Spherical particles, production and use thereof

Patent metadata

Field	Value
Publication number	US-10069144-B2
Application number	US-201414889663-A
Country	US
Kind code	B2
Filing date	May 2, 2014
Priority date	May 8, 2013
Publication date	Sep 4, 2018
Grant date	Sep 4, 2018

Abstract

Spherical particles of transition metal carbonates, transition metal hydroxides or transition metal carbonate hydroxides comprising cations of at least two transition metals selected from nickel, cobalt, manganese, titanium, vanadium, chromium and iron, wherein the concentration of at least one of the transition metal cations, plotted against the radius of the particle in question, has at least one relative extreme value which is neither in the center nor at the edge of the particle in question.

First claim

The invention claimed is:

1. Spherical particles of transition metal carbonates, transition metal hydroxides or transition metal carbonate hydroxides comprising cations of at least two transition metals selected from nickel, cobalt, manganese, titanium, vanadium, chromium and iron, wherein the concentration of at least one of the transition metal cations, plotted against the radius of the particles, has at least one relative extreme value which is neither in the center nor at the edge of the particle, wherein at least one of the transition metals is cobalt, wherein the spherical particles have a constant concentration of cobalt throughout a diameter of the spherical particle.

2. Spherical particles according to claim 1 , wherein the concentration of the cations of at least two transition metals, plotted against the radius of the particles, has at least one relative extreme value in each case which is neither in the center nor at the edge of the particle.

3. Spherical particles according to claim 1 , wherein the concentration of the cations of at least one of the transition metals, plotted against the radius of the particle, has at least one turning point.

4. Spherical particles according to claim 1 , which include cations of nickel, cobalt and manganese and optionally at least one further transition metal.

5. Spherical particles according to claim 1 , wherein the concentration of nickel is within a range from 40 to 80 mol %, determine over the radius of the particles.

6. Spherical particles according to claim 1 , wherein the concentration of the cations of at least one of the transition metals changes within the particle in the manner of a constant function or in steps of not more than 10 mol %.

7. Spherical particles according to claim 1 , which have a median diameter (D50) in the range from 1 to 30 μm.

8. Spherical particles according to claim 1 , which have a constant concentration of manganese over the diameter.

9. A process for producing spherical particles according to claim 1 having the following steps:
(A) providing an aqueous solution of at least one alkali metal (hydrogen)carbonate or at least one alkali metal hydroxide and optionally at least one compound L,
(B) providing at least two aqueous solutions (B1) and (B2) of transition metal salts which comprise at least two transition metals overall, the aqueous solutions (B1) and (B2) having different molar ratios of the transition metals,
(C) performing a precipitation of mixed transition metal carbonates, transition metal hydroxides or transition metal carbonate hydroxides in a stirred tank cascade of at least two stirred tanks or in a batch reactor, bringing about precipitations at different transition metal concentrations by
(C1) feeding solutions (B1) and (B2) into various stirred tanks of the stirred tank cascade or by
(C2) feeding solutions (B1) and (B2) into the batch reactor at different times or in different amounts,
(D) removing the spherical particles thus precipitated.

10. A method for production of lithiated mixed transition metal oxides comprising converting the spherical particles according to claim 1 into lithiated mixed transition metal oxides.

11. A process for producing lithiated mixed transition metal oxides, which comprises mixing spherical particles according to claim 1 with at least one lithium compound selected from LiOH, Li 2 O and Li 2 CO 3 , and reacting them with one another at a temperature in the range from 600 to 1000° C.

12. A lithiated mixed transition metal oxide in particulate form having cations of at least two transition metals selected from nickel, cobalt, manganese, titanium, vanadium, chromium and iron, wherein the concentration of at least one of the transition metal cations, plotted against the radius of the mixed transition metal oxide, has at least one relative extreme value which is neither in the center nor at the edge of the particle, wherein at least one of the transition metals is cobalt, wherein the spherical particles have a constant concentration of cobalt throughout a diameter of the spherical particle.

13. The lithiated mixed transition metal oxide according to claim 12 , wherein the concentration of the cations of at least two transition metals plotted against the radius of the particle have at least one relative extreme value in each case which is neither in the center nor at the edge of the particle.

14. The lithiated mixed transition metal oxide according to claim 12 , wherein the concentration of the cations of at least one of the transition metals plotted against the radius of the particle has at least one turning point.

15. The lithiated mixed transition metal oxide according to claim 12 , which includes cations of nickel, cobalt and manganese and optionally at least one further transition metal in ionic form.

16. The lithiated mixed transition metal oxide according to claim 12 , wherein the concentration of nickel is within a range from 40 to 80 mol %, determined over the radius of the particles.

17. The lithiated mixed transition metal oxide according to claim 12 , wherein the concentration of the cations of at least one of the transition metals changes within the particle in the manner of a constant function or in steps of not more than 10 mol %.

18. A method for production of cathodes for lithium ion batteries comprising converting the lithiated mixed transition metal oxide according to claim 12 into a cathode.

Assignees

• Basf Se

Inventors

• Schroedle Simon
• Schulz-Dobrick Martin

Classifications

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• C01G53/44

  containing manganese · CPC title

• H01M2220/30

  Batteries in portable systems, e.g. mobile phone, laptop · CPC title