IP Library Granted Patent US 12,706,308
Granted Patent B2
US 12,706,308 · App. 17/618,832 · Granted Aug 11, 2026

Cathode material and a method of preparing the same

Inventors: Jackie Y. Ying (Singapore, SG); Jian Liang Cheong (Singapore, SG)
Assignee: AGENCY FOR SCIENCE, TECHNOLOGY AND RESEARCH
H01M4/5815H01M4/622H01M4/625H01M4/80H01M10/052H01M2004/021H01M2004/028
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Quick Facts
Patent No.
US 12,706,308
App. No.
17/618,832
Granted
Aug 11, 2026
Kind
B2
Abstract

There is provided a cathode material comprising a layer of sulfur species dispersed within or thereon a porous matrix comprising a first conducting carbon material, a second conducting carbon material and a binder, wherein the second conducting carbon material is carbon fiber or carbon nanotube. There is also provided a cathode material comprising a layer of sulfur species dispersed within or thereon a porous matrix comprising a first conducting carbon material, a second conducting carbon material and a binder, wherein said porous matrix is interconnected with uniform pores. There are also provided methods for preparing the above cathode material(s).

Claims (31)

1 . A cathode material comprising a layer of sulfur species dispersed within or thereon a porous matrix comprising a first conducting carbon material, a second conducting carbon material and a binder, wherein the binder is a copolymer of acrylamide, lithium carboxylate and cyano group,

the second conducting carbon material is carbon fiber or carbon nanotube, and

said porous matrix is interconnected with uniform pores.

2 . The cathode material according to claim 1 , wherein the sulfur species is a polysulfide or elemental sulfur.

3 . The cathode material according to claim 1 , where the polysulfide has a formula of Li 2 S n , wherein 2<n≤8.

4 . The cathode material according to claim 1 , wherein the cathode material has a sulfur content in the range of about 30 wt % to about 80 wt % based on the total weight of the cathode material.

5 . The cathode material according to claim 1 , wherein the first conducting carbon material is selected from the group consisting of reduced graphene oxide, graphene, graphite, carbon nanotube, carbon fiber, acetylene black, and ketjenblack; wherein the first conducting carbon material is doped with nitrogen, oxygen, sulfur, boron, phosphorus or their mixtures thereof; or is different from the second conducting material.

6 . The cathode material according claim 1 , wherein the first conducting carbon material is reduced graphene oxide.

7 . The cathode material according claim 1 , wherein the amount of the first conducting carbon material is in the range of 20 wt % to 60 wt % based on the total weight of the cathode material.

8 . The cathode material according claim 1 , wherein the binder is water soluble.

9 . The cathode material according to claim 1 , wherein the amount of the binder is in the range of 5 wt % to 15 wt % based on the total weight of the cathode material.

10 . The cathode material according to claim 1 , wherein the second conducting carbon material is vapor grown carbon fiber (VCGF); or has a diameter in the range of about 0.1 nm to about 100 μm.

11 . The cathode material according to claim 1 , wherein the amount of the second conducting carbon material is in the range of 5 wt % to 35 wt % based on the total weight of the cathode material.

12 . The cathode material according to claim 1 , wherein the cathode material has a sulfur loading density in the range of 1.3 mg cm −2 to 15 mg cm −2 ; a surface area in the range of 200 m 2 /g to 900 m 2 /g; a pore volume in the range of 0.25 cm 3 /g to 3 cm 3 /g; or a pore size distribution of mesopore size in the range of 2.0 nm to 50 nm and macropore size larger than 50 nm.

13 . An electrochemical cell comprising a liquid electrolyte, and a cathode material comprising a layer of sulfur species dispersed within or thereon a porous matrix comprising a first conducting carbon material, a second conducting carbon material and a binder, wherein the binder is a copolymer of acrylamide, lithium carboxylate and cyano group,

the second conducting carbon material is carbon fiber or carbon nanotube, and

said porous matrix is interconnected with uniform pores.

14 . A lithium-sulfur battery comprising one or more electrochemical cells, each electrochemical cell comprising a liquid electrolyte, and a cathode material comprising

a layer of sulfur species dispersed within or thereon a porous matrix comprising a first conducting carbon material, a second conducting carbon material and a binder, wherein the binder is a copolymer of acrylamide, lithium carboxylate and cyano group,

the second conducting carbon material is carbon fiber or carbon nanotube, and

said porous matrix is interconnected with uniform pores.

15 . A method for preparing a cathode material comprising:

a) coating a support with a slurry formed by mixing a mixture of a first conducting carbon material, a second conducting carbon material and a binder, wherein the binder is a copolymer of acrylamide, lithium carboxylate and cyano group, and the second conducting carbon material is carbon fiber or carbon nanotube; and

b) adding a sulfur source in solution or gaseous state to the coated support to form a layer of sulfur species dispersed within or thereon the coated support to thereby obtain the cathode material, wherein the coated support is a porous matrix comprising the first conducting carbon material, the second conducting carbon material and the binder, and said porous matrix is interconnected with uniform pores.

16 . The method according to claim 15 , further comprising, before said coating operation (a), the operation of (a1) stirring said mixture in a solvent overnight with a solid content in the range of 3 wt % to 10 wt %, wherein the solvent is water or water mixture with polar organic solvents.

17 . The method according to claim 15 , wherein the first conducting carbon material is reduced graphene oxide; or has a concentration in the range of 60 wt % to 90 wt % based on the total weight of solid content in the slurry.

18 . The method according to claim 15 , wherein the second conducting carbon material has a concentration in the range of 5 wt % to 50 wt % based on the total weight of solid content.

19 . The method according to claim 15 , wherein the binder has a concentration in the range of 5 wt % to 20 wt % based on the total weight of solid content.

20 . The method according to claim 15 , further comprising, after said coating operation (a), the operation of (a2) drying the coated support at a temperature in the range of 40° C. to 80° C. for more than 2 hours.

21 . The method according to claim 15 , comprising preparing a polysulfide (PS) solution as the sulfur source in fluid state by stirring a mixture of sulfur (S) and lithium sulfide (Li 2 S); wherein the mixture has a S/Li 2 S mass ratio in the range of 2:1 to 5:1; and/or is stirred at a temperature in the range of 40° C. to 60° C. overnight in a glovebox.

22 . The method according to claim 15 , comprising the operation of obtaining said sulfur source in fluid state by heating elemental sulfur solid at a temperature in the range of 160° C. to 190° C. at a duration in the range of 5 minutes to 40 minutes.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 15, 2022
From: YING, JACKIE Y.; CHEONG, JIAN LIANG
To: AGENCY FOR SCIENCE, TECHNOLOGY AND RESEARCH
Reel/Frame 060216/0668 →
Priority Claims (1)
SG 10201905403Y · Jun 13, 2019 · national
Continuity (1)
Related Publication 20220293946A1 · Sep 15, 2022
References Cited (50)
US 20170352909A1 · Ainsworth · 2017 [cited by examiner]
CN 110265646A · 2019 [cited by applicant]
Wu et al. “A high efficiency N/P co-doped graphene/CNT @ porous carbon hybrid matrix as a cathode host for high performance lithium-sulfur batteries” 2017 J Mater. Chem A . 5. pp. 20458-20472. [cited by examiner]
Gao, F. et al., Graphene/Carbon Nanotubes Composite as a Polysulfide Trap for Lithium-Sulfur Batteries. Int. J. Electrochem. Sci., Mar. 10, 2019, vol. 14, pp. 3301-3314. [cited by examiner]
Wu, H. et al., A high-efficiency N/P co-doped graphene/CNT@porous carbon hybrid matrix as cathode host for high performance lithium-sulfur batteries. J. Mater. Chem. A, Sep. 6, 2017, vol. 5, pp. 20458-20472. [cited by examiner]
Cleaver, Tom et al., “Commercializing Lithium Sulfur Batteries: Are We Doing the Right Research?” Journal of The Electrochemical Society, Oct. 31, 2017, 5 pages. [cited by applicant]
Zhang, Sheng S., “Liquid Electrolyte Lithium/Sulfur Battery: Fundamental Chemistry, Problems, and Solutions,” Journal of Power Sources, 231 (2013), 10 pages. [cited by applicant]
Manthiram, Arumugam et al., “Rechargeable Lithium-Sulfur Batteries,” Chemical Reviews, (2014) 114, 37 pages. [cited by applicant]
Fang, Ruopian et al., “More Reliable Lithium-Sulfur Batteries: Status, Solutions and Prospects,” Advanced Materials, (2017) 29, 25 pages. [cited by applicant]
Elazari, Ran et al., “Morphological and Structural Studies of Composite Sulfur Electrodes Upon Cycling By HRTEM, AFM and Raman Spectroscopy,” Journal of The Electrochemical Society, 157, (2010), 8 pages. [cited by applicant]
Li, Gaoran et al., “Revisiting the Role of Polysulfides in Lithium-Sulfur Batteries,” Advanced Materials, (2018) 30, 19 pages. [cited by applicant]
Zhang, Sheng S. et al., “A New Direction For the Performance Improvement of Rechargeable Lithium/Sulfur Batteries,” Journal of Power Sources, 200 (2012), 6 pages. [cited by applicant]
Fu, Yongzhu et al., “Highly Reversible Lithuim/Dissolved Polysulfide Batteries with Carbon Nanotube Electrodes,” Angewandte Communications, (2013), 52, 6 pages. [cited by applicant]
Zu, Chenxi et al., “Highly Reversible Li/Dissolved Polysulfide Batteries With Binder-Free Carbon Nanofiber Electrodes,” Journal of Materials Chemistry A, (2013) 1, 6 pages. [cited by applicant]
Yang, Yuan et al., “A Membrane-Free Lithium/Polysulfide Semi-Liquid Battery For Large-Scale Energy Storage,” Energy & Environmental Science, (2013), 6, 7 pages. [cited by applicant]
Zu, Chenxi et al., “High-Performance Li/Dissolved Polysulfide Batteries With an Advanced Cathode Structure and High Sulfur Content,” Advanced Energy Materials, (2014) 4, 6 pages. [cited by applicant]
Pu, Xiong et al., “Liquid-Type Cathode Enabled By 3D Sponge-Like Carbon Nanotubes For High Energy Density and Long Cycling Life of Li—S Batteries,” Advanced Materials, (2014), 26, 6 pages. [cited by applicant]
Fang, Ruopian et al., “An Integrated Electrode/Separator With Nitrogen and Nickel Functionalized Carbon Hybrids For Advanced Lithium/Polysulfide Batteries,” Elsevier Ltd., (2016), 8 pages. [cited by applicant]
Li, Xiaolong et al., “Enhanced Performances of Li/Polysulfide Batteries With 3D Reduced Graphene Oxide/Carbon Nanotube Hybrid Aerogel as the Polysulfide Host,” Elsevier Ltd., (2016), 7 pages. [cited by applicant]
Xu, Rui et al., “Role of Polysulfides in Self-Healing Lithium-Sulfur Batteries,” Advanced Energy Materials, (2013) 3, 6 pages. [cited by applicant]
Demir-Cakan, Rezan et al., “Li—S Batteries: Simple Approaches for Superior Performance,” Energy & Environmental Science, (2013), 6, 7 pages. [cited by applicant]
Han, Kai et al., “Free-Standing Nitrogen-Doped Graphene Paper As Electrodes For High-Performance Lithium/Dissolved Polysulfide Batteries,” ChemSusChem, (2014), 7, 9 pages. [cited by applicant]
Zhou, Guangmin et al., “Free-Standing TiO2 Nanowire-Embedded Graphene Hybrid Membrane for Advanced Li/Dissolved Polysulfide Batteries,” Elsevier Ltd., (2014), 10 pages. [cited by applicant]
Zhou, Guangmin et al., “Long-Life Li/Polysulphide Batteries With High Sulphur Loading Enabled By Lightweight Three-Dimensional Nitrogen/Sulphur-Codoped Graphene Sponge,” Nature Communications, Jul. 2015, 11 pages. [cited by applicant]
Babu, Ganguli et al., “Transition Metal Dichalcogenide Atomic Layers for Lithium Polysulfides Electrocatalysis,” Journal of the American Chemical Society, Aug. 19, 2016, 8 pages. [cited by applicant]
Luo, Shuwen et al., “Freestanding Reduced Graphene Oxide-Sulfur Composite Films for Highly Stable Lithium-Sulfur Batteries,” The Royal Society of Chemistry, (2017), 9, 6 pages. [cited by applicant]
Kraytsberg, Alexander et al., “Conveying Advanced Li-Ion Battery Materials Into Practice The Impact of Electrode Slurry Preparation Skills,” Advanced Energy Materials, (2016), 6, 23 pages. [cited by applicant]
Rauh, R. D. et al., “A Lithium/Dissolved Sulfur Battery With An Organic Electrolyte,” EIC Corporation, (2018), 5 pages. [cited by applicant]
Agostini, Marco et al., “Characteristics of Li2S8-Tetraglyme Catholyte in a Semi-Liquid Lithium-Sulfur Battery,” Elsevier, (2014), 6 pages. [cited by applicant]
Hendrickson, Kenville E. et al., “Model Membrane-Free Li—S Batteries for Enhanced Performance and Cycle Life,” Advanced Science, (2015), 2, 9 pages. [cited by applicant]
Mosavati, Negar et al., “Nanostructured Titanium Nitride as a Novel Cathode for High Performance Lithium/Dissolved Polysulfide Batteries,” Elsevier, (2016), 7 pages. [cited by applicant]
Mosavati, Negar et al., “Characterization and Electrochemical Activities of Nanostructured Transition Metal Nitrides as Cathode Materials for Lithium Sulfur Batteries,” Elsevier, (2016), 7 pages. [cited by applicant]
Salem, Hesham Al et al., “Electrocatalytic Polysulfide Traps for Controlling Redox Shuttle Process of Li—S Batteries,” Journal of the American Chemical Society, (2015), 137, 4 pages. [cited by applicant]
Pan, Jin et al., “Enhanced Electrochemical Performance of Sulfur Cathodes With a Water-Soluble Binder,” Royal Society of Chemistry, (2015), 5, 6 pages. [cited by applicant]
Gogotsi, Y. et al., “True Performance Metrics in Electrochemical Energy Storage,” Science Magazine, vol. 334, Nov. 18, 2011, 4 pages. [cited by applicant]
Peng, Hong-Jie et al., “Review on High-Loading and High-Energy Lithium-Sulfur Batteries,” Advanced Energy Materials, (2017), 54 pages. [cited by applicant]
Cheon, Sang-Eun et al., “Rechargeable Lithium Sulfur Battery,” Journal of the Electrochemical Society, 150, (2003), 6 pages. [cited by applicant]
Barai, Pallab et al., “Poromechanical Effect in the Lithium-Sulfur Battery Cathode,” Elxevier Ltd., (2016) 12 pages. [cited by applicant]
Youn, Hee-Chang et al., “High-Surface-Area Nitrogen-Doped Reduced Graphene Oxide for Electric Double-Layer Capacitors,” ChemSusChem, (2015) 8, 10 pages. [cited by applicant]
Ossonon, Benjamin Diby et al., “Synthesis and Characterization of Sulfophenyl-functionalized Reduced Graphene Oxide Sheets,” Royal Society of Chemistry, (2017) 7, 11 pages. [cited by applicant]
Mistry, Aashutosh et al., “Precipitation—Microstructure Interactions in the Li-Sulfur Battery Electrode,” The Journal of Physical Chemistry, (2017) 121, 9 pages. [cited by applicant]
Wu, Huali et al., “A High-Efficiency N/P Co-Doped Graphene/CNT@Porous Carbon Hybrid Matrix As A Cathode Host For High Performance Lithium-Sulfur Batteries,” Journal of Materials Chemistry A, (2017) 5, 15 pages. [cited by applicant]
Deng, Wei et al., “Graphene/Sulfur Composites with a Foam-Like Porous Architecture and Controllable Pore Size for High Performance Lithium-Sulfur Batteries,” ChemNanoMat, Aug. 2016, 10 pages. [cited by applicant]
Gao, Feng et al., “Graphene/Carbon Nanotubes Composite as a Polysulfide Trap for Lithium-Sulfur Batteries,” International Journal of Electrochemical Science, 14 (2019) 3301-3314. [cited by applicant]
International Preliminary Report on Patentability for PCT International Application No. PCT/SG2020/050319, issued Dec. 14, 2021, 9 pages. [cited by applicant]
International Search Report for PCT International Application No. PCT/SG2020/050319, mailed Sep. 15, 2020, 4 pages. [cited by applicant]
Song, Ji-Yoon et al., “A Polysulfide-Infiltrated Carbon Cloth Cathode for High-Performance Flexible Lithium-Sulfur Batteries,” nanomaterials, Feb. 7, 2018, 10 pages. [cited by applicant]
Written Opinion of the International Searching Authority for PCT International Application No. PCT/SG2020/050319, mailed Sep. 15, 2020, 8 pages. [cited by applicant]
Zhang, Yongguang et al., A porous 3D-RGO@MWCNT hybrid material as Li—S battery cathode, Beilstein Journal of NanoTechnology, Feb. 21, 2019, 8 pages. [cited by applicant]
Cheong, Jian Liang et al., “A high-performance slurry-coated polysulfide cathode for lithium-sulfur battery,” Nano Energy, Sep. 14, 2019, vol. 66, 9 pages, 104114. [cited by applicant]