL, otherwise, stirring is continued until the standard is reached. And finally, coating the standard-reaching lead plaster on the positive grid, and performing a high-temperature curing process. The cathode adopts the traditional paste mixing and curing mode.
Wherein the positive electrode of the lead-acid storage battery adopts a high-temperature curing process. The process comprises the following steps:
(1) a high-temperature high-humidity curing stage, wherein the temperature is 90 ℃, the humidity is 99%, and the time of the stage is 10-15 h.
(2) A medium-temperature curing stage at 65 ℃ and 80% humidity for 3-5 h.
(3) A constant speed drying stage, the temperature is 85 ℃, the humidity is 20%, and the time of the stage is 5 h.
(4) A high temperature drying stage at 85 ℃ and humidity of 0, the time of the stage being 5 h.
And finally, polishing the solidified green plate lugs to be clean, assembling the positive plate lug and the negative plate lug into a battery in a matching way, and carrying out internal formation after acid filling, namely completing the manufacture of the lead-acid storage battery.
Through detection, the 12Ah battery has excellent performance, the initial capacity reaches 13.4Ah, and the 100% DOD discharge cycle life reaches more than 450 times (see figure 4).
Example 5
The lead oxide powder is α -PbO which is recovered from waste lead paste of a certain company based on an atom economy method, and is red tetragonal crystal, and the stacking mode is lamellar stacking.
The specific implementation process is as follows:
(1) accurately weighing 20kg of recovered lead oxide, 550g of metallic lead, 400g of tetrabasic lead sulfate and 50g of PTFE emulsion.
(2) Adding the recovered lead oxide powder and other additives except the binder into a paste mixer at the temperature of 90 ℃ and carrying out dry stirring for 5 min.
(3) Adding 2100g of boiled deionized water and stirring for 8-15 min.
(4) Adding the binder into the cream acid, uniformly mixing, and slowly mixing the mixed cream acid solutionAdding the mixture into the lead mixture obtained in the step (2), and adding the mixed solution of the paste acid within 15-20 min. Wherein the mixed cream acid has a density of 1.4g/cm31600g of sulfuric acid solution.
(5) After the cream acid mixed solution is added, stirring is continued for 5min, and the apparent density of the lead cream is measured and is required to reach more than 4.45g/mL, otherwise, stirring is continued until the standard is reached. And finally, coating the standard-reaching lead plaster on the positive grid, and performing a high-temperature curing process. The cathode adopts the traditional paste mixing and curing mode.
Wherein the positive electrode of the lead-acid storage battery adopts a high-temperature curing process. The process comprises the following steps:
(1) a high-temperature high-humidity curing stage, wherein the temperature is 90 ℃, the humidity is 99%, and the time of the stage is 10-15 h.
(2) A medium-temperature curing stage at 65 ℃ and 80% humidity for 3-5 h.
(3) A constant speed drying stage, the temperature is 85 ℃, the humidity is 20%, and the time of the stage is 5 h.
(4) A high temperature drying stage at 85 ℃ and humidity of 0, the time of the stage being 5 h.
And finally, polishing the solidified green plate lugs to be clean, assembling the positive plate lug and the negative plate lug into a battery in a matching way, and carrying out internal formation after acid filling, namely completing the manufacture of the lead-acid storage battery.
Through detection, the 12Ah battery has excellent performance, the initial capacity reaches 13.5Ah, and the 100% DOD discharge cycle life reaches more than 400 times (see figure 5).
Claims (8)
1. A high-performance lead-acid storage battery with recovered lead oxide as an active substance is characterized in that the raw materials in the positive electrode of the lead-acid storage battery comprise recovered lead oxide, metallic lead, tetrabasic lead sulfate, a battery additive, a binder, paste acid and water, the recovered lead oxide is α -PbO of red tetragonal crystal or/and β -PbO of yellow orthorhombic crystal, the oxidation degree of the recovered lead oxide is 100%, and the recovered lead oxide is single-component pure lead oxide;
wherein the mass sum of the recovered lead oxide, the metallic lead, the tetrabasic lead sulfate and the battery additive is 100 percent, wherein the metallic lead accounts for 1 to 20 percent, the tetrabasic lead sulfate accounts for 1 to 8 percent, and the battery additive accounts for 0 to 2 percent; the preparation method of the high-performance lead-acid storage battery by recovering lead oxide as an active substance comprises the following steps:
(1) adding the recovered lead oxide powder, the metallic lead, the tetrabasic lead sulfate and the electrolytic cell additive into a paste mixer at the temperature of 50-95 ℃ and uniformly mixing;
(2) adding boiled deionized water accounting for 10-11.5% of the total material mass in the step (1) into the step (1), and stirring for 8-15min to obtain a lead mixture;
(3) adding the binder into the cream acid, uniformly mixing, slowly adding the mixed cream acid solution into the lead mixture obtained in the step (2), and adding the cream acid solution within 15-20 min;
(4) after the cream acid solution is added and the stirring is continued for 5-10min, measuring the apparent density, wherein the apparent density is required to be more than 4.45g/mL, otherwise, continuing stirring until the standard is reached; finally, coating the standard-reaching lead plaster on a positive grid, and then curing by adopting a high-temperature curing process;
(5) and finally, polishing the solidified green plate lugs to be clean, assembling the positive plate lug and the negative plate lug into a battery in a matching way, and carrying out internal formation after acid filling, namely completing the manufacture of the lead-acid storage battery.
2. A high-performance lead-acid storage battery using recovered lead oxide as an active material according to claim 1, characterized in that the recovered lead oxide has a particle size of 1 to 20 μm and an apparent density of 0.6 to 1.5 g/mL.
3. A high performance lead-acid battery with recovered lead oxide as active material according to claim 1, characterized in that the metallic lead is elemental lead powder with a particle size of 1-10 μm.
4. A high performance lead-acid battery for the recovery of lead oxide as an active material according to claim 1, characterized in that said tetrabasic lead sulphate has a particle size of 10-100 μm.
5. A high performance lead-acid battery for recovering lead oxide as an active material according to claim 1, wherein the binder is at least one selected from PTFE emulsion, CMC, PVDF emulsion.
6. A high-performance lead-acid battery for recovering lead oxide as an active material according to claim 1, characterized in that the diacidic acid is a sulfuric acid solution and has a diacidic acid density of 1.4g/cm3The adding mass of the cream-mixing acid is 4-8% of the total mass of the materials in the step (1), and the binder is 0.1-1% of the total mass of the materials in the step (1).
7. A high performance lead-acid battery for the recovery of lead oxide as the active material according to claim 1, characterized in that the positive electrode of the lead-acid battery is subjected to a high temperature curing process comprising the following stages:
(1) a high-temperature high-humidity curing stage, wherein the temperature is 80-90 ℃, the humidity is 95-100%, and the time of the stage is 10-15 h;
(2) a medium-temperature curing stage, wherein the temperature is 60-70 ℃, the humidity is 80-90%, and the time of the stage is 3-5 h;
(3) a constant-speed drying stage, wherein the temperature is 80-90 ℃, the humidity is 0-20%, and the time of the stage is 5 hours;
(4) a high-temperature drying stage, wherein the temperature is 80-90 ℃, the humidity is 0, and the time of the high-temperature drying stage is 5 hours.
8. A high performance lead-acid battery for recovering lead oxide as an active material according to claim 1, further comprising the steps of: (5) and finally, polishing the solidified positive plate electrode lugs to be clean, assembling the positive plate electrode lug and the negative plate electrode lug into a battery in a matching way, and carrying out internal formation after acid filling, namely completing the manufacture of the lead-acid storage battery.
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| CN109585788B (en) * | 2018-11-20 | 2021-12-10 | 天能电池(芜湖)有限公司 | Curing process for 90 ℃ high-energy battery grid |
| CN109585900A (en) * | 2018-11-30 | 2019-04-05 | 天能电池(芜湖)有限公司 | A kind of long-life formula battery curing process |
| CN112945870B (en) * | 2019-11-26 | 2022-12-09 | 苏州阿特斯阳光电力科技有限公司 | Detection method and application of lead content |
| CN112687849A (en) * | 2020-12-28 | 2021-04-20 | 重庆万里新能源股份有限公司 | Efficient curing process for polar plate |
| CN113823769A (en) * | 2021-07-26 | 2021-12-21 | 安徽理士电源技术有限公司 | Method for curing lead-acid storage battery pole plate |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244261A (en) * | 2010-05-20 | 2011-11-16 | 江苏双登集团有限公司 | Anode active material of valve-regulated sealed lead acid battery for communication and preparation and curing method thereof |
| CN102610802A (en) * | 2012-03-22 | 2012-07-25 | 株洲冶炼集团股份有限公司 | Lead-acid storage battery and anode material thereof |
| CN102856535A (en) * | 2011-07-02 | 2013-01-02 | 湖南丰日电源电气股份有限公司 | High-temperature high-humidity electrode plate curing process |
| CN103014347A (en) * | 2012-12-12 | 2013-04-03 | 北京化工大学 | Method for recycling waste lead-acid cells to directly produce lead oxide |
| CN103184341A (en) * | 2011-12-31 | 2013-07-03 | 深圳市雄韬电源科技股份有限公司 | Method for recovering disused lead plaster to prepare superfine lead powder and application of superfine lead powder |
| CN103682331A (en) * | 2013-12-04 | 2014-03-26 | 河南超威电源有限公司 | Positive lead paste of storage battery and preparation method thereof |
| CN103762340A (en) * | 2014-01-14 | 2014-04-30 | 天能集团江苏科技有限公司 | Rapid high-temperature curing drying process of lead-acid storage battery unformed electrode plate |
| CN105206800A (en) * | 2015-08-20 | 2015-12-30 | 东南大学 | Lead-acid cell positive electrode with lead sulfate as active material and method for preparing lead-acid cell through positive electrode |
| CN105226343A (en) * | 2015-11-02 | 2016-01-06 | 扬州大学 | With the lead-containing compounds in waste lead accumulator for the method for positive plate of lead storage battery prepared by raw material |
| CN105355861A (en) * | 2015-11-23 | 2016-02-24 | 江苏海德森能源有限公司 | Preparation method of surface mount lead carbon battery electrode |
| CN105406143A (en) * | 2015-11-02 | 2016-03-16 | 扬州大学 | Method for preparing lead storage battery electrode plate from lead-bearing compound in waste lead storage battery as raw material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU701597B2 (en) * | 1996-03-05 | 1999-02-04 | Canon Kabushiki Kaisha | Process and apparatus for recovering components of sealed type battery |
| CN104868187B (en) * | 2014-02-21 | 2017-06-06 | 北京化工大学 | A kind of method that lead-acid battery cathode lead oxide is directly reclaimed in the cream from scrap lead |
-
2016
- 2016-04-15 CN CN201610237712.4A patent/CN107302118B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244261A (en) * | 2010-05-20 | 2011-11-16 | 江苏双登集团有限公司 | Anode active material of valve-regulated sealed lead acid battery for communication and preparation and curing method thereof |
| CN102856535A (en) * | 2011-07-02 | 2013-01-02 | 湖南丰日电源电气股份有限公司 | High-temperature high-humidity electrode plate curing process |
| CN103184341A (en) * | 2011-12-31 | 2013-07-03 | 深圳市雄韬电源科技股份有限公司 | Method for recovering disused lead plaster to prepare superfine lead powder and application of superfine lead powder |
| CN102610802A (en) * | 2012-03-22 | 2012-07-25 | 株洲冶炼集团股份有限公司 | Lead-acid storage battery and anode material thereof |
| CN103014347A (en) * | 2012-12-12 | 2013-04-03 | 北京化工大学 | Method for recycling waste lead-acid cells to directly produce lead oxide |
| CN103682331A (en) * | 2013-12-04 | 2014-03-26 | 河南超威电源有限公司 | Positive lead paste of storage battery and preparation method thereof |
| CN103762340A (en) * | 2014-01-14 | 2014-04-30 | 天能集团江苏科技有限公司 | Rapid high-temperature curing drying process of lead-acid storage battery unformed electrode plate |
| CN105206800A (en) * | 2015-08-20 | 2015-12-30 | 东南大学 | Lead-acid cell positive electrode with lead sulfate as active material and method for preparing lead-acid cell through positive electrode |
| CN105226343A (en) * | 2015-11-02 | 2016-01-06 | 扬州大学 | With the lead-containing compounds in waste lead accumulator for the method for positive plate of lead storage battery prepared by raw material |
| CN105406143A (en) * | 2015-11-02 | 2016-03-16 | 扬州大学 | Method for preparing lead storage battery electrode plate from lead-bearing compound in waste lead storage battery as raw material |
| CN105355861A (en) * | 2015-11-23 | 2016-02-24 | 江苏海德森能源有限公司 | Preparation method of surface mount lead carbon battery electrode |
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