IP Library Granted Patent US 9,805,880
Granted Patent B2
US 9,805,880 · App. 14/602,104 · Granted Oct 31, 2017

Fabrication of enhanced supercapacitors using atomic layer deposition of metal oxide on nanostructures

Inventors: Roseanne Warren (Berkeley, CA); Firas Sammoura (San Jose, CA); Liwei Lin (San Ramon, CA)
Assignee: Masdar Institute of Science and Technology
H01G11/46C25D11/26C25D11/34H01G11/36H01G11/86H01G11/04Y02E60/13
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Quick Facts
Patent No.
US 9,805,880
App. No.
14/602,104
Granted
Oct 31, 2017
Kind
B2
Abstract

A method to a fabricate high surface area, high performance supercapacitor includes include applying a metal layer to at least a portion of a nanostructure; after applying the metal layer, oxidizing the metal layer; applying a plurality of additional metal layers onto a previously oxidized metal layer; and after applying each additional metal layer, oxidizing the additional metal layer prior to applying a successive additional metal layer. The metal layers may include a composition comprising at least one metal, the at least one metal selected from the group consisting of ruthenium, titanium, manganese, vanadium, iron, tin, cobalt and nickel. Optionally, each of the additional metal layers may be applied using atomic layering deposition (ALD).

Claims (41)

1. A method to a fabricate high surface area, high performance supercapacitor, said method comprising:

forming a plurality of conductive, porous nanostructures on a substrate, said plurality of conductive, porous nanostructures extending from said substrate and forming a plurality of electrodes of said supercapacitor;

applying a metal layer to at least a portion of said plurality of conductive, porous nanostructure electrodes;

after applying said metal layer, oxidizing said metal layer;

applying a plurality of additional metal layers onto a previously oxidized metal layer; and

after applying each additional metal layer, oxidizing said additional metal layer prior to applying a successive additional metal layer;

wherein said metal layers includes a composition comprising at least one metal, said at least one metal selected from the group consisting of ruthenium, titanium, manganese, vanadium, iron, tin, cobalt and nickel.

2. The method of claim 1 , wherein each of said additional metal layers is applied using atomic layering deposition (ALD).

3. The method of claim 2 , wherein each of said additional metal layers includes a metal oxide or a metal precursor, and wherein said step of applying said additional metal layers includes using ALD to pulse said metal layer.

4. The method of claim 1 , further comprising a step of electrochemically oxidizing at least one of said oxidized additional metal layers.

5. The method of claim 4 , wherein said step of electrochemically oxidizing said at least one oxidized additional metal layers includes using an acidic electrolyte.

6. The method of claim 5 , wherein electrochemically oxidizing said at least one oxidized additional metal layers is performed for 3 to 120 minutes at a constant potential, said constant potential is 1.3 V versus Ag/AgCl using controlled potential coulometry.

7. The method of claim 2 , wherein said ALD is used to pulse said additional metal layers in a carrier gas at a temperature between 270° C. to 400° C.

8. The method of claim 3 , wherein said pseudocapacitive metal precursor layer is selected from the group consisting of bis(ethylcyclopentadienyl), cyclopentadienyl, (od) 3 /n-butylacetate solution, bis(2,4-dimethylpentadienyl)ruthenium(II), (thd) 3 , (EtCp)(DMPD), and (isopropylmethylbenzene)(cyclohexadiene).

9. The method of claim 1 , wherein oxidizing said additional metal layers comprises oxidizing said additional metal layers with oxygen, water, and hydrogen peroxide.

10. The method of claim 1 , wherein said plurality of porous, conductive nanostructures are selected from the group consisting of vertically aligned carbon nanotubes (CNT) or planar silicon.

11. The method of claim 1 , wherein the plurality of porous, conductive nanostructures comprise a substrate composed of materials selected from the group consisting of carbon, silicon, graphene, activated carbon, and phosphorene.

12. The method of claim 11 , wherein the plurality of porous, conductive nanostructures further comprise a conductive layer disposed on said substrate, said conductive layer selected from the group consisting of molybdenum, iron, aluminum, chromium and gold.

13. A method to a fabricate high surface area, high performance supercapacitor, said method comprising:

forming a plurality of conductive, porous nanostructures on a substrate, said plurality of conductive, porous nanostructures extending from said substrate and forming a plurality of electrodes of said supercapacitor;

using atomic layering deposition (ALD) to apply a metal precursor layer to a portion of said plurality of conductive, porous nanostructure electrodes;

after applying said metal precursor layer, oxidizing said metal precursor layer;

applying a plurality of additional metal precursor layers onto a previously oxidized metal precursor layer; and

after applying each additional metal precursor layer, oxidizing said additional metal precursor layer prior to applying a successive additional metal precursor layer to form a layer of a pseudocapacitive material disposed about at least a portion of said nanostructure.

14. The method of claim 13 , further comprising a step of electrochemically oxidizing at least one of said oxidized additional metal precursor layers.

15. The method of claim 14 , wherein said step of electrochemically oxidizing said at least one oxidized additional metal precursor layers includes using an acidic electrolyte.

16. The method of claim 15 , wherein electrochemically oxidizing said at least one oxidized additional metal precursor layers is performed for 3 to 120 minutes at a constant potential, said constant potential is 1.3 V versus Ag/AgCl using controlled potential coulometry.

17. The method of claim 13 , wherein said metal precursor layer is selected from the group consisting of bis(ethylcyclopentadienyl), cyclopentadienyl, (od) 3 /n-butylacetate solution, bis(2,4-dimethylpentadienyl)ruthenium(II), (thd) 3 , (EtCp)(DMPD), and (isopropylmethylbenzene)(cyclohexadiene).

18. The method of claim 13 , wherein said plurality of porous, conductive nanostructures are selected from the group consisting of vertically aligned carbon nanotubes (CNT) or planar silicon.

19. The method of claim 13 , wherein the plurality of porous, conductive nanostructures comprise a substrate composed of materials selected from the group consisting of carbon, silicon, graphene, activated carbon, and phosphorene.

20. The method of claim 19 , wherein the plurality of porous, conductive nanostructures further comprise a conductive layer disposed on said substrate, said conductive layer selected from the group consisting of molybdenum, iron, aluminum, chromium and gold.

21. A method to a fabricate high surface area, high performance supercapacitor, said method comprising:

forming a plurality of conductive, porous carbon nanotubes (CNTs) on a substrate, said plurality of conductive, porous CNTs extending from said substrate and forming a plurality of electrodes of said supercapacitor;

applying a metal layer to at least a portion of said plurality of conductive, porous CNTs using atomic layering deposition (ALD);

after applying said metal layer, oxidizing said metal layer;

applying a plurality of additional metal layers onto a previously oxidized metal layer using ALD; and

after applying each additional metal layer, oxidizing said additional metal layer prior to applying a successive additional metal layer;

wherein said metal layers includes a composition comprising at least one metal, said at least one metal selected from the group consisting of ruthenium, titanium, manganese, vanadium, iron, tin, cobalt and nickel.

22. The method of claim 21 , wherein each of said additional metal layers includes a metal oxide or a metal precursor, and wherein said step of applying said additional metal layers includes using ALD to pulse said metal layer.

23. The method of claim 22 , wherein said pseudocapacitive metal precursor layer is selected from the group consisting of bis(ethylcyclopentadienyl), cyclopentadienyl, (od) 3 /n-butylacetate solution, bis(2,4-dimethylpentadienyl)ruthenium(II), (thd) 3 , (EtCp)(DMPD), and (isopropylmethylbenzene)(cyclohexadiene).

24. The method of claim 21 , further comprising a step of electrochemically oxidizing at least one of said oxidized additional metal layers using an acidic electrolyte for 3 to 120 minutes at a constant potential, wherein said constant potential is 1.3 V versus Ag/AgCl using controlled potential coulometry.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 16, 2018
From: MASDAR INSTITUTE OF SCIENCE AND TECHNOLOGY
To: KHALIFA UNIVERSITY OF SCIENCE AND TECHNOLOGY
Reel/Frame 045356/0428 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 6, 2015
From: WARREN, ROSEANNE; SAMMOURA, FIRAS; LIN, LIWEI
To: MASDAR INSTITUTE OF SCIENCE AND TECHNOLOGY; THE REGENTS OF THE UNIVERSITY OF CALIFORNIA
Reel/Frame 035338/0383 →
Continuity (2)
Provisional Application 61930917 · Jan 23, 2014
Related Publication 20150303001A1 · Oct 22, 2015