Lithium nickel-based composite oxide as a positive electrode active material for rechargeable lithium-ion batteries

Patent metadata

Field	Value
Publication number	US-2024243277-A1
Application number	US-202218562318-A
Country	US
Kind code	A1
Filing date	May 27, 2022
Priority date	May 27, 2021
Publication date	Jul 18, 2024
Grant date	—

Abstract

The present invention provides a positive electrode active material for lithium-ion rechargeable batteries, wherein the positive electrode active material comprises Li, M′, and oxygen, wherein M′ comprises:Ni in a content x between 60.0 mol % and 95.0 mol %, relative to M′;Co in a content y, wherein 0≤y≤40.0 mol %, relative to M′;Mn in a content z, wherein 0≤z≤70.0 mol %, relative to M′;D in a content a, wherein 0≤a≤2.0 mol %, relative to M′, wherein D comprises an element other than Li, O, Ni, Co, Mn, F, W and S;F in a content b, wherein b>0, preferably b is between 0.1 mol % and 4.0 mol %, relative to M′;W in a content c, wherein c>0, preferably 0.01≤c≤4.0 mol %, relative to M′;S in a content d, wherein d>0, preferably between 0.01 mol % and 3.0 mol %, relative to M′; and,B in a content e, wherein 0≤e≤4.0 mol %, relative to M′; and,wherein x, y, z, a, c, and d are measured by Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES),wherein b is measured by Ion chromatography (IC),wherein x+y+z+a+b+c+d is 100.0 mol %,wherein the positive electrode active material has a F content FA defined asb(x+y+z+b+c+d),W content WA defined asc(x+y+z+b+c+d),and S content SA defined asd(x+y+z+b+c+d),wherein the positive electrode active material has a F content FB, W content WB, and S content SB wherein FB, WB, and SB are determined by X-ray photoelectron spectroscopy (XPS) analysis, wherein FB, WB, and SB are each expressed as molar fraction compared to the sum of molar fractions of Co, Mn, Ni, F, W and S as measured by XPS analysis,wherein the ratio FB/FA>1.0,wherein the ratio WB/WA>1.0, andwherein the ratio SB/SA>1.0.

First claim

1 - 16 . (canceled)

17 . A positive electrode active material for lithium-ion rechargeable batteries, wherein the positive electrode active material comprises Li, M′, and oxygen, wherein M′ comprises:
Ni in a content x between 60.0 mol % and 95.0 mol %, relative to M′;
Co in a content y, wherein 0≤y≤40.0 mol %, relative to M′;
Mn in a content z, wherein 0≤z≤70.0 mol %, relative to M′;
D in a content a, wherein 0≤a≤2.0 mol %, relative to M′, wherein D comprises an element other than Li, O, Ni, Co, Mn, F, W and S;
F in a content b, wherein b>0, relative to M′;
W in a content c, wherein c>0, relative to M′;
S in a content d, wherein d>0, relative to M′;
B in a content e, wherein 0≤e≤4.0 mol %, relative to M′; and,
wherein x, y, z, a, c, d, and e are measured by Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES),
wherein b is measured by Ion Chromatography (IC),
wherein x+y+z+a+b+c+d+e is 100.0 mol %,

wherein the positive electrode active material has a F content F A defined as

b

(

x
+
y
+
z
+
b
+
c
+
d
+
e

)

,

W content W A defined as

c

(

x
+
y
+
z
+
b
+
c
+
d
+
e

)

,

and S content S A defined as

d

(

x
+
y
+
z
+
b
+
c
+
d
+
e

)

,

wherein the positive electrode active material has a F content F B , W content W B , and S content S B , wherein F B , W B , and S B are determined by XPS analysis, wherein F B , W B , and S B are each expressed as molar fraction compared to the sum of molar fractions of Co, Mn, Ni, F, W and S as measured by X-ray photoelectron spectroscopy analysis,
wherein the ratio F B /F A >1.0,
wherein the ratio W B /W A >1.0, and
wherein the ratio S B /S A >1.0.

18 . The positive electrode active material according to claim 17 , wherein the positive electrode material further comprises B in a content e, wherein e>0, wherein the positive electrode active material has a B content B A defined as

e

(

x
+
y
+
z
+
b
+
c
+
d
+
e

)

,

wherein the positive electrode active material has a B content B B determined by XPS analysis,
wherein B B is expressed as molar fraction compared to the sum of molar fractions of Co, Mn, Ni, F, W, S, and B as measured by XPS analysis,
wherein the ratio B B /B A >1.0.

19 . The positive electrode active material according to claim 17 , wherein the ratio F B /F A >2.0

20 . The positive electrode active material according to claim 17 , wherein the ratio W B /W A >2.0.

21 . The positive electrode active material according to claim 17 , wherein the ratio S B /S A >2.0.

22 . The positive electrode active material according to claim 17 , wherein the ratio B B /B A >2.0

23 . The positive electrode active material according to claim 17 , wherein D comprises at least one element of the group consisting of: Al, Ba, Ca, Cr, Fe, Mg, Mo, Nb, Si, Sr, Ti, Y, V, Zn, and Zr.

24 . The positive electrode active material according to claim 17 , wherein D has a content a between 0.01 mol % and 2.0 mol %, relative to M.

25 . Method for manufacturing positive electrode active material according to claim 17 , wherein the method comprises the following consecutive steps of:
Step 1) mixing a lithium transition metal oxide with a F containing compound and a W containing compound, to obtain a first mixture, Step 2) mixing the dried powder with a solution comprising a S containing compound, to obtain a mixture, and Step 3) heating the mixture in an oxidizing atmosphere at a temperature between 250° C. and less than 500° C. so as to obtain the positive electrode active material.

26 . Method according to claim 25 , wherein the F containing compound used in Step 1) is PVDF.

27 . Method according to claim 25 , wherein the S containing compound used in Step 2) is Al 2 (SO 4 ) 3 .

28 . Method according to claim 25 , wherein the W containing compound is WO 3 .

29 . Method according to claim 25 , wherein in Step 1) a B containing compound is added together with F and W containing compound.

30 . Method according to claim 29 , wherein the B containing compound is H 3 BO 3 .

31 . A battery comprising the positive electrode active material according to claim 17 .

32 . A portable computer, a tablet, a mobile phone, an electrically powered vehicle, or an energy storage system comprising a battery according to claim 31 .

Assignees

• Umicore Nv

Inventors

• Yun Bin-Na
• Jung Kyungsub
• Kwon Ji-Yeong
• Ryu Woon-Hyoung
• Lee Seunghwan
• Blangero Maxime

Classifications

• H01M4/505

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

• H01M4/0471

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

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/0525

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

• H01M4/623

  fluorinated polymers · CPC title