Composite positive active material, method of preparing the same, positive electrode including the composite positive active material, and lithium battery including the positive electrode

Patent metadata

Field	Value
Publication number	US-2017179470-A1
Application number	US-201615161759-A
Country	US
Kind code	A1
Filing date	May 23, 2016
Priority date	Dec 18, 2015
Publication date	Jun 22, 2017
Grant date	—

Abstract

A composite positive active material includes: a composite including a first metal oxide represented by Formula 1 and having a layered structure, and a second metal oxide having at least one crystal structure selected from a layer structure, a perovskite structure, a rock salt structure, and a spinel structure, wherein a content of the second metal oxide is greater than 0 and equal to or less than 0.2 moles, per mole of the composite,
LiNi x M 1 1-x O 2-e M 2 e   Formula 1

wherein, in Formula 1, M 1 is at least one element selected from Group 4 to Group 14 of the Periodic Table of the Elements; M a is at least one element selected from F, S, Cl, and Br; 0.7≦x<1; and 0≦e<1. Also, a positive electrode including the composite positive active material, and a lithium battery including the positive electrode.

First claim

What is claimed is:

1 . A composite positive active material comprising:
a composite comprising
a first metal oxide represented by Formula 1 and having a layered structure, and
a second metal oxide having at least one crystal structure selected from a layered structure, a perovskite structure, a rock salt structure, and a spinel structure;
wherein a content of the second metal oxide is greater than 0 and equal to or less than 0.2 moles, per mole of the composite,
LiNi x M 1 1-x O 2-e M a e   Formula 1

wherein, in Formula 1, M 1 is at least one element selected from Group 4 to Group 14 element of the Periodic Table of the Elements; M a is at least one element selected from F, S, Cl, and Br 0.7≦x<1; and 0≦e<1.

2 . The composite positive active material of claim 1 , wherein an amount of residual lithium in the composite positive active material is about 15,000 parts per million or less, based on a total amount of the composite positive active material.

3 . The composite positive active material of claim 1 , wherein M 1 in Formula 1 comprises at least one metal selected from manganese, vanadium, chromium, iron, cobalt, nickel, zirconium, rhenium, aluminum, boron, germanium, ruthenium, tin, titanium, niobium, molybdenum, and platinum.

4 . The composite positive active material of claim 1 , wherein the first metal oxide of Formula 1 is a compound represented by Formula 2,
LiNi x Co y Mn z M 3 c O 2-e M a e   Formula 2
wherein, in Formula 2, 0.7≦x≦0.99; 0≦y<1; 0<z<1; 0≦c<1; 0<x+y+z+c≦1; 0≦e<1; M 3 is at least one selected from Group 4 to Group 14 elements of the Periodic Table of the Elements; and M a is at least one element selected from F, S, Cl, and Br.

5 . The composite positive active material of claim 1 , wherein the first metal oxide of Formula 1 is a compound represented by Formula 3:
LiNi x Co y Mn z O 2   Formula 3
wherein, in Formula 3, 0.7≦x≦0.99; 0<y<1; 0<z<1; and 0<x+y+z≦1.

6 . The composite positive active material of claim 1 , wherein the second metal oxide is a compound represented by Formula 4, a compound represented by Formula 5, a compound represented by Formula 6, or a compound represented by Formula 7,
A 2 M 2 O 3 ,  Formula 4
AM 2 O 3 ,  Formula 5
(A b M 2 1-b )O, or  Formula 6
AM 2 2 O 4 ,  Formula 7
wherein, in Formulae 4 to 7, A is at least one element selected from Group 1 to Group 3 elements of the Periodic Table of the Elements, M 2 is at least one element selected from Group 2 to Group 16 elements and rare earth elements, and 0≦b≦1.

7 . The composite positive active material of claim 6 , wherein, in Formulae 4 to 7,
A is at least one element selected from Li, Na, La, Sr, Ba, H, K, Ca, and Y; and M 2 is at least one element selected from Al, Ga, Ge, Mg, Nb, Zn, Cd, Ti, Co, Ni, Mn, Ca, Si, Fe, Cu, Sn, V, B, P, Se, Bi, As, Zr, Re, Ru, Cr, Sr, Sc, and Y.

8 . The composite positive active material of claim 6 , wherein the compound represented by Formula 4 is Li 2 MnO 3 , Li 2 TiO 3 , Li 2 SnO 3 , Li 2 ZrO 3 , Li 2 MoO 3 , or Li 2 RuO 3 .

9 . The composite positive active material of claim 6 , wherein the compound represented by Formula 5 is a compound represented by Formula 8,
(A 1 1-a A 2 a )M 1 O 3   Formula 8
wherein, in Formula 8,
A 1 is at least one selected from La, Sr, Ba, Ce, Y, and Sc;
A 2 is at least one selected from Li, Na, Ca, Ag, K, Mg, and Cu;
M 1 is at least one selected from Mn, V, Cr, Fe, Co, Ni, Zr, Ti, Mg, Cu, Nb, Ta, Ru, W, and Sn; and
0<a≦0.3.

10 . The composite positive active material of claim 6 , wherein the compound represented by Formula 6 is at least one selected from (Li b Ni 1-b )O, (Li b Co 1-b )O, (Li b Fe 1-b )O, (Li b Cu 1-b O, (Li b Zn 1-b )O, (Li b Ca 1-b )O, (Li b Sr 1-b )O, (Li b Mg 1-b )O, and (Li b Cr 1-b )O), wherein each b is independently selected and is 0≦b≦1.

11 . The composite positive active material of claim 6 , wherein the compound represented by Formula 7 is LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , LiCo 0.5 Mn 1.5 O 4 , Li[Co f Ni g Mn h ] 2 O 4 , or Li[Cu c Mn 2-c ] 2 O 4 , wherein 0<c≦2, 0<f≦2; 0<g≦2, 0<h≦2; and f+g+h=2.

12 . The composite positive active material of claim 1 , wherein the composite positive active material comprises at least one selected from compounds represented by Formulae 9 to 12,
(1− a )LiNi x M 1 1-x O 2 .a A 2 M 2 O 3 ,  Formula 9
(1− a )LiNi x M 1 1-x O 2 .a AM 2 O 3 ,  Formula 10
(1− a )LiNi x M 1 1-x O 2 .a (A b M 2 1-b )O, and  Formula 11
(1− a )LiNi x M 1 1-x O 2 .a AM 2 2 O 4 ,  Formula 12
wherein, in Formulae 9 to 12, A is at least one metal selected from Li, Na, La, Sr, Ba, H, K, Ca, and Y; M 2 is at least one selected from Al, Ga, Ge, Mg, Nb, Zn, Cd, Ti, Co, Ni, Mn, Ca, Si, Fe, Cu, Sn, V, B, P, Se, Bi, As, Zr, Re, Ru, Cr, Sr, Sc, Y, and a rare earth element; and 0<a≦0.2, 0<b≦1.

13 . The composite positive active material of claim 1 , wherein the composite positive active material is at least one selected from compounds represented by Formulae 9-1 to 12-1,
(1− a )LiNi x Co y Mn z O 2 .a Li 2 MnO 3 ,  Formula 9-1
(1− a )LiNi x Co y Mn z O 2 .a LiMnO 3 ,  Formula 10-1
(1− a )LiNi x Co y Mn z O 2 .a (Li b La 1-b )MnO 3 ,  Formula 10-2
(1− a )LiNi x Co y Mn z O 2 .a (Li b Ni 1-b )O, and  Formula 11-1
(1− a )LiNi x Co y Mn z O 2 .a LiMn 2 O 4 ,  Formula 12-1
wherein, in Formulae 9-1 to 12-1, 0.7≦x≦0.99, 0<y≦0.3, 0<z≦0.3, x+y+z=1, 0<b≦1, and 0<a≦0.2.

14 . The composite positive active material of claim 13 , wherein, in Formulae 9-1 to 12-1, LiNi x Co y Mn z O 2 is selected from LiNi 0.85 Co 0.10 Mn 0.05 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.75 Co 0.20 Mn 0.05 O 2 , and LiNi 0.9 Co 0.05 Mn 0.05 O 2 .

15 . The composite positive active material of claim 1 , wherein the second metal oxide is intermixed in the layered structure of the first metal oxide.

16 . The composite positive active material of claim 1 , wherein the composite positive active material is selected from 0.98LiNi 0.85 Co 0.10 Mn 0.05 O 2 .0.02Li 2 MnO 3 , 0.95LiNi 0.85 Co 0.10 Mn 0.05 O 2 .0.05Li 2 MnO 3 , 0.9LiNi 0.85 Co 0.10 Mn 0.05 O 2 .0.1Li 2 MnO 3 , 0.8LiNi 0.85 Co 0.10 Mn 0.05 O 2 .0.2Li 2 MnO 3 , 0.98LiNi 0.8 Co 0.1 Mn 0.1 O 2 .0.02Li 2 MnO 3 , 0.95LiNi 0.8 Co 0.1 Mn 0.1 O 2 .0.05Li 2 MnO 3 , 0.9LiNi 0.8 Co 0.1 Mn 0.1 O 2 .0.1Li 2 MnO 3 , 0.8LiNi 0.8 Co 0.1 Mn 0.1 MnO 2 .0.2Li 2 MnO 3 , 0.98LiNi 0.75 Co 0.20 Mn 0.05 O 2 .0.02Li 2 MnO 3 , 0.95LiNi 0.75 Co 0.20 Mn 0.05 O 2 .0.05Li 2 MnO 3 , 0.9LiNi 0.75 Co 0.20 Mn 0.05 O 2 .0.1Li 2 MnO 3 , 0.8LiNi 0.75 Co 0.20 Mn 0.05 O 2 .0.2Li 2 MnO 3 , 0.98LiNi 0.9 Co 0.05 Mn 0.05 O 2 .0.02Li 2 MnO 3 , 0.95LiNi 0.9 Co 0.05 Mn 0.05 O 2 .0.05Li 2 MnO 3 , 0.9LiNi 0.9 Co 0.05 Mn 0.05 O 2 .0.1Li 2 MnO 3 , and 0.8LiNi 0.8 Co 0.05 Mn 0.05 O 2 .0.2Li 2 MnO 3 .

17 . The composite positive active material of claim 1 , wherein, when evaluated by X-ray diffraction analysis with Cu—Kα radiation, a diffraction peak measured at a 2 theta value of about 18.5° to about 19.0° has a full width at half maximum of about 0.1968° to about 0.2362°.

18 . The composite positive active material of claim 1 , wherein a half cell having a positive element including the composite positive active material and lithium metal as a counter electrode has an average discharge voltage of about 92.5% to about 99.95% after a 50 th charging and discharging cycle, with respect to the average discharge voltage after a 1 st charging and discharging cycle.

19 . The

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Choi Byungjin
• Kapylou Andrei
• Kim Donghan
• Park Jinhwan
• Song Jayhyok
• Ahn Sungjin
• Yeon Donghee
• Yu Byongyong

Classifications

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/13

  Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof · CPC title

• H01M4/624

  Electric conductive fillers · CPC title

• H01M4/366

  as layered products · CPC title