Method of preparing positive electrode active material for secondary battery and positive electrode active material for secondary battery prepared thereby

Patent metadata

Field	Value
Publication number	US-2019036119-A1
Application number	US-201716069710-A
Country	US
Kind code	A1
Filing date	Jul 4, 2017
Priority date	Jul 4, 2016
Publication date	Jan 31, 2019
Grant date	—

Abstract

Provided are a method of preparing a positive electrode active material for a secondary battery, in which the positive electrode active material is uniformly doped with various doping elements without worrying about surface damage of the active material and characteristics degradation by including mixing a metal precursor for a positive electrode active material and a raw material including a doping element, in which an average particle diameter ratio is in a range of 5:1 to 2,000:1, using acoustic resonance to prepare a precursor doped with the doping element, and mixing the doped precursor with a lithium raw material and performing a heat treatment, and a positive electrode active material which has improved structure stability by being prepared by the above method and may improve battery characteristics, for example, capacity reduction may be minimized and cycle characteristics may be improved when used in the battery.

First claim

1 . A method of preparing a positive electrode active material for a secondary battery, the method comprising:
mixing a metal precursor for a positive electrode active material and a raw material including a doping element using acoustic resonance to prepare a precursor doped with the doping element; and mixing the doped precursor with a lithium raw material and performing a heat treatment, wherein an average particle diameter ratio of the metal precursor for a positive electrode active material to the raw material including a doping element is in a range of 5:1 to 2,000:1.

2 . The method of claim 1 , wherein the doping element comprises at least one element selected from the group consisting of yttrium (Y), zirconium (Zr), lanthanum (La), strontium (Sr), gallium (Ga), magnesium (Mg), scandium (Sc), gadolinium (Gd), samarium (Sm), calcium (Ca), cerium (Ce), iron (Fe), aluminum (Al), titanium (Ti), tantalum (Ta), niobium (Nb), tungsten (W), molybdenum (Mo), and chromium (Cr).

3 . The method of claim 1 , wherein the raw material including a doping element comprises one selected from the group consisting of an oxide, a hydroxide, and an oxyhydroxide which include the doping element, or a mixture of two or more thereof.

4 . The method of claim 1 , wherein the raw material including a doping element comprises one selected from the group consisting of yttria-stabilized zirconia, gadolinia-doped ceria, lanthanum strontium gallate magnesite, lanthanum strontium manganite, calcia-stabilized zirconia, scandia-stabilized zirconia, Ni-yttria stabilized zirconia cermet, and Al 2 O 3 , or a mixture of two or more thereof.

5 . The method of claim 1 , wherein an average particle diameter (D 50 ) of the raw material including a doping element is in a range of 4 nm to 5 μm.

6 . The method of claim 1 , wherein the raw material including a doping element is used in an amount of 500 ppm to 10,000 ppm based on a total amount of the metal precursor for a positive electrode active material and the raw material including a doping element.

7 . The method of claim 1 , wherein the metal precursor for a positive electrode active material comprises one selected from the group consisting of an oxide, a hydroxide, and an oxyhydroxide which include a metal for a positive electrode active material, or a mixture of two or more thereof,
wherein the metal for a positive electrode active material comprises at least one metallic element selected from the group consisting of nickel, cobalt, manganese, and aluminum.

8 . The method of claim 1 , wherein an average particle diameter (D 50 ) of the metal precursor for a positive electrode active material is in a range of 10 μm to 20 μm.

9 . The method of claim 1 , wherein the acoustic resonance is performed by applying an acoustic energy of 50 g to 90 g.

10 . The method of claim 1 , wherein the metal precursor for a positive electrode active material is a secondary particle in which plate-shaped primary particles are agglomerated, and the primary particles have an average plate thickness of 150 nm or less,
wherein the acoustic resonance is performed by applying an acoustic energy of 50 g to 90 g for 1 minute to 4 minutes.

11 . The method of claim 1 , wherein the metal precursor for a positive electrode active material is a secondary particle in which plate-shaped primary particles are agglomerated, and the primary particles have an average plate thickness of greater than 150 nm,
wherein the acoustic resonance is performed by applying an acoustic energy of 60 g to 90 g for 2 minutes to 5 minutes.

12 . The method of claim 1 , wherein the acoustic resonance is performed by using an acoustic mixer.

13 . The method of claim 1 , wherein the mixing of the doped precursor with the lithium raw material is performed by acoustic resonance.

14 . The method of claim 1 , wherein the heat treatment is performed in a temperature range of 700° C. to 950° C.

15 . The method of claim 1 , further comprising a washing process of a product obtained after the heat treatment,
wherein the washing process is performed using acoustic resonance.

16 . The method of claim 1 , further comprising a surface treatment process of a product obtained after the heat treatment,
wherein the surface treatment process is performed by mixing the product obtained after the heat treatment with a surface treatment agent using acoustic resonance and performing a heat treatment.

17 . A positive electrode active material for a secondary battery, the positive electrode active material prepared by the method of claim 1 and comprising a lithium composite metal oxide of Formula 2 which is doped with a metallic element:
ALi 1+a Ni 1-b-c M b Co c ·(1−A)M′ s O 2   [Formula 2]

wherein, in Formula 2,
M comprises at least one element of manganese (Mn) and aluminum (Al), and
M′ comprises at least one element selected from the group consisting of yttrium (Y), zirconium (Zr), lanthanum (La), strontium (Sr), gallium (Ga), magnesium (Mg), scandium (Sc), gadolinium (Gd), samarium (Sm), calcium (Ca), cerium (Ce), iron (Fe), aluminum (Al), titanium (Ti), tantalum (Ta), niobium (Nb), tungsten (W), molybdenum (Mo), and chromium (Cr),

wherein 0<A<1, 0≤a≤0.33, 0≤b≤0.5, 0≤c≤0.5, and 0<s≤0.2, but b and c are not 0.5 at a same time.

18 . A positive electrode comprising the positive electrode active material of claim 17 .

19 . A lithium secondary battery comprising the positive electrode of claim 18 .

Assignees

• Lg Chemical Ltd

Inventors

• Lee Hyuck
• Cho Seung Beom
• Son San Su
• Ju Jin Wook
• Choi Sang Soon
• Kim Jong Pil

Classifications

• C01G53/50 Primary

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

• H01M4/505

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

• C01G53/70

  containing rare earths, e.g. LaNiO3  (C01G53/68 takes precedence) · CPC title