Layered-spinel electrodes for lithium batteries

Patent metadata

Field	Value
Publication number	US-2016190577-A1
Application number	US-201514982226-A
Country	US
Kind code	A1
Filing date	Dec 29, 2015
Priority date	Dec 29, 2014
Publication date	Jun 30, 2016
Grant date	—

Abstract

An electrode for a lithium-ion cell comprising a ‘layered-spinel’ composite oxide material is disclosed. The ‘layered-spinel’ can be a material of formula xLiMO 2 .(1−x)Li y M′ z O 4 , wherein 0<x<1; LiMO 2 is a lithium metal oxide having a layered structure in which M comprises one or more transition metals and optionally lithium, and has a combined average oxidation state of +3; and Li y M′ z O 4 is a lithium metal oxide having a spinel structure, 1≦y≦1.33, 1.66≦z≦2, and M′ comprises one or more transition metals, and has a combined average metal oxidation state in the range of about +3.5 to about +4.

First claim

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1 . An electrode for a lithium-ion cell comprising a ‘layered-spinel’ composite oxide of formula xLiMO 2 (1−x)Li y M′ z O 4 , wherein 0<x<1; LiMO 2 is a lithium metal oxide having a layered structure in which M comprises one or more transition metal elements and optionally lithium, and has a combined average metal oxidation state of about +3 in an initial discharged state thereof; and Li y M′ z O 4 is a lithium metal oxide having a spinel structure, 1≦y≦1.33, 1.66≦z≦2, and M′ comprises one or more transition metal elements, and has a combined average metal oxidation state in the range of about +3.5 to about +4 in an initial discharged state thereof.

2 . The electrode of claim 1 , wherein M and M′ comprise one or more first row transition metal elements.

3 . The electrode of claim 1 , wherein the transition metal elements comprise one or more of Mn, Ni and Co.

4 . The electrode of claim 1 , wherein one or more of M and M′ comprises Ti.

5 . The electrode of claim 1 , wherein one or more of M and M′ comprises Al.

6 . The electrode of claim 1 , wherein the metal oxide having a layered structure comprises a material of formula Li[Li 0.33 Mn 0.67 ]O 2 .

7 . The electrode of claim 1 , wherein the metal oxide having a layered structure comprises a material of formula Li[Li 0.33 Ti 0.67 ]O 2 .

8 . The electrode of claim 1 , wherein the metal oxide having a layered structure comprises a LiCoO 2 material.

9 . The electrode of claim 1 , wherein the metal oxide having a layered structure comprises a LiNi 0.80 Co 0.15 Al 0.05 O 2 material.

10 . The electrode of claim 1 , wherein the metal oxide having a layered structure comprises a LiNi 1−a−b Mn a Co b O 2 , material, wherein 0≦a≦1; 0≦b≦1.

11 . The electrode of claim 1 , wherein the metal oxide having a spinel structure comprises a material of formula Li 1+w M′ 2−w O 4 (0≦w≦0.33).

12 . The electrode of claim 11 , wherein the metal oxide having a spinel structure comprises a material of formula Li 1+w Mn 2−w O 4 .

13 . The electrode of claim 11 , wherein the metal oxide having a spinel structure comprises a material of formula Li 1+w Ti 2−w O 4 .

14 . The electrode of claim 1 , wherein the metal oxide having a spinel structure comprises a material of formula Li 1+t M′ 2 O 4 , wherein 0≦t≦1.

15 . The electrode of claim 1 , wherein ‘layered-spinel’ composite oxide comprises a material selected from:
0.95LiCoO 2 .0.05LiMn 2 O 4 ;
0.95LiCoO 2 .0.05Li 1.1 Mn 1.9 O 4 ;
0.95LiCoO 2 .0.05Li 1.33 Mn 1.67 O 4 ;
0.95LiCoO 2 .0.05Li 1.33 Ti 1.67 O 4 ;
0.90LiCoO 2 .0.05Li 2 MnO 3 .0.05Li 1.1 Mn 1.9 O 4 ;
0.95LiNi 0.80 CO 0.15 Al 0.05 O 2 .0.05LiMn 2 O 4 ;
0.95LiNi 0.80 CO 0.15 Al 0.05 O 2 .0.05Li 1.1 Mn 1.9 O 4 ;
0.95LiNi 0.80 CO 0.15 Al 0.05 O 2 .0.05Li 1.33 Mn 1.67 O 4 ;
0.90LiNi 0.80 CO 0.15 Al 0.05 O 2 .0.10Li 1.33 Ti 1.67 O 4 ;
0.90LiNi 0.80 CO 0.15 Al 0.05 O 2 .0.05Li 2 MnO 3 .0.05Li 1.1 Mn 1.9 O 4 ;
0.95LiNi 0.33 Mn 0.33 CO 0.33 O 2 .0.05LiMn 2 O 4 ;
0.95LiNi 0.33 Mn 0.33 CO 0.33 O 2 .0.05Li 1.1 Mn 1.9 O 4 ;
0.95LiNi 0.33 Mn 0.33 CO 0.33 O 2 .0.05Li 1.33 Mn 1.67 O 4 ;
0.90LiNi 0.33 Mn 0.33 CO 0.33 O 2 .0.10Li 1.33 Ti 1.67 O 4 ; and
0.90LiNi 0.33 Mn 0.33 CO 0.33 O 2 .0.05Li 2 MnO 3 .0.05Li 1.1 Mn 1.9 O 4 .

16 . The electrode of claim 1 , wherein oxygen ions are partially substituted by fluorine ions, at the surface of particles of the composite oxide, within the interior of particles of the composite oxide, or both.

17 . The electrode of claim 1 , wherein the composite oxide includes one or more localized configurations or regions comprising (a) disordered layered-, spinel-, lithiated-spinel-, and/or rocksalt structures, (b) partially disordered layered-, spinel-, lithiated-spinel-, and/or rocksalt structures, (c) crystallographic cationic defects, (d) crystallographic anionic defects, and/or (e) cation distributions that are intermediate between layered, spinel, lithiated-spinel and/or rocksalt cation distributions.

18 . The electrode of claim 1 , wherein M and M′ of the composite oxide together comprise a combination of Co, Mn and Ni, in which the cobalt content of the combination is higher than the combined manganese and nickel content thereof.

19 . The electrode of claim 1 , wherein M and M′ of the composite oxide together comprise a combination of Co, Mn and Ni, in which the nickel content of the combination is higher than the combined manganese and the cobalt content thereof.

20 . The electrode of claim 1 , wherein M and M′ of the composite oxide together comprise a combination of Co, Mn and Ni, in which the combined content of cobalt and nickel in the composite oxide is higher than the manganese content thereof.

21 . An electrochemical cell comprising an anode, a cathode comprising the electrode of claim 1 , and a lithium-containing electrolyte contacting the anode and the cathode.

22 . The electrochemical cell of claim 21 , wherein the cathode further comprises carbon particles and a binder.

23 . The electrochemical cell of claim 22 , wherein the binder comprises polyvinylidene difluoride (PVDF).

24 . The electrochemical cell of claim 21 , wherein the electrolyte comprises a solution of LiPF 6 in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC).

25 . A battery comprising a plurality of electrically connected electrochemical cells of claim 21 , arranged in series, parallel, or both.

26 . A method for producing a stabilized electrode comprising a composite oxide material, the method comprising the step of heating LiMO 2 and/or a solid precursor compound or compounds of LiMO 2 at a temperature in the range of about 400 to 850° C. to form a stabilizing layered component and a stabilizing spinel component embed at the surface of and/or within particles of the composite oxide material.

27 . The method of claim 26 , wherein the precursor compounds comprise one or more material selected from lithium hydroxide, lithium carbonate, manganese oxalate, manganese hydroxide, manganese oxy-hydroxide, and manganese carbonate.

28 . The method of claim 26 , wherein the stabilizing spinel component comprises Li 2 [Co 2 ]O 4 and/or the stabilizing layered component comprises LiCoO 2 .

Assignees

• Uchicago Argonne Llc

Inventors

• Thackeray Michael M
• Croy Jason R
• Long Brandon R
• Lee Eungje
• Park Joong Sun

Classifications

• H01M4/623

  fluorinated polymers · CPC title

• H01M4/1315

  containing halogen atoms, e.g. LiCoOxFy · CPC title

• C01G23/005

  Alkali titanates · CPC title

• H01M2300/0037

  Mixture of solvents · CPC title

• H01M4/505

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