Synthesis of gamma monoclinic sulfur and sulfur batteries containing monoclinic sulfur
The present invention relates to a method for making a novel cathode employing a monoclinic sulfur phase that enables a single plateau lithium-sulfur reaction in, for example, a carbonate electrolyte system. The cathode is applicable to a variety of other types of anodes. The method produces a cathode suitable for use in an electrode of a cell or battery by depositing monoclinic phase sulfur via vapor deposition onto a substrate in a sealed vapor deposition apparatus.
1. A method of depositing monoclinic sulfur on a substrate of a porous material, comprising steps of:
depositing monoclinic phase sulfur that is stable at a temperature below 80° C. via vapor deposition onto the substrate of the porous material in a sealed vapor deposition apparatus at a temperature sufficient to vaporize sulfur and for a time sufficient to provide the monoclinic phase sulfur, and
cooling the monoclinic phase sulfur deposited on the substrate of the porous material to a temperature of 0-50° C.,
wherein the substrate is positioned in the vapor deposition apparatus with a gab between a surface of a liquid sulfur reservoir and the substrate such that the substrate does not come into contact with liquid sulfur during the vapor deposition step.
2. The method of claim 1 , wherein the method provides a substrate with monoclinic sulfur deposited therein that is suitable for use as a cathode in an electrode of a cell or battery and a loading of the monoclinic phase sulfur on the substrate is at least 0.05 mg/cm 2 .
3. The method of claim 1 , wherein the depositing step is carried out in the sealed vapor deposition apparatus at a temperature of from 140° C. to 350° C.
4. The method of claim 1 , wherein the depositing step is carried out for a period of at least about 1 minute.
5. The method of claim 1 , wherein the cooling step is carried out by exposing the vapor deposition apparatus or the cathode to a temperature of less than 50° C.
6. The method of claim 5 , wherein the vapor deposition apparatus is cooled immediately upon completion of the depositing step.
7. The method of claim 1 , wherein the substrate of the porous material has a pore volume of 10-95% after deposition of the monoclinic phase sulfur on the substrate.
8. The method of claim 1 , wherein the substrate is conductive.
9. The method of claim 1 , wherein the substrate comprises carbon nanofibers.
10. The method of claim 9 , wherein the carbon nanofibers onto which the monoclinic phase sulfur is deposited are free-standing carbon nanofibers.
11. The method of claim 1 , wherein the monoclinic phase sulfur comprises a form of sulfur selected from the group consisting of monoclinic gamma phase sulfur; monoclinic sulfur that best matches monoclinic gamma phase sulfur using PDXL Version 2.8.4.0 Integrated Powder Diffraction Software; monoclinic gamma phase sulfur oriented in the k direction; and monoclinic sulfur that best matches monoclinic gamma phase sulfur oriented in the k direction using PDXL Version 2.8.4.0 Integrated Powder Diffraction Software.
12. The method of claim 1 , wherein the method provides a substrate with monoclinic sulfur deposited therein that is suitable for use as a cathode in an electrode of a cell or battery and a loading of the monoclinic phase sulfur on the substrate is at least 0.5 mg/cm 2 .
13. The method of claim 1 , wherein the depositing step is carried out in the sealed vapor deposition apparatus at a temperature of from 150° C. to 210° C.
14. The method of claim 1 , wherein the depositing step is carried out for a period of 10 to 30 hours.
15. The method of claim 1 , wherein the cooling step is carried out by exposing the vapor deposition apparatus or the cathode to a temperature of from about −20° C. to about 25° C.
16. The method of claim 1 , wherein the monoclinic phase sulfur comprises a form of sulfur selected from the group consisting of monoclinic gamma phase sulfur; monoclinic sulfur that best matches PDF Card No.: 00-013-0141 Quality:B for Rosickyite, monoclinic gamma phase sulfur, using PDXL Version 2 Integrated Powder Diffraction Software.
17. The method of claim 16 , wherein the substrate is non-conductive and the method provides a substrate with monoclinic sulfur deposited therein that is suitable for use as a cathode in an electrode of a cell or battery and a loading of the monoclinic phase sulfur on the substrate is at least 0.5 mg/cm 2 and the depositing step is carried out in the sealed vapor deposition apparatus at a temperature of from 150° C. to 210° C. for a period of 10 to 30 hours.
18. A method of depositing monoclinic sulfur on a substrate of a porous material, comprising steps of:
depositing monoclinic phase sulfur that is stable at a temperature below 80° C. via vapor deposition onto the substrate of the porous material in a sealed vapor deposition apparatus at a temperature sufficient to vaporize sulfur and for a time sufficient to provide the monoclinic phase sulfur, and
cooling the monoclinic phase sulfur deposited on the substrate of the porous material to a temperature of 0-50° C.,
wherein the substrate is non-conductive.
19. A method of depositing monoclinic sulfur on a substrate of a porous material, comprising steps of:
depositing monoclinic phase sulfur that is stable at a temperature below 80° C. via vapor deposition onto the substrate of the porous material in a sealed vapor deposition apparatus at a temperature sufficient to vaporize sulfur and for a time sufficient to provide the monoclinic phase sulfur, and
cooling the monoclinic phase sulfur deposited on the substrate of the porous material to a temperature of 0-50° C.,
wherein the method provides a substrate with monoclinic sulfur deposited therein that is suitable for use as a cathode in an electrode of a cell or battery and a loading of the monoclinic phase sulfur on the substrate is at least 0.5 mg/cm 2 and the depositing step is carried out in the sealed vapor deposition apparatus at a temperature of from 150° C. to 210° C. for a period of 10 to 30 hours.
20. The method of claim 19 , wherein the cooling step is carried out by exposing the vapor deposition apparatus or the cathode to a temperature of from about −20° C. to about 25° C. immediately upon completion of the depositing step.