Composite positive active material, positive electrode including the same, and lithium battery including the positive electrode

Patent metadata

Field	Value
Publication number	US-10249873-B2
Application number	US-201715665132-A
Country	US
Kind code	B2
Filing date	Jul 31, 2017
Priority date	Aug 3, 2016
Publication date	Apr 2, 2019
Grant date	Apr 2, 2019

Abstract

A composite positive active material including a composite represented by Formula 1:

δLi 2 MO 3 .(1−δ)[ x Li 2 MnO 3 .(1− x )Li d Ni a CO b M′ c O 2 ]  Formula 1
wherein, in Formula 1, M is titanium (Ti) or zirconium (Zr); M′ is manganese (Mn), vanadium (V), magnesium (Mg), gallium (Ga), silicon (Si), tungsten (W), molybdenum (Mo), iron (Fe), chromium (Cr), copper (Cu), zinc (Zn), titanium (Ti), aluminum (Al), boron (B), or a combination thereof; and 0<δ<0.5; 0≤x<0.3; a+b+c≤1; 0<a<1; 0<b<1; 0<c<1, and 0.95≤d≤1.05.

First claim

What is claimed is:

1. A composite positive active material comprising a composite represented by Formula 1:
δLi 2 MO 3 .(1−δ)[ x Li 2 MnO 3 .(1 −x )Li d Ni a CO b M′ c O 2 ]  Formula 1

wherein, in Formula 1,
M is Ti or Zr;
M′ is Mn, V, Mg, Ga, Si, W, Mo, Fe, Cr, Cu, Zn, Ti, Al, B, or a combination thereof;
0<δ<0.5; 0≤x<0.3; a+b+c≤1; 0<a<1; 0<b<1; 0<c<1; and 0.95≤d≤1.05.

2. The composite positive active material of claim 1 , wherein, in Formula 1, 0<δ<0.1, and 0<x<0.1.

3. The composite positive active material of claim 1 , wherein, in Formula 1, 0<δ<0.05, and 0<x<0.05.

4. The composite positive active material of claim 1 , wherein, in Formula 1, M′ is Mn, Al, or a combination thereof.

5. The composite positive active material of claim 1 , wherein the compound represented by Formula 1 is a compound represented by Formula 2, a compound represented by Formula 3, a compound represented by Formula 4, or a compound represented by Formula 5:
δLi 2 TiO 3 .(1−δ)[ x Li 2 MnO 3 .(1 −x )Li d Ni a CO b Mn c O 2 ]  Formula 2

wherein, in Formula 2, 0<δ<0.1, 0≤x<0.1, a+b+c≤1, 0<a<1, 0<b<1, 0<c<1, and 0.95≤d≤1.05,
δLi 2 ZrO 3 .(1−δ)[ x Li 2 MnO 3 .(1 −x )Li d Ni a Co b Mn c O 2 ]  Formula 3

wherein, in Formula 3, 0<δ<0.1, 0≤x<0.1, a+b+c≤1, 0<a<1, 0<b<1, and 0<c<1, and 0.95≤d≤1.05,
δLi 2 TiO 3 .(1−δ)[ x Li 2 MnO 3 .(1 −x )Li d Ni a Co b Al c O 2 ]  Formula 4

wherein, in Formula 4, 0<δ<0.1, 0≤x<0.1, a+b+c≤1, 0<a<1, 0<b<1, and 0<c<1, and 0.95≤d≤1.05, and
δLi 2 ZrO 3 .(1−δ)[ x Li 2 MnO 3 .(1 −x )Li d Ni a Co b Al c O 2 ]  Formula 5

wherein, in Formula 5, 0<δ<0.1, 0≤x<0.1, a+b+c≤1, 0<a<1, 0<b<1, and 0<c<1, and 0.95≤d≤1.05.

6. The composite positive active material of claim 1 , wherein, in Formula 1, δ is from 0.01 to 0.03.

7. The composite positive active material of claim 1 , wherein, in Formula 1, a is from 0.7 to 0.95, b is from 0.01 to 0.15, c is 0.01 to 0.15, and d is 0.99 to 1.04.

8. The composite positive active material of claim 1 , wherein, in Formula 1, a molar ratio of Li to a total content of transition metal is from about 1.015 to about 1.055, wherein the transition metal comprises each of M, Mn, Ni, Co, and M′.

9. The composite positive active material of claim 1 , wherein the composite represented by Formula 1 is
0.01Li 2 TiO 3 .0.99[0.015Li 2 MnO 3 .0.985Li 0.99 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.02Li 2 TiO 3 .0.98[0.015Li 2 MnO 3 .0.985Li 0.99 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.03Li 2 TiO 3 .0.97[0.015Li 2 MnO 3 .0.985Li 0.99 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.01Li 2 TiO 3 .0.99[0.015Li 2 MnO 3 .0.985LiNi 0.91 Co 0.06 Mn 0.015 O 2 ];
0.02Li 2 TiO 3 .0.98[0.015Li 2 MnO 3 .0.985LiNi 0.91 Co 0.06 Mn 0.015 O 2 ];
0.03Li 2 TiO 3 .0.97[0.015Li 2 MnO 3 .0.985LiNi 0.91 Co 0.06 Mn 0.015 O 2 ];
0.01Li 2 TiO 3 .0.99[0.015Li 2 MnO 3 .0.985Li 1.01 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.02Li 2 TiO 3 .0.98[0.015Li 2 MnO 3 .0.985Li 1.01 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.03Li 2 TiO 3 .0.97[0.015Li 2 MnO 3 .0.985Li 1.01 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.01Li 2 TiO 3 .0.99[0.015Li 2 MnO 3 .0.985Li 1.02 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.02Li 2 TiO 3 .0.98[0.015Li 2 MnO 3 .0.985Li 1.02 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.03Li 2 TiO 3 .0.97[0.015Li 2 MnO 3 .0.985Li 1.02 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.01Li 2 TiO 3 .0.99[0.015Li 2 MnO 3 .0.985Li 1.03 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.02Li 2 TiO 3 .0.98[0.015Li 2 MnO 3 .0.985Li 1.03 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.03Li 2 TiO 3 .0.97[0.015Li 2 MnO 3 .0.985Li 1.03 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.01Li 2 TiO 3 .0.99[0.015Li 2 MnO 3 .0.985Li 1.04 Ni 0.91 Co 0.06 Mn 0.015 O 2 ];
0.02Li 2 TiO 3 .0.98[0.015Li 2 MnO 3 .0.985Li 1.04 Ni 0.91 Co 0.06 Mn 0.015 O 2 ]; or
0.03Li 2 TiO 3 .0.97[0.015Li 2 MnO 3 .0.985Li 1.04 Ni 0.91 Co 0.06 Mn 0.015 O 2 ].

10. The composite positive active material of claim 1 , wherein the composite positive active material has a first peak corresponding to Li 2 TiO 3 at about 0 parts per million, and a second peak at about 200 parts per million to about 1500 parts per million, when analyzed by lithium solid-state nuclear magnetic resonance spectroscopy.

11. The composite positive active material of claim 1 , wherein the composite positive active material has an intensity ratio of a peak of a 003 face to a peak of a 104 face of about 1.54 to about 1.64, when analyzed by X-ray diffraction analysis with Cu-Kα radiation.

12. The composite positive active material of claim 1 , wherein, the composite positive active material has a peak having a diffraction angle of about 18° 2-theta to about 19° 2-theta and a full width at half maximum of about 0.2° to about 0.28°, when analyzed by X-ray diffraction.

13. The composite positive active material of claim 1 , wherein the composite positive active material comprises a primary particle having a size of from about 100 nanometers to about 300 nanometers.

14. The composite positive active material of claim 1 , wherein the composite positive active material comprises a coating layer on a surface thereof, the coating layer comprising a conductive material, a metal oxide, an inorganic fluoride, or a combination thereof.

15. The composite positive active material of claim 14 , wherein the conductive material comprises a carbonaceous material, indium tin oxide, RuO 2 , ZnO, or a combination thereof.

16. The composite positive active material of claim 14 , wherein the metal oxide comprises silica, alumina, zirconium oxide, titanium oxide, or a combination thereof.

17. The composite positive active material of claim 14 , wherein the organic fluoride comprises AlF 3 , CsF, KF, LiF, NaF, RbF, AgF, AgF, BaF 2 , CaF 2 , CuF 2 , CdF 2 , FeF 2 , HgF 2 , Hg 2 F 2 , MnF 2 , MgF 2 , NiF 2 , PbF 2 , SnF 2 , SrF 2 , XeF 2 , ZnF 2 , BF 3 , BiF 3 , CeF 3 , CrF 3 , DyF 3 , EuF 3 , GaF 3 , GdF 3 , FeF 3 , HoF 3 , InF 3 , LaF 3 , LuF 3 , MnF 3 , NdF 3 , VOF 3 , PrF 3 , SbF 3 , ScF 3 , SmF 3 , TbF 3 , TiF 3 , TmF 3 , YF 3 , YbF 3 , TlF 3 , CeF 4 , GeF 4 , HfF 4 , SiF 4 , SnF 4 , TiF 4 , VF 4 , ZrF 4 , NbF 5 , SbF 5 , TaF 5 , BiF 5 , MoF 6 , ReF 6 , SF 6 , WF 6 , or a combination thereof.

18. The composite positive active material of claim 1 , wherein the Li 2 MO 3 is electrochemically inactive with respect to lithium in a voltage range of about 4.0 volts to about 4.5 volts versus Li/Li + .

19. The composite positive active material of claim 1 , wherein the composite is represented by Formula 6:
δLi 2 MO 3 .(1−δ)Li d Ni a CO b M′ c O 2   Formula 6

wherein, in Formula 6,
M is Ti or Zr,
M′ is Mn, V, Mg, Ga, Si, W, Mo, Fe, Cr, Cu, Zn, Ti, Al, B, or a combination thereof;
0<δ<0.5; a+b+c=1; 0<a<1; 0<b<1; 0<c<1; and 1<d≤1.05.

20. A positive electrode comprising a composite positive active material comprising a composite represented by Formula 1:
δLi 2 MO 3 .(1−δ)[ x Li 2 MnO 3 .(1 −x )Li d Ni a CO b M′ c O 2 ]  Formula 1

wherein, in Formula 1,
M is Ti or Zr,
M′ is Mn, V, Mg, Ga, Si, W, Mo, Fe, Cr, Cu, Zn, Ti, aluminum (Al), B, or a combination thereof, and
0<δ<0.5, 0≤x<0.3, a+b+c≤1, 0<a<1, 0<b<1, 0<c<1, and 0.95≤d≤1.05.

21. A lithium battery comprising:
the positive electrode of claim 20 ,
a negative electrode, and
an electrolyte disposed between the positive electrode and the negative electrode.

22. The lithium battery of claim 21 , wherein the lithium battery has a voltage of about 4.5 volts or greater.

23. The lithium battery of claim 21 , wherein the negative electrode comprises a lithium metal elect

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Kim Donghan
• Song Jayhyok
• Park Jinhwan

Classifications

• H01M10/0568

  characterised by the solutes · CPC title

• H01M2300/004

  Three solvents · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title