Composite cathode active material, cathode and lithium battery containing the composite cathode active material

Patent metadata

Field	Value
Publication number	US-2016190550-A1
Application number	US-201514806903-A
Country	US
Kind code	A1
Filing date	Jul 23, 2015
Priority date	Dec 29, 2014
Publication date	Jun 30, 2016
Grant date	—

Abstract

A composite cathode active material including: a first metal oxide having a layered crystal structure; and a second metal oxide having a perovskite crystal structure, wherein the second metal oxide includes a first metal and a second metal that are each 12-fold cubooctahedrally coordinated to oxygen. Also a cathode including the composite cathode material and a lithium battery containing the cathode.

First claim

What is claimed is:

1 . A composite cathode active material comprising:
a first metal oxide having a layered crystal structure; and a second metal oxide having a perovskite crystal structure, wherein the second metal oxide comprises a first metal and a second metal that are each 12-fold cuboctahedrally coordinated to oxygen.

2 . The composite cathode active material of claim 1 , wherein the first metal is selected from elements belonging to Group 2 and Group 3 of the Periodic Table.

3 . The composite cathode active material of claim 1 , wherein the first metal is selected from La, Sr, Ba, Ce, Y, and Sc.

4 . The composite cathode active material of claim 1 , wherein the second metal is selected from elements belonging to Group 1, Group 2, and Group 11 of the Periodic Table.

5 . The composite cathode active material of claim 1 , wherein the second metal is selected from Li, Na, Ca, Ag, K, Mg, and Cu.

6 . The composite cathode active material of claim 1 , wherein the second metal oxide further comprises a third metal that is 6-fold octahedrally coordinated to oxygen.

7 . The composite cathode active material of claim 6 , wherein the third metal is selected from elements belonging to Group 4, Group 5, Group, 6, Group 7, Group 8, Group 9, Group 10, Group 11, and Groups 12 to 14.

8 . The composite cathode active material of claim 6 , wherein the third metal is selected from Mn, V, Cr, Fe, Co, Ni, Zr, Ti, Mg, Cu, Nb, Ta, Ru, W, and Sn.

9 . The composite cathode active material of claim 1 , wherein the second metal oxide has a composition represented by Formula 1:
(A 1-a A′ a )M 1 O 3   Formula 1
wherein, in Formula 1, A is a metal selected from La, Sr, Ba, Ce, Y, and Sc, A′ is a metal selected from Li, Na, Ca, Ag, K, Mg, and Cu, M 1 is at least one metal 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 cathode active material of claim 1 , wherein the second metal oxide comprises at least one metal oxide selected from (La 1-a Na a )MnO 3 , (La 1-a Li a )MnO 3 , (Ba 1-a Na a )TiO 3 , (Ba 1-a Li a )TiO 3 , (La 1-a Na a )NiO 3 , (La 1-a Li a )NiO 3 , (La 1-a Na a )CoO 3 , (La 1-a Li a )CoO 3 , (La 1-a Na a )MgO 3 , (La 1-a Li a )MgO 3 , (La 1-a Na a )FeO 3 , (La 1-a Li a )FeO 3 , (5r 1-a Na a )NiO 3 , (Sr 1-a Li a )NiO 3 , (Sr 1-a Na a )CoO 3 , (Sr 1-a Li a )CoO 3 , (Sr 1-a Na a )MnO 3 , (Sr 1-a Li a )MnO 3 , (Sr 1-a Na a )MgO 3 , (Sr 1-a Li a )MgO 3 , (Sr 1-a Na a )FeO 3 , (Sr 1-a Li a )FeO 3 , (Ba 1-z Na a )NiO 3 , (Ba 1-a Li a )NiO 3 , (Ba 1-a Na a )Co0 3 , (Ba 1-a Li a )CoO 3 , (Ba 1-a Na a )MnO 3 , (Ba 1-a Li a )MnO 3 , (Ba 1-a Na a )MgO 3 , (Ba 1-a Li a )MgO 3 , (Ba 1-a Na a )FeO 3 , (Ba 1-a Li a )FeO 3 , (Ca 1-a Na a )NiO 3 , (Ca 1-a Li a )NiO 3 , (Ca 1-a Na a )CoO 3 , (Ca 1-a Li a )CoO 3 , (Ca 1-a Na a )MnO 3 , (Ca 1-a Li a )MnO 3 , (Ca 1-a Na a )MgO 3 , (Ca 1-a Li a )MgO 3 , (Ca 1-a Na a )FeO 3 , and (Ca 1-a Li a )FeO 3 , wherein, in the metal oxides, 0<a≦0.3.

11 . The composite cathode active material of claim 1 , wherein the first metal oxide comprises a plurality of crystal phases, and wherein a first crystal phase and a second crystal phase of the plurality of crystal phases have different compositions.

12 . The composite cathode active material of claim 11 , wherein composite cathode active material comprises a composite phase comprising the plurality of crystal phases.

13 . The composite cathode active material of claim 1 , wherein the first metal oxide has a composition represented by Formula 2:
v[Li 2-b A′ b ][M 1-c A′ c ]O 3 −w[Li 1-d A′ d ][Me 1-e N′ e ]O 2   Formula 2
wherein, in Formula 2, A′ is a metal selected from Li, Na, Ca, Ag, K, Mg, and Cu, M is at least one metal selected from Al, Ga, Ge, Mg, Nb, Zn, Cd, Ti, Co, Ni, K, Na, Ca, Si, Fe, Cu, Sn, V, B, P, Se, Bi, As, Zr, Re, Ru, Mn, Cr, Sr, Sc, Y, and a rare earth element, Me is at least one metal selected from Mn, V, Cr, Fe, Co, Ni, Zr, Re, Al, B, Ge, Ru, Sn, Ti, Nb, Mo, and Pt,
0< v< 1, 0< w< 1, and v+w= 1,
0 ≦b< 1, 0 ≦c< 1, 0 ≦d< 1, 0 ≦e< 1, and 0 ≦Al ′/Li≦ 0.3,
wherein, A′/Li is a ratio of a mole ratio of A′ to Li in the composite cathode active material.

14 . The composite cathode active material of claim 1 , wherein the composite cathode active material comprises a composite of the first metal oxide and the second metal oxide.

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

16 . The composite cathode active material of claim 1 having a composition represented by Formula 3:
Formula 3   Formula 3

wherein, in Formula 3,
A′ is a metal selected from Li, Na, Ca, Ag, K, Mg, and Cu,
A is a metal selected from La, Sr, Ba, Ce, Y, and Sc,
M 1 is at least one metal selected from Mn, V, Cr, Fe, Co, Ni, Zr, Ti, Mg, Cu, Nb, Ta, Ru, W, and Sn,
M is at least one metal selected from Al, Ga, Ge, Mg, Nb, Zn, Cd, Ti, Co, Ni, K, Na, Ca, Si, Fe, Cu, Sn, V, B, P, Se, Bi, As, Zr, Re, Ru, Mn, Cr, Sr, Sc, Y, and a rare earth element,
Me is at least one metal selected from Mn, V, Cr, Fe, Co, Ni, Zr, Re, Al, B, Ge, Ru, Sn, Ti, Nb, Mo, and Pt
021 x< 1, 0< y< 1, 0< z< 0.1, and x+y+z= 1, and
0 ≦a 0.3, 0≦ b< 1, 0≦ c< 1, 0≦ d< 1, 0≦ e< 1, 0< a+b+c+d+e< 0.3, and 0A′/Li<0.3,

wherein A′/Li is a ratio of a mole ratio of A′ and Li in the composite cathode active material.

17 . The composite cathode active material of claim 1 having a composition represented by Formula 4:
x[Li 2-b A′ b ][Mn 1-c A′ c ]O 3 −y[Li 1-d A′ d ][(Ni p Co q Mn r ) 1-e A′ e ]O 2 −z[La 1-a A′ a ]MnO 3   Formula 4

wherein, in Formula 4,
A′ is a metal selected from Li, Na, Ca, Ag, K, Mg, and Cu,
0< x< 1, 0< y< 1, 0< z< 0.1, and x+y+z= 1,
0 <p< 1, 0 <q< 1, 0 <r< 1, and p+q+r= 1, and
0< a≦ 0.3, 0 ≦b< 1, 0 ≦c< 1, 0 ≦d< 1, 0 ≦e< 1, 0≦ a+b+c+d+e< 0.3, and 0≦A′/Li<0.3

wherein A′/Li is a ratio of a mole ratio of A′ and Li in the composite cathode active material.

18 . The composite cathode active material of claim 1 having a composition represented by Formula 5:
x[Li 2-b Na b ][Mn 1-c Na c ]O 3 −y[Li 1-d Na d ][(Ni p Co q Mn r ) 1-e Na e ]O 2 −z[La 1-a Na a ]MnO 3    Formula 5

wherein, in Formula 5,
0< x< 1, 0< y< 1, 0< z< 0.1, and x+y+z= 1,
0< p< 1, 0< q< 1, 0< r< 1, and p+q+r= 1, and
0< a≦ 0.3,0 ≦b< 1, 0 ≦c< 1, 0 ≦d< 1, 0 ≦e< 1, 0 a+b+c+d+e< 0.3, and 0≦Na/Li<0.3,

wherein Na/Li is a ratio of a mole ratio of Na and Li in the composite cathode active material.

19 . A cathode comprising the composite cathode active material of claim 1 .

20 . A lithium battery comprising the cathode of claim 19 .

Assignees

• Samsung Electronics Co Ltd
• Samsung Fine Chemicals Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Choi Byungjin
• Kim Donghan
• Kim Ryounghee
• Park Jinhwan

Classifications

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M4/505

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

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/364 Primary

  as mixtures · CPC title