CN109576499A

CN109576499A - A method of recycling lithium from battery electrode material leachate

Info

Publication number: CN109576499A
Application number: CN201910093369.4A
Authority: CN
Inventors: 刘志强; 王东兴; 张魁芳; 饶帅; 李伟; 曹洪杨
Original assignee: Guangdong Institute of Rare Metals
Current assignee: Guangdong Institute of Rare Metals
Priority date: 2019-01-30
Filing date: 2019-01-30
Publication date: 2019-04-05

Abstract

A method of recycling lithium from battery electrode material leachate, leachate of the present invention is isolated nickeliferous, cobalt and lithium the solution of waste lithium ion battery electrode material leachate.Recovery method is as follows: by leachate and the acidic phosphorus-containing extractant extraction and separation of 1:1~5 by volume, obtaining the raffinate containing lithium；By lithium and carbonate molar ratio 1:0.4~0.6, it is to stir 0.5~3 hour in 90 DEG C or more sodium carbonate liquors, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium that the raffinate containing lithium, which is added to temperature,；Mother liquor of precipitation of ammonium is mixed with acidity containing extractant, is stirred 0.5~3 hour, it is acid containing extractant and saponification mother liquor to obtain saponification；Evaporation saponification mother liquor, cooled and filtered obtain sulfate crystal and crystalline mother solution, and crystalline mother solution is added to the recycling of the raffinate containing lithium.The method of the present invention improves the rate of recovery of lithium, and has recycled sodium sulphate, reduces cost recovery, improves the economic benefit of lithium battery recycling.

Description

A method of recycling lithium from battery electrode material leachate

Technical field

The invention belongs to from waste lithium ion battery electrode material leachate recycle lithium method, more particularly, to lithium from The method of lithium is recycled in sub- battery ternary material leachate.

Background technique

With the rapid development of lithium ion battery, lithium ion battery captured portable consumer electronics market and Constantly expanded to fields such as New-energy electric vehicles.China has become maximum lithium battery production, consumption in the world today and goes out Mouth state, it is contemplated that the demand to the year two thousand twenty power lithium-ion battery is up to 125Gwh, and learies are up to 2.2Gwh, about 500,000 Ton.By 2023, learies were up to 101Gwh, and about 1,160,000 tons.In short, power battery recycling is concerning safety, pollution, resource Problem also affects the sustainable development of new-energy automobile.The exploitation of recovery technology of spent lithium ion batteries, not only contributes to ring Border protection, there are also biggish economic benefits.

Common anode material for lithium-ion batteries mainly has cobalt acid lithium, lithium nickelate, LiMn2O4, nickel cobalt manganese three currently on the market First positive electrode and LiFePO4 etc..When being recycled these old and useless batterys, generalling use the acid such as sulfuric acid, nitric acid, hydrochloric acid will Valuable metal in electrode material leaches, and the metals such as nickel, cobalt, lithium, copper, manganese, aluminium, iron are contained in leachate.In order to which lithium is recycled, Most of research at present is all after separating nickel, cobalt, copper, manganese, aluminium, the iron in leachate, using carbonate or calcium phosphate precipitation Lithium.Since lithium carbonate solubility product constant is 8.15 × 10^-4, in order to improve the rate of deposition of lithium, universal excessive addition sodium carbonate, but sink Lithium in lithium mother liquor is still up to 1.5g/L or so, major impurity CO₃ ^2-、SO₄ ^2-、Na⁺Plasma is a kind of water of multielement complexity Salt system.Sinker mother liquor system is complicated, and lithium content is relatively low in mother liquor, dry by different kinds of ions in directly use or enrichment process It disturbs, easily introduce impurity or lithium is precipitated, the direct utility value of mother liquor is poor.How low cost carries out improving the lithium rate of recovery, And utilize disposing mother liquor, become the target that everybody constantly pursues.Therefore, a kind of low in cost, environmental-friendly, adaptability is developed The great meaning of technology of lithium is recycled in strong slave waste lithium ion battery electrode material leachate.

Summary of the invention

The purpose of the present invention is to provide a kind of reduction cost recovery, improve the slave applying waste lithium ionic electricity of recycling economic benefit The method of lithium is recycled in the electrode material leachate of pond.

Leachate of the present invention is the isolated nickeliferous, cobalt of waste lithium ion battery electrode material leachate and lithium Solution, wherein nickeliferous 2~20g/L, 2~20g/L of lithium, 2~20g/L of cobalt, aluminium < 0.01g/L, manganese < 0.01g/L, 0.01 < g/L of copper With 0.01 < g/L of iron.

The recovery method of lithium is as follows in waste lithium ion battery electrode material of the invention:

1) by leachate and the saponification acidic phosphorus-containing extractant extraction and separation nickel cobalt of 1:1~5 by volume, the extraction containing lithium is obtained Extraction raffinate；

2) by lithium and carbonate molar ratio 1:0.4~0.6, it is 90 DEG C or more carbonic acid that the raffinate containing lithium, which is added to temperature, In sodium solution, stirs 0.5~3 hour, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium；

3) the resulting mother liquor of precipitation of ammonium of step 2) is mixed into saponification with acidic phosphorus-containing extractant, stirs 0.5~3 hour, obtains It is saponified acidic phosphorus-containing extractant and saponification mother liquor, is saponified acidic phosphorus-containing extractant return step 1) separation nickel cobalt；

4) evaporation step 3) resulting saponification mother liquor, cooled and filtered obtains sulfate crystal and crystalline mother solution, and crystallization is female Liquid is added to raffinate of the step 2) containing lithium and recycles.

Step 1) the saponification acidic phosphorus-containing extractant is phosphorous for the acidity of sodium hydroxide or sodium carbonate saponification 50~90% Extractant.

The acidic phosphorus-containing extractant is one of P204, P507 or Cyanex272 of 0.5~2mol/L of concentration or several The kerosin of kind.

In order to reduce the rate of recovery of lithium and the warp of raising lithium battery recycling in waste lithium ion battery electrode material leachate Ji benefit.It is to try to reduce the element composition of salt-water system according to the purification key problem in technology point of compound；The circulation of mother liquor Using ionic species should be reduced to the greatest extent, make solution based on sulfate.The present invention is to reduce cation type, is contained in saponification acidity When phosphorus extractant, using sodium carbonate or sodium hydroxide, anions in solution is made there was only lithium and sodium.Due to being added in precipitation process Sodium carbonate, causes to contain CO in mother liquor of precipitation of ammonium₃ ^2-, mother liquor of precipitation of ammonium is in evaporation and crystal process, CO₃ ^2-Meeting and Li⁺Generate precipitating It is precipitated with one piece of sodium sulphate.In order to remove the CO in mother liquor of precipitation of ammonium₃ ^2-, mother liquor of precipitation of ammonium is used for the saponification of acidic phosphorus-containing extractant, Chemical formula is such as: 2HL+Na₂CO₃→2NaL+H₂O+CO₂(HL is acidic phosphorus-containing extractant, and NaL is saponification acidic phosphorus-containing extractant), It both can be except the CO in mother liquor of precipitation of ammonium₃ ^2-, while acidic phosphorus-containing extractant saponification required sodium carbonate or hydroxide can also be saved Sodium.

Specific implementation method

Embodiment 1

Certain leachate, wherein nickeliferous 18g/L, lithium 2g/L, cobalt 19g/L, aluminium 0.008g/L, manganese 0.006g/L, copper 0.007g/ L and iron 0.008g/L；With the 0.5mol/L P204 kerosin of 50% concentration of sodium hydroxide saponification, by volume 1:5 extraction point From obtaining the raffinate containing lithium；By lithium and carbonate molar ratio 1:0.4, it is 92 DEG C that the raffinate containing lithium, which is added to temperature, In saturated sodium carbonate solution, stirs 0.5 hour, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium；By mother liquor of precipitation of ammonium and concentration 0.5mol/L P204 kerosin stirs 3 hours, obtains saponification P204 kerosin and is saponified mother liquor, saponification P204 kerosene is molten Liquid returns to separation nickel cobalt；Saponification mother liquid evaporation to lithium concentration is greater than 10g/L, cooled and filtered obtains sulfate crystal and knot Brilliant mother liquor, crystalline mother solution are added to the recycling of the raffinate containing lithium.The lithium rate of recovery is computed greater than 95%.

Embodiment 2

Certain leachate, wherein nickeliferous 3g/L, lithium 19g/L, cobalt 3g/L, aluminium 0.003g/L, manganese 0.003g/L, copper 0.003g/L With iron 0.003g/L；With the concentration 2mol/L P507 kerosin 1:1 extraction and separation by volume of sodium hydroxide saponification 90%, Obtain the raffinate containing lithium；By lithium and carbonate molar ratio 1:0.6, it is 98 DEG C, concentration that the raffinate containing lithium, which is added to temperature, To stir 3 hours, filtering while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium in the sodium carbonate liquor of 200g/L；By mother liquor of precipitation of ammonium with it is dense It spends 2mol/L P507 kerosin to stir 0.5 hour, obtain saponification P507 kerosin and is saponified mother liquor, be saponified P507 kerosene Solution returns to separation nickel cobalt；Will saponification mother liquid evaporation to lithium concentration be greater than 8g/L, cooled and filtered, obtain sulfate crystal object and Crystalline mother solution, crystalline mother solution are added to the recycling of the raffinate containing lithium.The lithium rate of recovery is computed greater than 98%.

Embodiment 3

Certain leachate, wherein nickeliferous 18g/L, lithium 2g/L, cobalt 19g/L, aluminium 0.008g/L, manganese 0.006g/L, copper 0.007g/ L and iron 0.008g/L；Body is pressed with concentration 0.5mol/L P204 and the 0.5mol/LP507 kerosin of sodium hydroxide saponification 70% Product obtains the raffinate containing lithium than 1:2 extraction and separation；By lithium and carbonate molar ratio 1:0.5, by the raffinate containing lithium be added to Temperature is to stir 1.5 hours in 95 DEG C of saturated sodium carbonate strength solutions, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium；It will sink Shallow lake mother liquor and concentration 0.5mol/L P204 and 0.5mol/LCyanex272 kerosin stir 2 hours, obtain saponification P204 and It is saponified Cyanex272 kerosin and saponification mother liquor, saponification P204 and saponification Cyanex272 kerosin return to separation nickel cobalt； Saponification mother liquid evaporation to lithium concentration is greater than 12g/L, cooled and filtered obtains sulfate crystal object and crystalline mother solution, and crystallization is female Liquid is added to the recycling of the raffinate containing lithium.The lithium rate of recovery is computed greater than 97%.

Embodiment 4

Certain leachate, wherein nickeliferous 3g/L, lithium 19g/L, cobalt 3g/L, aluminium 0.003g/L, manganese 0.003g/L, copper 0.003g/L With iron 0.003g/L；It is pressed with concentration 0.5mol/L P507 and the 0.5mol/LCyanex272 kerosin of sodium carbonate saponification 60% Volume ratio 1:3 extraction and separation, obtain the raffinate containing lithium；By lithium and carbonate molar ratio 1:0.5, the raffinate containing lithium is added It is to stir 2 hours in 94 DEG C of saturated sodium carbonate strength solutions, filter while hot, obtain lithium carbonate and mother liquor of precipitation of ammonium to temperature；It will sink Shallow lake mother liquor and concentration 0.5mol/L P507 and 0.5mol/LCyanex272 kerosin stir 1 hour, obtain saponification P507 and It is saponified Cyanex272 kerosin and saponification mother liquor, saponification P507 and saponification Cyanex272 kerosin return to separation nickel cobalt； Saponification mother liquid evaporation to lithium concentration is greater than 11g/L, cooled and filtered obtains sulfate crystal object and crystalline mother solution, and crystallization is female Liquid is added to the recycling of the raffinate containing lithium.The lithium rate of recovery is computed greater than 96%.

Claims

1. a method for reclaiming lithium from battery electrode material leachate, described leachate is the solution containing nickel, cobalt and lithium that waste and old lithium ion battery electrode material leachate is separated and obtained, it is characterized in that step is as follows:

1) extracting and separating nickel and cobalt with the leaching solution and the saponified acidic phosphorus-containing extractant in a volume ratio of 1:1 to 5 to obtain a lithium-containing raffinate;

2) According to the molar ratio of lithium and carbonate radicals of 1:0.4～0.6, adding the raffinate containing lithium to the sodium carbonate solution with a temperature of more than 90°C, stirring for 0.5～3 hours, filtering while hot to obtain lithium carbonate and the precipitation mother liquor ;

3) mixing and saponifying the precipitation mother liquor obtained in step 2) with an acidic phosphorus-containing extractant, and stirring for 0.5 to 3 hours to obtain a saponified acidic phosphorus-containing extractant and a saponified mother liquor, and returning the saponified acidic phosphorus-containing extractant to step 1) to separate nickel and cobalt;

4) Evaporate the saponification mother liquor obtained in step 3), and filter after cooling to obtain sodium sulfate crystallization and crystallization mother liquor. The crystallization mother liquor is added to step 2) lithium-containing raffinate for recycling.

2 . The method for recovering lithium from battery electrode material leachate according to claim 1 , wherein the saponified acidic phosphorus-containing extractant is an acidic phosphorus-containing extractant saponified by 50-90% of sodium hydroxide or sodium carbonate. 3 .

3. the method for reclaiming lithium from battery electrode material leachate according to claim 1, is characterized in that described acid phosphorus-containing extractant is one or more in P204, P507 or Cyanex272 of concentration 0.5～2mol/L kerosene solution.