Nitrate process for manufacturing transition metal hydroxide precursors

Patent metadata

Field	Value
Publication number	US-11401167-B2
Application number	US-201816492721-A
Country	US
Kind code	B2
Filing date	Mar 15, 2018
Priority date	Mar 15, 2017
Publication date	Aug 2, 2022
Grant date	Aug 2, 2022

Abstract

This invention relates to an industrial process of manufacturing hydroxide precursor for lithium transition metal oxide used in secondary lithium ion batteries. More particularly, this process utilizes highly concentrated nitrate salts and is designed to mitigate waste production.

First claim

The invention claimed is:

1. A process for the preparation of a metal-bearing precursor for the synthesis of cathode material suitable for secondary lithium-based batteries, comprising the steps of:
leaching one or more metals and/or metal compounds using HNO 3 in an aqueous solution, thereby producing an aqueous solution containing metal nitrates, and, optionally, a first gaseous phase containing NO x , which is separated;
precipitating a precursor from the solution containing metal nitrates using an alkali hydroxide or carbonate in an aqueous solution, thereby producing a solution containing alkali nitrates, and a solid phase containing the metal-bearing precursor, which is separated, and optionally washed;
decomposing the alkali nitrates in the solution containing alkali nitrates, thereby producing a solid or liquid phase containing the alkali, and a second gaseous phase containing NO x , which is separated; and
regenerating HNO 3 using the first and second NO x gaseous phases separated in the steps of leaching and of decomposition, and recycling the HNO 3 to the step of leaching.

2. The process according to claim 1 , wherein, in the step of metal leaching, the metals and/or metal compounds comprise one or more metals selected from the group consisting of nickel, manganese, and cobalt.

3. The process according to claim 1 , wherein, in the step of metal leaching, the metals and/or metal compounds comprise metallic compounds, alloys, oxides, or hydroxides.

4. The process according to claim 1 , wherein, in the step of metal leaching, the HNO 3 in aqueous solution is concentrated to at least 50%.

5. The process according to claim 1 , wherein, in the step of metal leaching, the aqueous solution containing metal nitrates has a metal concentration of at least 4 mol/L.

6. The process according to claim 1 , wherein the solution containing metal nitrates is subjected to a step of concentrating by evaporation of water, thereby obtaining a brine containing metal nitrates, which can be further processed in the step of precursor precipitation.

7. The process according to claim 1 , wherein, in the step of precursor precipitation, the alkali hydroxide or carbonate is selected from the group consisting of NaOH, Na 2 CO 3 , KOH, K 2 CO 3 , and LiOH or mixtures thereof, in a solution or slurry containing at least 4 mol/L of alkali.

8. The process according to claim 1 , wherein, in the step of precursor precipitation, one or both of the solution containing metal nitrates, and the alkali hydroxide or carbonate in an aqueous solution, are pre-heated to a temperature of at least 30° C.

9. The process according to claim 1 , wherein, in the step of precursor precipitation, the solution containing alkali nitrates is maintained at a temperature of at least 30° C.

10. The process according to claim 1 , wherein the step of precursor precipitation is performed in ammonia-free conditions.

11. The process according to claim 1 , wherein, in the step of precursor precipitation, an ammonium compound is added as complexing agent, wherein the ammonium compound is selected from ammonia or ammonia salts.

12. The process according to claim 11 , wherein the solution containing alkali nitrates is subjected to a step of ammonia recovery, thereby producing an ammonia-free solution containing alkali nitrates, and an ammonium compound, which is separated, and optionally recycled to the step of precursor precipitation.

13. The process according to claim 1 , wherein the solution containing alkali nitrates is subjected to a step of concentrating by water evaporation, thereby obtaining a brine containing alkali nitrates with at least 4 mol/L of alkali, which is further processed in a step of alkali nitrate decomposition.

14. The process according to claim 1 , wherein the solid or liquid phase containing the alkali comprises an alkali oxide, which is reacted to alkali hydroxide or carbonate, and recycled to the step of precursor precipitation.

15. The process according to any claim 14 , wherein the alkali hydroxide or carbonate is NaOH, and the alkali oxide is Na 2 O, which is reacted with water for the regeneration of NaOH.

16. The process according to claim 1 , wherein, in the step of alkali nitrate decomposition, SiO 2 is added to the brine containing alkali nitrates, thereby producing a solid phase containing the alkali comprising alkali silicates.

17. The process according to claim 1 , wherein the amount of HNO 3 obtained in the step of HNO 3 regeneration corresponds to at least 50% of the HNO 3 consumed in the step of metal leaching.

18. The process according to claim 1 , wherein the solid phase containing the metal-bearing precursor is subjected to a step of roasting at a temperature of 200 to 700° C., thereby producing a nitrate-free solid phase containing the metal-bearing precursor, and a third gaseous phase containing NO x , which is separated.

19. The process according to claim 18 , wherein, the third gaseous phase containing NO x is fed to the HNO 3 regeneration step, along with the first and second NO x gaseous phases.

20. The process according to claim 1 , wherein the solid phase containing the metal-bearing precursor is blended with a source of lithium, and optionally with a source of sulfur or chlorine, after which it is subjected to a step of lithiation by high-temperature firing, thereby producing the cathode material for use in secondary lithium-based batteries.

21. The process according to claim 20 , wherein, in the step of lithiation, a fourth gaseous phase containing NO x is produced, which is separated.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Paulsen Jens
• Robert Eric
• Vanhoutte Dirk
• Nelis Daniël
• De Palma Randy
• Kim Dae-Hyun

Classifications

• C01G53/82 Primary

  Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• C01P2002/70

  defined by measured X-ray, neutron or electron diffraction data · CPC title

• H01B1/08

  oxides · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• C01P2006/11

  Powder tap density · CPC title