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WO2011091553A1 - Procédé pour recycler une plaque d'électrode négative de batterie électrique plomb-acide usagée - Google Patents

Procédé pour recycler une plaque d'électrode négative de batterie électrique plomb-acide usagée Download PDF

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Publication number
WO2011091553A1
WO2011091553A1 PCT/CN2010/000136 CN2010000136W WO2011091553A1 WO 2011091553 A1 WO2011091553 A1 WO 2011091553A1 CN 2010000136 W CN2010000136 W CN 2010000136W WO 2011091553 A1 WO2011091553 A1 WO 2011091553A1
Authority
WO
WIPO (PCT)
Prior art keywords
battery
negative electrode
negative
capacity
lead
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2010/000136
Other languages
English (en)
Chinese (zh)
Inventor
张华农
衣守忠
胡金丰
陈宏�
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Center Power Tech Co Ltd
Original Assignee
Shenzhen Center Power Tech Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Center Power Tech Co Ltd filed Critical Shenzhen Center Power Tech Co Ltd
Priority to CN201080014440.2A priority Critical patent/CN102396099B/zh
Priority to PCT/CN2010/000136 priority patent/WO2011091553A1/fr
Publication of WO2011091553A1 publication Critical patent/WO2011091553A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M10/06—Lead-acid accumulators
    • 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
    • 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

Definitions

  • the present invention relates to an electrode for a lead-acid battery, and more particularly to the regeneration of useful components of a used battery, and more particularly to a method for recycling a waste lead-acid battery negative plate.
  • the power battery is known as the "engine” of electric vehicles, and it is the most concerned. At present, it can be put into mass production, and only the lead-acid battery is acceptable at the cost. According to conservative estimates, global electric bicycle sales in the first half of 2009 were $1,501.71 million. Under normal circumstances, batteries accounted for 20% of their sales price, which means that lead-acid battery sales in the first half of 2009 were about 300.404 million yuan. However, lead-acid batteries, as power batteries for electric vehicles, have a cycle life of only one to two years.
  • lead-acid batteries have another use, which is used as a floating charging backup power source, such as a backup power source for large telecom base stations, banks, solar street lights, and the like.
  • the main mode of life termination of lead-acid batteries for this purpose is the loss of conductivity of the grid corrosion in the plates. Then we will find that the negative plate with the end of cycle life, although the capacity has decreased, but it can still meet the life requirement for the floating charging backup power supply. The grid structure is intact, the corrosion is slight, and the spongy lead has good electrical conductivity. . Since the battery life termination modes are different for these two modes of use, we believe that it is perfectly possible to use a negative life plate of a cycle end-of-life battery to assemble a lead-acid battery for use as a float charger.
  • Chinese patent application CN 101286583A proposes a processing technology for recycling and recycling waste lead-acid batteries, wherein the lead-acid battery after recycling is mechanically opened, the negative plate is taken out, and after being charged and reduced in a dilute sulfuric acid solution, the anti-defense The oxidant is treated and dried.
  • the treated negative electrode plate can be used in combination with or separately with a new positive electrode plate and assembled into a battery.
  • the negative electrode plate needs to be taken out from the battery, placed in a chemical conversion tank, charged in a dilute sulfuric acid solution for reduction, and then washed and dried in an aqueous solution having an antioxidant.
  • This method is similar to the lead-acid battery plate fabrication process, which consumes a large amount of water and produces waste acid and wastewater that are difficult to handle. At the same time, the plates are taken out and welded again in the formation tank, which wastes a lot of manpower.
  • the patent does not classify the recovered batteries, but only uses the cell voltage higher than 1.0V as the standard for normal recovery of batteries. In fact, the cell voltage above 1.0V does not mean that the conductivity of the negative electrode of the battery and the grid structure are mostly intact. It is entirely possible that the battery with partial floating life is terminated. The negative grid is fully corroded and cannot be discharged normally. However, because it still has a small amount of capacity and conductivity, the open circuit voltage can still reach 1.0V or more. It is clear that a standard with a cell voltage above 1.0V is not reliable.
  • the technical problem to be solved by the present invention is to provide a recycling method for a waste lead-acid battery negative plate by avoiding the above-mentioned deficiencies of the prior art, and solving the prior art, which consumes a large amount of water and is difficult to handle.
  • the waste acid and waste water, and the negative classification of the negative electrode plate make the recovery performance not high.
  • the technical problem is solved by the present invention by adopting the following technical solutions: Providing a recycling method for a waste lead-acid power battery negative plate, which comprises the following steps in sequence:
  • waste lead-acid batteries are connected in series, and dilute sulfuric acid having a specific gravity of 1.28 ⁇ 1.34 is added to each battery cell, and the added amount is 5 - 20% of the normal acid amount of the battery monomer, to observe the battery separator The top is clearly free acid; and adjust the battery electrolyte to the same 1.28 - 1.32 of the normal battery, and then set aside for 4 - 24 hours.
  • the cut negative plates are then separately transferred to a vacuum-protected vacuum oven in units of volume groups until the moisture content in the vacuum oven is no longer changed.
  • the step B “charges the diluted electrolyte to the desired waste lead-acid battery by a pulse charging method to restore part or all of the battery negative capacity to the original capacity value", including a sub-step: bl
  • the battery is charged at a current of 0.05 to 0.1 times the rated capacity of the battery, and the amount of charge is one to four times the rated capacity of the battery.
  • Step B2 Discharge at a current of 0.05 - 0.1 times the rated capacity of the battery to its allowable termination voltage value. Repeat steps bl and b2 three times until the discharge time of the used lead-acid battery no longer changes significantly.
  • Step C "Discharge the battery at a constant current and record the discharge amount of the negative electrode. When the battery is discharged to an allowable electrical termination voltage, the recorded negative discharge amount is the negative capacitance value of the battery. ", including sub-steps:
  • step F "the negative plate that has been cut is still moved to the vacuum oven with nitrogen protection in each capacity group, until the moisture content in the vacuum oven does not change” : each of the negative plates is baked in a vacuum oven at a temperature of 40'C ⁇ 10 (TC), and the vacuum oven is vacuumed every 10 to 30 minutes to discharge the water in the vacuum oven until the vacuum The moisture content in the oven is no longer changed.
  • the step of "extending the tabs of the dried negative plate to make the length coincide with the positive plate” includes the following steps:
  • R. 6 is the arc radius of the curved joint 06 of the main body of the tab and the negative plate, D, which is the reserved value of the negative electrode, generally takes 1 ⁇ 5 mm;
  • the groove width of the tab ⁇ adapting the width W, of the tab 4 than the groove depth H E3 H comparing thickness 0.5 - second surface; its length L 4 is adapted to the length L to which the tab is to be lengthened;
  • L 3 L - L, -D 2 ,
  • L is the length of the main body of the negative plate to be lengthened, 1 ⁇ is the remaining length of the ear in step gl; D 2 lead reserve value, taking l ⁇ 3mm;
  • the capacity of the positive electrode plate in the positive electrode plate in which the current capacity of the negative electrode plates of the respective capacity groups is selected in the step G is 90 to 95% of the existing capacity of the negative electrode plate.
  • the allowable termination voltage is: 6. 8 - 5. 4V for a 6V battery and 9. 6 - 10. 8V for a 12V battery.
  • the reference electrode is a cadmium electrode for bismuth or a mercury sulphate electrode.
  • the invention has the following advantages: the capacity recovery process is performed on the recovered battery, and the negative electrodes of different capacities are classified, and the corresponding positive electrode can be conveniently selected for matching to form a battery with reasonable design. .
  • the anode is not required to be subjected to an oxidation treatment, and no new wastewater or waste acid is produced.
  • FIG. 1 is a schematic flow chart of a preferred embodiment of the present invention
  • 2 is a diagram showing the negative electrode 01 and the lead strip 03 placed in the IHJ slot mold in a preferred embodiment of the present invention.
  • Figure 3 is a cross-sectional view of the A-A of Figure 2;
  • Figure 4 is a cross-sectional view of B-B in Figure 2.
  • a preferred embodiment of the recycling method for the waste lead-acid battery of the present invention is as follows:
  • waste lead-acid batteries are connected in series, and dilute sulfuric acid having a specific gravity of 1.28 - 1.34 is added to each battery cell, and the added amount is 5 - 20% of the normal acid amount of the battery monomer, to observe the battery separator The top is clearly free acid; and adjust the battery electrolyte to the same 1.28 - 1.32 of the normal battery, and then set aside for 4 ⁇ 24 hours.
  • the cut negative plates are still separately transferred to a nitrogen-protected vacuum oven in units of volume groups until the moisture content in the vacuum oven is no longer changed.
  • the negative electrode plate elongated by the tabs is formed into a complete negative electrode group by a bus bar by welding or casting, and a positive electrode group composed of the positive electrode sheets is matched to form a new lead.
  • Acid battery. The step B "charges the diluted electrolyte to the desired waste lead-acid battery by a pulse charging method to restore part or all of the battery negative capacity to the original capacity value", including a sub-step: bl Charging the battery with a current of 0.05 - 0.1 times the rated capacity of the battery, the amount of charge is the battery rating One to four times the capacity;
  • Step B2 Discharge at a current of 0.05 - 0.1 times the rated capacity of the battery to its allowable termination voltage value. Repeat steps bl and b2 for 1 ⁇ 3 times until the discharge time of the used lead-acid battery no longer changes significantly.
  • Step C "discharge the battery at a constant current, and record the discharge amount of the negative electrode. When the battery is discharged to the discharge termination voltage, the recorded negative discharge amount, that is, the negative electrode capacity value of the battery", Including sub-steps:
  • the ratio of the relative voltage of the reference electrode and the negative electrode plate is recorded, and then discharged at a constant current, which is 0. 05 - 0. 5 times, when the allowable termination is reached.
  • the capacity of the negative electrode discharged from the single cell is calculated, which is the current capacity of the negative electrode of the battery.
  • the reference electrode in this example is a cadmium electrode or a mercury sulphate electrode.
  • step F the negative electrode plate is moved to a nitrogen-protected vacuum oven for baking until the moisture content in the vacuum oven is no longer changed. That is: the negative plate is at temperature 4 (The TC- ⁇ vacuum oven was flooded and the vacuum oven was evacuated every 10-30 minutes to drain the water in the vacuum oven until the moisture content in the vacuum oven no longer changed.
  • step G "the length of the tab of the dried negative electrode plate is lengthened to be the same as the length of the positive electrode plate", including the steps of:
  • R. 6 is the arc radius of the arc joint 02 of the tab 02 and the negative plate main body 01
  • D which is the reserved value of the negative pole, generally takes 1 - 5
  • the width W 4 of the groove 0401 is adapted to the width W of the tab 02,
  • the depth H 4 of the groove 0401 is higher than the thickness H of the tab 02 by 0.5 to 2 faces; and the length L 4 thereof coincides with the length L to which the tab 02 is to be elongated.
  • L is the length to which the tab 02 of the negative plate body 01 is to be lengthened
  • 1 ⁇ is the remaining length of the tab 02 in the step gl
  • D 2 is the reserved value of the lead strip, and takes 1 - 3 to let.
  • the tab 02 of the negative plate main body 01 is placed in the groove 0401 of the mold 04, and the lead strip 03 is also placed in the groove 0401, so that the lead strip 03 and the groove 0401 are The top contact, and the gap 05 between the tab 02 and the lead strip 03 is the same as the lead strip reserve value D 2 .
  • the capacity of the positive electrode plate in the "positive plate with which the existing capacity of the negative electrode plate is selected" in step G is 90 - 95% of the existing capacity of the negative electrode plate, as shown in the following table:
  • the concentration of the electrolyte has been adjusted to the same in step A of the scheme, the amount of sulfuric acid contained in each of the recovered negative plates is the same.
  • the acid specific gravity of each unit cell is also the same. Therefore, it is sufficient to calculate the concentration and amount of sulfuric acid to be added in accordance with the final desired sulfuric acid concentration in combination with the amount of sulfuric acid contained in the negative electrode plate.
  • the allowable termination voltages in this embodiment are: 6. 8 - 5. 4V for a 6V battery and 9. 6 ⁇ 10. 8V for a 12V battery.
  • the lead-acid battery produced by the method of the present invention can be used for various purposes, such as recycling as a power battery, and using it as a floating charging backup power source.
  • the most suitable use case is the floating charging standby power supply, which is a 2.28 - 2.3V/cell, long-term small current charging, only the mode of discharge is occasionally performed.
  • the above-described process is a preferred implementation process of the present invention, and it is within the scope of the present invention to make the usual changes and substitutions of the present invention substantially by those skilled in the art.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

L'invention porte sur un procédé pour recycler des plaques d'électrode négatives de batteries électriques plomb-acide usagées, lequel procédé met en œuvre la connexion série de chaque batterie plomb-acide usagée; l'addition d'acide sulfurique dilué dans chaque batterie; la charge des batteries plomb-acide usagées avec un électrolyte régulé avec une densité désirée dans un mode de charge pulsé afin de récupérer les capacités d'électrodes négatives de batterie à des capacités initiales de façon partielle ou totale; la décharge des batteries à courant constant, et l'enregistrement des capacités actuelles des plaques d'électrode négatives des batteries; la sélection par élimination des plaques d'électrode négatives irrécupérables sur la base des capacités actuelles, et le classement des autres plaques d'électrode négatives en plusieurs groupes sur la base des capacités actuelles; la coupe des plaques d'électrodes négatives vis-à-vis de la barre-bus des batteries groupe par groupe et leur séchage; le choix de plaques d'électrode positives correspondantes en fonction des capacités actuelles de chaque groupe de plaques d'électrode négatives, et l'allongement de la longueur des pattes des plaques d'électrode négatives séchées afin de s'accorder à la longueur des pattes des plaques d'électrode positives; la préparation d'un ensemble de plaques négatives complet à l'aide de la barre-bus par soudage par combustion ou par soudage par coulée; puis la préparation d'une nouvelle batterie plomb-acide avec l'ensemble de plaques négatives et l'ensemble de plaques positives constitué par les plaques d'électrodes positives correspondantes. Les effets bénéfiques de l'invention sont les suivants : la récupération des capacités des batteries recyclées, le classement des plaques d'électrode négatives en différentes capacités de façon à choisir de façon appropriée les plaques d'électrode positives correspondantes de façon à correspondre aux plaques d'électrode négatives, et la formation de batteries avec une configuration raisonnable. Simultanément, l'électrode négative ne nécessite pas un traitement antioxydant, et, par conséquent, des eaux usées ou de l'acide usagé supplémentaires ne sont pas nécessaires dans l'invention.
PCT/CN2010/000136 2010-02-01 2010-02-01 Procédé pour recycler une plaque d'électrode négative de batterie électrique plomb-acide usagée Ceased WO2011091553A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201080014440.2A CN102396099B (zh) 2010-02-01 2010-02-01 废旧铅酸动力电池负极板的回收利用方法
PCT/CN2010/000136 WO2011091553A1 (fr) 2010-02-01 2010-02-01 Procédé pour recycler une plaque d'électrode négative de batterie électrique plomb-acide usagée

Applications Claiming Priority (1)

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PCT/CN2010/000136 WO2011091553A1 (fr) 2010-02-01 2010-02-01 Procédé pour recycler une plaque d'électrode négative de batterie électrique plomb-acide usagée

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103296335A (zh) * 2013-05-03 2013-09-11 超威电源有限公司 蓄电池报废极板回收方法
CN108631018A (zh) * 2018-04-27 2018-10-09 朱伟 一种利用回收资源制备锂离子电池的方法

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US9555386B2 (en) 2014-06-20 2017-01-31 Johnson Controls Technology Company Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries
US9670565B2 (en) 2014-06-20 2017-06-06 Johnson Controls Technology Company Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries
US10062933B2 (en) 2015-12-14 2018-08-28 Johnson Controls Technology Company Hydrometallurgical electrowinning of lead from spent lead-acid batteries
CN106920998B (zh) * 2017-03-22 2019-02-15 超威电源有限公司 利用废旧电池含铅废料制备金属铅的方法
CN112034372A (zh) * 2020-09-04 2020-12-04 超威电源集团有限公司 铅酸电池失效原因检测方法
CN112698211B (zh) * 2020-12-16 2023-05-26 超威电源集团有限公司 一种用于检测蓄电池单片极板容量的方法

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US6730428B1 (en) * 1998-07-24 2004-05-04 T & K Co., Ltd. Method of recycling lead-acid storage battery
CN1496592A (zh) * 2002-02-12 2004-05-12 ���µ�����ҵ��ʽ���� 二次电池的再利用方法
CN101286583A (zh) * 2008-05-22 2008-10-15 潘孝坤 废铅酸蓄电池回收再利用加工工艺
CN101291008A (zh) * 2008-06-03 2008-10-22 北京化工大学 酸式湿法电解回收废铅酸蓄电池铅的方法

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US5789095A (en) * 1995-10-26 1998-08-04 Mitsui Mining & Smelting Co., Ltd. Method of recovering useful materials from spent secondary batteries for electric vehicles
US6730428B1 (en) * 1998-07-24 2004-05-04 T & K Co., Ltd. Method of recycling lead-acid storage battery
CN1496592A (zh) * 2002-02-12 2004-05-12 ���µ�����ҵ��ʽ���� 二次电池的再利用方法
CN101286583A (zh) * 2008-05-22 2008-10-15 潘孝坤 废铅酸蓄电池回收再利用加工工艺
CN101291008A (zh) * 2008-06-03 2008-10-22 北京化工大学 酸式湿法电解回收废铅酸蓄电池铅的方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103296335A (zh) * 2013-05-03 2013-09-11 超威电源有限公司 蓄电池报废极板回收方法
CN108631018A (zh) * 2018-04-27 2018-10-09 朱伟 一种利用回收资源制备锂离子电池的方法
CN108631018B (zh) * 2018-04-27 2020-01-10 贵州中伟资源循环产业发展有限公司 一种利用回收资源制备锂离子电池的方法

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CN102396099A (zh) 2012-03-28

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