Methods of charging lithium-sulfur batteries

• US 6,329,789 B1
• Filed: 12/21/1999
• Issued: 12/11/2001
• Est. Priority Date: 12/21/1999
• Status: Expired due to Term

• Current Assignee: Sion Power Corporation
• Original Assignee: Moltech Corporation
• Inventors: Gavrilov, Alexei B., Mikhaylik, Yuriy V.
• Primary Examiner(s): TOATLEY, GREGORY J
• Application Number:
  US09/469,736
• Time in Patent Office: 721 Days
• Field of Search: 320/128, 320/130, 320/131, 320/160, 320/125
• US Class Current: 320/125
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 10/44 Methods for charging or discharging circuits for charging H02J7/00
• CPC Class Codes: H01M 4/5815 Sulfides
• CPC Class Codes: H01M 4/602 Polymers
• CPC Class Codes: H02J 7/0069 Charging or discharging for charge maintenance, battery initiation or rejuvenation
• CPC Class Codes: H02J 7/007182 in response to battery voltage
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Provided is a method for increasing the cycle life of discharged lithium electrochemical cells, wherein the cell comprises (i) an anode comprising lithium; (ii) a cathode comprising an electroactive sulfur-containing material; and (iii) a liquid electrolyte interposed between the anode and cathode; wherein the method comprises the steps of: (a) charging the cell at an initial low rate of less than 0.2 mA/cm² to a cell voltage in the range of 2.1 to 2.3 V followed by (b) a subsequent high rate of greater than 0.2 mA/cm² to a cell voltage of at least 2.4 V.

Claims

1. A method of increasing the cycle life of a lithium electrochemical cell, wherein said method comprises the steps of:

(a) discharging said cell at an overall rate of less than 0.5 mA/cm²;

(b) charging said cell at an initial low charge rate of less than 0.2 mA/cm² to a cell voltage in the range of 2.1 to 2.3 V; and

(c) subsequently charging said cell at a high charge rate of greater than 0.2 mA/cm² to a cell voltage of at least 2.4 V;

 

wherein said cell comprises;

(i) an anode comprising lithium;

(ii) a cathode comprising an electroactive sulfur-containing material; and

(iii) a liquid electrolyte interposed between said anode and said cathode.

2. The method of claim 1, wherein the low charge rate in the initial charging step (b) is from 0.03 mA/cm² to 0.15 mA/cm², and the high charge rate in the subsequent charging step (c) is from greater than 0.20 mA/cm² to 0.75 mA/cm².

3. The method of claim 1, wherein the initial low rate charging step (b) comprises two or more sub-steps of less than 0.2 mA/cm² in a sequence of increasing charge rate.

4. The method of claim 1, wherein the subsequent high rate charging step (c) comprises two or more sub-steps of greater than 0.2 mA/cm² in a sequence of increasing charge rate.

5. The method of claim 1, wherein said cell is charged to a voltage in the range of 2.2 to 2.3 V in said initial charging step (b).

6. The method of claim 1, wherein the combined sum of the charge provided in said initial charging step (b) and said subsequent charging step (c) is from 105% to 180% of the discharge capacity of the last half discharge cycle.

7. The method of claim 1, wherein the combined sum of the charge provided in said initial charge step (b) and said subsequent charging step (c) is from 105% to 120% of the discharge capacity of the last half discharge cycle.

8. The method of claim 1, wherein the overall discharge rate of said cell is from 0.025 mA/cm² to 0.25 mA/cm².

9. The method of claim 8, wherein the charge rate in said initial charging step is from 0.03 mA/cm² to 0.15 mA/cm² and the charge rate in said subsequent charging step is more than 0.20 mA/cm² to 0.75 mA/cm².

10. The method of claim 1, wherein said electroactive sulfur-containing material comprises elemental sulfur.

11. The method of claim 1, wherein said electroactive sulfur-containing material, in its oxidized state, comprises one or more polysulfide moieties, —

S_m—

, where m is an integer equal to or greater than 3.

12. The method of claim 1, wherein said electroactive sulfur-containing material, in its oxidized state, comprises one or more polysulfide moieties, —

S_m⁻

, where m is an integer equal to or greater than 3.

13. The method of claim 1, wherein said electroactive sulfur-containing material, in its oxidized state, comprises one or more polysulfide moieties, S_m²⁻

, where m is an integer equal to or greater than 3.

14. The method of claim 1, wherein said electroactive sulfur-containing material, in its oxidized state, is of the general formula

15. The method of claim 1, wherein said electroactive sulfur-containing material, in its oxidized state, comprises one or more of the polysulfur moieties:

wherein m, the same or different at each occurrence, is an integer and is greater than 2, and y, the same or different at each occurrence, is an integer and is equal to or greater than 1.

16. The method of claim 1, wherein said electroactive sulfur-containing material, in its oxidized state, comprises one or more of the moieties:

wherein m is the same or different at each occurrence and is greater than 2.

17. The method of claim 1, wherein said electroactive sulfur-containing material is a polymer comprising polymeric segments of the formula:

wherein;

Q denotes a carbocyclic repeat unit comprising a carbocycle having from 3 to 12 ring carbon atoms;

S denotes a sulfur atom;

m is the number of sulfur atoms in a given polysulfide linkage, is an integer from 3 to 10, and is the same or different at each occurrence;

n denotes the number of crosslinking polysulfide linkages, is an integer from 1 to 20, and is the same or different at each occurrence; and

p is an integer greater than 1.

18. The method of claim 1, wherein said electroactive sulfur-containing material comprises greater than 50% by weight of sulfur.

19. The method of claim 1, wherein said electroactive sulfur-containing material comprises greater than 75% by weight of sulfur.

20. The method of claim 1, wherein said electroactive sulfur-containing material comprises greater than 90% by weight of sulfur.

21. The method of claim 1, wherein said anode comprises lithium metal.

22. The method of claim 1, wherein said liquid electrolyte comprises:

(i) one or more lithium salts; and

(ii) one or more non-aqueous solvents.

23. The method of claim 22, wherein said one or more lithium salts are selected from the group consisting of LiBr, LiI, LiSCN, LiBF₄, LiPF₆, LiAsF₆, LiSO₃CF₃, LiN(SO₂CF₃)₂, LiC(SO₂CF₃)₃, (LiS_x)_zR, and Li₂S_x, where x is an integer from 1 to 20, z is an integer from 1 to 3, and R is an organic group.

24. The method of claim 22, wherein said one or more non-aqueous solvents are selected from the group consisting of ethers, cyclic ethers, polyethers, esters, sulfones, and sulfolanes.