Low porosity electrodes for rechargeable batteries

Patent metadata

Field	Value
Publication number	US-10862121-B2
Application number	US-201816212244-A
Country	US
Kind code	B2
Filing date	Dec 6, 2018
Priority date	Dec 14, 2012
Publication date	Dec 8, 2020
Grant date	Dec 8, 2020

Abstract

A positive electrode for a rechargeable battery comprising at least 95% active cathode material with an electrode loading of at least 6 mg/cm 2 , and preferably at least 10 mg/cm 2 , and an electrode porosity of less than 2%, and preferably less than 1%. The active cathode material may comprise a bimodal composition wherein at least 70% consists of a first lithium cobalt based oxide powder having an average particle size (D50) of at least 25 μm and a BET value <0.2 m 2 /g, and a second lithium transition metal oxide based powder having the formula Li 1+b N 1−b O 2 , wherein 0.10≤b≤0.25, and N=Ni x Mn y Co 2 A d , wherein 0.10≤x≤0.40, 0.30≤y≤0.80, 0≤z≤0.20 and 0≤d≤0.10, A being a dopant, the second powder having an average particle size (D50) of less than 10 μm.

First claim

The invention claimed is:

1. A positive electrode configured for use in a liquid electrolyte-based rechargeable battery comprising at least 95 wt % active cathode material with an electrode loading of at least 25 mg/cm 2 , and having an electrode porosity of less than 10 vol %, wherein the active cathode material comprises a bimodal powder mixture composition wherein at least 70 wt % consists of a first lithium cobalt based oxide powder having an average particle size (D50) of more than 25 μm and a BET value <0.2 m 2 /g.

2. The positive electrode of claim 1 , the positive electrode being porous, and the pores in the positive electrode being filled with electrolyte, wherein the electrolyte content in the electrode is less than 6 wt % of the weight of the active material.

3. The positive electrode of claim 1 , wherein the first lithium cobalt based oxide powder comprises a core material and a surface layer, the core material having a layered crystal structure comprising the elements Li, a metal M and oxygen, wherein the Li content is stoichiometrically controlled, wherein the metal M has the formula M=Co 1−a M′ a , with 0≤a≤0.05, wherein M′ is one or more metals selected from the group consisting of Al, Ga and B; and the surface layer comprising a mixture of the elements of the core material and inorganic N-based oxides, wherein N is one or more metals selected from the group consisting of Mg, Ti, Fe, Cu, Ca, Ba, Y, Sn, Sb, Na, Zn, Zr, Si, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Sc, Ce, Pr, Nd, Gd, Dy, and Er.

4. The positive electrode of claim 3 , wherein during charging of the first lithium cobalt based oxide powder, at least 0.675 mol Li per mol M is extracted from the powder.

5. The positive electrode of claim 1 , wherein the first lithium cobalt based oxide powder has a BET value <0.18 m 2 /g.

6. The positive electrode of claim 5 , wherein the first lithium cobalt based oxide powder has an average particle size (D50) of more than 40 μm.

7. The positive electrode of claim 5 , wherein the second lithium transition metal oxide based powder has an average particle size (D50) of less than 5 μm.

8. The positive electrode of claim 7 , wherein the second lithium transition metal oxide based powder has the formula Li 1+b N 1−b O 2 , wherein 0.10≤b≤0.25, and N=Ni x Mn y Co z A d , wherein 0.10≤x≤0.40, 0.30≤y≤0.80, 0<z≤0.20 and 0≤d≤0.10, wherein A is a dopant.

9. The positive electrode of claim 7 , wherein the first lithium cobalt based oxide powder comprises a core material and a surface layer, the core material having a layered crystal structure comprising the elements Li, a metal M and oxygen, wherein the Li content is stoichiometrically controlled, wherein the metal M has the formula M=Co 1−a M′ a , with 0≤a≤0.05, wherein M′ is one or more metals selected from the group consisting of Al, Ga and B;
and the surface layer comprising a mixture of the elements of the core material and inorganic N-based oxides, wherein N is one or more metals selected from the group consisting of Mg, Ti, Fe, Cu, Ca, Ba, Y, Sn, Sb, Na, Zn, Zr, Si, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Sc, Ce, Pr, Nd, Gd, Dy, and Er.

10. The positive electrode of claim 9 , wherein the first lithium cobalt based oxide powder has an average particle size (D50) of more than 40 μm, wherein the second lithium transition metal oxide based powder has the formula Li 1+b N 1−b O 2 , wherein 0.18≤b≤0.25, and N=Ni x Mn y Co z A d , wherein 0.15≤x≤0.30, 0.50≤y≤0.75, 0.05<z≤0.15 and 0≤d≤0.10, wherein A is a dopant.

11. The positive electrode of claim 9 , wherein the second lithium transition metal oxide based powder comprises Li 1+a′ M′ 1−a′ O 2 with −0.03<a′<0.06, wherein at least 95 mol % of M′=Ni a″ Mn b″ Co c″ , with a″>0, b″>0, c″>0, a″+b″+c″=1 and a″/b″>1.

12. The positive electrode of claim 11 , wherein the first lithium cobalt based oxide powder has an average particle size (D50) of more than 40 μm.

13. The positive electrode of claim 1 , wherein the active cathode material comprises a second lithium transition metal oxide based powder, wherein the second lithium transition metal oxide based powder has an average particle size (D50) of less than 10 μm.

14. The positive electrode of claim 13 , wherein the second lithium transition metal oxide based powder comprises Li 1+a′ M′ 1−a′ O 2 with −0.03<a′<0.06, wherein at least 95 mol % of M′=Ni a″ Mn b″ Co c″ , with a″>0, b″>0, c″>0, a″+b″+c′=1 and a″/b″>1.

15. The positive electrode of claim 13 , wherein the first lithium cobalt based oxide powder comprises a core material and a surface layer, the core material having a layered crystal structure comprising the elements Li, a metal M and oxygen, wherein the Li content is stoichiometrically controlled, wherein the metal M has the formula M=Co 1−a M′ a , with 0≤a≤0.05, wherein M′ is one or more metals selected from the group consisting of Al, Ga and B; and the surface layer comprising a mixture of the elements of the core material and inorganic N-based oxides, wherein N is one or more metals selected from the group consisting of Mg, Ti, Fe, Cu, Ca, Ba, Y, Sn, Sb, Na, Zn, Zr, Si, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Sc, Ce, Pr, Nd, Gd, Dy, and Er.

16. The positive electrode of claim 15 , wherein the second lithium transition metal oxide based powder has the formula Li 1+b N 1−b O 2 , wherein 0.10≤b≤0.25, and N=Ni x Mn y Co z A d , wherein 0.10≤x≤0.40, 0.30≤y≤0.80, 0<z≤0.20 and 0≤d≤0.10, wherein A is a dopant.

17. The positive electrode of claim 13 , wherein the second lithium transition metal oxide based powder has the formula Li 1+b N 1−b O 2 , wherein 0.10≤b≤0.25, and N=Ni x Mn y Co z A d , wherein 0.10≤x≤0.40, 0.30≤y≤0.80, 0<z≤0.20 and 0≤d≤0.10, wherein A is a dopant.

18. The positive electrode of claim 17 , wherein 0.15≤x≤0.30, 0.50≤y≤0.75, 0.05<z≤0.15 and 0.18≤b≤0.25.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Paulsen Jens
• Yang Hyeyun

Classifications

• H01M4/525 Primary

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

• H01M4/131

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

• H01M4/364

  as mixtures · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M4/02 Primary

  Electrodes composed of, or comprising, active material · CPC title