Carbonate Precursors for Lithium Nickel Manganese Cobalt Oxide Cathode Material and the Method of Making Same

Patent metadata

Field	Value
Publication number	US-2017309894-A1
Application number	US-201515517276-A
Country	US
Kind code	A1
Filing date	Sep 30, 2015
Priority date	Oct 8, 2014
Publication date	Oct 26, 2017
Grant date	—

Abstract

A method for producing a M-carbonate precursor of a Li-M oxide cathode material in a continuous reactor, wherein M=NixMnyCozAn, A being a dopant, with x>0, y>0, 0≦z≦0.35, 0≦n≦0.02 and x+y+z+n=1, the method comprising the steps of: —providing a feed solution comprising Ni-, Mn-, Co- and A-ions, and having a molar metal content M″ feed, —providing an ionic solution comprising either one or both of a carbonate and a bicarbonate solution, the ionic solution further comprising either one or both of Na- and K-ions, —providing a slurry comprising seeds comprising M′-ions and having a molar metal content M′ seeds, wherein M′=Nix′Mny′Coz′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, and wherein the molar ratio M′ seeds/M″ feed is between 0.001 and 0.1, —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 M-carbonate precursor, and —separating the M-carbonate precursor from the reacted liquid mixture.

First claim

1 . A method for producing a M-carbonate precursor of a Li-M oxide cathode material in a continuous reactor, wherein M=Ni x Mn y Co z A n , A being a dopant, with x>0, y>0, 0≦z≦0.35, 0≦n≦0.02 and x+y+z+n=1, the method comprising:
providing a feed solution comprising Ni-, Mn-, Co- and A-ions, and having a molar metal content M″ feed ,
providing an ionic solution comprising either one or both of a carbonate and a bicarbonate solution, the ionic solution further comprising either one or both of Na- and K-ions,
providing a slurry comprising seeds comprising M′-ions and having a molar metal content M′ seeds , 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, and wherein the molar ratio M′ seeds /M″ feed is between 0.001 and 0.1,
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 M-carbonate precursor, and
separating the M-carbonate precursor from the reacted liquid mixture.

2 . The method according to claim 1 , wherein the seeds have a median particle size D50 between 0.1 and 3 μm.

3 . The method according to claim 1 , 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.

4 . The method according to claim 1 , wherein the Ni-, Mn-, Co- and A-ions are present in a water soluble sulfate compound.

5 . The method according to claim 1 , wherein M′ seeds /M″ feed is between 0.001 and 0.05.

6 . The method according to claim 1 , wherein A and A′ comprise one or more elements selected from the group consisting of Mg, Al, Ti, Zr, Ca, Ce, Cr, Nb, Sn, Zn and B.

7 . The method according to claim 1 , wherein the concentration of NH 3 in the reactor is less than 5.0 g/L.

8 . The method according to claim 1 , wherein M=M′.

9 . The method according to claim 1 , wherein the solid content in the slurry is between 30 and 300 g/L.

10 . The method according to claim 1 , wherein the reactor is a continuous stirred tank reactor (CSTR).

11 . The method according to claim 5 , wherein the median particle size of the M-carbonate precursor is determined by the ratio M′ seeds /M″ feed .

12 . The method according to claim 3 , wherein the water insoluble compound is either MnCO 3 or TiO 2 .

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

14 . The method according to claim 1 , further comprising the final step of drying and pulverizing the separated M-carbonate precursor, and wherein the ratio M′ seeds /M″ feed is selected to obtain a span <2 of the dried and pulverized M-carbonate precursor.

15 . A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 1 , providing a Li precursor compound, mixing the M-carbonate and the Li precursor, and firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

16 . A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 4 , providing a Li precursor compound, mixing the M-carbonate and the Li precursor, and firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

17 . A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 5 , providing a Li precursor compound, mixing the M-carbonate and the Li precursor, and firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

18 . A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 6 , providing a Li precursor compound, mixing the M-carbonate and the Li precursor, and firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

19 . A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 8 , providing a Li precursor compound, mixing the M-carbonate and the Li precursor, and firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

20 . A method for producing a lithium M-oxide cathode material for a rechargeable battery, comprising:
providing a M-carbonate precursor by the method according to claim 14 , providing a Li precursor compound, mixing the M-carbonate and the Li precursor, and firing the mixture at a temperature between 600 and 1100° C. for at least 1 hr.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Hu Jin
• Hong Heonpyo
• Paulsen Jens
• Oh Jindoo
• Nelis Daniël
• Robert Eric

Classifications

• H01M4/1391 Primary

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

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• C01G53/06

  Carbonates · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• C01P2006/11

  Powder tap density · CPC title