Lithium nickel manganese cobalt composite oxide as a positive electrode active material for rechargeable lithium ion batteries

Patent metadata

Field	Value
Publication number	US-12294077-B2
Application number	US-202017623676-A
Country	US
Kind code	B2
Filing date	Jul 2, 2020
Priority date	Jul 3, 2019
Publication date	May 6, 2025
Grant date	May 6, 2025

Abstract

A positive electrode active material powder suitable for lithium-ion batteries, comprising lithium transition metal-based oxide particles, said particles comprising a core and a surface layer, said surface layer being on top of said core, said particles comprising the elements: Li, M′ and oxygen, wherein M′ has a formula: M′=Ni z Mn y Co x A k , wherein A is a dopant, 0.60≤z≤0.86, 0.05≤x≤0.20, x+y+z+k=1, and k≤0.01,
said positive electrode active material powder having a median particle size D50 ranging from 5 μm to 15 μm and a surface layer thickness ranging from 10 nm to 200 nm,
said surface layer comprising:
sulfur in a content superior or equal to 0.150 wt % and inferior or equal to 0.375 wt % with respect to the total weight of the positive electrode active material powder, and sulfate ion (SO 4 2− ) in a content superior or equal to 4500 ppm and inferior or equal to 11250 ppm.

First claim

The invention claimed is:

1. A positive electrode active material powder suitable for lithium-ion batteries, comprising lithium transition metal-based oxide particles, said particles comprising a core and a surface layer, said surface layer being on top of said core, said particles comprising the elements:
Li, M′ and oxygen, wherein M′ has a formula: M′=Ni z Mn y Co x A k , wherein A is a dopant, 0.80≤z≤0.86, 0.05≤y≤0.20, 0.05≤x≤0.20, x+y+z+k=1, and k≤0.01,
said positive electrode active material powder having a median particle size D50 ranging from 5 μm to 15 μm and a surface layer thickness ranging from 10 nm to 200 nm,
said surface layer comprising:
sulfur in a content superior or equal to 0.150 wt % and inferior or equal to 0.375 wt % with respect to the total weight of the positive electrode active material powder,
sulfate ion (SO 4 2− ) in a content superior or equal to 4500 ppm and inferior or equal to 11250 ppm; and
aluminum and having an Al surface value A1/A2 that is superior or equal to 100, wherein A1 is an atomic ratio Al/(Ni+Mn+Co+Al+S) of the elements Al, Ni, Mn, Co, and S contained in the surface layer, said atomic ratio A1 being obtained by XPS spectrum analysis and wherein A2 is an atomic ratio Al/(Ni+Mn+Co+Al+S) obtained by ICP.

2. The positive electrode active material powder according to claim 1 , wherein said particles comprises the elements: Li, M′ and oxygen, wherein M′ has a formula:
M′=Ni z Mn y Co x A k , wherein A is a dopant, 0.80≤z≤0.86, 0.05≤y≤0.20, 0.05≤x≤0.20, x+y+z+k=1, and k≤0.01.

3. The positive electrode active material powder according to claim 1 , having a carbon content of less than 200 ppm.

4. The positive electrode active material powder according to claim 1 , having a Li/(Ni+Mn+Co+A) atomic ratio or a Li/(Ni+Mn+Co+A+Al) atomic ratio superior or equal to 0.96 and inferior or equal to 1.05.

5. The positive electrode active material powder according to claim 1 , wherein said surface layer exhibits an Al2p peak with a maximum peak intensity in the binding energies range from 73.0±0.2 eV to 74.5±0.2 eV, said intensity being obtained by XPS spectrum analysis.

6. The positive electrode active material powder according to claim 1 , wherein said surface layer of lithium transition metal-based oxide particles comprises a LiAlO 2 phase and a LiM″ 1-a Al a O 2 phase wherein M″ comprising Ni, Mn, and Co, said LiAlO 2 phase being present in the surface layer in a content superior or equal to 0.10 at % and inferior or equal to 0.30 at % with respect to the total atomic content of M′ in the positive electrode active material powder, said LiM″ 1-a Al a O 2 phase being present in the surface layer in a content inferior to 0.14 at % with respect to the total atomic content of M′ in the positive electrode active material powder.

7. The positive electrode active material powder according to claim 1 , wherein said lithium transition metal-based oxide particles have a sulfate ion surface coverage S1/S2 that is superior to 0.85 and inferior or equal to 1.00, wherein S1 is an amount of sulfate ion contained in the surface layer, and wherein S2 is a total amount of sulfate ion contained in the particles.

8. The positive electrode active material powder according to claim 1 , having a general formula: Li 1+a′ ((Ni z′ Mn y′ Co x′ Al v S w ) 1-k A k ) 1-a′ O 2 , wherein only A is a dopant, wherein 0.80≤z′≤0.86 or 0.70≤z′≤0.86, 0.05≤y′≤0.20, 0.05≤x′≤0.20, x′y′+z′+v+w+k=1, 0.0018≤v≤0.0053, 0.006≤w≤0.012, −0.05≤a′≤0.05, and k≤0.01.

9. The positive electrode active material powder according to claim 1 , wherein A is either one or more of Al, B, S, Mg, Zr, Nb, W, Si, Ba, Sr, Ca, Zn, Cr, V, Y, and Ti, wherein the amount of each of the elements of A is superior to 100 ppm with respect to the total weight of the positive electrode active material powder.

10. The positive electrode active material powder according to claim 1 , wherein the thickness of the surface layer corresponds to a minimal distance D defined as:
D (in nm)= L S1 −L S2
wherein L S1 is a first point location at the edge of a particle, L S2 is a second point location in a line defined between said first point location and a geometric center of said particle,
wherein a content of S is measured by TEM-EDS at the second point location L S2 is superior or equal to 0 at % and inferior or equal to 5.0 at % of a content of S measured at the first point location (L S1 ), said second content of S (S 2 ) being defined as:
S 2 (in at %)= S 3 ±0.1 at %,

S 3 being a content of S (in at %) at a third point location (LS 3 ) in said line, said third point being located at any location between the geometric center of said particle and the second point location L S2 .

11. The positive electrode active material powder according to claim 10 , wherein:
S 1 −S 2 ≥10.0 at %

S 1 being the first content of S (in at %) at the first point location (LS 1 ).

12. The positive electrode active material powder according to claim 10 , wherein Al is present in the surface layer in a content/defined as:

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Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Blangero Maxime
• Jung Kyungsub
• Yun Bin-Na
• Karakulina Olesia

Classifications

• H01M4/5815

  Sulfides · CPC title

• H01M4/364

  as mixtures · CPC title

• H01M4/131

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

• H01M10/0525

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

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title