Positive electrode materials having a superior hardness strength

Patent metadata

Field	Value
Publication number	US-10833328-B2
Application number	US-201515317161-A
Country	US
Kind code	B2
Filing date	Jun 1, 2015
Priority date	Jun 10, 2014
Publication date	Nov 10, 2020
Grant date	Nov 10, 2020

Abstract

A powderous positive electrode material for a lithium secondary battery, the material having the general formula Li 1 +x[Ni1−a−b−cMaM′bM″c]1−xO2−z; M being either one or more elements of the group Mn, Zr and Ti, M′ being either one or more elements of the group 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; and wherein the powderous material is characterized by having a BET value ≤0.37 m 2 /g, a Dmax<50 μm, and a hardness strength index ΔΓ(P) of no more than 100%+(1−2a−b)×160% for P=200 MPa, wherein (Formula I) (I) with D 10p=0 being the D10 value of the unconstrained powder (P=0 M Pa), r°(D 10p=0) being the cumulative volume particle size distribution of the unconstrained powder at D 10p=0, and Γ p (D 10p=0) being the cumulative volume particle size distribution at D10p=0 of the pressed samples with P being expressed in M Pa.

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 selected from the group consisting of Mn, Zr and Ti,
M′ being either one or more elements selected from 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 powderous material is subject to controlled milling to result in a BET value ≤0.37 m 2 /g, a D max <50 μm, and wherein the powderous material in an unconstrained state has a first cumulative particle size distribution having a D10 value represented by D10 P=0 , wherein the powderous material after being pressed at 200 MPa and subsequently being gently deagglomerated has a second cumulative particle size distribution, wherein Γ P (D10 P=0 ) represents a percentage of particles of the second cumulative particle size distribution having a size smaller than or equal to D10 P=0 , wherein Γ P (D10 P=0 ) is no more than 36%-16%(2a+b), and
wherein the powderous material is formed from a precursor material comprising a metal oxy-hydroxide.

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

3. The powderous positive electrode material of claim 1 , wherein Γ P (D10 P=0 ) is no more than 41%-16%(2a+b) for P=300 MPa.

4. The powderous positive electrode material of claim 1 , wherein Γ P (D10 P=0 ) is no more than 32.5%-10%(2a+b) for P=300 MPa.

5. The powderous positive electrode material of claim 1 , wherein Γ P (D10 P=0 ) is no more than 28% for P=300 MPa.

6. The powderous positive electrode material of claim 1 , wherein 1-a−b≥0.5 and 1+x<1.

7. The powderous positive electrode material of claim 1 , having a BET value after wash >1 m 2 /g.

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

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

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

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

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

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

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

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

16. The powderous positive electrode material of claim 1 , having a second phase LiNx′Oy′ with 0<x′<1 and 0<y′<2, where N is selected from the group consisting of either one or more of W, Mo, Nb, Zr and rare earth elements.

17. A method for preparing the powderous positive electrode material according to claim 1 , 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 , the method comprising:
providing a mixture of one or more precursor materials comprising either one or more of Ni, M, M′ or M″, and a precursor material comprising Li,
sintering the mixture at a temperature T expressed in ° C., with (945 (248*(1−2a−b)≤T≤(985−(248*(1−2a−b)), thereby obtaining agglomerated particles, and
pulverizing the agglomerated particles whereby a powder is obtained having the BET≤0.37 m 2 /g and the D max <50 μm.

18. The powderous positive electrode material of claim 1 , wherein Γ P (D10 P=0 ) is no more than 24% for P=300 MPa.

19. The powderous positive electrode material of claim 1 , wherein Γ P (D10 P=0 ) is no more than 20% for P=300 MPa.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

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

Classifications

• H01M4/131

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

• C01P2004/61

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

• H01M10/052

  Li-accumulators · CPC title

• H01M4/1391

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

• 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