Positive electrode materials having a superior hardness strength

Patent metadata

Field	Value
Publication number	US-11335907-B2
Application number	US-202017019626-A
Country	US
Kind code	B2
Filing date	Sep 14, 2020
Priority date	Jun 10, 2014
Publication date	May 17, 2022
Grant date	May 17, 2022

Abstract

A powderous positive electrode material for a lithium secondary battery has the general formula Li1+x[Ni1−a−b−cMaM′bM″c]1−xO2−z. M is one or more elements of the group Mn, Zr and Ti. M′ is one or more elements of the group Al, B and Co. M″ is a dopant different from M and M′, and x, a, b and c are expressed in mol with −0.02≤x≤0.02, 0≤c≤0.05, 0.10≤(a+b)≤0.65 and 0≤z≤0.05. The material has an unconstrained cumulative volume particle size distribution value (Γ0(D10P=0)), a cumulative volume particle size distribution value after having been pressed at a pressure of 200 MPa (ΓP(D10P=200)) and a cumulative volume particle size distribution value after having been pressed at a pressure of 300 MPa (ΓP(D10P=300)). When ΓP(D10P=200) is compared to Γ0(D10P=0), the relative increase in value is less than 100%. When ΓP(D10P=300) is compared to Γ0(D10P=0), the relative increase in value is less than 120%.

First claim

The invention claimed is:

1. A powderous positive electrode material for a lithium secondary battery, the material having the general formula Li 1+x [Ni 1−a−b−c M a M′ b M″ c ] 1−x O 2−z ;
M being either one or more elements of the group consisting of Mn, Zr and Ti,
M′ being either one or more elements of the group consisting of Al, B and Co,
M″ being a dopant different from M and M′,
x, a, b and c being expressed in mol with −0.02≤x≤0.02, 0≤c≤0.05, 0.10≤(a+b)≤0.65 and 0≤z≤0.05;
wherein the material has an unconstrained cumulative volume particle size distribution value (Γ 0 (D10 P=0 )), a cumulative volume particle size distribution value after having been pressed at a pressure of 200 MPa (Γ P (D10 P=200 )) and a cumulative volume particle size distribution value after having been pressed at a pressure of 300 MPa (Γ P (D10 P=300 )),
wherein when Γ P (D10 P=200 ) is compared to Γ 0 (D10 P=0 ), the relative increase in value is less than 100%,
wherein when Γ P (D10 P=300 ) is compared to Γ 0 (D10 P=0 ), the relative increase in value is less than 120%,
wherein the material has a molar amount of Ni 3+ that equals 1−2a−b, and the molar amount of Ni 3+ is greater than or equal to 0.2 and less than or equal to 0.4, and
wherein the material has a D max ≤45 μm.

2. The powderous positive electrode material of claim 1 , wherein M′=Mn and M″ is either one of Al or Co.

3. The powderous positive electrode material of claim 1 , wherein 1+x<1.

4. The powderous positive electrode material of claim 1 having a BET value≤0.37 m 2 /g.

5. The powderous positive electrode material of claim 1 having a pressed density greater than 3.0 g/cm 3 .

6. The powderous positive electrode material of claim 1 comprising up to 2 mol % of W, Mo, Nb, Zr, or a rare earth element.

7. The powderous positive electrode material of claim 1 having a soluble base content (Li 2 CO 3 +LiOH)<0.8 wt %.

8. The powderous positive electrode material of claim 1 comprising secondary particles substantially free from porosities larger than 20 nm.

9. The powderous positive electrode material of claim 1 comprising secondary particles containing less than 20 voids larger than 20 nm.

10. The powderous positive electrode material of claim 1 having a FWHM value of the (104) peak as defined by the pseudo hexagonal lattice with R-3m space group which is greater than 0.125 2-theta degrees.

11. The powderous positive electrode material of claim 1 having a FWHM value of the (015) peak as defined by the pseudo hexagonal lattice with R-3m space group which is greater than 0.125 2-theta degrees.

12. The powderous positive electrode material of claim 1 having a FWHM value of the (113) peak as defined by the pseudo hexagonal lattice with R-3m space group which is greater than 0.16 2-theta degrees.

13. The powderous positive electrode material of claim 1 having a second phase LiN x′ O y′ with 0<x′<1 and 0<y′<2, where N is either one or more of W, Mo, Nb, Zr or rare earth elements.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Blangero Maxime
• Choi Da-In
• Cho Wooram
• Kim Jihye

Classifications

• C01P2006/12

  Surface area · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• C01P2006/40

  Electric properties · CPC title

• H01M4/505 Primary

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

• C01P2004/03

  obtained by SEM · CPC title