COMPOSITE CATHODE ACTIVE MATERIAL, CATHODE AND LITHIUM BATTERY EACH CONTAINING COMPOSITE CATHODE ACTIVE MATERIAL, AND PREPARATION METHOD OF CATHODE ACTIVE MATERIAL

• US 20200136132A1
• Filed: 07/08/2019
• Published: 04/30/2020
• Est. Priority Date: 10/24/2018
• Status: Active Grant

• Current Assignee: Samsung Electronics Co. Ltd., Samsung SDI Company Limited
• Original Assignee: Samsung Electronics Co. Ltd., Samsung SDI Company Limited
• Inventors: Hong, Sukgi, Yu, Byongyong, Yeon, Donghee, Choi, Byungjin
• Granted Patent: US 11,909,032 B2
• Time in Patent Office: Days
• CPC Class Codes: C01G 53/04 Oxides; Hydroxides
• CPC Class Codes: C01G 53/42 containing alkali metals, e.g. LiNiO2
• CPC Class Codes: C01G 53/50 of the type [MnO2]n- , e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• CPC Class Codes: C01P 2002/20 Two-dimensional structures
• CPC Class Codes: C01P 2002/32 spinel-type (AB2O4)
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2002/54 one element only
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/76 by a space-group or by other symmetry indications
• CPC Class Codes: C01P 2002/85 by XPS, EDX or EDAX data
• CPC Class Codes: C01P 2002/88 by thermal analysis data, e.g. TGA, DTA, DSC
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/366 : as layered products
• CPC Class Codes: H01M 4/525 : of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/5825 : Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/626 : Metals
• CPC Class Codes: H01M 4/628 : Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

A composite cathode active material includes: a core including a plurality of primary particles; and a shell on the core, wherein the primary particles include a first lithium transition metal oxide comprising nickel, the shell includes a first layer and a second layer on the first layer, the first layer includes a first composition containing a first metal, the second layer includes a second composition containing phosphorus, and the first metal includes at least one or more metal, other than nickel, belonging to any of Groups 2 to 5 and Groups 7 to 15 of the Periodic Table of the Elements. Also a cathode, and a lithium battery each including the composite cathode active material, and a method of preparing the composite cathode active material.

Claims

1. A composite cathode active material comprising:

a core comprising a plurality of primary particles; and

a shell formed on the core,

wherein the primary particles comprise a first lithium transition metal oxide comprising nickel,

the shell comprises a first layer and a second layer on the first layer,

the first layer comprises a first composition containing a first metal,

the second layer comprises a second composition containing phosphorus, and

the first metal comprises at least one metal, other than nickel, belonging to any of Groups 2 to 5 and Groups 7 to 15 of the Periodic Table of the Elements.

2. The composite cathode active material of claim 1, wherein the first composition comprises a first phase, and the second composition comprises a second phase, which is different than the first phase in at least one of composition and structure.

3. The composite cathode active material of claim 1, wherein the first composition comprises at least one phase of a phase having a layered crystal structure and a phase having a spinel crystal structure.

4. The composite cathode active material of claim 3, wherein the layered crystal structure belongs to an R−

3m space group, and the spinel crystal structure belongs to an Fd−

3m space group.

5. The composite cathode active material of claim 1, wherein the first layer is on a surface of a primary particle of the plurality of primary particles, and a concentration of the first metal comprised in the first layer is greater than a concentration of the first metal comprised in the plurality of primary particles.

6. The composite cathode active material of claim 1, wherein a thickness of the second layer is greater than a thickness of the first layer, the thickness of the first layer is 50 nanometers or less, and the thickness of the second layer is 500 nanometers or less.

7. The composite cathode active material of claim 1, wherein the first metal comprises at least one of cobalt, magnesium, zirconium, aluminum, manganese, silicon, palladium, titanium, tin, iridium, platinum, ruthenium, cerium, boron, niobium, vanadium, iron, and zinc.

8. The composite cathode active material of claim 1,

wherein the first composition is a composition comprising the first metal and oxygen or is a composition comprising lithium, the first metal, and oxygen,

wherein the first composition comprises

0 moles to about 3.3 moles of lithium per 1 mole of the first composition,

about 0.7 moles to about 3.3 moles of the first metal per 1 mole of the first composition, and

about 1.7 moles to about 4.3 moles of oxygen per 1 mole of the first composition.

9. The composite cathode active material of claim 1, wherein the first composition is represented by Formula 1:

Li_aM1_bO_c 

 

Formula 1

wherein, in Formula 1, M1 is at least one of cobalt, magnesium, zirconium, aluminum, manganese, silicon, palladium, titanium, tin, iridium, platinum, ruthenium, cerium, boron, niobium, vanadium, iron, and zinc,

0≤

a≤

3.1, 0.9≤

b≤

3.1, and 1.9≤

c≤

4.1.

10. The composite cathode active material of claim 1, wherein the first composition comprises at least one of Co₃O₄, MgO, Li_xCoO₂ wherein 0<

x≤

1.5, and Li₂ZrO₃.

11. The composite cathode active material of claim 1, wherein an amount of the first composition contained in the first layer is 10 parts by weight or less, based on 100 parts by weight of the first lithium transition metal oxide, or

wherein an amount of the first metal contained in the first layer is 10 parts by weight or less, based on 100 parts by weight of the first lithium transition metal oxide.

12. The composite cathode active material of claim 1,

wherein the second composition is a composition comprising the first metal, phosphorus, and oxygen, or a composition comprising lithium, the first metal, phosphorus, and oxygen,

wherein the second composition comprises

0 moles to about 3.3 moles of lithium, per 1 mole of the second composition,

about 0.7 moles to about 3.3 moles of the first metal, per 1 mole of the second composition,

about 0.7 moles to about 2.3 moles of phosphorus, per 1 mole of the second composition, and

about 3.7 moles to about 8.3 moles of the oxygen, per 1 mole of the second composition.

13. The composite cathode active material of claim 1, wherein the second composition is represented by Formula 2 below:

Li_aM2_b(PO₄)_c 

 

Formula 2

wherein, in Formula 2, M2 is at least one of cobalt, magnesium, zirconium, aluminum, manganese, silicon, palladium, nickel, titanium, tin, molybdenum, iridium, platinum, ruthenium, cerium, boron, niobium, vanadium, iron, and zinc, and

0≤

a≤

3.1, 0.9≤

b≤

3.1, and 0.9≤

c≤

2.1.

14. The composite cathode active material of claim 1, wherein the second composition comprises at least one of Li₃PO₄, LiCoPO₄, and Co₃(PO₄)₂.

15. The composite cathode active material of claim 1, wherein an amount of the second composition or phosphorus contained in the second layer is 10 parts by weight or less, based on 100 parts by weight of the first lithium transition metal oxide.

16. The composite cathode active material of claim 1, wherein the core comprises a grain boundary located between a plurality of primary particles, and the grain boundary comprises a third composition containing a second metal.

17. The composite cathode active material of claim 16, wherein the third composition comprises a third phase having a monoclinic crystal structure, and the monoclinic crystal structure belongs to a C2/m, C12/c1, or C2/c space group.

18. The composite cathode active material of claim 16, wherein the second metal is of zirconium, aluminum, cobalt, magnesium, manganese, silicon, molybdenum, palladium, titanium, tin, iridium, platinum, ruthenium, cerium, boron, niobium, vanadium, iron, and zinc.

19. The composite cathode active material of claim 16,

wherein the third composition comprises lithium, the second metal, and oxygen, and

wherein the third composition comprises

about 1.7 moles to about 2.3 moles of lithium, per 1 mole of the third composition,

about 0.7 moles to about 1.3 moles of the second metal, per 1 mole of the third composition, and

about 2.7 moles to about 3.3 moles of oxygen, per 1 mole of the third composition.

20. The composite cathode active material of claim 16, wherein the third composition is represented by Formula 3 below:

Li_aM3_bO_c 

 

Formula 3

wherein, in Formula 3, M3 is at least one of zirconium, aluminum, cobalt, magnesium, manganese, silicon, palladium, nickel, titanium, tin, iridium, platinum, and ruthenium,

0.9≤

a≤

1.1, 0.9≤

b≤

1.1, and 2.9≤

a≤

3.1.

21. The composite cathode active material of claim 1, wherein the shell further comprises a third composition containing a second metal.

22. The composite cathode active material of claim 1, wherein the first lithium transition metal oxide comprises a second metal.

23. The composite cathode active material of claim 1,

wherein the first lithium transition metal oxide comprises lithium, nickel, a second metal, a third metal, and oxygen,

wherein the first lithium transition metal oxide comprises

about 0.1 moles to about 1.3 moles of lithium, per 1 mole of the first lithium transition metal oxide,

about 0.7 moles to about 0.99 moles of nickel, per 1 mole of the first lithium transition metal oxide,

about 0.001 moles to about 0.01 moles of the second metal, per 1 mole of the first lithium transition metal oxide,

about 0.01 moles to about 0.3 moles of the third metal, per 1 mole of the first lithium transition metal oxide, and

about 1.7 moles to about 2.3 moles of oxygen, per 1 mole of the first lithium transition metal oxide, and

wherein the third metal is a metal other than lithium, nickel, and the second metal.

24. The composite cathode active material of claim 1, wherein the first lithium transition metal oxide is represented by Formula 4:

Li_aM4O_2-α

X_α

 

 

Formula 4

wherein, in Formula 4, 0.9≤

a≤

1.1 and 0≤

α

≤

2,

M4 is nickel, a second metal, and a third metal, wherein the third metal comprises at least one element of Groups 2 to 13 of the Periodic Table, other than nickel and the second metal, an amount of nickel contained in M4 is about 70 mole percent to about 100 mole percent, and

X is of oxygen, fluorine, sulfur, and phosphorus.

25. The composite cathode active material of claim 1, wherein the first lithium transition metal oxide is represented by Formula 5:

Li_aNi_bM5_cM6_dM7_eO_2-α

X_α

 

 

Formula 5

wherein, in Formula 5, 0.9≤

a≤

1.1, 0.7<

b<

1.0, 0<

c<

0.3, 0<

d<

0.3, 0≤

e<

0.1, b+c+d+e=1, and 0≤

α

<

2,

M5, M6, and M7 are different from each other and are each independently cobalt, manganese, zirconium, aluminum, rhenium, vanadium, chromium, iron, boron, ruthenium, titanium, niobium, molybdenum, magnesium, and platinum, and

X is of oxygen, fluorine, sulfur, and phosphorus.

26. The composite cathode active material of claim 1, wherein the first lithium transition metal oxide is represented by at least one of Formula 6, and Formula 7:

Li_aNi_bCo_cMn_dM8_eO<sub>2−

α</sub>

X_α

, and 

 

Formula 6

Li_aNi_bCo_cAl_dM8_eO_2-α

X_α

 

 

Formula 7

wherein, in Formulae 6 and 7, a, b, c, d, e, and a are each independently 0.9≤

a≤

1.1, 0.7<

b<

1.0, 0<

c<

0.1, 0<

d<

0.1, 0≤

e<

0.01, b+c+d+e=1, and 0≤

α

<

2,

M8 is at least one of zirconium, aluminum, vanadium, chromium, iron, rhenium, boron, ruthenium, titanium, niobium, molybdenum, magnesium, and platinum, and

X is of oxygen, fluorine, sulfur, and phosphorus.

27. The composite cathode active material of claim 1, wherein the first lithium transition metal oxide is represented by Formula 8:

aLi₂MnO₃.(1−

a)LiMO_2-α

X_α

 

 

Formula 8

wherein, in Formula 8, 0<

a<

1 and 0≤

α

<

2,

M is at least two elements of nickel, cobalt, manganese, zirconium, aluminum, rhenium, vanadium, chromium, iron, boron, ruthenium, titanium, niobium, molybdenum, magnesium, and platinum, and

X is of oxygen, fluorine, sulfur, and phosphorus.

28. A cathode comprising the composite cathode active material according to claim 1.

29. The cathode of claim 28, wherein the cathode further comprises cathode active material having an olivine structure.

30. The cathode of claim 29, wherein an amount of the cathode active material having the olivine structure is 10 weight percent or less, based on a total weight of the cathode active material.

31. A lithium battery comprising:

the cathode according to claim 28;

an anode; and

an electrolyte between the cathode and the anode.

32. A method of preparing a composite cathode active material, the method comprising:

providing a first lithium transition metal oxide;

mixing the first lithium transition metal oxide with a first metal precursor to prepare a first composition;

mixing the first composition with a phosphorus precursor to preparing a second composition;

drying the second composition; and

heat-treating the dried second composition at a temperature of about 400°

C. to about 1000°

C. under an oxidizing atmosphere to prepare the composite cathode active material.

33. The method of claim 32, wherein the providing the first lithium transition metal oxide comprises:

mixing a precursor of the first lithium transition metal oxide and a second metal precursor to prepare a mixture; and

heat-treating the mixture at a temperature of about 400°

C. to about 1000°

C. under an oxidizing atmosphere to prepare the first lithium transition metal oxide.