Lithium metal oxide electrodes for lithium batteries

• US 7,314,682 B2
• Filed: 04/15/2004
• Issued: 01/01/2008
• Est. Priority Date: 04/24/2003
• Status: Active Grant

• Current Assignee: U Chicago Argonne, LLC
• Original Assignee: UChicago Argonne LLC
• Inventors: Kim, Jeom-Soo, Johnson, Christopher S., Thackeray, Michael M.
• Primary Examiner(s): Kalafut; Stephen J.
• Application Number:
  US10/825,931
• Publication Number:
  US 20050026040A1
• Time in Patent Office: 1,356 Days
• Field of Search: 429/223, 429/224, 429/231.1, 429/231.3, 429/231.5, 429/231.6, 423/594.15, 423/594.4, 423/599
• US Class Current: 429/223
• CPC Class Codes: C01G 45/1228 of the type [MnO2]n- , e.g. LiMnO2, Li[MxMn1-x]O2
• CPC Class Codes: C01G 45/125 of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
• CPC Class Codes: C01G 51/50 of the type [MnO2]n- , e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
• CPC Class Codes: C01G 53/50 of the type [MnO2]n- , e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/77 by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2004/80 Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An uncycled electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula Li_(2+2x)/(2+x)M′_2x/(2+x)M_{(2−2x)/(2+x)}O_2−δ, in which 0≦x<1 and δ is less than 0.2, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M′ is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. Methods of preconditioning the electrodes are disclosed as are electrochemical cells and batteries containing the electrodes.

Claims

1. An electrode for a non-aqueous lithium electrochemical cell, comprising a lithium metal oxide having the formula, Li_(2+2x)/(2+x)M′

_2x/(2+x)M<sub>(2−

2x)/(2+x)</sub>O<sub>2−

δ</sub>

, in which 0<

x<

1 and δ

is greater than zero and less than 0.2, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M′

is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn.

2. The electrode of claim 1, where δ

is less than 0.1.

3. The electrode of claim 1, in which M is selected from Co, Ni, Mn, Ti, Mg and Al, and M′

is selected from Ti, Mn, Zr, Ru and Sn.

4. The electrode of claim 3, in which M is selected from Co, Ni and Mn, and M′

is selected from Ti and Mn.

5. The electrode of claim 4, in which M is selected from Co, Ni and Mn, and M′

is selected from Mn.

6. The electrode of claim 5, in which M is selected from Ni and Mn, and M′

is selected from Mn.

7. The electrode of claim 1, in which M is selected from Co, Ni and Mn and x=0.

8. A method of synthesizing the electrode of claim 1 in which a xLi₂M′

O₃.(1−

x)LiMO₂ electrode is subjected to a reducing environment at a temperature between about 150°

C. and about 1000°

C.

9. A method according to claim 8 in which the reducing environment consists of one or more of ammonia gas, hydrogen gas, nitrogen gas and carbon.

10. A method according to claim 9, in which the reducing environment is ammonia gas.

11. A method according to claim 8, in which the reducing temperature is between 150°

C. and 600°

C.

12. A method according to claim 11, in which the reducing temperature is between 150°

C. and 400°

C.

13. An electrode made according to the method of claim 8.

14. An electrode for a non-aqueous lithium cell, having the formula of xLi₂₋

yH_yO.xM′

O₂.(1−

x)Li<sub>1−

z</sub>H_zMO₂ compounds in which 0<

x<

1, 0<

y<

1 and 0<

z<

1 made from a lithium metal oxide xLi₂M′

O₃.(1−

x)LiMO₂, in which 0<

x<

1, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more first-row transition metals or lighter metal elements in the periodic table, and M′

is one or more ions with an average tetravalent oxidation state selected from the first- and second-row transition metal elements and Sn, the electrodes being preconditioned in a proton-containing medium with a pH<

7.0.

15. The electrode of claim 14, in which M is selected from Co, Ni, Mn, Ti, Mg and Al, and M′

is selected from Ti, Mn, Zr, Ru and Sn.

16. The electrode of claim 15, in which M is selected from Co, Ni and Mn, and M′

is selected from Ti and Mn.

17. The electrode of claim 16, in which M is selected from Co, Ni and Mn, and M′

is selected from Mn.

18. The electrode of claim 17, in which M is selected from Ni and Mn, and M′

is selected from Mn.

19. A method of synthesizing the electrode of claim 14 by subjecting the xLi₂M′

O₃.(1−

x)LiMO₂ electrode to a proton-containing medium with pH<

7.0 and thereafter heating the electrode above 100°

C. for less than 24 hours.

20. A method according to claim 19 in which the electrode is heated below 400°

C.

21. A method according to claim 19 in which the proton-containing medium consists of de-ionized water, nitric acid, acetic acid, or hydrochloric acid.

22. An electrode made according to the method of claim 19.

23. The electrode of claim 14, wherein said preconditioned electrode is at least partially dehydrated at a temperature above about 100°

C.

24. A non-aqueous lithium electrochemical cell having a negative electrode, an electrolyte and a positive electrode according to claim 23.

25. A non-aqueous lithium battery comprising a plurality of electrically connected electrochemical cells according to claim 24.

26. The electrode of claim 14, wherein said proton-containing medium contains an inorganic acid.

27. The electrode of claim 14, wherein said proton-containing medium contains HF.

28. The electrode of claim 14, wherein said proton-containing medium contains fluoride ions.

29. A non-aqueous lithium electrochemical cell comprising a negative electrode, an electrolyte and an positive electrode having a lithium metal oxide having the formula in which Li_(2+2x)/(2+x)M′

_2x/(2+x)M<sub>(2−

2x)/(2+x)</sub>O<sub>2−

δ</sub>

, in which 0<

x<

1 and δ

is greater than zero and less than 0.2, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M′

is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn.

30. A non-aqueous lithium electrochemical cell comprising a negative electrode, an electrolyte and an positive electrode having the formula of xLi₂₋

yH_yO.xM′

O₂.(1−

x) Li<sub>1−

z</sub>H_zMO₂ compounds in which 0<

x<

1, 0<

y<

1 and 0<

z<

1 made from a lithium metal oxide of xLi₂M′

O₃.(1−

x)LiMO₂, in which 0<

x<

1, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more first-row transition metals or lighter metal elements in the periodic table, and M′

is one or more ions with an average tetravalent oxidation state selected from the first- and second-row transition metal elements and Sn.

31. A non-aqueous lithium battery comprising a plurality of electrically connected electrochemical cells, each cell having a negative electrode, an electrolyte and a positive electrode formula xLi₂₋

yH_yO·

xM′

O₂.(1x)Li<sub>1−

z</sub>H_zMO₂ compounds in xLi₂M′

O₃.(1−

x)LiMO₂, in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M′

is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn.

32. A non-aqueous lithium battery comprising a plurality of electrically connected electrochemical cells, each cell having a negative electrode, an electrolyte and a positive electrode having the formula xLi₂₋

yH_yO.xM′

O₂.(1−

x)Li<sub>1−

z</sub>H_zMO₂ compounds in which 0<

x<

1, 0<

y<

1 and 0<

z<

1 made from a lithium metal oxide of xLi₂M′

O₃. (1−

x)LiMO₂, in which 0<

x<

1, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more first-row transition metals or lighter metal elements in the periodic table, and M′

is one or more ions with an average tetravalent oxidation state selected from the first- and second-row transition metal elements and Sn.