Zinc ion-exchanging energy storage device

Patent metadata

Field	Value
Publication number	US-10826113-B2
Application number	US-201514545240-A
Country	US
Kind code	B2
Filing date	Apr 13, 2015
Priority date	Apr 13, 2015
Publication date	Nov 3, 2020
Grant date	Nov 3, 2020

Abstract

A zinc ion-exchanging battery device comprising: (A) a cathode comprising two cathode active materials (a zinc ion intercalation compound and a surface-mediating material); (B) an anode containing zinc metal or zinc alloy; (C) a porous separator disposed between the cathode and the anode; and (D) an electrolyte containing zinc ions that are exchanged between the cathode and the anode during battery charge/discharge. The zinc ion intercalation compound is selected from chemically treated carbon or graphite material having an expanded inter-graphene spacing d002 of at least 0.5 nm, or an oxide, carbide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, nickel, or a combination thereof. The surface-mediating material contains exfoliated graphite or multiple single-layer sheets or multi-layer platelets of a graphene material.

First claim

We claim:

1. A zinc ion-exchanging battery device comprising:
(A) a positive electrode or cathode comprising two cathode active materials, an optional binder, and an optional cathode current collector;
(B) a negative electrode or anode containing zinc metal or zinc alloy;
(C) a porous separator disposed between said cathode and said anode; and
(D) a non-aqueous or aqueous electrolyte in physical contact with said cathode and said anode, wherein said electrolyte contains zinc ions that are exchanged between said cathode and said anode during a charge and discharge operation of said battery device;
wherein said two cathode active materials consist of (a) at least a zinc ion intercalation compound having inter-planar spaces sufficiently large to reversibly intercalate/deintercalate zinc ions and (b) a surface-mediating material having a surface-borne zinc ion-capturing functional group or zinc ion-storing surfaces in direct contact with said electrolyte to reversibly capture or store zinc ions thereon during the charge and discharge operation of said battery device; and
wherein said two cathode active materials contain a combination of MoS 2 and RGO, or a combination of two-dimensional layered Bi 2 Se 3 Chalcogenide nanoribbons and said surface-mediating material.

2. The battery device of claim 1 wherein said electrolyte comprises a zinc metal salt-doped ionic liquid, aqueous electrolyte, or organic electrolyte.

3. The battery device of claim 1 wherein the electrolyte contains at least two different types of metal ions that participate in storing and releasing electrons.

4. The battery device of claim 1 , wherein the electrolyte comprises at least a metal ion salt selected from a transition metal sulphate, transition metal phosphate, transition metal nitrate, transition metal acetate, transition metal carboxylate, transition metal chloride, transition metal bromide, transition metal perchlorate, transition metal hexafluorophosphate, transition metal borofluoride, transition metal hexafluoroarsenide, or a combination thereof.

5. The battery device of claim 1 , wherein the electrolyte comprises at least a metal ion salt selected from zinc sulphate, zinc phosphate, zinc nitrate, zinc acetate, zinc carboxylate, zinc chloride, zinc bromide, zinc perchlorate, manganese sulphate, manganese phosphate, manganese nitrate, manganese acetate, manganese carboxylate, manganese chloride, manganese bromide, manganese perchlorate, cobalt sulphate, cobalt phosphate, cobalt nitrate, cobalt acetate, cobalt carboxylate, cobalt chloride, cobalt bromide, cobalt perchlorate, nickel sulphate, nickel phosphate, nickel nitrate, nickel acetate, nickel carboxylate, nickel chloride, nickel bromide, nickel perchlorate, iron sulphate, iron phosphate, iron nitrate, iron acetate, iron carboxylate, iron chloride, iron bromide, iron perchlorate, vanadium sulphate, vanadium phosphate, vanadium nitrate, vanadium acetate, vanadium carboxylate, vanadium chloride, vanadium bromide, vanadium perchlorate, or a combination thereof.

6. The battery device of claim 1 , wherein the electrolyte comprises an organic solvent selected from ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), methyl butyrate (MB), ethyl propionate, methyl propionate, propylene carbonate (PC), γ-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), or a combination thereof.

7. The battery device of claim 1 , wherein said surface-mediating material has a functional group that reversibly reacts with a zinc ion, forms a redox pair with a zinc ion, or forms a chemical complex with a zinc ion.

8. The battery device of claim 7 , wherein the cathode has a specific surface area no less than 200 m 2 /g and mesopores having a size from 2 to 50 nm.

9. The battery device of claim 1 , wherein the zinc metal or zinc alloy comprises a zinc metal or alloy chip, foil, powder, filament, surface stabilized particle, or a combination thereof.

10. The battery device of claim 1 , wherein said surface-mediating material occupies a weight fraction between 0.1% and 5% based on the combined weights of the surface-mediating material and the zinc ion intercalation compound.

11. The battery device of claim 1 , wherein said surface-mediating material occupies a weight fraction between 0.1% and 50% based on the combined weights of the surface-mediating material and the zinc ion intercalation compound.

12. The battery device of claim 1 , wherein said surface-mediating material occupies a weight fraction between 50% and 99% based on the combined weights of the surface-mediating material and the zinc ion intercalation compound.

13. The battery device of claim 1 , wherein said surface-mediating material occupies a weight fraction between 0.1% and 99% based on the combined weights of the surface-mediating material and the zinc ion intercalation compound.

14. The battery device of claim 1 wherein said functional group is selected from —COOH, ═O, —NH 2 , —OR, or —COOR, where R is a hydrocarbon radical.

15. The battery device of claim 1 wherein said device provides a power density no less than 15 Kw/kg, all based on total battery device weight.

16. The battery device of claim 1 wherein said device provides an energy density of no less than 1,000 Wh/kg or power density no less than 20 Kw/kg, all based on total battery device weight.

17. The battery device of claim 1 , wherein said anode further contains a porous anode current collector selected from a porous sheet, paper, web, film, fabric, non-woven, mat, aggregate, or foam of a carbon or graphite material selected from graphene, graphene oxide, reduced graphene oxide, graphene fluoride, doped graphene, functionalized graphene, expanded graphite with an inter-graphene spacing greater than 0.4 nm, exfoliated graphite or graphite worms, chemically etched or expanded soft carbon, chemically etched or expanded hard carbon, exfoliated activated carbon, chemically etched or expanded carbon black, chemically etched multi-walled carbon nanotube, nitrogen-doped carbon nanotube with an enhanced metal ion capturing ability, boron-doped carbon nanotube with an enhanced metal ion capturing ability, chemically doped carbon nanotube with an enhanced metal ion capturing ability, ion-implanted carbon nanotube with an enhanced metal ion capturing ability, chemically treated multi-walled carbon nanotube with an inter-graphene planar separation no less than 0.4 nm, chemically expanded carbon nanofiber, chemically activated carbon nanotube, chemically treated carbon fiber, chemically activated graphite fiber, chemically activated carbonized polymer fiber, chemically treated coke, mesophase carbon, or a combination thereof.

18. The battery device of claim 17 , wherein said zinc metal or zinc alloy is preloaded or pre-coated on said porous anode current collector.

19. The battery device of claim 1 , wherein said anode further contains an anode current collector which is a porous, electrically conductive material selected from metal foam, carbon-coated metal foam, graphene-coated metal foam, metal web or screen, carbon-coated metal web or screen, graphene-coated metal web or screen, perforated metal sheet, carbon-coated porous metal sheet, graphene-coated porous metal sheet, metal fiber mat, carbon-coated metal-fiber mat, graphene-coated metal-fiber mat, metal nanowire mat, carbon-coated metal nanowire mat, graphene-coated metal nanowire mat, surface-passivated porous metal, porous conductive

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01G11/04

  Hybrid capacitors · CPC title

• H01M4/42

  Alloys based on zinc · CPC title

• H01G11/60

  characterised by the solvent · CPC title

• H01G11/30

  characterised by their material · CPC title

• H01M2300/0045

  Room temperature molten salts comprising at least one organic ion · CPC title