Positive electrode materials having a superior hardness strength

Patent metadata

Field	Value
Publication number	US-11811061-B2
Application number	US-202217718515-A
Country	US
Kind code	B2
Filing date	Apr 12, 2022
Priority date	Jun 10, 2014
Publication date	Nov 7, 2023
Grant date	Nov 7, 2023

Abstract

A powderous positive electrode material for a lithium secondary battery has the general formula Li 1+x [Ni 1−a−b−c M a M′ b M″ c ] 1−x O 2−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 (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 )). When Γ P (D10 P=200 ) is compared to Γ 0 (D10 P=0 ), the relative increase in value is less than 100%. When Γ P (D10 P=300 ) is compared to Γ 0 (D10 P=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 powderous positive electrode 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; and wherein the powderous positive electrode material is characterized by having a BET value ≤0.37 m 2 /g, a D max <50 μm, and a hardness strength index Δ Γ(P) of no more than 100%+(1−2a−b)×160% for P=200 MPa, wherein

ΔΓ
⁡

(
P
)

=

Γ
P

⁡

(

D
⁢

⁢

10

P
=
0

)

-

Γ
0

⁡

(

D
⁢

⁢

10

P
=
0

)

Γ
0

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(

D
⁢

⁢

10

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0

)

×
100
⁢

⁢

(

in
⁢

⁢
%

)

with D10 P=0 being the D10 value of an unconstrained powder (P=0 MPa), Γ 0 (D10 P=0 ) being a cumulative volume particle size distribution of the unconstrained powder at D10 P=0 , and Γ P (D10 P=0 ) being the cumulative volume particle size distribution at D10 P=0 of pressed samples with P being expressed in MPa.

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

3. The powderous positive electrode material of claim 1 , wherein Δ Γ(P)≤150%+(1−2a−b)×160% for P=300 MPa.

4. The powderous positive electrode material of claim 1 , wherein Δ Γ(P)≤125%+(1−2a−b)×100% for P=300 MPa.

5. The powderous positive electrode material of claim 1 , wherein either:
Δ Γ(P)≤180% for P=300 MPa, or
Δ Γ(P)≤140% for P=300 MPa, or
Δ Γ(P)≤100% 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 the pseudo hexagonal lattice with R-3 m 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 the pseudo hexagonal lattice with R-3 m 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 the pseudo hexagonal lattice with R-3 m space group which is greater than 0.16 2-theta degrees.

16. 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 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 a BET≤0.37 m 2 /g and a D max <50 μm.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

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

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

• C01G53/42

  containing alkali metals, e.g. LiNiO2 · CPC title

• C01G53/50

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

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title