Zinc Ion-Exchanging Energy Storage Device

Patent metadata

Field	Value
Publication number	US-2016301096-A1
Application number	US-201514545240-A
Country	US
Kind code	A1
Filing date	Apr 13, 2015
Priority date	Apr 13, 2015
Publication date	Oct 13, 2016
Grant date	—

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 d 002 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;
wherein the zinc ion intercalation compound is selected from chemically treated carbon or graphite material having an expanded inter-graphene spacing d 002 of at least 0.5 nm, layered zinc hydroxide salt, 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; and
wherein the surface-mediating material contains exfoliated graphite or multiple single-layer sheets or multi-layer platelets of a graphene material selected from pristine graphene, graphene oxide having 2% to 46% by weight of oxygen, reduced graphene oxide having 0.01% to 2% by weight of oxygen, chemically functionalized graphene, nitrogen-doped graphene, boron-doped graphene, fluorinated graphene, or a combination thereof and these graphene sheets or platelets or exfoliated graphite flakes form a network of interconnected electron-conducting paths and the zinc ion intercalation compound is physically connected or chemically bonded to said sheets, platelets, or flakes, and wherein said two cathode active materials do not include combinations of non-nanowire manganese oxide and pristine graphene or reduced graphene oxide.

2 . The battery device of claim 1 , wherein said zinc ion intercalation compound contains an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in a nanowire, nano-disc, nano-ribbon, or nano platelet form.

3 . The battery device of claim 1 wherein said zinc ion intercalation material includes MnO 2 in a nanowire form having a diameter or thickness less than 100 nm.

4 . The battery device of claim 1 wherein said zinc ion intercalation compound contains MnO 2 , which is supported by a surface-mediating material selected from graphene oxide having 2% to 46% by weight of oxygen, chemically functionalized graphene, nitrogen-doped graphene, boron-doped graphene, fluorinated graphene, or exfoliated graphite.

5 . The battery device of claim 1 wherein said carbide contains a 2D MXene material, denoted by M n+1 X n T x , having a surface being terminated by a terminating group selected from O, OH, and/or F group, wherein M is an early transition metal selected from Ti, Nb, V, or Ta, X is C and/or N, T represents said terminating group, n=1, 2, or 3, and x is the number of terminating groups, and wherein the MXene material is selected from Ti 2 CT x , (Ti 0.5 , Nb 0.5 ) 2 CT x , Nb 2 CT x , V 2 CT x , Ti 3 C 2 T x , (V 0.5 , Cr 0.5 ) 3 C 2 T x , Ti 3 CNT x , Ta 4 C 3 T x , and Nb 4 C 3 T x .

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

7 . 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.

8 . 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.

9 . 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.

10 . 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.

11 . 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.

12 . The battery device of claim 1 , wherein said multiple sheets or platelets of the graphene material, prior to being made into said cathode, have a specific surface area no less than 100 m 2 /g to store or support zinc ions or atoms thereon and the resulting cathode also has a specific surface area no less than 100 m 2 /g and meso-pores having a size from 2 to 50 nm.

13 . The battery device of claim 11 , wherein the cathode has a specific surface area no less than 200 m 2 /g and meso-pores having a size from 2 to 50 nm.

14 . 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.

15 . 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.

16 . 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.

17 . The battery device of claim 1 , wherein said surface-mediating material occupies a weight fraction between 50% and 99% based on th

Assignees

• Zhamu Aruna
• Jang Bor Z

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01G11/36

  Nanostructures, e.g. nanofibres, nanotubes or fullerenes · CPC title

• H01G11/02

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

• H01M4/583

  Carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M10/054 Primary

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• H01M10/0568

  characterised by the solutes · CPC title