Method for recycling valuable metal in waste nickel-cobalt-manganese ternary lithium-ion battery

A lithium-ion battery and valuable metal technology, which is applied in the field of waste lithium-ion battery recycling, can solve the problems of high impurity removal depth requirements of leaching solution, long co-precipitation reaction time, and high recovery cost, so as to improve the recovery effect and improve the comprehensive recovery rate. , the effect of high recovery rate

Active Publication Date: 2018-08-31
CENT SOUTH UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] However, the current domestic technical route for recycling waste nickel-cobalt-manganese acid batteries still has defects. The mainstream methods for treating the leachate of waste nickel-cobalt-manganese-manganese acid batteries are: 1) Precipitate to remove copper and then adjust the ratio of nickel, cobalt, manganese, and manganese. Precipitation; 2) extraction to remove copper, then extracting nickel, cobalt, manganese and acid stripping to obtain a salt solution containing only nickel or cobalt or manganese
For example, the Chinese patent CN105206889 A published "a treatment method for the positive electrode material of waste nickel-cobalt lithium manganese oxide ternary battery" utilizes acid leaching to recover valuable metals in nickel-cobalt lithium manganese oxide waste batteries, and first removes impurities by precipitation. Then add alkali to co-precipitate nickel-cobalt-manganese to prepare the precursor. Although this method overcomes the problem

Method used

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  • Method for recycling valuable metal in waste nickel-cobalt-manganese ternary lithium-ion battery

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Soak the waste nickel-cobalt-lithium-manganese-oxide battery in 5% sodium chloride solution until the end-of-discharge voltage is 1V, mechanically crush and sieve the broken materials with a particle size of less than 0.1mm and send them to the roasting process. The crushed material is roasted in air at 450°C for 1 hour to remove the binder, and the exhaust gas from roasting is absorbed with 50mg / L lime aqueous solution. After roasting, the material is sent to the leaching process. The leaching parameters are as follows: 1mol / L H 2 SO 4 , 2g / L sucrose, solid-to-liquid ratio 50g / L, leaching time 60min, leaching temperature 60°C, filter and separate to obtain carbon residue and leaching solution. Then add an appropriate amount of 1mol / L NaOH solution to the leaching solution, adjust the pH to 3-5 and filter to obtain Fe(OH) 3 and Al(OH) 3 . Then the filtrate (removal filtrate; wherein, Li + 、Ni 2+ 、Co 2+ , Mn 2+ The ion concentrations are 1.71g / L, 5.54g / L, 3.32g / L,...

Embodiment 2

[0056] Soak the waste nickel-cobalt-lithium-manganese-oxide battery in 10% sodium chloride solution until the end-of-discharge voltage is 0.7V, mechanically crush and sieve the fragments with a particle size of less than 0.2mm and send them to the roasting process. The crushed material is roasted in air at 500°C for 2 hours to remove the binder, and the exhaust gas from roasting is absorbed with 60 mg / L lime aqueous solution. After roasting, the material is sent to the leaching process. The leaching parameters are as follows: 2mol / L H 2 SO 4 , 4g / L sucrose, solid-to-liquid ratio 70g / L, leaching time 90min, leaching temperature 70°C, filter and separate to obtain carbon residue and leaching solution. Then add an appropriate amount of 2mol / L NaOH solution to the leaching solution, adjust the pH to 4-5 and filter to obtain Fe(OH) 3 and Al(OH) 3 . Then the filtrate (removal filtrate; wherein, Li + 、Ni 2+ 、Co 2+ , Mn 2+ The ion concentrations of the ions are 2.39g / L, 7.86g / L...

Embodiment 3

[0059] Soak the waste nickel-cobalt-lithium-manganese-oxide battery in 15% sodium chloride solution until the end-of-discharge voltage is 0.5V, mechanically crush and sieve the fragments with a particle size of less than 0.25mm and send them to the roasting process. The crushed material is roasted in the air at 550°C for 3 hours to remove the binder, and the roasting waste gas is absorbed with 70mg / L lime aqueous solution. After roasting, the material is sent to the leaching process. The leaching parameters are as follows: 2.5mol / L H 2 SO 4 , 6g / L sucrose, solid-to-liquid ratio 90g / L, leaching time 120min, leaching temperature 80°C, filter and separate to obtain carbon residue and leaching solution. Then add an appropriate amount of 3mol / L NaOH solution to the leaching solution, adjust the pH to 6 and filter to obtain Fe(OH) 3 and Al(OH) 3 . Then the filtrate (removal of impurities; wherein, Li + 、Ni 2+ 、Co 2+ , Mn 2+ The ion concentration of the ions are 3.12g / L, 9.26g...

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Abstract

The invention belongs to the field of recycling of valuable materials of waste lithium-ion batteries and particularly discloses a method for efficiently cleaning and recycling valuable metal in a waste ternary lithium-ion battery. The method comprises the following steps that (1) the waste ternary LNCM lithium-ion battery is subjected to short-circuit discharging, disassembly, stripping through abinding agent and smashing screening to obtain an electrode active material; the electrode active material is subjected to reduction-acid leaching, and solid-liquid separation is conducted to obtain acarbon material and an acid leachate containing Li+, Ni2+, Co2+, Mn2+, Fe3+, Al3+ and Cu2+; (2) the pH of the acid leachate is regulated and controlled within 3-5, and Fe3+ and Al3+ in the acid leachate are precipitated; then through solid-liquid separation, impurity-removal filtrate with Li+, Ni2+, Co2+ and Mn2+ is obtained; (3) the pH of the impurity-removal filtrate is adjusted to 1-6, then the filtrate is used as an electrolyte and subjected to rotational flow electrolysis, Cu/Co-Ni alloy composite film is collected at a negative electrode, and MnO2 is collected at a positive electrode. According to the method, a rotational flow electrolysis mode is innovatively adopted, and effective components in the leachate is efficiently recycled.

Description

technical field [0001] The invention relates to the field of waste lithium ion battery recycling, in particular to a high-value recovery of waste ternary nickel-cobalt lithium manganate lithium ion battery, which belongs to the field of waste lithium ion battery recycling. Background technique [0002] With the rapid development of modern science and technology, the problem of social energy and environmental ecological pollution has become increasingly prominent, and the environmental and ecological pollution of various waste batteries has become the focus of social attention. Nickel-cobalt manganese oxide lithium-ion batteries are widely used in power batteries and energy storage batteries due to their high capacity, stable cycle performance, and high working platform voltage. Power and energy storage batteries usually require more battery materials than conventional small batteries. Therefore, in the next 3-5 years, a large number of nickel-cobalt lithium-manganese oxide b...

Claims

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Application Information

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IPC IPC(8): H01M10/54C25C1/24C22B7/00
CPCC22B7/007C25C1/24H01M10/54Y02P10/20Y02W30/84
Inventor 蒋良兴杨健刘芳洋赖延清李劼杨凡
Owner CENT SOUTH UNIV
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