Voltage cycling method for lithium ion battery comprising sulfur polymer composite in active material

• US 9,450,234 B2
• Filed: 10/16/2012
• Issued: 09/20/2016
• Est. Priority Date: 05/15/2012
• Status: Active Grant

• Current Assignee: Hon Hai Precision Industry Co., Ltd., Tsinghua University
• Original Assignee: Hon Hai Precision Industry Co., Ltd., Tsinghua University
• Inventors: He, Xiang-Ming, Wang, Li, Li, Jian-Jun, Gao, Jian, Sun, Wen-Ting
• Primary Examiner(s): Dunn, Drew A
• Assistant Examiner(s): Trischler, John
• Application Number:
  US13/652,613
• Publication Number:
  US 20130307485A1
• Time in Patent Office: 1,435 Days
• Field of Search: 320/130, 320/124
• US Class Current: 1/1
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/446 Initial charging measures
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/604 containing aliphatic main chain polymers
• CPC Class Codes: H01M 4/608 containing heterocyclic rings
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A method for cycling a sulfur composite lithium ion battery includes a step of charging and discharging the sulfur composite lithium ion battery at a first voltage range between a predetermined highest voltage and a predetermined lowest voltage. The lithium ion battery includes an electrode active material. The electrode active material includes a sulfur composite. The step of charging and discharging satisfies at least one conditions of (1) and (2): (1) the predetermined lowest voltage of the first voltage range is larger than a discharge cutoff voltage of the sulfur composite; and (2) the predetermined highest voltage of the first voltage range is smaller than a charge cutoff voltage of the sulfur composite. A method for using a sulfur composite as an electrode active material of a lithium ion battery is also disclosed.

Claims

1. A method for cycling a sulfur composite lithium ion battery, the method comprising a step of charging and discharging the sulfur composite lithium ion battery at a first voltage range having a predetermined highest voltage and a predetermined lowest voltage, wherein the sulfur composite lithium ion battery comprises a cathode active material and an anode active material, the cathode active material comprising a sulfur composite, the sulfur composite is a sulfur based polymer, the anode active material is lithium metal, the first voltage range is smaller than and located in a range having a charge cutoff voltage and a discharge cutoff voltage, the charge cutoff voltage is 3V, and the discharge cutoff voltage is 0V, the first voltage range is 30% to 50% smaller than the range from 0V to 3V, and the step of charging and discharging satisfies at least one condition of (1) and (2):

(1) the predetermined lowest voltage of the first voltage range is larger than the discharge cutoff voltage of the sulfur composite; and

(2) the predetermined highest voltage of the first voltage range is smaller than the charge cutoff voltage of the sulfur composite,

wherein the cycling the sulfur composite lithium ion battery is defined as;

when a voltage of the sulfur composite lithium ion battery is charged to the predetermined highest voltage, the charging stops;

when the voltage of the sulfur composite lithium ion battery is discharged to the predetermined lowest voltage, the discharging stops; and

the sulfur composite lithium ion battery is not charged above the charge cutoff voltage and the sulfur composite lithium ion battery is not discharged below the discharge cutoff voltage.

2. The method of claim 1, wherein the sulfur composite lithium ion battery is cycled at the first voltage range for at least 5 cycles.

3. The method of claim 1, wherein the sulfur composite lithium ion battery has a plurality of reversible redox reactions at different voltages, the first voltage range only has one reversible redox reaction processed during the charging and discharging.

4. The method of claim 1, wherein the sulfur composite is sulfur grafted poly(pyridinopyridine), and the predetermined lowest voltage Vx and the predetermined highest voltage Vy satisfy 0.25V<

Vx<

2.25V<

Vy, or satisfy Vx<

0.1V<

Vy<

2V.

5. The method of claim 1, wherein the sulfur composite is a product formed from a pyrolysis reaction of a mixture of conducting polymer and elemental sulfur.

6. The method of claim 1, wherein the sulfur composite is selected from the group consisting of sulfur grafted poly(pyridinopyridine), sulfurized polystyrene, sulfurized polyoxyethylene, sulfurized polyvinyl alcohol, sulfurized poly(vinylidene chloride), sulfurized poly(vinylidene difluoride), sulfurized polyvinylchloride, sulfurized polyvinyl fluoride, sulfurized poly(1,2-dichloroethylene), sulfurized poly(1,2-difluoroethylene), sulfurized polymethyl methacrylate, sulfurized phenolic resin, and combinations thereof.

7. The method of claim 6, wherein the sulfur grafted poly(pyridinopyridine) comprises a poly(pyridinopyridine) matrix and a plurality of poly-sulfur groups dispersed in the poly(pyridinopyridine) matrix, each of the plurality of poly-sulfur groups consists of one or more sulfur elements represented by a formula of S_x, wherein x is an integer between 1 and 8, and the plurality of poly-sulfur groups are combined with the poly(pyridinopyridine) matrix with covalent bonds.

8. The method of claim 7, wherein sulfur grafted poly(pyridinopyridine) comprises at least one chemical group of formulas:

9. The method of claim 6, wherein the sulfur grafted poly(pyridinopyridine) comprises a poly(pyridinopyridine) matrix and elemental sulfur dispersed in the poly(pyridinopyridine) matrix.

10. The method of claim 9, wherein the elemental sulfur has a shape of particles or grains, and one elemental sulfur particle is one sulfur molecule or a sulfur atom cluster consisting of a plurality of sulfur atoms.

11. A method for cycling a sulfur composite lithium ion battery, the lithium ion battery comprising a cathode active material and an anode active material, the cathode active material comprising a sulfur composite, the sulfur composite is a sulfur based polymer, the anode active material is lithium metal, and the method comprising:

S1, charging and discharging the lithium ion battery at a first voltage range having a first predetermined highest voltage and a first predetermined lowest voltage, wherein when a voltage of the lithium ion battery is charged to the first predetermined highest voltage, the charging stops, and when the voltage of the lithium ion battery is discharged to the first predetermined lowest voltage, the discharging stops; and

S2, after the step S1, charging and discharging the lithium ion battery at a second voltage range having a second predetermined highest voltage and a second predetermined lowest voltage, wherein the second predetermined highest voltage of the second voltage range is smaller than or equal to 3V, and the second predetermined lowest voltage of the second voltage range is larger than or equal to 0V, when the voltage of the lithium ion battery is charged to the second predetermined highest voltage, the charging stops, and when the voltage of the sulfur composite lithium ion battery is discharged to the second predetermined lowest voltage, the discharging stops;

wherein the step S1 satisfies at least one condition of (1) and (2);

(1) the first predetermined lowest voltage of the first voltage range is larger than the second predetermined lowest voltage of the second voltage range, the first predetermined highest voltage of the first voltage range is smaller than or equal to the second predetermined highest voltage of the second voltage range; and

(2) the first predetermined highest voltage of the first voltage range is smaller than the second predetermined highest voltage of the second voltage range, the first predetermined lowest voltage of the first voltage range is larger than or equal to the second predetermined lowest voltage of the second voltage range.

12. The method of claim 11, wherein the first voltage range is 30% to 50% smaller than the second voltage range.

13. The method of claim 11, wherein the sulfur based polymer comprises a conducting matrix and sulfur dispersed in the conducting matrix.