Zinc-iodine secondary energy storage methods, devices, and electrolytes

Patent metadata

Field	Value
Publication number	US-2018342771-A1
Application number	US-201715724051-A
Country	US
Kind code	A1
Filing date	Oct 3, 2017
Priority date	May 26, 2017
Publication date	Nov 29, 2018
Grant date	—

Abstract

Disclosed are cathodes having electron-conductive high-surface-area materials, aqueous non-halide-containing electrolytes, secondary zinc-iodine energy storage devices using the same, and methods for assembling the same. The disclosed high-surface-area materials and the aqueous non-halide-containing electrolyte solutions can contribute together to the confinement of the active iodine species in the cathode and to the minimization of shuttle effects and self-discharging. The non-halide-containing electrolyte salts can facilitate preferential adsorption of the iodine species to the cathode material rather than dissolution in the aqueous electrolyte solution, thereby contributing to the confinement of the active iodine species.

First claim

What is claimed is:

1 . A method of assembling a zinc-iodine secondary energy storage device, the method comprising the steps of:
Loading I 2 on an electron conductive, high-surface-area material, wherein the electron conductive, high-surface-area material having I 2 is located on a cathode side of the device and is counter to an anode side comprising a zinc-containing electrode; Arranging between the anode and cathode sides an aqueous electrolyte solution having no halides and having a non-halide-containing electrolyte salt dissolved therein.

2 . The method of claim 1 , wherein said arranging step further comprises arranging between the anode and cathode sides an aqueous electrolyte solution having no halides and having a non-halide-containing electrolyte salt comprising ZnSO 4 dissolved therein at a concentration greater than or equal to 0.5M.

3 . The method of claim 1 , wherein said arranging step further comprises arranging between the anode and cathode sides an aqueous electrolyte solution having no halides and having a non-halide-containing electrolyte salt comprising Zn(CH 3 COO) 2 dissolved therein at a concentration greater than or equal to 0.1M.

4 . A secondary energy storage device comprising:
an anode comprising zinc; a cathode comprising an electron conductive, high-surface-area material and active iodine species adsorbed to the material when the device is in a non-discharged state; and an aqueous electrolyte solution having substantially no halides when the device is in a charged state.

5 . The secondary energy storage device of claim 4 , wherein the electron conductive, high-surface-area material comprises graphene.

6 . The secondary energy storage device of claim 4 , wherein the electron conductive, high-surface-area material comprises a conductive polymer material, a conductive Metal-organic framework (MOF)-based material, or a combination thereof.

7 . The secondary energy storage device of claim 4 , wherein the electron conductive, high-surface-area material comprises activated carbon.

8 . The secondary energy storage device of claim 4 , wherein the electron conductive, high-surface-area material comprises a porous material having pores with average pore diameters less than or equal to 50 nm, less than or equal to 40 nm, less than or equal to 25 nm, less than or equal to 10 nm, less than or equal to 5 nm, or less than or equal to 2 nm.

9 . The secondary energy storage device of claim 4 , wherein no ion selective membrane separates the anode and the cathode.

10 . The secondary energy storage device of claim 4 , wherein the zinc comprises zinc metal.

11 . The secondary energy storage device of claim 4 , wherein the zinc comprises zinc ions and the anode further comprises an intercalation material into which zinc ions are intercalated and deintercalated.

12 . The secondary energy storage device of claim 11 , wherein the intercalation material comprises Zn x Mo 6 S 8 .

13 . The secondary energy storage device of claim 4 , wherein the aqueous electrolyte solution comprises a non-halide-containing, electrolyte salt dissolved therein.

14 . The secondary energy storage device of claim 13 , wherein the non-halide-containing, electrolyte salt comprises MSO 4 , wherein M is a metal.

15 . The secondary energy storage device of claim 13 , wherein the non-halide-containing, electrolyte salt comprises M(NO 3 ) 2 , M(CF 3 SO 3 ) 2 , or M(CH 3 COO) 2 , wherein M is a metal.

16 . The secondary energy storage device of claim 15 , wherein M is Zn, K, or Na or other alkaline metals.

17 . The secondary energy storage device of claim 13 , wherein the non-halide-containing, electrolyte salt comprises ZnSO 4 .

18 . The secondary energy storage device of claim 17 , wherein the ZnSO 4 has a concentration in the aqueous electrolyte solution greater than or equal to 0.5M.

19 . The secondary energy storage device of claim 17 , wherein the ZnSO 4 has a concentration in the aqueous electrolyte solution greater than or equal to 1M, greater than or equal to 1.5M, greater than or equal to 2M, or greater than or equal to 3M.

20 . The secondary energy storage device of claim 4 , wherein an interaction energy difference (AE) between adsorption to the high-surface-area material and solvation in the aqueous electrolyte solution is less than zero for each of I 2 and Zn(I 3 ) 2 such that the I 2 and Zn(I 3 ) 2 are preferentially adsorbed to the high-surface-area material.

21 . The secondary energy storage device of claim 4 , having a capacity retention greater than or equal to 90% after at least 3000 cycles at a rate of 2 C.

22 . A secondary energy storage device comprising:
an anode comprising zinc; a cathode comprising a mesoporous or a microporous, activated carbon material and active iodine species adsorbed thereto when the device is in a non-discharged state; and an aqueous electrolyte solution having substantially no halides when the device is in a charged state and having ZnSO 4 dissolved therein at a concentration greater than or equal to 0.5M; wherein no ion selective membrane separates the anode and cathode and wherein an interaction energy difference (AE) between adsorption to the activated carbon material and solvation in the aqueous electrolyte solution is less than or equal to zero for each of I 2 and Zn(I 3 ) 2 such that the I 2 and Zn(I 3 ) 2 are preferentially adsorbed to the activated carbon material.

Assignees

• Battelle Memorial Institute

Inventors

• Li Bin
• Pan Huilin
• Nie Zimin
• Liu Jun
• Sprenkle Vincent L

Classifications

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/42

  Alloys based on zinc · CPC title

• H01M10/365 Primary

  Zinc-halogen accumulators · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M10/04

  Construction or manufacture in general (H01M10/058, H01M10/12, H01M10/28, H01M10/38 take precedence) · CPC title