Yolk-shell nanoparticle, method and applications

Patent metadata

Field	Value
Publication number	US-10978700-B2
Application number	US-202016806529-A
Country	US
Kind code	B2
Filing date	Mar 2, 2020
Priority date	Jul 5, 2013
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

A nanoparticle and a method for fabricating the nanoparticle utilize a decomposable material yoke located within permeable organic polymer material shell and separated from the permeable organic polymer material shell by a void space. When the decomposable material yoke comprises a sulfur material and the permeable organic polymer material shell comprises a material permeable to both a sulfur material vapor and a lithium ion within a battery electrolyte the nanoparticle may be used within an electrode for a Li/S battery absent the negative effects of battery electrode materials expansion.

First claim

What is claimed is:

1. A method of making a yolk shell sulfur nanoparticle, the method comprising:
providing a sulfur nanoparticle;
coating the sulfur nanoparticle with a polymer to produce a core-shell nanoparticle comprising a sulfur core and a polymer shell; and
heating the core-shell nanoparticle such that a portion of the sulfur core is removed and the polymer shell is concomitantly vulcanized.

2. The method of claim 1 , wherein the polymer is an electronically conductive polymer.

3. The method of claim 2 , wherein the electronically conducting polymer comprises polyaniline.

4. The method of claim 1 , wherein the step of coating the sulfur nanoparticle with a polymer comprises polymerizing a monomer in the presence of the sulfur nanoparticle.

5. The method of claim 4 , wherein the monomer comprises aniline.

6. The method of claim 4 , wherein the step of polymerizing comprises contacting the monomer with an oxidant.

7. The method of claim 1 , wherein the step of providing a sulfur nanoparticle comprises decomposing thiosulfate anions in the presence of an acid.

8. The method of claim 1 , wherein the step of heating the core-shell nanoparticle comprises treating the core shell nanoparticle at approximately 150 to 200° C.

9. The method of claim 1 , wherein the step of heating the core-shell nanoparticle comprises treating the core shell nanoparticle for approximately 6 to 18 hours.

10. The method of claim 1 , wherein the sulfur core comprises a sulfur material selected from the group consisting of elemental sulfur, S 8 , Li 2 S n , and other polysulfides.

11. The method of claim 1 , wherein the vulcanized polymer shell comprises a permeable, sulfur-functionalized organic polymer shell, and wherein the polymer is cross-linked by sulfide, disulfide, or a combination thereof.

12. The method of claim 11 , wherein the permeable, sulfur-functionalized organic polymer shell is permeable to vapors, or to ions including lithium ions, or to a combination thereof.

13. The method of claim 1 , wherein the sulfur core has a diameter from about 200 to about 300 nanometers, and the polymer shell has a a thickness from about 10 to about 20 nanometers.

14. The method of claim 1 , wherein the yolk shell nanoparticle comprises a void space within the vulcanized polymer shell.

15. The method of claim 14 , wherein the void space is interposed between the sulfur core and the polymer shell.

16. The method of claim 14 , wherein the void space comprises from about 25 to about 75 percent of a volume enclosed by the polymer shell.

17. A method of making an electrode, the method comprising:
providing a conductive substrate;
coating at least a portion of the conductive substrate with a yolk shell sulfur nanoparticle, the yolk shell sulfur nanoparticle comprising a sulfur core and a permeable organic polymer shell surrounding the sulfur core, wherein the polymer of the polymer shell is cross-linked by sulfide, disulfide, or a combination thereof.

18. The method of claim 16 , wherein the polymer comprises polyaniline.

19. The method of claim 16 , wherein the sulfur core comprises a sulfur material selected from the group consisting of elemental sulfur, S 8 , Li 2 S n , and other polysulfides.

20. The method of claim 16 , wherein the permeable organic polymer shell is permeable to vapors, or to ions including lithium ions, or to a combination thereof.

21. The method of claim 16 , wherein the sulfur core has a diameter from about 200 to about 300 nanometers, and the polymer shell has a thickness from about 10 to about 20 nanometers.

22. The method of claim 16 , wherein the yolk shell nanoparticle comprises a void space within the vulcanized polymer shell.

23. The method of claim 22 , wherein the void space comprises from about 25 to about 75 percent of a volume enclosed by the polymer shell.

24. The method of claim 16 , further comprising the step of making the yolk shell sulfur nanoparticle, comprising:
providing a sulfur nanoparticle;
coating the sulfur nanoparticle with the polymer to produce a core-shell nanoparticle comprising the sulfur core and the polymer shell; and
heating the core-shell nanoparticle such that a portion of the sulfur core is removed and the polymer shell is concomitantly vulcanized.

25. A method of making a battery comprising an electrode, comprising:
providing a conductive substrate;
coating at least a portion of the conductive substrate with a yolk shell sulfur nanoparticle, the yolk shell sulfur nanoparticle comprising a sulfur core and a permeable organic polymer shell surrounding the sulfur core, wherein the polymer of the polymer shell is cross-linked by sulfide, disulfide, or a combination thereof.

26. The method of claim 25 , wherein the battery comprises a Li/S battery.

27. The method of claim 25 , wherein the polymer comprises polyaniline.

28. The method of claim 25 , wherein the sulfur core comprises a sulfur material selected from the group consisting of elemental sulfur, S 8 , Li 2 S n , and other polysulfides.

29. The method of claim 25 , wherein the permeable organic polymer shell is permeable to vapors, or to ions including lithium ions, or to a combination thereof.

30. The method of claim 25 , wherein the sulfur core has a diameter from about 200 to about 300 nanometers, and the polymer shell has a a thickness from about 10 to about 20 nanometers.

31. The method of claim 25 , wherein the yolk shell nanoparticle comprises a void space interposed between the sulfur core and the permeable organic polymer shell surrounding the sulfur core.

32. The method of claim 31 , wherein the void space comprises from about 25 to about 75 percent of a volume enclosed by the polymer shell.

33. The method of claim 25 , further comprising the step of making the yolk shell sulfur nanoparticle, comprising:
providing a sulfur nanoparticle;
coating the sulfur nanoparticle with the polymer to produce the core-shell nanoparticle comprising the sulfur core and the polymer shell; and
heating the core-shell nanoparticle such that a portion of the sulfur core is removed and the polymer shell is concomitantly vulcanized.

34. The method of claim 25 , wherein the battery has a capacity retention after 200 cycles of at least approximately 68% of its initial capacity.

35. The method of claim 25 , wherein the battery retains a capacity of at least approximately 765 mAh g −1 S at 0.2 C after 200 cycles.

36. The method of claim 25 , wherein the battery retains a capacity of at least approximately 628 mAh g −1 S at 0.5 C after 200 cycles.

Assignees

• Univ Cornell

Inventors

• Yu Yingchao
• Zhou Weidong
• Chen Hao
• Abruna Hector D

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M4/1395

  of electrodes based on metals, Si or alloys · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M4/602

  Polymers · CPC title

• H01M4/5815

  Sulfides · CPC title