Method to produce cathode materials for Li-ion batteries
This invention provides an environmental friendly method for the production of high capacity cathode materials for use in Li-ion batteries. Traditional methods for producing lithium mixed metal oxide cathode materials typically generate large amounts of effluent which effluent must be treated prior to discharge. The present process uses mixed metals as raw materials, in a wet chemical reaction with an oxidant, in order to make high-quality metal hydroxide precursors which can be used to prepare high-quality cathode materials after lithiation. As a key feature, in the precursor preparation process, the bulk of the aqueous solution used for the wet chemical reaction can be recycled back to the reactor, so that the total process has little or no effluent generated during production of the cathode precursor material.
1. A process to produce a lithium mixed metal oxide cathode active material for use in lithium ion batteries comprising:
in a precursor preparation step, adding solid metal particles of selected metals to a reaction system containing a mixture comprising the solid metal particles, an aqueous solution, and at least one oxidant, under alkaline conditions to form a slurry comprising a precursor product and unreacted metals, wherein the selected metals are selected from the group consisting of nickel, manganese, cobalt, aluminum, and magnesium;
in a recycling step, separating the unreacted metals from the slurry to form a first solution and collected unreacted metals, separating the precursor product from the first solution to form a second solution and a collected precursor product, and recycling the collected unreacted metals and the second solution directly to the reaction system; and
in a lithiation step, mixing the collected precursor product with lithium-containing compounds to produce a final mixture, and calcining the final mixture to obtain a lithium mixed metal oxide cathode active material;
wherein the mixture of the precursor preparation step further comprises seed metal hydroxide particles.
2. The process of claim 1 , wherein the precursor preparation step is performed at a pH in a range of between 7.5 to 13, and a temperature in a range of between 20° C. to the boiling point of the slurry.
3. The process of claim 2 , wherein the precursor preparation step further comprises adding at least one of sulfuric acid, nitric acid, acetic acid, lithium hydroxide or oxide, sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, and ammonia to the mixture.
4. The process of claim 1 , wherein the aqueous solution further comprises dissolved salts.
5. The process of claim 1 , wherein the aqueous solution further comprises a complexing agent.
6. The process of claim 1 , wherein the oxidant is selected from the group consisting of air, oxygen, metal nitrates, nitric acid, and combinations thereof.
7. The process of claim 1 , wherein the oxidant comprises oxygen.
8. The process of claim 1 , wherein the reaction system comprises at least one agitated tank.
9. The process of claim 1 , wherein the precursor preparation step is performed under steady state conditions and continuous operation.
10. The process of claim 9 , wherein each individual metal element of the selected metals is added continuously at the same ratio to produce the precursor product with a uniform element distribution in each particle of the precursor product.
11. The process of claim 1 , wherein at least 90% of the second solution is directly recycled to the reaction system.
12. The process of claim 1 , wherein solid particles with the same or similar compositions as the precursor product, and a smaller particle size than the precursor product, are introduced into the reaction system during the precursor preparation step.
13. The process of claim 1 , wherein an artificial solution with the same or similar composition as the aqueous solution is used in the precursor preparation step until a suitable second solution is generated from the recycling step and recycled to the reaction system.
14. The process of claim 1 , further comprising drying the collected precursor product.
15. The process of claim 14 , wherein the lithium mixed metal oxide cathode active material is subjected to a size reduction operation.
16. The process of claim 1 , wherein the lithium-containing compounds are selected from lithium hydroxide and lithium carbonate.
17. The process of claim 1 , wherein the final mixture is calcined at a temperature of from 600° C. to 1100° C.
18. The process of claim 1 , wherein the lithium mixed metal oxide cathode active material is subjected to a further treatment selected from washing, coating, and combinations thereof.
19. The process of claim 1 , wherein the seed metal hydroxide particles comprise at least one ionic metal selected from the group consisting of nickel, manganese, cobalt, aluminum, magnesium, zirconium, yttrium, titanium, vanadium and molybdenum.
20. A process to produce a lithium mixed metal oxide cathode active material for use in lithium ion batteries comprising:
in a precursor preparation step, adding solid metal particles of selected metals to a reaction system containing a mixture comprising the solid metal particles, an aqueous solution, and at least one oxidant, under alkaline conditions to form a slurry comprising a precursor product and unreacted metals, wherein the selected metals are selected from the group consisting of nickel, manganese, cobalt, aluminum, and magnesium;
in a recycling step, separating the unreacted metals from the slurry to form a first solution and collected unreacted metals, separating the precursor product from the first solution to form a second solution and a collected precursor product, and recycling the collected unreacted metals and the second solution directly to the reaction system; and
in a lithiation step, mixing the collected precursor product with lithium-containing compounds to produce a final mixture, and calcining the final mixture to obtain a lithium mixed metal oxide cathode active material;
wherein solid particles with the same or similar compositions as the precursor product, and a smaller particle size than the precursor product, are introduced into the reaction system during the precursor preparation step.