Rapid sulfur melt diffusion into carbon host for making electrodes
A free-standing electrically conductive porous structure suitable to be used as a cathode of a battery, including an electrically conductive porous substrate with sulfur diffused into the electrically conductive porous substrate to create a substantially uniform layer of sulfur on a surface of the electrically conductive porous substrate. The free-standing electrically conductive porous structure has a high performance when used in a rechargeable battery. A method of manufacturing the electrically conductive porous structure is also provided.
1. A free-standing electrically conductive porous structure, consisting essentially of:
an electrically conductive porous substrate with a layer of sulfur on a surface of the electrically conductive porous substrate, wherein the sulfur layer includes an additive to reduce the viscosity of melted sulfur for diffusing the melted sulfur into the substrate;
wherein at least a portion of the layer of sulfur is in pores of the substrate and located on a surface of the pores of the substrate,
the free-standing electrically conductive porous structure contains at least 50 wt.% of sulfur and less than 10 wt.% of graphene, both based on a total weight of the electrically conductive porous structure,
the additive to reduce the viscosity of melted sulfur for diffusing the sulfur into the substrate comprises an element selected from the group consisting of selenium, tellurium, bromine and iodine,
the sulfur layer contains less than 30 wt.% of a combination of the additive to reduce the viscosity of melted sulfur for diffusing the sulfur into the substrate and one or more optional additives selected from a conductive additive and an additive that prevent or reduces active material dissolution or loss into an electrolyte during device operation, and
when the porous structure is configured as a cathode for a battery, the battery including the cathode has a C rate of at least 0.2 C at a discharge capacity of from about 400 mAh g −1 to about 1675 mAh g −1 with a cycling stability of at least 100 cycles.
2. The free-standing electrically conductive porous structure of claim 1 wherein the electrically conductive porous structure has a sulfur loading of at least about 1.0 mg cm −2 .
3. The free-standing electrically conductive porous structure of claim 1 , wherein the C rate is at least 0.5 C and the cycling stability is at least 120 cycles.
4. The free-standing electrically conductive porous structure of claim 1 , wherein the free-standing electrically conductive porous structure has a flexibility that passes a Mandrel Bend test of ASTM D522.
5. The free-standing electrically conductive porous structure of claim 1 , wherein the discharge capacity is in a range of from about 700 mAh g −1 to about 1625 mAh g −1 .
6. The free-standing electrically conductive porous structure of claim 1 , wherein the sulfur layer comprises the conductive additive and the conductive additive is selected from the group consisting of conductive carbon powders, graphite powders, mesoporous carbons, activated carbons, carbon nanotubes, MXenes, conductive polymers, conductive metal oxides/suboxides, metals and any other material that conducts electrons.
7. The free-standing electrically conductive porous structure of claim 1 , wherein the electrically conductive porous substrate comprises a material selected from carbon nanofibers, carbon nanotubes, carbon rods, and combinations thereof.
8. The free-standing electrically conductive porous structure of claim 1 , wherein the electrically conductive porous substrate has a porosity in a range of from about 10% to about 90% and a conductivity in a range of from about 10 −3 S/cm to about 10 5 S/cm.
9. The free-standing electrically conductive porous structure of claim 1 , wherein the sulfur layer comprises the additive that prevents or reduces active material dissolution or loss into an electrolyte during device operation and the additive that prevents or reduces active material dissolution or loss into an electrolyte during device operation comprises an additive that interacts with sulfur or polysulfides by polar interaction or Lewis-acid base interaction, said additive being selected from the group consisting of compounds containing polar elements, polymers and compounds containing metals such as titanium or vanadium.
10. The free-standing electrically conductive porous structure of claim 1 , wherein the electrically conductive porous structure has a sulfur content in a range of from about 50 wt.% to about 90 wt.%, based on a total weight of the structure.
11. The free-standing electrically conductive porous structure of claim 1 , wherein the sulfur in the electrically conductive porous structure has an average particle size in a range of from 10 nm to 1000 nm.
12. A cathode of a battery comprising the electrically conductive porous structure of claim 1 .
13. The cathode of claim 12 , wherein the cathode has a sulfur loading in a range of from about 0.1 mg cm −2 to about 15 mg cm −2 .
14. The cathode of claim 12 , wherein the cathode does not include a separate current collector.
15. The free-standing electrically conductive porous structure of claim 1 , wherein the electrically conductive porous structure has a sulfur content in a range of from about 50 wt.% to about 80 wt.%, based on a total weight of the structure.
16. The free-standing electrically conductive porous structure of claim 1 , wherein the sulfur layer is applied by a method comprising steps of:
applying sulfur in powder or particle form to the electrically conductive substrate; and
heating the powder form of the sulfur to a temperature of from about 119° C. to about 170° C. with the electrically conductive porous substrate under a pressure of from about 100 psi to about 2000 psi.
17. The free-standing electrically conductive porous structure of claim 16 , wherein the heating step is carried out for a period of from 5 seconds to about 100 seconds.
18. The free-standing electrically conductive porous structure of claim 17 , wherein the electrically conductive porous substrate is a carbon nanofiber mat and the heating step is carried out by roll-pressing or by using press plates.
19. The free-standing electrically conductive porous structure of claim 17 , wherein the sulfur in powder form or particle form has a particle size not greater than 100 mesh.
20. The free-standing electrically conductive porous structure of claim 17 , wherein the porous substrate has a porosity of at least about 50%.
21. The free-standing electrically conductive porous structure of claim 1 , wherein the sulfur layer comprises up to 10 wt.% of the one or more additives selected from a conductive additive, the additive to reduce the viscosity of melted sulfur for diffusing the sulfur into the substrate and the additive that prevents or reduces active material dissolution or loss into an electrolyte during device operation.
22. The free-standing electrically conductive porous structure of claim 1 , wherein the sulfur layer comprises the conductive additive.