Multifunctional mixed metal olivines for lithium ion batteries

• US 9,509,019 B2
• Filed: 05/29/2012
• Issued: 11/29/2016
• Est. Priority Date: 07/12/2007
• Status: Active Grant

• Current Assignee: A123 Systems Incorporated
• Original Assignee: A123 Systems Incorporated
• Inventors: Jang, Young-Il, Chiang, Yet-Ming, Chu, Andrew C., Meethong, Nonglak, Kao, Yu-Hua, Riley, Gilbert N. Jr., Pullen, Anthony E., Thomas-Alyea, Karen E.
• Primary Examiner(s): GATEWOOD, DANIEL S
• Application Number:
  US13/482,649
• Publication Number:
  US 20120231308A1
• Time in Patent Office: 1,645 Days
• US Class Current: 1/1
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/44 Methods for charging or discharging circuits for charging H02J7/00
• CPC Class Codes: H01M 10/48 Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte constructional details of current conducting connections for detecting conditions inside cells or batteries, e.g. details of voltage sensing terminals, H01M50/569
• CPC Class Codes: H01M 4/364 as mixtures
• 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 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Electroactive compositions are disclosed for use in lithium ion battery electrodes. The compositions, such as multifunctional mixed metal olivines, provide an electrochemical cell having a plurality of open circuit voltages at different states of charge. The compositions afford improved state-of-charge monitoring, overcharge protection and/or overdischarge protection for lithium ion batteries.

Claims

1. An electroactive composition for use as a positive electrode material in an electrochemical cell comprising a high voltage indicator and a low voltage indicator, said composition comprising an olivine lithium metal phosphate material having the formula Li_xM′

_yM″

_zM′

″

_wPO₄, wherein

M′

is one or more of Mn and Fe;

M″

is one or more of Mn, Co and Ni, wherein M″

is a high voltage indicator with a high voltage plateau, where the high voltage plateau is between 0.5 and 2.0 V higher than a working voltage of the cell;

M′

″

is one or more of Ti, Zr and Mg, wherein M′

″

is a low voltage indicator with a low voltage plateau, where the low voltage plateau is between 0.1 and 0.7 V lower than a working voltage of the cell;

M′

is not the same as M″

;

M″

is not the same as M′

″

;

0≦

x≦

0.1.2;

0.5≦

y≦

0.95;

0.05≦

z≦

0.2;

0.025≦

w≦

0.25;

0.8≦

y+z+w≦

1.2; and

where the high voltage plateau of the high voltage indicator and the low voltage plateau of the low voltage indicator are different than the working voltage of the cell.

3. The composition of claim 1, wherein 0.6≦

y≦

0.9.

4. The composition of claim 1, wherein 0.05≦

w≦

0.2.

5. The composition of claim 1, wherein 0.6≦

y≦

0.9, 0.05≦

z≦

0.2 and 0.05≦

w≦

0.2.

6. The composition of claim 1, wherein M′

is Mn.

7. The composition of claim 1, wherein M′

is Fe.

8. The composition of claim 1, wherein M″

is Mn.

9. The composition of claim 1, wherein M″

in Co.

10. The composition of claim 1, wherein M″

in Ni.

11. The composition of claim 1, wherein M′

″

is Ti.

12. The composition of claim 1, wherein Mi′

″

in Zr.

13. The composition of claim 1, wherein M′

″

in Mg.

2. An electrochemical cell comprising a high voltage indicator and a low voltage indicator, comprising:

(a) a positive electrode comprising a positive electrode electroactive material including an olivine lithium metal phosphate having the formula Li_xM′

_yM″

_zM′

″

_wPO₄, wherein

M′

is one or more of Mn and Fe;

M″

is one or more of Mn, Co and Ni, wherein M″

is a high voltage indicator, with a high voltage plateau, where the high voltage plateau is between 0.5 and 2.0 V higher than a working voltage of the cell;

M′

″

is one or more of Ti, Zr and Mg, wherein M′

″

is a low voltage indicator, with a low voltage plateau, where the low voltage plateau is between 0.1 and 0.7 V lower than a working voltage of the cell;

M′

is not the same as M″

;

M″

is not the same as M′

″

;

0≦

x≦

1.2;

0.5≦

y≦

0.95;

0.05≦

z≦

0.2;

0.025≦

w≦

0.25; and

0.8≦

y+z+w≦

1.2, where the high voltage indicator and the low voltage indicator are different than the working voltage of the cell; and

(b) a negative electrode separated from the positive electrode by an electrolyte.

14. The electrochemical cell of claim 2, wherein 0.6≦

y≦

0.9.

15. The electrochemical cell of claim 2, wherein 0.05≦

w≦

0.2.

16. The electrochemical cell of claim 2, wherein 0.6≦

y≦

0.9, 0.05≦

z≦

0.2 and 0.05≦

w≦

0.2.

17. The electrochemical cell of claim 2, wherein M′

is Mn.

18. The electrochemical cell of claim 2, wherein M′

is Fe.

19. The electrochemical cell of claim 2, wherein M″

is Mn.

20. The electrochemical cell of claim 2, wherein M″

in Co.

21. The electrochemical cell of claim 2, wherein M″

in Ni.

22. The electrochemical cell of claim 2, wherein M′

″

is Ti.

23. The electrochemical cell of claim 2, wherein M′

″

in Zr.

24. The electrochemical cell of claim 2, wherein M′

″

in Mg.