Lithium battery using lithium polysulfide as the cathode active material

Patent metadata

Field	Value
Publication number	US-11329311-B2
Application number	US-201816194572-A
Country	US
Kind code	B2
Filing date	Nov 19, 2018
Priority date	Jan 19, 2018
Publication date	May 10, 2022
Grant date	May 10, 2022

Abstract

A lithium-sulfur battery comprises a cathode electrode comprising from 80% to 100% lithium polysulfide based on the total weight of sulfur adsorbed at the cathode when the lithium sulfur battery is fully charged, and a high specific surface area electrically conductive material. An anode electrode comprises lithium. A porous and electrically insulating membrane is provided between the cathode and the anode electrodes. An electrolyte is adsorbed into and between cathode electrode, the anode electrode, and the membrane. A cathode current collector is electrically connected to the cathode and an anode current collector is electrically connected to the anode. A porous and electrically conductive interlayer can be provided between the membrane and at least one selected from the group consisting of the cathode and the anode. A method of making a battery is also disclosed.

First claim

We claim:

1. A lithium-sulfur battery, comprising:
a cathode electrode comprising from 80% to 100% Li 2 S 4 , based on the total weight of sulfur adsorbed at the cathode when the lithium-sulfur battery is fully charged, and a high specific surface area electrically conductive material having a specific surface area of between 50 m 2 /g to 1000 m 2 /g;
an anode electrode comprising lithium;
a porous and electrically insulating membrane between the cathode and the anode electrodes;
an electrolyte adsorbed into and between cathode electrode, the anode electrode, and the membrane, the ratio of electrolyte volume to the weight of Li 2 S 4 being from 5 to 1 mL g −1 ;
wherein the electrolyte comprises lithium salts and organic solvent, wherein the lithium salt comprises at least one selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium oxalyldifluoroborate (LiODFB), lithium bis(oxalato)borate (LiBOB), lithium fluoroalkylphosphate (LiFAP), lithium difluoro(oxalato)borate (LiDFOB), LiPF 6 , LiBF 4 , LiClO 4 , LiNO 3 , Li 2 S 4 , Li 2 S 6 , and Li 2 S 8 , and wherein the solvent comprises at least one selected from the group consisting of 1,3-dioxolane (DOL), 1,2-dimethoxy ethane (DME), tri(ethylene glycol) dimethyl ether (triglyme, G3), tetra(ethylene glycol) dimethyl ether (TEGDME, tetraglyme, G4), and tetrahydrofuran (THF); and,
a cathode current collector and an anode current collector.

2. The lithium-sulfur battery of claim 1 , wherein the weight ratio of Li 2 S 4 and high specific surface area electrically conductive material is within a range of 1:5 to 10:1.

3. The lithium-sulfur battery of claim 1 , wherein the ratio of Li 2 S 4 in the cathode to lithium in the anode is between 3.4 to 1.7 by weight or between 1/6 to 1/12 by mole.

4. The lithium-sulfur battery of claim 1 , wherein the high specific surface area electrically conductive material is at least one selected from the group consisting of carbon nanotube, graphene, activated carbon, graphite, carbon black, carbon micro bead, hard carbon, and soft carbon.

5. The lithium-sulfur battery of claim 4 , wherein the high specific surface area electrically conductive material is nitrogen doped, nitrogen comprising up to 40% by weight based on the total weight of the cathode.

6. The lithium-sulfur battery of claim 1 , wherein the electrical conductivity of the high specific surface/electrical conductive material is greater than 1 S/cm.

7. The lithium-sulfur battery of claim 1 , wherein the cathode current collector comprises aluminum and the anode current collector comprises copper.

8. A lithium-sulfur battery, comprising:
a cathode electrode with a mixture of from 80% to 100% Li 2 S 4 based on the total weight of sulfur adsorbed at the cathode when the lithium-sulfur battery is fully charged, and high specific surface area electrically conductive material having a specific surface area of between 50 m 2 /g to 1000 m 2 /g;
an anode electrode comprising lithium;
a porous and electrically insulating membrane between cathode and anode electrodes;
an electrolyte adsorbed into and between the cathode electrode, the anode electrode, and the membrane, the ratio of electrolyte volume to the weight of Li 2 S 4 being from 5 to 1 mL g −1 ;
wherein the electrolyte comprises lithium salts and organic solvent, wherein the lithium salt comprises at least one selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium oxalyldifluoroborate (LiODFB), lithium bis(oxalato)borate (LiBOB), lithium fluoroalkylphosphate (LiFAP), lithium difluoro(oxalato)borate (LiDFOB), LiPF 6 , LiBF 4 , LiClO 4 , LiNO 3 , Li 2 S 4 , Li 2 S 6 , and Li 2 S 8 , and wherein the solvent comprises at least one selected from the group consisting of 1,3-dioxolane (DOL), 1,2-dimethoxy ethane (DME), tri(ethylene glycol) dimethyl ether (triglyme, G3), tetra(ethylene glycol) dimethyl ether (TEGDME, tetraglyme, G 4 ), and tetrahydrofuran (THF);
a porous and electrically conductive interlayer between the membrane and at least one selected from the group consisting of the cathode electrode and the anode electrode; and,
a cathode current collector and an anode current collector.

9. The lithium-sulfur battery of claim 8 , wherein the ratio of Li 2 S 4 in the cathode to lithium in the anode is between 3.4 to 1.7 by weight or between 1/6 to 1/12 by mole.

10. The lithium-sulfur battery of claim 8 , wherein the ratio between Li 2 S 4 in the cathode and lithium in the anode is between 2.8 to 1.4 by weight or 1/14 to 1/28 by mole.

11. A method of making a lithium-sulfur battery, comprising the steps of:
providing a mixture of from 80% to 100% Li 2 S 4 based on the total weight of sulfur adsorbed at the cathode when the lithium-sulfur battery is fully charged, and a high specific surface area electrically conductive material having a specific surface area of between 50 m 2 /g to 1000 m 2 /g;
providing an anode electrode comprising lithium;
providing a porous and electrically insulating membrane between the cathode and the anode electrodes;
electrically connecting the cathode electrode to a cathode current collector and the anode electrode to an anode current collector; and
applying an electrolyte such that the electrolyte is between and adsorbed into the cathode electrode, the anode electrode, and the membrane, the ratio of electrolyte volume to the weight of Li 2 S 4 being from 5 to 1 mL g −1 ;
wherein the electrolyte comprises lithium salts and organic solvent, wherein the lithium salt comprises at least one selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium oxalyldifluoroborate (LiODFB), lithium bis(oxalato)borate (LiBOB), lithium fluoroalkylphosphate (LiFAP), lithium difluoro(oxalato)borate (LiDFOB), LiPF 6 , LiBF 4 , LiClO 4 , LiNO 3 , Li 2 S 4 , Li 2 S 6 , and Li 2 S 8 , and wherein the solvent comprises at least one selected from the group consisting of 1,3-dioxolane (DOL), 1,2-dimethoxy ethane (DME), tri(ethylene glycol) dimethyl ether (triglyme, G3), tetra(ethylene glycol) dimethyl ether (TEGDME, tetraglyme, G4), and tetrahydrofuran (THF).

12. The method of claim 11 , wherein the electrical conductivity of the high specific surface electrical conductive material is greater than 1 S/cm.

13. The method of claim 11 , wherein the ratio between Li 2 S 4 in the cathode and lithium in the anode is between 2.8 to 1.4 by weight or 1/14 to 1/28 by mole.

14. The method of claim 11 , further comprising the step of providing a porous and electrically conductive interlayer between the membrane and at least one selected from the group consisting of the cathode electrode and the anode electrode.

Assignees

• Univ Florida State Res Found

Inventors

• Zheng Jian-Ping
• Shen Chao

Classifications

• H01M4/5815

  Sulfides · CPC title

• H01M10/052 Primary

  Li-accumulators · CPC title

• H01M10/058

  Construction or manufacture · CPC title

• H01M10/0566

  Liquid materials · CPC title

• H01M4/625

  Carbon or graphite · CPC title