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Recovery method of positive electrode material of waste ternary lithium ion battery

A technology for lithium-ion batteries and positive electrode materials, which is applied in the field of recycling waste ternary lithium-ion battery positive electrode materials, can solve the problems of complex recycling process, long process flow, and low recovery rate, and achieve simplified process, cost reduction, and high-efficiency recycling Effect

Inactive Publication Date: 2020-06-09
GUANGXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] At present, the method of recycling the positive electrode material of the ternary lithium-ion battery is mainly based on the wet process. The valuable metals in the positive electrode material are transferred to the solution in the form of ions by acid leaching or alkali leaching, and then separated, purified, and multi-step Salts or oxides such as nickel sulfate, cobalt sulfate, manganese sulfate, lithium carbonate, cobalt oxide, and nickel oxide can be obtained by precipitation, but this recovery process is complicated, costly, and recovery rate is low
In addition, in the prior art, nickel-cobalt-manganese-lithium and other elements in the waste ternary lithium-ion battery are used to re-prepare the positive electrode material of the ternary lithium-ion battery, and the nickel-cobalt-manganese and lithium in the leaching solution must be separated to prepare nickel-cobalt-manganese hydroxide respectively. precursors and lithium carbonate or lithium hydroxide, and then synthesize ternary materials, the process is longer

Method used

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  • Recovery method of positive electrode material of waste ternary lithium ion battery
  • Recovery method of positive electrode material of waste ternary lithium ion battery
  • Recovery method of positive electrode material of waste ternary lithium ion battery

Examples

Experimental program
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Effect test

Embodiment 1

[0031] 1) Discharge the waste ternary lithium-ion battery, disassemble to obtain the positive electrode, negative electrode and separator, put the positive electrode in 30v / v% ethanol for cleaning, dry it and place it in a muffle furnace to heat up to 400°C for calcination 2h, continue to heat up to 600°C and calcined for 2h to remove the binder on the pole piece;

[0032] 2) Mechanically pulverize the calcined positive electrode sheet and pass through a 150-mesh sieve to separate the powder from the current collector, and collect the powder to be the positive electrode powder;

[0033] 3) The positive electrode powder is leached with 2mol / L sulfuric acid and 5vol% hydrogen peroxide, the solid-to-liquid ratio is 40g:1L, the leaching temperature is 85°C, and the leaching time is 80min, and the solid-liquid separation is carried out on the material to obtain Leaching solution and leaching slag; the content of nickel ion, cobalt ion, manganese ion and lithium ion in the leach sol...

Embodiment 2

[0040] 1) Discharge the waste ternary lithium-ion battery, disassemble to obtain the positive electrode, negative electrode and separator, put the positive electrode in 60v / v% ethanol for cleaning, dry it and place it in a muffle furnace to heat up to 550°C for calcination 6h, remove the adhesive on the pole piece;

[0041] 2) Mechanically pulverize the calcined positive electrode sheet and pass through a 150-mesh sieve to separate the powder from the current collector, and collect the powder to be the positive electrode powder;

[0042] 3) Leach the positive electrode powder with 1.5mol / L nitric acid and 4.5wt% citric acid, the solid-liquid ratio is 45g:1L, the leaching temperature is 85°C, and the leaching time is 45min. Obtain leaching solution and leaching slag; measure the content of nickel ion, cobalt ion, manganese ion and lithium ion in the leaching solution, they are 16%, 17.1%, 16.4%, 5.2% respectively;

[0043] 4) Add nickel nitrate, cobalt nitrate, manganese nitra...

Embodiment 3

[0049] 1) Discharge the waste ternary lithium-ion battery, disassemble to obtain the positive electrode, negative electrode and separator, put the positive electrode in 75v / v% ethanol to clean, dry and heat up to 370°C in a muffle furnace for calcination 2h, continue to heat up to 600°C and calcined for 2h to remove the binder on the pole piece;

[0050] 2) Mechanically pulverize the calcined positive electrode sheet and pass through a 150-mesh sieve to separate the powder from the current collector, and collect the powder to be the positive electrode powder;

[0051] 3) Leach the positive electrode powder with 4mol / L acetic acid and 5wt% ammonium sulfite solution, the solid-to-liquid ratio is 30g:1L, the leaching temperature is 80°C, and the leaching time is 60min, and the material is subjected to solid-liquid separation, respectively Obtain leaching solution and leaching slag; measure the content of nickel ion, cobalt ion, manganese ion and lithium ion in the leaching soluti...

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Abstract

The invention discloses a recovery method of a positive electrode material of a waste ternary lithium ion battery. The method specifically comprises the steps: leaching the ternary material in the waste ternary lithium ion battery by adopting acid and a reducing agent, adding a precipitant and a complexing agent into the leachate to obtain a nickel-cobalt-manganese-lithium coprecipitation precursor, and calcining the precursor at high temperature to obtain the nickel-cobalt-lithium manganate ternary material. According to the method, nickel, cobalt, manganese and lithium in the positive electrode material of the waste ternary battery are recycled at the same time through a one-step coprecipitation method, valuable metals in the positive electrode material of the waste ternary lithium ion battery are efficiently recycled, meanwhile, the regenerated ternary positive electrode material can be obtained, and the obtained regenerated ternary positive electrode material has good electrochemical performance. According to the recycling process, the step of separating lithium from nickel, cobalt and manganese and the step of preparing lithium salt and nickel, cobalt and manganese precursorsare omitted, the process is greatly simplified, and the recycling cost is remarkably reduced.

Description

technical field [0001] The invention relates to recycling and processing of waste lithium ion batteries, in particular to a method for recycling positive electrode materials of waste and old ternary lithium ion batteries. Background technique [0002] Lithium-ion batteries are widely used in electronic devices such as portable electronic devices, pure electric vehicles and hybrid electric vehicles due to their high energy density, long cycle life, and no memory effect. Among them, nickel-cobalt lithium manganese oxide batteries (ternary Lithium-ion batteries) are widely used in electric vehicles due to their high energy density. With the mass production and widespread use of lithium-ion batteries, the disposal of used batteries has also increased. If used batteries cannot be disposed of in a timely and reasonable manner, it will not only cause a waste of resources but also cause environmental pollution. Therefore, it is very important to recycle waste lithium-ion batteries...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01G53/00H01M10/0525H01M10/54
CPCC01G53/50C01P2002/72C01P2004/03C01P2006/40H01M10/0525H01M10/54Y02E60/10Y02W30/84
Inventor 刘葵范小萍黄玲玲李庆余王红强郑锋华潘齐常吴强蔡业政马兆玲黄有国
Owner GUANGXI NORMAL UNIV
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