CN102747227B - Method for preparing superfine lead oxide by using electrode active materials of wasted lead acid batteries - Google Patents
Method for preparing superfine lead oxide by using electrode active materials of wasted lead acid batteries Download PDFInfo
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- CN102747227B CN102747227B CN201210201272.9A CN201210201272A CN102747227B CN 102747227 B CN102747227 B CN 102747227B CN 201210201272 A CN201210201272 A CN 201210201272A CN 102747227 B CN102747227 B CN 102747227B
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention discloses a method for preparing superfine lead oxide by using electrode active materials of wasted lead acid batteries. According to the invention, the superfine powder disclosed herein can be directly used for producing new lead acid batteries by the prior art, lead acid batteries can be recycled, and the method is a production technology which accords with circular economy principles. The method can eliminate the pollution generated by the waste lead acid batteries at the source, has the characteristics of low production cost and high economic benefit, and is suitable for existing lead acid battery production enterprises to let practical and affordable lead acid batteries be used with persistence and reassurance.
Description
Technical field
The present invention relates to a kind of cyclic production technical field of lead-acid cell, be specifically related to there is the method for ultra-fine yellow lead oxide powder for the corresponding lead-acid cell electrode of high electrochemical activity with waste lead acid battery positive pole and negative active core-shell material preparation.
Background technology
Lead-acid cell is a kind of rechargeable cell, has low price, safeguards demand simple, that can meet multiple user, has obtained application widely in uninterruptible power supply, electromobile, automobile starting power supply, electric bicycle.In lead-acid cell, contain in a large number to environment and the harmful lead of human body, also contain the sulfuric acid of some severe corrosives, arrive after work-ing life, as do not processed well, can produce serious environmental pollution.
In order to reduce lead-acid cell resource utilization process required energy consumption and material consumption, thereby reduce the environmental influence that resource utilization process produces, we carried out the cyclic production research of lead-acid cell from 2009.Its core concept is that not take the metallic element extracting be wherein target to resource utilization process, but by various electrode materialss in old and useless battery by physical method for separation out, then by its positive active material and negative electrode active material through minimum chemical treatment, obtain being respectively directly used in and produce new secondary battery electrode material.The benefit of doing like this mainly contains, and chemical treatment is farthest reduced, and has therefore farthest reduced risk of environmental pollution.Secondly, energy and material consumption reduces greatly, and remarkable in economical benefits increases.The 3rd, can realize the cyclic production of secondary cell.
We disclose and have used electrochemical method that the material electrolysis in positive plate and negative plate is formed to Pb and PbO in granted patent ZL 200910024467.9
2method; In patent application 201110172238.9, disclose the PbO in positive plate
2and PbSO
4by medium and low temperature chemical reduction, be converted into PbO and Pb, by the Pb in negative plate and PbSO
4by medium and low temperature atmospheric oxidation, be converted into the method for PbO and Pb.This patent discloses a kind of novel method of preparing the ultra-fine yellow lead oxide of nano-micro level from waste lead acid battery negative or positive electrode active material.
In the literature, existing people reports and uses waste lead acid battery active substance or its model substance to prepare the method for ultra-fine lead oxide as lead sulfate, plumbic oxide, also has the method for using other pure lead compound to prepare ultra-fine lead oxide.But, existing research does not separate positive electrode active materials and negative active core-shell material, does not manage to control the structure of plumbous oxide yet.For example, Australia Wollongong university has reported use solubility lead salt during 2001 ~ 2004 years, as lead nitrate is prepared a series of researchs of the plumbous oxide of nano-micro level, wherein some data also illustrates that performance is better than the performance of the leaded plumbous oxide of industrial preparation (Journal of Alloys and Compounds 2001,327 (1-2): 141-145; Journal of Applied Electrochemistry 2004,34 (11): 1127-1133).Univ cambridge uk had once reported a kind of technique (Hydrometallurgy, 2009,95 (1-2): 53-60 that utilize citric acid wet-method ultra-fine lead oxide powder for 2009; 95 (1-2): 82-86).This technique is used citric acid and Trisodium Citrate to process lead sulfate, plumbous oxide and the plumbic oxide in waste and old electrode materials, makes them all change into lead citrate, then passes through low-temperature bake (300～500 ° of C) and obtains product.Afterwards, the Yang Jiakuan study group of the Central China University of Science and Technology makes further research this technique, also reported the corresponding research (Hydrometallurgy, 2012.doi:10.1016/j.hydromet.2012.01.006) of using waste lead acid battery active material.A subject matter of citric acid technique is as above, when processing plumbic oxide, need add hydrogen peroxide as reductive agent, and the citric acid of use and Trisodium Citrate are all somewhat expensive.Therefore Technical Economy has problems.
Summary of the invention
The object of this invention is to provide a kind of novel method of preparing the nano-micro level yellow lead oxide powder (or claiming ultra-fine PbO powder) of high electrochemical activity from waste lead acid battery negative or positive electrode active material.
The technical solution used in the present invention is: a kind of electrode active material with waste lead acid battery is prepared the method for ultra-fine yellow lead oxide, and the method comprises the steps:
1) waste lead acid battery is cut from top, separation obtains positive plate and negative plate, electrolytic solution sulfuric acid, plastic casing;
2) by current rinse, ultrasonic or mechanical impacting process respectively positive plate and negative plate, obtains positive powder (positive active material powder), negative pole powder (negative electrode active material powder), anodal lead alloy grid, negative electrode lead alloy grid;
3) described positive powder and a kind of reaction medium and a kind of reductive agent are mixed in an airtight reactor, under stirring, be no more than 24 hours being no more than reaction under 300 ° of C conditions;
4) aqueous solution that adds pattern and/or constitution controller, carbonate or oxyhydroxide in the suspension liquid obtaining to step 3), at the temperature higher than 200 ° of C not, continue stirring reaction and be no more than 24 hours, then filter, then wash the vitriol of removing solid product absorption with water;
5) by step 4) gained solid after preheating and drying in 200 ~ 500 ° of C heating, obtain having the lead-acid cell of good electrochemical activity anodal for ultra-fine yellow lead oxide powder;
6) described negative pole powder is mixed in reactor with a kind of reaction medium, a kind of morphology control agent and/or a kind of constitution controller, under stirring, reaction is no more than 24 hours at not higher than the temperature of 200 ° of C, the suspension liquid obtaining is filtered, wash the vitriol of removing solid product with water;
7) solid step 6) being obtained does not heat at the temperature higher than 500 ° of C after preheating and drying in air atmosphere; Or, the solid that also step 6) can be obtained is dissolved in nitric acid or hot hydrochloric acid, then use the aqueous solution of alkali metal hydroxide or ammonia to process, then under the condition existing at morphology control agent and/or constitution controller in an encloses container stirring reaction, its temperature of reaction is not higher than 300 ° of C, and the time is no more than 24 hours; Can obtain having the ultra-fine yellow lead oxide powder for lead-acid cell negative pole of good electrochemical activity.
As preferably, the reaction medium in described step 3) is the aqueous solution of pure water or acid and alkali substance.Described acid and alkali substance is sulfuric acid, hydrochloric acid, soluble carbonate salt, solubility oxyhydroxide or ammonia etc.Described reductive agent is can be by PbO
2material, especially sulphite, nitrite, organic alcohols, aldehydes and the acids etc. of reduction.
As preferably, the reaction medium in described step 6) is to contain any soluble carbonate salt, particularly its sodium salt and ammonium salt; Or the aqueous solution of any solubility oxyhydroxide, particularly sodium hydroxide and ammoniacal liquor.
As preferably, described morphology control agent and constitution controller are any organism or inorganicss with this kind of effect, and their guarantee that the yellow lead oxide of gained has definite pattern, structure and granular size.
Beneficial effect: the inventive method will be disassembled the negative or positive electrode active material admixture that process obtains and forms the PbO ultra-fine micropowder of the nano-micro level with specific morphology and ad hoc structure through less chemical process through a series of, this powder can directly be pressed the new lead-acid cell of existing explained hereafter, it is a kind of production technology that meets recycling economy principle, this technology can reduce the Pollution risk that waste lead acid battery resource utilization process produces greatly, there is production cost low, the feature that economic benefit is high, being suitable for existing lead-acid cell manufacturing enterprise uses, make the inexpensive lead-acid cell can be by lasting relieved use.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Positive powder and the negative pole powder being applicable to the waste lead acid battery of gentle mechanical means separation of the present invention.Concrete steps are:
1), by waste lead acid battery gentle cutting from top, separation obtains positive plate and negative plate, electrolytic solution sulfuric acid, plastic casing.By high velocity flow rinse, ultrasonic or mechanical impacting process respectively positive plate and negative plate, obtains positive powder, negative pole powder, anodal lead alloy grid, negative electrode lead alloy grid.
2) under the condition negative pole powder obtaining being existed at pattern and constitution controller with carbonate or oxyhydroxide desulfurization, then under 200 ° of C ~ 500 ° C, in air, heating makes its partial oxidation and thermolysis, produces the negative pole powder of the nano-micro level with good electrochemical activity.The contingent chemical reaction of this process has (take carbonate as sweetening agent time be example):
Sweetening process: PbSO
4+ CO
3 2-=PbCO
3+ SO
4 2-
Thermolysis/oxidising process: PbCO
3=PbO+CO
2
2Pb+O
2=2PbO
3) by the positive powder obtaining organic or inorganic reductive agent reduction for ° C 100 ° of C ~ 300 under the condition of carbonate or oxyhydroxide, pattern and constitution controller existence.The solid matter obtaining is through desulfurization, and then washing is removed after sulfate ion, proceeds to process furnace.In process furnace, this solid matter is dry first at a lower temperature, is then warming up under 200 ° of C ~ 500 ° C and heats and make its thermolysis in air, produces the positive powder of the nano-micro level with good electrochemical activity.The contingent chemical reaction of this process has (take methyl alcohol as reductive agent, sulfuric acid as medium, carbonate as sweetening agent time be example):
Reduction process: 3PbO
2+ CH
3oH+3H
2sO
4=3PbSO
4+ CO
2+ 5H
2o
Sweetening process: PbSO
4+ CO
3 2-=PbCO
3+ SO
4 2-
Thermal decomposition process: PbCO
3=PbO+CO
2
Described carbonate can be any soluble carbonate salt, particularly its sodium salt and ammonium salt; Oxyhydroxide can be any solubility oxyhydroxide, particularly sodium hydroxide and ammoniacal liquor.
Described reductive agent can be any organic reducing substances, particularly methyl alcohol, formaldehyde and formic acid.
Described crystallization and morphology control agent can be any auxiliary agents that contributes to form the plumbous oxide of specific crystal formation and pattern.
1. the treatment process of negative pole powder
Embodiment 1: use sodium hydroxide desulfurization, then calcination in air
The sodium hydroxide solution that is 0.5 ~ 3.0mol/L in the concentration that contains a small amount of sodium-chlor by the negative pole powder obtaining from waste lead acid battery is processed under ~ 100 ° of C conditions, makes PbSO in negative pole powder
4all change into fine Pb (OH)
2.
After getting desulfurization, negative pole powder is placed in crucible, and then in electric furnace, 200 ° of C ~ 500, ° C heats 1 ~ 4h, can obtain the PbO micro mist needing.
Embodiment 2: use volatile salt desulfurization, then calcination in air
The sal volatile that is 0.5 ~ 3.0mol/L in the use concentration that contains polyvinylpyrrolidone by the negative pole powder obtaining from waste lead acid battery is processed under ~ 50 ° of C conditions, makes PbSO in negative pole powder
4all change into fine PbCO
3.
After getting desulfurization, negative pole powder is placed in crucible, and then 200 ° of C ~ 500 ° C heating 1 ~ 4h in electric furnace, can obtain the PbO micro mist needing.
Embodiment 3: use volatile salt desulfurization, be then dissolved in hydrochloric acid, then precipitate with sodium hydroxide
The sal volatile that is 0.5 ~ 3.0mol/L in concentration by the negative pole powder obtaining from waste lead acid battery is processed under ~ 50 ° of C conditions, makes PbSO in negative pole powder
4the PbCO all changing into
3.All sulfate radicals are removed in washing.
In a hydrothermal reaction kettle by the PbCO obtaining
380 ° of C left and right, be dissolved in hydrochloric acid, then to solution, add ammoniacal liquor.The temperature of solution in reactor is increased to 180 ° of C, is incubated 0.5 ~ 4 hour, can obtain the PbO micro mist needing.
2. the treatment process of positive powder
Embodiment 4: with methyl alcohol, in sulfuric acid medium, reduce, then use volatile salt desulfurization
First, the positive powder obtaining from waste lead acid battery is added and contained polyvinylpyrrolidone, excessive methanol and sulphur aqueous acid, sealed reactor, under 120 ° of C ~ 180 ° C stirs, reaction is no more than 24 hours.Cooling reactor makes pressure decreased to normal pressure, removes by filter liquid.Then adding by concentration is that 0.5 ~ 3.0mol/L carbonate (ammonium salt or sodium salt) solution is done desulfurization processing, makes wherein PbSO
4all change into PbCO
3.All vitriol is removed in washing.
The solid obtaining moves into crucible, calcines 0.5 ~ 4h and can obtain ultra-fine lead oxide powder in retort furnace under 200 ° of C ~ 500 ° C.
Embodiment 5: with the Reduction of methanol that contains sulfuric acid, then use volatile salt desulfurization
First, the positive powder obtaining from waste lead acid battery is added to excessive methyl alcohol, add enough sulfuric acid, sealed reactor, under 120 ° of C ~ 300 ° C stirs, reaction is no more than 24 hours.Cooling reactor makes pressure decreased to normal pressure, removes by filter all liquid.Then adding concentration is that 0.5 ~ 3.0mol/L carbonate (ammonium salt or sodium salt) solution is done desulfurization processing, makes PbSO
4all change into PbCO
3.All vitriol is removed in washing.
The solid obtaining moves into crucible, calcines 0.5 ~ 4h and can obtain ultra-fine lead oxide powder in retort furnace under 200 ° of C ~ 500 ° C.
Embodiment 6: with S-WAT, in alkaline medium, reduce, then thermolysis
First, the positive powder obtaining is added the aqueous solution of the excessive sodium hydrate that contains a small amount of sodium-chlor, enough S-WATs from waste lead acid battery, sealed reactor, under 120 ° of C ~ 300 ° C stirs, reaction is no more than 24 hours.Cooling reactor makes pressure decreased to normal pressure, removes by filter liquid.Then with water purification washing, remove all vitriol.
The solid obtaining moves into crucible, calcines 1 ~ 4h and can obtain ultra-fine lead oxide powder in retort furnace under 200 ° of C ~ 500 ° C.
It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.In the present embodiment not clear and definite each integral part all available prior art realized.
Claims (2)
1. with the electrode active material of waste lead acid battery, prepare a method for ultra-fine yellow lead oxide, it is characterized in that: the method comprises the steps:
1) waste lead acid battery is cut from top, separation obtains positive plate and negative plate, electrolytic solution sulfuric acid, plastic casing;
2) by current rinse, ultrasonic or mechanical impacting process respectively positive plate and negative plate, obtains positive powder, negative pole powder, anodal lead alloy grid, negative electrode lead alloy grid;
3) described positive powder and a kind of reaction medium and a kind of reductive agent are mixed in an airtight reactor, under stirring, be no more than 24 hours being no more than reaction under 300 ° of C conditions;
4) aqueous solution that adds pattern and/or constitution controller, carbonate or oxyhydroxide in the suspension liquid obtaining to step 3), at the temperature higher than 200 ° of C not, continue stirring reaction and be no more than 24 hours, then filter, then wash the vitriol of removing solid product absorption with water;
5) by step 4) gained solid after preheating and drying in 200～500 ° of C heating, obtain having the lead-acid cell of good electrochemical activity anodal for ultra-fine yellow lead oxide powder;
6) described negative pole powder is mixed in reactor with a kind of reaction medium, a kind of morphology control agent and/or a kind of constitution controller, under stirring, reaction is no more than 24 hours at not higher than the temperature of 200 ° of C, the suspension liquid obtaining is filtered, wash the vitriol of removing solid product with water;
7) solid step 6) being obtained does not heat at the temperature higher than 500 ° of C after preheating and drying in air atmosphere; Or, the solid that also step 6) can be obtained is dissolved in nitric acid or hot hydrochloric acid, then use the aqueous solution of alkali metal hydroxide or ammonia to process, then under the condition existing at morphology control agent and/or constitution controller in an encloses container stirring reaction, its temperature of reaction is not higher than 300 ° of C, and the time is no more than 24 hours; Can obtain having the ultra-fine yellow lead oxide powder for lead-acid cell negative pole of good electrochemical activity;
Reaction medium in described step 3) is the aqueous solution of pure water or acid and alkali substance;
Described acid and alkali substance is sulfuric acid, hydrochloric acid, soluble carbonate salt, solubility oxyhydroxide or ammonia;
Reductive agent in described step 3) is sulphite, nitrite, organic alcohols, aldehydes and acids;
Reaction medium in described step 6) is to contain any soluble carbonate salt, or the aqueous solution of any solubility oxyhydroxide.
2. the electrode active material with waste lead acid battery according to claim 1 is prepared the method for ultra-fine yellow lead oxide, it is characterized in that: described morphology control agent and constitution controller are organism or the inorganicss that the yellow lead oxide of any assurance gained has definite pattern, structure and granular size.
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|---|---|---|---|---|
| CN103014347B (en) * | 2012-12-12 | 2014-12-03 | 北京化工大学 | Method for recycling waste lead-acid cells to directly produce lead oxide |
| 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 |
| CN104862481A (en) * | 2014-02-21 | 2015-08-26 | 超威电源有限公司 | Recycling method of waste material containing lead oxide |
| CN104393364B (en) * | 2014-11-13 | 2017-07-14 | 张家港智电芳华蓄电研究所有限公司 | A kind of method for preparing PbO from the direct wet method of waste lead acid battery |
| CN104953192A (en) * | 2015-06-12 | 2015-09-30 | 河北师范大学 | Preparation method of Pb-containing lead-acid battery negative electrode additive |
| CN105441686A (en) * | 2016-01-06 | 2016-03-30 | 湘潭大学 | Reducing method for lead dioxide in waste lead plaster |
| CN106587140B (en) * | 2016-11-03 | 2017-11-24 | 华东师范大学 | A kind of method for preparing nano oxidized lead powder using waste and old leaded scolding tin |
| CN106711531A (en) * | 2016-12-21 | 2017-05-24 | 东南大学 | Method for preparing basic lead sulfates from PbO and producing lead-acid battery from basic lead sulfates |
| CN107164636B (en) * | 2017-05-27 | 2019-03-26 | 湘潭大学 | A kind of method that high-purity lead oxide is recycled in waste lead acid battery processing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ183268A (en) * | 1976-02-19 | 1978-09-20 | Gould Inc | Process for recycling junk lead-acid batteries comprising the formation of lead carbonate lead monoxide |
| US4229271A (en) * | 1979-05-24 | 1980-10-21 | Rsr Corporation | Method of recovering lead values from battery sludge |
| CN1248801A (en) * | 1999-08-31 | 2000-03-29 | 沈阳环境科学研究所 | Technology for cleaning and recovering lead from waste accumulator |
| CN1258753A (en) * | 2000-01-19 | 2000-07-05 | 过康民 | Production of regenerated lead, red lead and lead nitrate with waste lead-acid accumulator |
| CN1303234C (en) * | 2004-03-02 | 2007-03-07 | 环境保护危险废物处置工程技术(沈阳)中心 | Environmental protection method for extracting lead in waste storage battery |
| GB0622249D0 (en) * | 2006-11-08 | 2006-12-20 | Univ Cambridge Tech | Lead recycling |
| CN101514395B (en) * | 2009-03-31 | 2010-11-10 | 大连物华天宝科技发展有限公司 | Method for recovering lead oxide by waste lead-acid storage battery |
| CN101624211B (en) * | 2009-04-27 | 2011-03-16 | 北京信息科技大学 | Method for preparing lead hydroxide nano-rod based on liquid-phase chemical reaction |
| CN101712487B (en) * | 2009-10-29 | 2012-07-11 | 无锡润鹏复合新材料有限公司 | Method for preparing beta-type lead dioxide nanometer particles |
| CN102263309B (en) * | 2011-06-24 | 2013-07-31 | 东南大学 | Recycle method of waste lead-acid cell |
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Effective date of registration: 20140930 Address after: 225600, Gaoyou Town, Jiangsu City, Gaoyou province Yangzhou industrial concentration area Patentee after: Jiangsu Huafu Storage New Technology Co., Ltd. Patentee after: Southeast University Address before: 211103, No. 5, RT Mart Road, Jiangning District, Jiangsu, Nanjing Patentee before: Southeast University |