Cathodes for solid-state lithium sulfur batteries and methods of manufacturing thereof

Patent metadata

Field	Value
Publication number	US-12034152-B2
Application number	US-201917255274-A
Country	US
Kind code	B2
Filing date	Jun 20, 2019
Priority date	Jun 25, 2018
Publication date	Jul 9, 2024
Grant date	Jul 9, 2024

Abstract

A cathode for a lithium-sulfur battery includes a sulfur-based composite layer having a porosity in a range of 60% to 99%; and a conductive polymer disposed atop the composite layer and within pores of the composite layer. Moreover, a method of forming a cathode for a lithium-sulfur battery includes providing a substrate; disposing a sulfur-based slurry layer on the substrate; freeze-drying the slurry layer to form a sulfur-based composite layer having a porosity in a range of 60% to 99%; and disposing a conductive polymer atop the composite layer and within pores of the composite layer.

First claim

What is claimed is:

1. A cathode for a lithium-sulfur battery, comprising:
a sulfur-based composite layer having a porosity in a range of 60% to 99%; and
a conductive polymer disposed atop the sulfur-based composite layer and within pores of the sulfur-based composite layer.

2. The cathode of claim 1 , wherein the sulfur-based composite layer has a porosity in a range of 60% to 80%.

3. The cathode of claim 1 , wherein the pores of the sulfur-based composite layer have a pore size in a range of 1 μm to 50 μm.

4. The cathode of claim 3 , wherein the pore size is in a range of 2 μm to 10 μm.

5. The cathode of claim 1 , wherein the sulfur-based composite layer comprises a carbon material present as at least one of nanoparticles, nanowires, nanofibers, nanorods, nanotubes, nanospheres, graphene, or combinations thereof.

6. The cathode of claim 5 , wherein the carbon material is present in a range of 5 wt % to 40 wt %.

7. The cathode of claim 1 , wherein the sulfur-based composite layer comprises a metal carbide in a range of 1 wt % to 20 wt %.

8. The cathode of claim 1 , wherein the conductive polymer comprises at least one of carbon polysulfides (CS), polyethylene oxides (PEO), polyaniline (PANI), polypyrrole (PPY), poly(3,4-ethylenedioxythiophene) (PEDOT), polystyrenesulfonic acid (PSS), polyacrylonitrile (PAN), polyacrylic acid (PAA), polyallylamine hydrochloride (PAH), poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-co-HFP)), poly(methylmethacrylate) (PMMA), polyvinylidene fluoride (PVDF), poly(diallyldimethyl ammonium) bis(trifluoromethanesulfonyl)imide (TFSI) (PDDATFSI), or combinations thereof.

9. The cathode of claim 1 , wherein the conductive polymer comprises polyethylene oxide (PEO).

10. A lithium-sulfur (Li—S) battery, comprising:
a lithium anode;
a solid-state electrolyte; and
a cathode as in claim 1 .

11. A method of forming a cathode for a lithium-sulfur battery, comprising:
providing a substrate;
disposing a sulfur-based slurry layer on the substrate;
freeze-drying the sulfur-based slurry layer to form a sulfur-based composite layer having a porosity in a range of 60% to 99%; and
disposing a conductive polymer atop the sulfur-based composite layer and within pores of the sulfur-based composite layer.

12. The method of claim 11 , wherein the substrate is a current collector.

13. The method of claim 11 , further comprising:
mixing a metal carbide, carbon material, and sulfur material in a solvent to form a sulfur precursor;
dry milling the sulfur precursor to form a sulfur composite; and
agitating the sulfur composite with a binder to form a sulfur-based slurry that is disposed to form the sulfur-based slurry layer.

14. The method of claim 13 , wherein:
the carbon material is at least one of: nanoparticles, nanowires, nanofibers, nanorods, nanotubes, nanospheres, graphene, or combinations thereof, and
the binder comprises at least one of styrene-butadiene rubber, carboxyl methyl cellulose, water, or combinations thereof.

15. The method of claim 11 , wherein the porosity of the sulfur-based composite layer is in a range of 60% to 80%.

16. The method of claim 11 , wherein the pores of the sulfur-based composite layer have a pore size in a range of 1 μm to 50 μm.

17. The method of claim 16 , wherein the pore size is in a range of 2 μm to 10 μm.

18. The method of claim 11 , wherein the step of freeze-drying comprises:
freezing the sulfur-based slurry layer at a temperature in a range of −50° C. and 0° C. for a time in a range of 1 hour to 12 hours; and
drying the frozen sulfur-based slurry layer in a freeze drier for a time in a range of 1 hour to 24 hours.

19. The method of claim 11 , wherein the step of disposing the conductive polymer is conducted by at least one of spin coating, dip coating, layer-by-layer deposition, sol-gel deposition, inkjet printing, or combinations thereof.

Assignees

• Corning Inc
• Shanghai Inst Ceramics Cas

Inventors

• Badding Michael Edward
• Jin Jun
• Lu Yang
• Song Zhen
• Wen Zhaoyin
• Xiu Tongping

Classifications

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/624

  Electric conductive fillers · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M4/139

  Processes of manufacture · CPC title