Method of producing supercapacitor electrodes and cells having high active mass loading

Patent metadata

Field	Value
Publication number	US-9779882-B2
Application number	US-201514757124-A
Country	US
Kind code	B2
Filing date	Nov 23, 2015
Priority date	Nov 23, 2015
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

A process for producing an electrode for a supercapacitor cell, said process comprising: (A) preparing a plurality of electrically conductive porous layers and a plurality of wet electrode layers composed of an electrode active material and an optional conductive additive mixed with a liquid or gel electrolyte, wherein the conductive porous layers contain interconnected conductive pathways and at least 80% by volume of pores; and (B) stacking and consolidating a desired number of the porous layers and a desired number of the wet electrode layers in an alternating sequence to form an electrode having a thickness no less than 100 μm (preferably greater than 200 μm, more preferably greater than 400 μm, further more preferably greater than 600 μm, and most preferably greater than 1,000 μm).

First claim

We claim:

1. A process for producing a supercapacitor cell, said process comprising:
(a) preparing a plurality of electrically conductive porous layers, a plurality of wet anode layers of an anode active material and an optional conductive additive mixed with a first liquid or gel electrolyte, and a plurality of wet cathode layers of a cathode active material and an optional conductive additive mixed with a second liquid or gel electrolyte, wherein said conductive porous layers contain interconnected conductive pathways and at least 80% by volume of pores;
(b) stacking and consolidating a desired number of said porous layers and a desired number of said wet anode layers to form an anode electrode having a thickness from 100 μm to 5 mm;
(c) placing a porous separator layer in contact with said anode electrode;
(d) stacking and consolidating a desired number of said porous layers and a desired number of said wet cathode layers to form a cathode electrode in contact with said porous separator, wherein said cathode electrode has a thickness from 100 μm to 5 mm; wherein said step (d) is conducted before or after step (B); and
(e) assembling and sealing said anode electrode, porous separator, and cathode electrode in a housing to produce said supercapacitor cell;
wherein said anode electrode and/or said cathode electrode has a material mass loading from 7 mg/cm 2 to 100 mg/cm 2 .

2. The process of claim 1 , wherein said anode active material and/or said cathode active material contains multiple particles of a carbon material and/or multiple graphene sheets, wherein said multiple graphene sheets contain single-layer graphene or few-layer graphene each having from 1 to 10 graphene planes and said multiple particles of carbon material have a specific surface area from 500 m 2 /g to 2600 m 2 g when measured in a dried state.

3. The process of claim 2 , wherein said graphene sheets are selected from the group consisting of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, physically or chemically activated or etched versions thereof, and combinations thereof.

4. The process of claim 2 , wherein said anode active material or cathode active material further contains a redox pair partner material selected from a metal oxide, a conducting polymer, an organic material, a non-graphene carbon material, an inorganic material, or a combination thereof, wherein said partner material, in combination with graphene or a carbon material, form a redox pair for pseudo-capacitance.

5. The process of claim 4 , wherein said metal oxide is selected from RuO 2 , IrO 2 , NiO, MnO 2 , VO 2 , V 2 O 5 , V 3 O 8 , TiO 2 , Cr 2 O 3 , Co 2 O 3 , Co 3 O 4 , PbO 2 , Ag 2 O, or a combination thereof.

6. The process of claim 4 , wherein said inorganic material is selected from a metal carbide, metal nitride, metal boride, metal dichalcogenide, or a combination thereof.

7. The process of claim 4 , wherein said inorganic material is selected from nano discs, nanoplatelets, nano-coating, or nanosheets of an inorganic material selected from: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, or (e) a combination thereof; wherein said discs, platelets, or sheets have a thickness less than 100 nm.

8. The process of claim 2 , wherein said carbon material is selected from activated carbon, activated meso-carbon micro beads, activated graphite, activated or chemically etched carbon black, activated hard carbon, activated soft carbon, carbon nanotube, carbon nanofiber, activated carbon fiber, activated graphite fiber, exfoliated graphite worms, activated graphite worms, activated expanded graphite flakes, or a combination thereof.

9. The process of claim 1 , wherein said electrically conductive porous layer has a thickness from 200 μm to 5 mm, 85% by volume of pores, and/or said electrode active material loading is from 10 mg/cm 2 to 100 mg/cm 2 .

10. The process of claim 1 , wherein said electrically conductive porous layer has a thickness from 300 μm to 5 mm, has at least 90% by volume of pores, and/or said electrode active material loading is from 15 mg/cm 2 to 100 mg/cm 2 .

11. The process of claim 1 , wherein said electrically conductive porous layer has a thickness from 400 μm to 5 mm, has at least 95% by volume of pores, and/or said electrode active material loading is from 20 mg/cm 2 to 100 mg/cm 2 .

12. The process of claim 1 , wherein said electrically conductive porous layer is selected from metal foam, metal web or screen, perforated metal sheet-based 3-D structure, metal fiber mat, metal nanowire mat, conductive polymer nanofiber mat, conductive polymer foam, conductive polymer-coated fiber foam, carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or a combination thereof.

13. The process of claim 1 , wherein said anode active material or cathode active material is selected from (a) graphene sheets alone; (b) graphene sheets mixed with a carbon material; (c) graphene sheets mixed with a partner material that forms a redox pair with said graphene sheets to develop pseudo-capacitance; or (d) graphene sheets and a carbon material mixed with a partner material that forms a redox pair with said graphene sheets or said carbon material to develop pseudo-capacitance, and wherein there is no other anode active material in said anode electrode and no other cathode active material in said cathode electrode.

14. The process of claim 1 , wherein a volume ratio of said anode active material-to-said electrolyte in said wet anode layer is from 1/5 to 20/1 and/or a volume ratio of said cathode active material-to-said electrolyte in said wet cathode layer is from 1/5 to 20/1.

15. The process of claim 1 , wherein a volume ratio of said anode active material-to-said electrolyte in said wet anode layer is from 1/3 to 5/1 and/or a volume ratio of said cathode active material-to-said electrolyte in said wet cathode layer is from 1/3 to 5/1.

16. The process of claim 1 , wherein said anode active material and/or said cathode active material contains nanodiscs, nanoplatelets, nano-coating, or nanosheets of an inorganic material selected from: (i) bismuth selenide or bismuth telluride, (ii) transition metal dichalcogenide or trichalcogenide, (iii) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (iv) boron nitride, or (v) a combination thereof, wherein said discs, platelets, coating, or sheets have a thickness less than 100 nm and a specific surface area from 200 m 2 /g to 2600 m 2 /g when measured in a dried state.

17. The process of claim 16 , wherein said anode active material or cathode active material further contains graphene sheets selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, or a combination thereof.

18. The process of

Assignees

• Nanotek Instruments Inc

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01G11/28

  arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives · CPC title

• H01G11/86 Primary

  specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34) · CPC title

• H01G11/04

  Hybrid capacitors · CPC title

• H01G11/02 Primary

  using combined reduction-oxidation reactions, e.g. redox arrangement or solion · CPC title

• H01G11/24

  characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor · CPC title