PROCESS OF EXTRACTION OF LITHIUM FROM A MATERIAL COMPRISING LITHIUM AND AT LEAST ANOTHER METAL

Abstract

The present invention is in the field of the extraction of lithium from a material comprising lithium and at least another metal. In particular, the invention concerns a process of extraction of lithium at least, from a material comprising lithium and at least another metal.

Claims

1. Process of extraction of lithium from a material comprising lithium and at least another metal, said process comprising the following steps: a) contacting said material with a polyol solvent and a carbonate to obtain a reaction mixture; b) performing a solvothermal treatment of the reaction mixture obtained in step a) to obtain a solvothermally treated composition SP1; c) separating the liquid L1 containing lithium carbonate and the solid S1 forming the composition SP1 obtained in step b); d) optionally, isolating solid lithium carbonate from the liquid L1.

2. Process according to claim 1, comprising after step d), the following steps: e) contacting the solid S1 with water to obtain a composition SP2; f) separating the liquid L2 containing lithium carbonate and the solid S2 forming the composition SP2 obtained in step e); g) optionally, isolating solid lithium carbonate from the liquid L2.

3. Process according to claim 1, wherein the at least another metal is chosen from transition metals and post-transition metals.

4. Process according to claim 1, wherein the material is a lithium-ion battery cathode material or a lithium ore.

5. (canceled)

6. Process according to claim 1, wherein the polyol solvent is chosen from the group comprising ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene diol, liquid polyethylene glycols, butylene glycol, and glycerol.

7. Process according to claim 1, wherein the carbonate is at least one metal carbonate.

8. Process according to claim 1, further including steps of repeating steps a)-d) on a fresh batch of said material, wherein the polyol solvent used in the repeated step a) is the liquid L1 of the previous step a).

9. Process according to claim 1, wherein the solvothermal treatment of step b) is performed at a temperature over the boiling point of the polyol solvent and under 500° C.

10. Process according to claim 1, wherein the solvothermal treatment of step b) is performed at a pressure above atmospheric pressure.

11. Process according to claim 1, wherein the solvothermal treatment of step b) is performed for 1 hour to 1 week.

12. Process according to claim 1, wherein the solid S1 obtained in step c) is prior to step e) washed with a solvent in which lithium carbonate is not soluble.

13. Process according to claim 1, wherein the at least another metal is at least a magnetic metal, or at least a magnetic metal and at least a non magnetic metal, and wherein the separating step f) may comprise a magnetic separating sub-step f1), to isolate the at least a magnetic metal from the composition SP1, followed by a separating sub-step f2) corresponding to the separating step f) as defined above.

14. Process according to claim 1, of lithium-ion battery cathode recycling, wherein step a) is preceded by a step of recovery of a lithium-ion battery cathode material from a lithium-ion battery, and last step d) being optionally followed by a step of use of at least one of the above-mentioned metals in a new process or device.

15. Composition SP1 obtainable by the process defined in claim 4.

16. Composition comprising: a material chosen from lithium-ion battery cathode materials and lithium ores; a carbonate; and a polyol solvent.

17. Process according to claim 2, of lithium-ion battery cathode recycling, wherein step a) is preceded by a step of recovery of a lithium-ion battery cathode material from a lithium-ion battery, and last step g) being optionally followed by a step of use of at least one of the above-mentioned metals in a new process or device.

Description

EXAMPLES

Example 1

Extraction of Lithium and Other Metals According to the Invention from Lithium-Ion Battery Cathode Material

[0162] The extraction of lithium and other metals according to the invention from lithium-ion battery cathode material is for instance performed as follows:

[0163] Step 1:

[0164] This step is carried out in a solvothermal vessel, for example a steel or titanium vessel, in the presence of ethylene glycol or diethylene glycol and sodium carbonate and/or potassium carbonate.

[0165] After dissolving the carbonate in the solvent, lithium-ion battery cathode material (in powder form) is added. The materials tested were as follows: LiCoO.sub.2, LiMn.sub.2O.sub.4, LiNi.sub.0.33Mn.sub.0.33Co.sub.0.33O.sub.2 and Li.sub.3Fe.sub.2(PO.sub.4).sub.3, and LiNi.sub.0.8Co.sub.0.15Al.sub.0.05O.sub.2. The vessel is then closed and introduced into a heating chamber.

[0166] Examples of processing conditions for the different battery materials are summarized in Table 1. The pressure in the vessel was of 125 bar and can be higher than 125 bar, if achievable by the chosen vessel.

TABLE-US-00001 Treatment Treated Mass of Volume of Treatment temperature mass of Na.sub.2CO.sub.3 ethylene Material duration (h) (° C.) material (g) (g) glycol (mL) LiCoO.sub.2 5 225 0.5 0.541 30 LiNi.sub.0.33Mn.sub.0.33Co.sub.0.33O.sub.2 72 225 0.5 0.552 30 LiMn.sub.2O.sub.4 5 225 0.5 0.15 30 Li.sub.3Fe.sub.2(PO.sub.4).sub.3 18 225 0.5 0.19 30 LiNi.sub.0.8Co.sub.0.15Al.sub.0.05O.sub.2 40 225 0.5 1.1 30

[0167] At the end of this stage, the vessel, after cooling to room temperature, contains a powder in suspension in a liquid. The liquid L1 and powder S1 are separated by centrifugation.

[0168] The recovered powder S1 then undergoes the following steps.

[0169] Step 2:

[0170] The powder S1 recovered in step 1 may be washed with ethanol: the powder is contacted with ethanol under ultrasound for a few minutes, then separated from the liquid by centrifugation. The purpose of this washing is to remove the residual sodium carbonate and ethylene glycol.

[0171] Step 3:

[0172] The powder obtained in step 1 or 2 is then washed with water, to obtain a solid S2 suspended in a water based liquid L2.

[0173] The solid S2 is recovered and then dried at 90° C. for a maximum of 2 hours.

[0174] In the case of LiNi.sub.0.33Mn.sub.0.33Co.sub.0.33O.sub.2, step 3 is slightly modified (Step 3′), as the washing is followed by magnetic separation: the powder dispersed in water is placed in the vicinity of a magnet, so as to separate the magnetic and non-magnetic fractions of the powder. In fact, only one of the phases formed during the treatment (the nickel-cobalt alloy) is magnetic and thus attracted by a magnet.

[0175] The supernatant liquid L2 then undergoes the next step.

[0176] Step 4:

[0177] The liquid L2 is dried under air at 90° C. for 3 to 5 hours.

[0178] The powders obtained after steps 3 and 4 can possibly be subjected to a last step.

[0179] Step 5:

[0180] Calcination under air for 2 hours at 500 or 800° C.

[0181] The composition of solid S2 and liquid L2 for some materials is presented in the following table 2.

TABLE-US-00002 Supernatant L2 dried (s)/ Material Powder S2 calcinated (c) LiCoO.sub.2 Co (s) Li.sub.2CO.sub.3 LiNi.sub.0.33Mn.sub.0.33Co.sub.0.33O.sub.2 Magnetic: Ni/Co alloy (s) Li.sub.2CO.sub.3 Non magnetic: MnCO.sub.3 LiMn.sub.2O.sub.4 MnCO.sub.3/Mn.sub.3O.sub.4 then Mn.sub.2O.sub.3 (c) Li.sub.2CO.sub.3 after heating at 800° C.

[0182] The extraction yields for some materials is presented in the following table 3.

TABLE-US-00003 Li Li Li Co Ni Mn Content content content of content content content Material of L1 of L2 L1 + L2 of S2 of S2 of S2 LiCoO.sub.2 18.8% of 63.5% of 82.3% of 78.8% of — — initial Li initial Li initial Li initial Co LiNi.sub.0.33Mn.sub.0.33Co.sub.0.33O.sub.2 73.8% of 25.67% of 99.47% of 75.2% of 76.5% of 48.1% of initial Li initial Li initial Li initial Co initial Ni initial Mn LiMn.sub.2O.sub.4 34.7% of 65% of 99.7% of — — 93.8% of initial Li initial Li initial Li initial Mn

[0183] It has been found that the yield of extraction of the metals recovered in the form of a powder (Co, Ni, Mn) can be improved by reusing the polyol solvent and the aqueous solution (i.e. by using the L1 and/or L2 liquids of previous processes).

Example 2

Extraction of Lithium from Lithium Ores

[0184] It has been shown that a process that is analogous to the one mentioned in example 1 is successfully performed on lithium ores such as spodumene.

[0185] For example, 1.0 g of β LiAlSi.sub.2O.sub.6 was successfully treated with 0.85 g of Na.sub.2CO.sub.3 in 30 ml of EG at 225° C. for 12 hours.

[0186] The EG solvent can be reused as described above.

Example 3

Extraction of Lithium and Other Metals with Recycling of the Polyol Solvent

[0187] The ethylene glycol solvent (EG) can be reused without filtration at least 4 times. Reused EG retains its reducing properties.

[0188] On LiMn.sub.2O.sub.4 electrode powder Two runs as defined below were performed in the same treatment conditions using the same solvent.

[0189] 0.5 g of LiMn.sub.2O.sub.4 was treated with 0.2 g of K.sub.2CO.sub.3 in 30 ml of EG at 225° C. for 5 hours.

[0190] The obtained SP1 composition was analyzed by Inductively Coupled Plasma (ICP). Results are presented in following table 4.

TABLE-US-00004 Li in Mn in S1 solution Li in S1 (MnCO.sub.3/ Comp. of SP1 V.sub.EG (L1) (Li.sub.2CO.sub.3) Mn.sub.3O.sub.4) 1.sup.st use of EG/Li in Sol./ ~93% of undetectable 56.96% of 94.61% of the EG Li.sub.2CO.sub.3/MnCO.sub.3/ the initial (because too initial Li initial Mn Mn.sub.3O.sub.4 volume diluted in view of the large volume of solvent dosed) 2.sup.nd use of EG/Li in Sol./ ~93% of 32.6% of 112.99% of 107.07% of the EG Li.sub.2CO.sub.3/MnCO.sub.3/ the initial initial Li initial Li initial Mn Mn.sub.3O.sub.4 volume

[0191] The yield in Mn can generally be increased for example by increasing the centrifugation speed. From the 2.sup.nd use of the solvent, the yield of recovered Li and/or Mn in S1 powders can be close to or above 100%, as residual material (Mn oxide particles) or dissolved material (Li carbonate) is being recovered in the EG originating from the first runs.

[0192] On LiMn.sub.2O.sub.4 Electrode Powder (Doubled Quantity)

[0193] Three runs as defined below were performed in the same treatment conditions using the same solvent. 1.0 g of LiMn.sub.2O.sub.4 was treated with 0.2 g of K.sub.2CO.sub.3 in 30 ml of EG at 225° C. for 8 hours.

[0194] The obtained SP1 composition was analyzed by Inductively Coupled Plasma (ICP). Results are presented in following table 5.

TABLE-US-00005 Li in Mn in S1 solution Li in S1 (MnCO.sub.3/ Comp. of SP1 V.sub.EG (L1) (Li.sub.2CO.sub.3) Mn.sub.3O.sub.4) 1.sup.st use of EG/Li in Sol./ ~93% of — 73.53% of 87.15% of the EG Li.sub.2CO.sub.3/MnCO.sub.3/ the initial initial Li initial Mn Mn.sub.3O.sub.4 volume 2.sup.nd use of EG/Li in Sol./ ~93% of — 99.77% of 90.68% of the EG Li.sub.2CO.sub.3/MnCO.sub.3/ the initial initial Li initial Mn Mn.sub.3O.sub.4 volume 3.sup.rd use of EG/Li in Sol./ ~93% of 57.69% of 118.34% of 101.05% of the EG Li.sub.2CO.sub.3/MnCO.sub.3/ the initial initial Li initial Li initial Mn Mn.sub.3O.sub.4 volume

[0195] The yield in Mn can generally be increased by for example increasing the centrifugation speed.

[0196] From the 2.sup.nd use of the solvent, the yield of recovered Li and/or Mn in S1 powders can be close to or above 100%, as residual material (Mn oxide particles) or dissolved material (Li carbonate) is being recovered in the EG originating from the first runs.

Example 4

Extraction of Lithium and Other Metals from a Mixture of Electrode Powders (LiCoO.SUB.2.; LiMn.SUB.2.O.SUB.4.; LiNi.SUB.0.33.Mn.SUB.0.33.Co.SUB.0.33.O.SUB.2.; LiNi.SUB.0.8.Co.SUB.0.15.Al.SUB.0.05.O.SUB.2.)

[0197] Four runs as defined below were performed in the same treatment conditions using the same solvent. 1.0 g of a mixture containing 0.25 g of LiCoO.sub.2, 0.25 g of NMC, 0.25 g of NCA and 0.25 g of LiMn.sub.2O.sub.4 was treated with 1.52 g of K.sub.2CO.sub.3 in 60 ml of EG at 225° C. for 45 hours.

[0198] The obtained SP1 composition was analyzed by Inductively Coupled Plasma (ICP). Results are presented in following table 6.

TABLE-US-00006 Li in Co in S1 Mn in S1 solution Li in S1 (CoO/Co.sub.α, β/ Ni in S1 (MnCO.sub.3/ Electrode Comp. of SP1 V.sub.EG (L1) (Li.sub.2CO.sub.3) Ni—Co) (Ni—Co) Mn.sub.3O.sub.4) 1.sup.st use of EG/Li in Sol./ ~93% of traces 39.44% of 73.5% of 47.01% of 89.33% of the EG Li.sub.2CO.sub.3/Ni—Co/ the initial initial Li initial Co initial Ni initial Mn MnCO.sub.3/Al/ volume Li.sub.0.125(NiCo).sub.0.875O 2.sup.nd use of EG/Li in Sol./ ~93% of 94.32% of 60.86% of 67.91% of 40.25% of 73.7% of the EG Li.sub.2CO.sub.3/Ni—Co/ the initial initial Li initial Li initial Co initial Ni initial Mn MnCO.sub.3/Al/ volume Li.sub.0.125(NiCo).sub.0.875O 3.sup.rd use of EG/Li in Sol./ ~93% of 86.05% of the EG Li.sub.2CO.sub.3/Ni—Co/ the initial initial Li MnCO.sub.3/Al/ volume Li.sub.0.125(NiCo).sub.0.875O 4.sup.th use of EG/Li in Sol./ ~93% of 99.07% of 89.45% of 113.02% of 152.20% of 66.04% of the EG Li.sub.2CO.sub.3/Ni—Co/ the initial initial Li initial Li initial Co initial Ni initial Mn MnCO.sub.3/Al/ volume Li.sub.0.125(NiCo).sub.0.875O

[0199] Three powders could be obtained: [0200] from S2, a powder attracted by a magnet, essentially containing the Ni—Co alloy; [0201] also from S2, a free powder, containing essentially MnCO.sub.3; [0202] from L2, a powder obtained after drying of the water supernatant, containing pure Li.sub.2CO.sub.3.

[0203] Example 4 shows that even when mixing electrode powders, separation of the desired elements is still achieved.

[0204] The process of the invention thus makes it possible to recycle a mixture of battery powders without going through a sorting stage.

[0205] Furthermore, by reusing the same solvent several times, the purity of the recovered compounds is preserved.

Example 5

On a Whole Battery

[0206] After dismantling a MI battery, a powder from the electrodes (mixture of anode and cathode) was recovered.

[0207] The recovered powder was sieved using three different mesh sieves: [0208] 630 μm, to obtain a powder hereinafter referred to as ‘MI T630’. [0209] 200 μm, to obtain a powder hereinafter referred to as ‘MI T200’. [0210] 40 μm, to obtain a powder hereinafter referred to as ‘MI T40’.

[0211] The MI T200 powder was analyzed by Inductively Coupled Plasma (ICP). Results are presented in following table 7.

TABLE-US-00007 MI T200 sieved before treatment Al 0.69% Co 56.83% Li 5.10%

[0212] 1.0 g of the MI T200 powder was treated with 0.5 g of K.sub.2CO.sub.3 in 30 ml of EG at 225° C. for 8 hours.

[0213] The obtained SP1 composition was analyzed by Inductively Coupled Plasma (ICP). Results are presented in following table 7.

TABLE-US-00008 Li in Co in S1 solution Li in S1 (CoO/ Al in Comp. Of SP1 V.sub.EG (L1) (Li.sub.2CO.sub.3) Co.sub.α, β) S1 MI T200 EG/Li in Sol./ ~93% of 32.64% of 58.75% of 90.66% of 30.53% of powder Li.sub.2CO.sub.3/Co/ the initial initial Li initial LI initial Co initial Al CoO/K/Al/P volume

[0214] Lithium carbonate can be separated from Al by sieving.

[0215] Lithium carbonate can also be re-dissolve in water, filtered and the solution dried to separate from the aluminium. This step can replace centrifugation.

[0216] The powder attracted (from the S2 solid) by a magnet essentially contains CoO, alpha- and beta-Co.

[0217] 1.0 g of the MI T40 powder was treated with 0.5 g of K.sub.2CO.sub.3 in 30 ml of EG (already used one time) at 225° C. for 16 hours.

[0218] From the obtained SP1 and then the S2 solid, the powder attracted by a magnet essentially contains alpha- and beta-Co, and the free fraction could be sieved to recover the graphite alone.

[0219] Lithium carbonate can be separated from Al by sieving.

[0220] Lithium carbonate can also be re-dissolve in water, filtered and the solution dried to separate from the aluminium. This step can replace centrifugation.

[0221] Most of the graphite remained in the 200 micron and mostly in the 630 micron sieves, and is in any case not affected by the recycling process.