Impurity containing cathode material with preferred morphology and method to prepare from impurity containing metal carbonate

Patent metadata

Field	Value
Publication number	US-11462735-B2
Application number	US-201916521846-A
Country	US
Kind code	B2
Filing date	Jul 25, 2019
Priority date	Oct 8, 2014
Publication date	Oct 4, 2022
Grant date	Oct 4, 2022

Abstract

A carbonate precursor compound for manufacturing a lithium metal (M)-oxide powder usable as an active positive electrode material in lithium-ion batteries, M comprising 20 to 90 mol % Ni, 10 to 70 mol % Mn and 10 to 40 mol % Co, the precursor further comprising a sodium and sulfur impurity, wherein the sodium to sulfur molar ratio (Na/S) is 0.4<Na/S<2. Thes lithium metal (M)-oxide powder has a particle size distribution with 10 μm≤D50≤20 μm, a specific surface with 0.9≤BET≤5, the BET being expressed in g/cm 2 , the powder further comprises a sodium and sulfur impurity, wherein the sum (2*Na wt )+S wt of the sodium (Na wt ) and sulfur (S wt ) content expressed in wt % is more than 0.4 wt % and less than 1.6 wt %, and wherein the sodium to sulfur molar ratio (Na/S) is 0.4<Na/S<2.

First claim

The invention claimed is:

1. A carbonate precursor compound for manufacturing a lithium metal (M)-oxide powder usable as an active positive electrode material in lithium-ion batteries, M comprising 20 to 90 mol % Ni, 10 to 70 mol % Mn and 10 to 40 mol % Co, the precursor further comprising a sodium and sulfur impurity, wherein the sodium to sulfur molar ratio (Na/S) is 0.4<Na/S<2, and wherein the sum (2*Na wt )+S wt of the sodium (Na wt ) and sulfur (S wt ) content expressed in wt % is more than 0.4 wt % and less than 1.6 wt %, wherein the sodium content is between 0.1 and 0.7 wt %, and the sulfur content is between 0.2 and 0.9 wt %.

2. The carbonate precursor compound of claim 1 , having the general formula MCO 3 , wherein M=Ni x Mn y Co z A v , A being a dopant, wherein 0.20<x<0.90, 0.10<y<0.67, and 0.10<z<0.40, v<0.05, and x+y+z+v=1.

3. The carbonate precursor compound of claim 2 , wherein A is selected from the group consisting of Mg, Al, Ti, Zr, Ca, Ce, Cr, Nb, Sn, Zn and B.

4. A method for preparing a carbonate precursor compound according to claim 1 , comprising:
providing a feed solution comprising Ni-, Mn- and Co-ions, and a source of A, wherein the Ni-, Mn-, Co-and A-ions are present in a water soluble sulfate compound,
providing an ionic solution comprising a carbonate solution and Na-ions, wherein the CO 3 /SO 4 rate is selected so as to obtain a Na/S molar ratio with 0.4<Na/S<2 and the sodium (Na wt ) and sulfur (S wt ) content expressed in wt % yield a sum (2*Na wt )+S wt of more than 0.4 wt % and less than 1.6 wt %,
providing a slurry comprising seeds comprising M′-ions, wherein M′=Ni x Mn y Co z A′ n ,
A′ being a dopant, with 0<x′<1, 0<y′<1, 0<z′<1, 0<n′<1 and x′+y′+z′+n′=1,
mixing the feed solution, the ionic solution and the slurry in the reactor, thereby obtaining a reactive liquid mixture,
precipitating a carbonate onto the seeds in the reactive liquid mixture, thereby obtaining a reacted liquid mixture and the carbonate precursor, and
separating the carbonate precursor from the reacted liquid mixture.

5. The method according to claim 4 , wherein the M′-ions are present in a water insoluble compound that is selected from the group consisting of M′CO 3 , M′(OH) 2 , M′-oxide and M′OOH.

6. The method according to claim 4 , wherein the molar ratio (M ′ seeds /M feed ) of the metal content in the seed slurry to the metal content in the feed solution is between 0.001 and 0.1, and wherein the median particle size of the carbonate precursor is determined by the ratio M ′ seeds /M feed .

7. The method according to claim 4 , wherein A and A′ are selected from the group consisting of Mg, Al, Ti, Zr, Ca, Ce, Cr, Nb, Sn, Zn and B.

8. The method according to claim 4 , wherein the concentration of NH 3 in the reactor is less than 5.0 g/L.

9. The method according to claim 4 , wherein M=M′.

10. The method according to claim 4 , wherein the ionic solution further comprises either one or both of a hydroxide and a bicarbonate solution, and the ratio OH/CO 3 , or OH/HCO 3 , or both these ratios are less than 1/10.

11. The method according to claim 4 , wherein the seeds have a median particle size D50 between 0.1 and 3 μm.

12. A method for preparing the carbonate precursor compound of claim 2 , comprising:
providing a feed solution comprising Ni-, Mn- and Co-ions, and a source of A, wherein the Ni-, Mn-, Co-and A-ions are present in a water soluble sulfate compound,
providing an ionic solution comprising a carbonate solution and Na-ions, wherein the CO 3 /SO 4 rate is selected so as to obtain a Na/S molar ratio with 0.4<Na/S<2 and the sodium (Na wt ) and sulfur (S wt ) content expressed in wt % yield a sum (2*Na wt )+S wt of more than 0.4 wt % and less than 1.6 wt %,
providing a slurry comprising seeds comprising M′-ions, wherein M′=Ni x Mn y Co z A′ n ,
A′ being a dopant, with 0<x′<1, 0<y′<1, 0<z′<1, 0<n′<1 and x′+y′+z′+n′=1,
mixing the feed solution, the ionic solution and the slurry in the reactor, thereby obtaining a reactive liquid mixture,
precipitating a carbonate onto the seeds in the reactive liquid mixture, thereby obtaining a reacted liquid mixture and the carbonate precursor, and
separating the carbonate precursor from the reacted liquid mixture.

13. A carbonate precursor compound for manufacturing a lithium metal (M)-oxide powder usable as an active positive electrode material in lithium-ion batteries, having the general formula MCO 3 , wherein M=Ni x Mn y Co z A v , A being a dopant, wherein 0.10<x<0.30, 0.55<y<0.80, and 0<z<0.30, v<0.05, and x+y+z+v=1, the precursor further comprising a sodium and sulfur impurity, wherein the sodium to sulfur molar ratio (Na/S) is 0.4<Na/S<2.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Paulsen Jens
• Hong Heonpyo
• Oh Jindoo

Classifications

• C01P2004/51

  Particles with a specific particle size distribution · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01G53/50

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · CPC title

• C01P2006/80

  Compositional purity · CPC title

• C01P2002/50

  Solid solutions · CPC title