Recycling treatment method of waste and old lithium iron phosphate battery anode materials

A lithium iron phosphate battery and positive electrode material technology, applied in the direction of battery recycling, waste collector recycling, recycling technology, etc., can solve the problems of difficult control conditions, difficult wastewater treatment, difficult environmental pollution, etc., to achieve easy access to equipment, easy operation Easy, simple process effect

Inactive Publication Date: 2011-10-05
HEFEI GUOXUAN HIGH TECH POWER ENERGY
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AI Technical Summary

Problems solved by technology

Although Lithium Iron Phosphate material is rich in Li, Fe, and P, and the price is relatively cheap, the composition of Lithium Iron Phosphate material is complex. Once it is widely promoted in the future, it will be difficult to recycle scrapped lithium-ion batteries, which will become environmental pollution to a certain extent. problem
The patent with the publication number CN101383441A "Comprehensive recovery method for lithium iron phosphate battery positive electrode waste", the patent with the publication number CN101394015A "The regeneration method of lithium iron phosphate positive electrode material waste" and the patent with the publication number CN101359756A "A lithium iron phosphate "Recycling method of lithium iron phosphate positive electrode material in ion battery waste" is mainly applicable to the recovery and treatment of lithium iron phosphate whose chemical composition has not been destroyed, such as waste slurry, waste electrode pieces and scraps produced in the battery production process, and is not applicable to Recycling and processing of waste lithium iron phosphate batteries after use; the patent "a method for comprehensive recovery of waste lithium iron phosphate batteries" with the publication number CN101847763A adopts a hydrometallurgical process, and the waste and old lithium iron phosphate materials are respectively acid-dissolved, purified and Precipitate to obtain a precipitate rich in iron, lithium, and phosphorus ions, then add iron source, lithium source or phosphorus source compound to the precipitate to adjust the molar ratio of iron, lithium, and phosphorus, and finally add carbon source, through ball milling, inert atmosphere The new lithium iron phosphate positive electrode material is obtained by calcination in the process. This method has a wide range of raw materials, but it is difficult to control the conditions in the actual operation process, and the wastewater generated during the operation process is difficult to treat. At the same time, the operation process has high requirements for equipment anti-corrosion. Poor operating environment

Method used

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  • Recycling treatment method of waste and old lithium iron phosphate battery anode materials
  • Recycling treatment method of waste and old lithium iron phosphate battery anode materials
  • Recycling treatment method of waste and old lithium iron phosphate battery anode materials

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Experimental program
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Effect test

Embodiment 1

[0024] Two 1865140 steel shell 10Ah cells after 2500 cycles were fully discharged and then peeled off the battery case, the positive and negative electrodes and separators were manually separated, and the lithium iron phosphate positive electrode was placed in NMP at room temperature for ultrasonic treatment to the positive electrode. The powder is completely separated from the aluminum foil current collector; the aluminum foil is taken out, the positive electrode powder is collected by filtration, and the residue is distilled and recycled for recycling; the filtered lithium iron phosphate positive electrode powder is placed in a muffle furnace and kept at 500°C for 3 hours in air Obtain 157.2g dark red solid powder, the XRD figure of this powder is referring to figure 1 , it can be seen that the waste lithium iron phosphate material after heat preservation treatment at 500°C still retains the pure phase structure of lithium iron phosphate to a certain extent, but at the same t...

Embodiment 2

[0026] Get the 70g solid powder sample after insulation treatment in embodiment 1, pour in the ball mill jar that fills dehydrated alcohol, add Li 2 CO 3 The molar ratio of Li:Fe:P in the sample was adjusted to be 1.05:1:1, and then 8 g of graphite carbon black was added and mixed by ball milling for 5 hours. After drying, grinding and sieving the ball-milled samples, they were calcined at 700°C for 18 hours in a nitrogen protective atmosphere to obtain the regenerated lithium iron phosphate product. The carbon content was 4.1% as detected by the carbon-sulfur analyzer, and its XRD data ( figure 2 ) shows that the regenerated sample is lithium iron phosphate, containing a very small amount of impurities. The lithium iron phosphate sample, conductive carbon black and polytetrafluoroethylene (PTFE) were uniformly mixed at a mass ratio of 82:10:8 to make a simulated battery positive electrode sheet, which was assembled with a metal lithium sheet to form a half-cell, which was t...

Embodiment 3

[0028] Get 70g solid powder sample after insulation treatment in embodiment 1, pour in the ball mill jar that fills acetone, add Li 2 CO 3 and LiH 2 PO 4 Adjust the molar ratio of Li:Fe:P in the sample to 1.02:1:1.02, then add 8g of graphite carbon black and 2g of glucose and fully ball mill and mix for 6h. After drying, grinding and sieving the ball-milled samples, they were calcined at 750°C for 20 hours in a nitrogen protective atmosphere to obtain the regenerated lithium iron phosphate product. The carbon content was 3.4% as detected by a carbon-sulfur analyzer, and its XRD data ( image 3 ) shows that the regenerated sample is relatively pure lithium iron phosphate. Then the lithium iron phosphate sample, conductive carbon black and polytetrafluoroethylene (PTFE) were uniformly mixed at a mass ratio of 82:10:8 to make a simulated battery positive pole piece, which was assembled with a metal lithium sheet to form a half-cell. According to the analysis and detection of ...

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Abstract

The invention discloses a recycling treatment method of waste and old lithium iron phosphate battery anode materials, which comprises the following steps of: firstly, scattering waste and old lithium iron phosphate batteries and stripping and collecting anode materials in the waste batteries; heating the collected anode materials at high temperature and removing carbon and an adhesion agent to obtain solid powder; adding a lithium source compound and a carbon source into the solid mixture; ball-milling the mixture through a high-energy wet method; and finally, charging the ball-milled powder into a non-oxide atmosphere and roasting at high temperature to obtain the qualified lithium iron phosphate anode materials. The recycling method disclosed by the invention has the advantages of simple process, convenience for operation and high recovery rate.

Description

technical field [0001] The invention relates to the field of recovery and treatment of waste lithium ion batteries, in particular to a method for recovery and regeneration treatment of positive electrode materials of waste lithium iron phosphate batteries. Background technique [0002] By 2011, China will have 500,000 new energy vehicles based on electric vehicles, hybrid vehicles, and hydrogen fuel cell vehicles; and through the "ten cities, one thousand vehicles" policy, there will be 10,000 new energy buses driving on the streets of cities . Therefore, a major issue related to environmental protection is in front of the industry: lithium-ion batteries have high energy storage per unit weight, abundant lithium resources and low prices, so now new energy buses generally use lithium iron phosphate and lithium manganese oxide batteries , although lithium-ion batteries do not contain mercury, cadmium, lead and other highly toxic heavy metal elements, the positive and negative...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/54B09B3/00
CPCY02E60/12Y02W30/84
Inventor 杨续来韦佳兵杨茂萍刘大军徐小明
Owner HEFEI GUOXUAN HIGH TECH POWER ENERGY
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