Polycrystalline lithium manganese oxide particles, preparation method thereof, and cathode active material including the same

Patent metadata

Field	Value
Publication number	US-2015030927-A1
Application number	US-201414514788-A
Country	US
Kind code	A1
Filing date	Oct 15, 2014
Priority date	Jul 26, 2013
Publication date	Jan 29, 2015
Grant date	—

Abstract

Provided are polycrystalline lithium manganese oxide particles represented by Chemical Formula 1 and a method of preparing the same:
Li (1+x) Mn (2-x-y-f) Al y M f O (4-z)   <Chemical Formula 1>
where M is sodium (Na), or two or more mixed elements including Na, 1≦x≦0.2, 0<y≦0.2, 0<f≦0.2, and 0≦z≦0.2. According to an embodiment of the present invention, limitations, such as the Jahn-Teller distortion and the dissolution of Mn 2+ , may be addressed by structurally stabilizing the polycrystalline lithium manganese oxide particles. Thus, life characteristics and charge and discharge capacity characteristics of a secondary battery may be improved.

First claim

1 . Polycrystalline lithium manganese oxide particles represented by Chemical Formula 1:
Li (1+x) Mn (2-x-y-f) Al y M f O (4-z)   <Chemical Formula 1>
where M is sodium (Na), or two or more mixed elements including Na, 0≦x≦0.2, 0<y≦0.2, 0<f≦0.2, and 0≦z≦0.2.

2 . The polycrystalline lithium manganese oxide particles of claim 1 , wherein, in Chemical Formula 1, f satisfies 0.001≦f≦0.03.

3 . The polycrystalline lithium manganese oxide particles of claim 1 , wherein, in Chemical Formula 1, the mixed element comprises any one selected from the group consisting of boron (B), cobalt (Co), vanadium (V), lanthanum (La), titanium (Ti), nickel (Ni), zirconium (Zr), yttrium (Y), and gallium (Ga), or two or more mixed elements thereof.

4 . The polycrystalline lithium manganese oxide particles of claim 3 , wherein, in Chemical Formula 1, M is Na, or a mixed element of Na and B.

5 . The polycrystalline lithium manganese oxide particles of claim 1 , wherein the polycrystalline lithium manganese oxide particles are in a form of secondary particles in which two or more primary particles having an average crystal diameter of 152 nm to 300 nm are agglomerated.

6 . The polycrystalline lithium manganese oxide particles of claim 5 , wherein an average particle diameter (D 50 ) of the secondary particle is in a range of 5 μm to 20 μm.

7 . The polycrystalline lithium manganese oxide particles of claim 1 , wherein an amount of Na in the polycrystalline lithium manganese oxide particles is in a range of 700 ppm to 3,000 ppm.

8 . The polycrystalline lithium manganese oxide particles of claim 1 , wherein I(311)/I(111) of the lithium manganese oxide particles is 40% or more when a peak intensity ratio of I(111)/I(111) is defined as 100% in X-ray diffraction analysis.

9 . The polycrystalline lithium manganese oxide particles of claim 1 , wherein I(400)/I(111) and I(440)/I(111) of the lithium manganese oxide particles are respectively 40% or more and 20% or more when a peak intensity ratio of I(111)/I(111) is defined as 100% in X-ray diffraction analysis.

10 . The polycrystalline lithium manganese oxide particles of claim 1 , wherein a full width at half maximum (FWHM) of a (311) peak of the lithium manganese oxide particles in X-ray diffraction analysis is 0.3 degrees or less.

11 . The polycrystalline lithium manganese oxide particles of claim 1 , wherein a Brunauer-Emmett-Teller (BET) specific surface area of the lithium manganese oxide particles is 0.5 m 2 /g or less.

12 . A method of preparing polycrystalline lithium manganese oxide particles represented by Chemical Formula 1 comprising:
(i) obtaining a precursor mixture including a polycrystalline manganese precursor, a lithium precursor, and a sintering aid; and (ii) sintering the precursor mixture obtained in step (i),
Li (1+x) Mn (2-x-y-f) Al y M f O (4-z)   <Chemical Formula 1>

where M is sodium (Na), or two or more mixed elements including Na, 0≦x≦0.2, 0<y≦0.2, 0<f≦0.2, and 0≦z≦0.2.

13 . The method of claim 12 , wherein the polycrystalline manganese precursor is in a form of secondary particles in which two or more primary particles having an average crystal diameter of 100 nm to 300 nm are agglomerated.

14 . The method of claim 13 , wherein an average particle diameter (D 50 ) of the secondary particle is in a range of 9 μm to 25 μm.

15 . The method of claim 14 , wherein the average particle diameter (D 50 ) of the secondary particle is in a range of 9 μm to 15 μm.

16 . The method of claim 12 , wherein the polycrystalline manganese precursor comprises aluminum (Al) in an amount of 0.01 wt % to 10 wt %.

17 . The method of claim 16 , wherein the polycrystalline manganese precursor comprises (Mn (1-y) Al y ) 3 O 4 (0<y≦0.2).

18 . The method of claim 17 , wherein the polycrystalline manganese precursor is formed by coprecipitating an aluminum compound and any one selected from the group consisting of MnCO 3 , Mn 3 O 4 , MnSO 4 , and Mn 2 O 3 , or a mixture of two or more thereof.

19 . The method of claim 18 , wherein the aluminum compound comprises any one selected from the group consisting of AlSO 4 , AlCl, and AlNO 3 , or a mixture of two or more thereof.

20 . The method of claim 12 , wherein the sintering aid comprises a sodium compound.

21 . The method of claim 20 , wherein the sintering aid further comprises any one selected from the group consisting of a boron compound, a cobalt compound, a vanadium compound, a lanthanum compound, a zirconium compound, an yttrium compound, and a gallium compound, or a mixture of two or more thereof.

22 . The method of claim 21 , wherein the sintering aid is the sodium compound, or a mixture of the sodium compound and the boron compound.

23 . The method of claim 20 , wherein the sodium compound comprises sodium carbonate, sodium silicate, sodium hydroxide, or a mixture of two or more thereof.

24 . The method of claim 22 , wherein the boron compound comprises any one selected from the group consisting of boron, lithium tetraborate, boron oxide, and ammonium borate, or a mixture of two or more thereof.

25 . The method of claim 12 , wherein the sintering aid is used in an amount of 0.2 parts by weight to 2 parts by weight based on a total weight of the polycrystalline manganese precursor.

26 . The method of claim 12 , wherein the sintering is performed in a temperature range of 700° C. to 1,000° C.

27 . The method of claim 12 , wherein the lithium precursor comprises any one selected from the group consisting of lithium chloride (LiCl), lithium carbonate (LiCO 3 ), lithium hydroxide (LiOH), lithium phosphate (Li 3 PO 4 ), and lithium nitrate (LiNO 3 ), or a mixture of two or more thereof.

28 . A cathode active material comprising the polycrystalline lithium manganese oxide particles of claim 1 .

29 . A cathode comprising the cathode active material of claim 28 .

30 . A lithium secondary battery comprising the cathode of claim 29 .

Assignees

• Lg Chemical Ltd

Inventors

• Kwak Ick Soon
• Cho Seung Beom
• Chae Hwa Seok

Classifications

• H01M4/505 Primary

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

• C01G45/1214

  containing alkali metals · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• C01P2004/03

  obtained by SEM · CPC title

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title