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Waste lithium ion battery recovery method

A lithium-ion battery and a recovery method technology, which is applied in the field of recovery of waste positive electrode active materials, can solve the problems of low purity of recovered products, low lithium recovery rate, increased production cost, etc., and achieve good Li separation selectivity and recovery rate, avoiding the effects of leaching

Active Publication Date: 2021-02-19
CENT SOUTH UNIV
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AI Technical Summary

Problems solved by technology

[0003] However, there are still defects in the current domestic technical route for recycling waste lithium-ion batteries. The mainstream way to deal with the electrode active materials of waste lithium-ion batteries is acidic reduction leaching to obtain Li + 、Ni 2+ 、Co 2+ , Mn 2+ 、Al 3+ and Fe 3+ Plasma leaching solution, precipitation and removal of iron and aluminum, and then adjusting the pH value to obtain a single metal precipitate or nickel-cobalt-manganese precursor, and finally Li 2 CO 3
Such as Chinese patent CN 104538695 A published "recovering valuable metals in nickel-cobalt lithium manganese oxide battery and preparing method for nickel-cobalt manganese oxide lithium" utilizes acid leaching method to recover valuable metals in nickel-cobalt lithium manganate waste batteries, first use Inorganic acid leaching electrode active materials to obtain leaching solution, precipitation to remove iron and aluminum, then adding alkali to control different pH values ​​to obtain the precipitate corresponding to a single metal, and finally recovering lithium. This method realizes the recovery of waste ternary lithium-ion batteries. However, there is the problem that the purity of the recovered product is not high, and the non-degradable inorganic acid wastewater generated during the acid leaching process causes secondary pollution
Another example is the "recycling method of waste lithium-ion battery positive electrode powder" published by Chinese patent CN 201810834647.2, which uses inorganic acid and hydrogen peroxide to leach the waste lithium-ion battery negative electrode material, then uses precipitation to purify and remove impurities, and finally uses an extractant to extract and separate Nickel salt, cobalt salt and manganese salt are obtained. This method realizes the recovery of waste ternary lithium-ion batteries, but the extraction and separation of nickel, cobalt and manganese will increase the production cost, and the long process and efficiency brought by the deep separation of manganese and cobalt cannot be avoided. low problem
[0004] The existing conventional positive electrode material recovery method is easy to cause loss of lithium, and the recovery rate of lithium is not high. In addition, the separation selectivity of Li and other metal elements is not high, which easily affects the quality of recovered products.

Method used

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Examples

Experimental program
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Effect test

Embodiment 1

[0079] waste LiNi 0.5 co 0.2 mn 0.3 o 2 The ternary lithium-ion battery is soaked in 5% sulfurous acid solution until the end-of-discharge voltage is 1V, disassembled to obtain the cell, and then mechanically crushed as a whole, and sieved out the debris with a particle size of less than 0.1mm (cell mix material). Gained fragments are uniformly mixed with sodium bisulfate, and the specific parameters are as follows: the positive active material and NaHSO in the battery compound (the weight content of the positive active material is 80%) 4 Mix evenly at a mass ratio of 5:6. Then put the mixed powder into a tube furnace for roasting, the specific parameters are as follows: the roasting temperature is 600° C., and the roasting time is 60 minutes. After the roasting is completed, the obtained samples are subjected to water leaching, and the specific parameters are as follows: leaching temperature 25°C, leaching time 20min, leaching solid-liquid ratio 60g / L; Li leaching soluti...

Embodiment 2

[0084] Compared with Example 1, the main difference is that the mass ratio of the positive electrode active material to sodium bisulfate is controlled to be 5:3. Specifically:

[0085] Adopt the electric core compound material of embodiment 1, the electric core compound material (based on the positive electrode active material weight) and NaHSO 4 Mix evenly at a mass ratio of 5:3. Then put the mixed powder into a tube furnace for roasting, the specific parameters are as follows: the roasting temperature is 600° C., and the roasting time is 60 minutes. After the roasting is completed, the obtained samples are subjected to water leaching, and the specific parameters are as follows: leaching temperature 25°C, leaching time 20min, leaching solid-liquid ratio 60g / L; Li leaching solution and NCM leaching slag (water leaching slag) are obtained.

[0086] Add NaOH to the Li leaching solution, adjust the pH value of the water leaching to 4 to remove iron and aluminum, continue to add...

Embodiment 3

[0090] Compared with Example 2, the difference mainly lies in the use of MnSO 4 As additives, specifically:

[0091] Adopt the cell compound material of embodiment 2, take the positive electrode active material in the cell compound material as a benchmark, combine it with MnSO 4 Mix evenly at a mass ratio of 5:3. Then put the mixed powder into a tube furnace for roasting, the specific parameters are as follows: the roasting temperature is 600° C., and the roasting time is 60 minutes. After the roasting is completed, the obtained samples are subjected to water leaching, and the specific parameters are as follows: leaching temperature 25°C, leaching time 20min, leaching solid-liquid ratio 60g / L; Li leaching solution and NCM leaching slag (water leaching slag) are obtained.

[0092] Add NaOH to the Li leaching solution, adjust the pH value of water leaching to 4 to remove iron and aluminum, continue to add NaOH to the filtrate to adjust the pH value to 10, and then add Na 2 S ...

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Abstract

The invention belongs to the technical field of waste battery treatment, and particularly discloses a waste lithium ion battery recovery method. A to-be-recovered raw material containing a waste positive electrode active material and an auxiliary agent are roasted at 500-800 DEG C, and then water extraction treatment is performed; and the auxiliary agent is at least one of NaHSO4, KHSO4, CoSO4, NiSO4, MnSO4, NH4HSO4 and (NH4)2SO4. The method overcomes the disadvantages of a traditional recovery method, is simple, practical and economically feasible, realizes comprehensive utilization of wastelithium ion batteries, and is suitable for industrial production.

Description

technical field [0001] The invention relates to the field of recycling waste lithium ion batteries, in particular to a method for recycling waste and old positive electrode active materials. 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. 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 lithium-ion batteries will be scrapped, and their recycling has high social value. [0003] However, there are still defects in the current domestic te...

Claims

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Application Information

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IPC IPC(8): C22B7/00C22B1/06C22B3/04C22B3/44C22B26/12C22B23/00C22B47/00
CPCC22B1/005C22B1/06C22B3/04C22B3/44C22B7/006C22B23/0453C22B26/12C22B47/00Y02P10/20
Inventor 蒋良兴赖延清杨健刘芳洋贾明李芳成
Owner CENT SOUTH UNIV
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