WO2011079409A1 - Procédé de recyclage et de réutilisation de batterie d'alimentation au phosphate de fer et de lithium usée - Google Patents

Procédé de recyclage et de réutilisation de batterie d'alimentation au phosphate de fer et de lithium usée Download PDF

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Publication number
WO2011079409A1
WO2011079409A1 PCT/CN2009/001570 CN2009001570W WO2011079409A1 WO 2011079409 A1 WO2011079409 A1 WO 2011079409A1 CN 2009001570 W CN2009001570 W CN 2009001570W WO 2011079409 A1 WO2011079409 A1 WO 2011079409A1
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WO
WIPO (PCT)
Prior art keywords
battery
iron phosphate
electrode sheet
lithium iron
positive electrode
Prior art date
Application number
PCT/CN2009/001570
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English (en)
Chinese (zh)
Inventor
胡金丰
张华农
衣守忠
涂继军
Original Assignee
深圳市雄韬电源科技股份有限公司
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 深圳市雄韬电源科技股份有限公司 filed Critical 深圳市雄韬电源科技股份有限公司
Priority to CN200980100912.3A priority Critical patent/CN102017276B/zh
Priority to PCT/CN2009/001570 priority patent/WO2011079409A1/fr
Publication of WO2011079409A1 publication Critical patent/WO2011079409A1/fr

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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
    • 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 a secondary battery, and more particularly to the regeneration of useful components of a waste battery, and more particularly to a recycling method of a waste lithium iron phosphate power battery.
  • BACKGROUND OF THE INVENTION With the development of the electric vehicle industry, the demand for high-energy power batteries has rapidly increased. Recently, the lithium iron phosphate battery is the most representative one, which has good safety, high energy consumption and long service life, and has reached 5-7 years. With the development of the lithium iron phosphate battery industry, end-of-life batteries will gradually be withdrawn, and how to dispose of these used batteries will be an important issue.
  • lithium-ion secondary batteries used in mobile phones and personal portable terminals power batteries generally have higher single-cell energy storage, mostly in the range of 30 to 700 Wh, and even some reach 10 kWh, and lithium ion secondary to traditional small personal portable terminals. Compared to the battery's 1 - 8 Wh, the battery is nearly 100 times more bulky and bulky. Moreover, the lithium iron phosphate power battery is expensive, and is more than 0. 5 USD/Wh. Naturally, the residual value of a single used battery is also unmatched by a small lithium ion secondary battery. A lithium iron phosphate power battery, its positive electrode sheet accounts for about 30% of the total cost, which means that the value of a single lithium iron phosphate battery positive electrode sheet is 4 - 110 USD.
  • the liquid solvent is a small molecule organic substance, such as carbonate, which is directly discarded without treatment. Once the electrolyte leaks, it will pollute the environment and even cause fire.
  • the lithium iron phosphate battery is excellent in safety but in extreme conditions. Under impact, such as impact, short circuit or high temperature, there is a potential danger of burning or explosion. Recycling and regeneration of end-of-life lithium iron phosphate power batteries is necessary and necessary for economic, environmental, and safety reasons.
  • Lithium iron phosphate battery is a kind of lithium ion secondary battery.
  • the recycling of waste small lithium ion secondary battery is usually firstly decomposed by mechanical pressure, and then the active material and foil are incinerated or chemically. The piece is separated from the outer casing.
  • a method for recovering a positive electrode material for a lithium ion battery is to take out the positive electrode sheet and then soak it in a solvent.
  • the solvent is organic or water: the immersed pole piece is divided into two parts. One is a metal current collector, and the other is an active material, and the metal current collector is taken out by filtration or the like. The remaining mixture with the active material is obtained by drying or the like.
  • Another Chinese patent application CN 101383441A discloses "a comprehensive recovery method for a positive electrode waste sheet of lithium iron phosphate battery", which is to mechanically pulverize the recovered lithium iron phosphate positive electrode sheet, and then put the obtained fragments into ⁇ .
  • the high temperature heat treatment is performed in a sintering furnace protected by an oxidizing inert gas, and then the aluminum foil and the active material are separated by mechanical separation or ultrasonic vibration.
  • the active material is then baked at a certain temperature and classified and recovered.
  • “Clean Process of Recovering Metals from Wa ter Lithium Iron Equipment” (a non-contaminating method for recovering metals from waste lithium ion batteries), which is a method of calcining a battery by US Pat. No. 6,514,311 B1
  • the decomposition is broken, and then the current collector of the battery and the active material are separated by electrolysis, and precious metals are extracted therefrom.
  • the battery is first decomposed by mechanical or incineration, and the active material and the current collector are separated by a chemical solvent.
  • the method has the following disadvantages:
  • lithium iron phosphate is used as a positive electrode active material material for power batteries. It is an olivine structure and its crystal structure is very stable. When lithium ions are embedded and removed, the crystal structure changes little, which determines its long cycle use. life. Both A123 and Va lance claim that their battery cycle life can reach more than 7,000 times. It was also found that the lithium iron phosphate power battery after the end of the cycle of 2000 cycles showed that the lithium iron phosphate positive electrode sheet had a good appearance, and there was no serious active material swelling and falling off, but the negative electrode active material expanded and fell off severely.
  • the technical problem to be solved by the present invention is to provide a recycling method for a waste lithium iron phosphate power battery by avoiding the above-mentioned deficiencies of the prior art.
  • the method of the present invention is based on the characteristics of a lithium iron phosphate electrode, and is not completely used.
  • the method of destroying the positive electrode sheet is to continue to utilize the remaining capacity and life of the recovered positive electrode sheet, and directly combine the lithium iron phosphate positive electrode sheet with the new negative electrode sheet to form a new battery, thereby achieving the purpose of prolonging the service life of the positive electrode sheet.
  • the recovered battery case ' ⁇ is generally steel, polypropylene plastic or aluminum-magnesium alloy. These materials can be reused after simple processing.
  • a method for recycling waste lithium iron phosphate power battery comprising the following steps:
  • cover plate and the battery slot from the glove box, place it in a confined space, and use water or salt to fully decompose and decompose the electrolyte attached to the cover plate and the wall of the battery case.
  • the cover plate and the battery tank of polypropylene PP plastic, steel or aluminum;
  • the dried positive electrode sheet is screened, it is made into a new lithium iron phosphate power battery with the new negative electrode sheet.
  • the step A "completely discharging the waste lithium iron phosphate battery” means: according to the capacity of the lithium iron phosphate battery, a load is connected between the positive electrode and the negative electrode of the battery, and the initial discharge current is controlled in the battery Ah. Between 0.1 and 0.5 times the capacity value, the discharge time is controlled within 2 to 20 hours until the battery voltage drops to zero.
  • the relative humidity in the vacuum glove box is controlled in the range of 0 to 10%.
  • step C means: placing the negative electrode sheet and the separator in a sealed space, spraying with water, and fully dissolving the electrolyte solvent attached to the shell wall; or the cover plate
  • the battery cell is placed in a high temperature chamber with a stainless steel inner tank, and baked in a 25 to 80 ⁇ environment to decompose the electrolyte solvent.
  • the temperature of the "negative electrode sheet subjected to temperature heating" in step D is controlled at 100 400, and the calcination time is controlled at 1 - 12 hours.
  • step F the transfer of the cleaned positive electrode sheet to an oven with a solvent recovery system is carried out. 5 ⁇ 10 ⁇
  • the oven temperature should be 25 ⁇ 200'C, the drying time is 0. 5 - 10 hours.
  • the "positive electrode which has been dried ⁇ selected” means: a positive electrode sheet having no appearance and damage, and the active material peeling off an area not exceeding 5% of its surface area.
  • step G "making a new lithium iron phosphate power battery with a new negative electrode sheet”, further includes the steps of:
  • FIG. 1 is a schematic flow chart of a preferred embodiment of the present invention.
  • FIG. 2 is a circuit diagram showing a complete discharge treatment of a spent lithium iron phosphate battery in a preferred embodiment of the present invention.
  • a preferred embodiment of the recycling method of the waste lithium iron phosphate power battery of the present invention adopts the following steps:
  • cover plate and the battery slot from the glove box, place it in a confined space, and use water or salt to fully decompose and decompose the electrolyte attached to the cover plate and the wall of the battery case.
  • the cover plate and the battery tank of polypropylene PP plastic, steel or aluminum;
  • the positive electrode sheet of the battery cell remaining in the glove box is washed with a carbonate small molecule solvent, acetone or N-methylpyrrolidone, and the LiFP6 lithium salt attached to the surface thereof is washed to the Cleaning solvent;
  • the step A "completely discharging the waste lithium iron phosphate battery” means that: according to the capacity of the lithium iron phosphate battery, a load is connected between the positive electrode and the negative electrode of the battery to control initial discharge.
  • the current is between 0.1 and 0.5 times the capacity of the battery Ah, and the discharge time is controlled within 2 to 20 hours until the battery voltage drops to zero.
  • the relative humidity in the vacuum glove box is controlled in the range of 0-10%.
  • step C means: placing the negative electrode sheet and the separator in a sealed space', spraying with water, causing the electrolyte solvent attached to the shell wall to be fully reacted and decomposed; or the cover
  • the plate and the battery cell are placed in a high temperature chamber with a stainless steel inner tank, and baked at 25 to 80 ° C to decompose the electrolyte solvent.
  • the temperature of the "negative electrode sheet subjected to high temperature calcination" in step D is controlled at 100 to 40 (TC, and the calcination time is controlled at 1 to 12 hours.
  • step F "the positive electrode sheet after washing is transferred to an oven with a solvent recovery system for drying"
  • the oven temperature should be 25 - the drying time is 0.5 - 10 hours.
  • the positive electrode sheet of the ⁇ Honggan is screened means: a positive electrode sheet having no appearance and damage, and the active material falling off an area not exceeding 5% of its surface area.
  • step G "making a new lithium iron phosphate power battery with a new negative electrode sheet”, further includes the steps of:
  • the prepared positive electrode sheet and the graphite negative electrode sheet matched thereto are assembled into a new lithium iron phosphate power battery, and the battery is infused into liquid according to the capacity calculated in steps G1 and G2.
  • 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)
  • Primary Cells (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention porte sur un procédé de recyclage et de réutilisation de batterie d'alimentation au phosphate de fer et de lithium usée. D'abord, ladite batterie au phosphate de fer et de lithium est complètement déchargée, puis elle est déplacée dans la boîte à gants sous vide remplie d'azote; le couvercle de la batterie est ouvert par la force mécanique et le cœur de la batterie est enlevé du contenant de la batterie; ledit couvercle de batterie et ledit contenant de batterie sont enlevés de la boîte à gants sous vide, le couvercle de batterie et la matière plastique en polypropylène, le matériau en acier ou le matériau en aluminium fixé au contenant de batterie sont réutilisés après traitement; puis l'électrode plane négative, le séparateur et l'électrode plane positive sont séparés dans ladite boîte à gants sous vide, ladite électrode plane négative et ledit séparateur étant réutilisés après traitement; puis après nettoyage, séchage et criblage de l'électrode plane positive, elle est assortie à une nouvelle électrode plane négative pour assembler une nouvelle batterie d'alimentation au phosphate de fer et de lithium. L'effet avantageux de cette invention consiste simplement à classer, recycler et réutiliser les diverses parties de la batterie d'alimentation usée sans procédés physiques ou chimiques complexes. En même temps, l'électrode plane positive au phosphate de fer et de lithium recyclée selon cette invention peut être directement utilisée comme électrode plane positive normale sans séparation de la matière active et la feuille d'aluminium, puis le taux d'utilisation efficace de l'électrode plane positive au phosphate de fer et de lithium peut être amélioré.
PCT/CN2009/001570 2009-12-28 2009-12-28 Procédé de recyclage et de réutilisation de batterie d'alimentation au phosphate de fer et de lithium usée WO2011079409A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN200980100912.3A CN102017276B (zh) 2009-12-28 2009-12-28 废旧磷酸铁锂动力电池的回收利用方法
PCT/CN2009/001570 WO2011079409A1 (fr) 2009-12-28 2009-12-28 Procédé de recyclage et de réutilisation de batterie d'alimentation au phosphate de fer et de lithium usée

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2009/001570 WO2011079409A1 (fr) 2009-12-28 2009-12-28 Procédé de recyclage et de réutilisation de batterie d'alimentation au phosphate de fer et de lithium usée

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WO2011079409A1 true WO2011079409A1 (fr) 2011-07-07

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CN102969546B (zh) * 2012-11-01 2016-01-06 中航锂电（洛阳）有限公司 电芯拆解分类回收方法及使用该方法拆解回收电芯的装置
CN103199318A (zh) * 2013-03-07 2013-07-10 上海电气钠硫储能技术有限公司 一种废旧钠硫电池的拆解处理方法
CN103346365B (zh) * 2013-07-22 2015-06-24 田东 一种从废旧锂离子电池中对负极材料循环再生利用的方法
CN103367839B (zh) * 2013-07-22 2015-12-02 深圳市斯诺实业发展有限公司 一种从废旧锂离子电池中回收分离正极极片的方法
CN103413991B (zh) * 2013-09-05 2015-09-23 天津量诺科技发展有限公司 一种利用废极片制造锂离子电池的方法
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CN103825064B (zh) * 2014-02-27 2016-05-25 北京工业大学 一种废旧动力磷酸铁锂电池环保回收示范工艺方法
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CN111224188A (zh) * 2020-01-11 2020-06-02 合肥工业大学 一种废动力锂电池的绿色回收工艺
CN111430831B (zh) * 2020-03-11 2022-02-15 中南大学 一种废旧锂离子电池负极材料的回收方法
CN112490527B (zh) * 2020-12-03 2022-04-01 东莞理工学院 锂离子电池正极材料再生方法、正极材料和锂离子电池
CN113013515B (zh) * 2021-02-23 2022-04-01 山东泰一新能源股份有限公司 聚合物圆柱锂离子电池的回收利用方法及其回收利用装置
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