Amine-bromine two electron electrolyte of flow battery and use thereof, and flow battery

Patent metadata

Field	Value
Publication number	US-2025038241-A1
Application number	US-202218716946-A
Country	US
Kind code	A1
Filing date	Jun 10, 2022
Priority date	Dec 6, 2021
Publication date	Jan 30, 2025
Grant date	—

Abstract

An amine-bromine two electron electrolyte of flow battery and the use thereof, and a flow battery are provided. In the electrolyte, an amino compound with an electron-withdrawing group at the ortho-position of an amino group is used to react with bromine charged to a positive valence so as to form an amine-bromine compound, such that positive-valence bromine is stabilized, and a reversible two-electron transfer reaction from bromine ions to amino compounds is achieved. The amine compounds have different solubilities and produce different voltages depending on their substituent groups, and thus have extensive adjustability and applicability for use in acidic, neutral, and weak alkaline flow battery systems. Flow batteries assembled with the electrolyte prepared using this reaction has the advantages of low cost and high energy density, and can achieve a longer cycle life and higher battery efficiency.

First claim

What is claimed is:

1 . A flow battery electrolyte, wherein the flow battery electrolyte comprises bromine ions, an amine compound with an electron-withdrawing group at an ortho-position of an amino group, and a supporting electrolyte; when the amine compound with the electron-withdrawing group at the ortho-position of the amino group carries an ion-conducting group, the flow battery electrolyte does not comprise the supporting electrolyte.

2 . The flow battery electrolyte according to claim 1 , wherein the flow battery electrolyte consists of the bromine ions, the amine compound with the electron-withdrawing group at the ortho-position of the amino group, and the supporting electrolyte; when the amine compound with the electron-withdrawing group at the ortho-position of the amino group carries the ion-conducting group, the flow battery electrolyte does not comprise the supporting electrolyte.

3 . The flow battery electrolyte according to claim 1 , wherein the bromine ions, and the amine compound with the electron-withdrawing group at the ortho-position of the amino group are used as a positive active material; and
the bromine ions, and the amine compound with the electron-withdrawing group at the ortho-position of the amino group undergo an oxidation reaction and/or a reduction reaction during a cycling process of a flow battery.

4 . The flow battery electrolyte according to claim 1 , wherein the bromine ions comprise at least one of hydrobromic acid, sodium bromide, potassium bromide, zinc bromide, ammonium bromide, and other salts containing the bromide ions.

5 . The flow battery electrolyte according to claim 1 , wherein the amine compound comprises at least one of sulfamic acid, sodium sulfamate, potassium sulfamate, ammonium sulfamate, sulfonamide, succinimide, acetamide, phthalimide, saccharin, sodium pyrrolidonecarboxylate, barbituric acid, dicyandiamide, methanesulfonamide, cyanuric acid, trifluoromethanesulfonamide, and 2-aminopyrimidine.

6 . The flow battery electrolyte according to claim 1 , wherein the supporting electrolyte comprises at least one of sulfuric acid, acetic acid, glycolic acid, bromoacetic acid, potassium chloride, potassium acetate, sodium chloride, sodium acetate, and sodium sulfate.

7 . The flow battery electrolyte according to claim 1 , wherein the flow battery electrolyte is an aqueous solution comprising the bromine ions, the amine compound with the electron-withdrawing group at the ortho-position of the amino group, and the supporting electrolyte; and
wherein a concentration of the bromine ions is from 0.1 mol L −1 to 5 mol L −1 ; a concentration of the amine compound is from 0.1 mol L −1 to 5 mol L −1 ; a concentration of the supporting electrolyte is from 0.1 mol L −1 to 4 mol L −1 .

8 . A use of the flow battery electrolyte according to claim 1 as a positive electrolyte in a flow battery.

9 . The method according to claim 8 , wherein a negative electrolyte active material of the flow battery comprises at least one of titanium sulfate, hexafluorotitanic acid, titanium bromide, cadmium sulfate, cadmium bromide, cadmium chloride, lead chloride, stannous chloride, zinc bromide, and zinc acetate.

10 . A flow battery, wherein the flow battery comprises a positive electrode, a negative electrode, and a separator for separating the positive electrode and the negative electrode; a chamber on a positive electrode side is filled with a positive electrolyte, and a chamber on a negative electrode side is filled with a negative electrolyte; the positive electrolyte comprises the flow battery electrolyte according to claim 1 ; and
an active material of the negative electrolyte is at least one of titanium sulfate, hexafluorotitanic acid, titanium bromide, cadmium sulfate, cadmium bromide, cadmium chloride, lead chloride, stannous chloride, zinc bromide, and zinc acetate.

11 . The flow battery electrolyte according to claim 7 , wherein the concentration of the bromine ions is from 1 mol L −1 to 2 mol L −1 ; the concentration of the amine compound is from 1 mol L −1 to 2 mol L −1 ; the concentration of the supporting electrolyte is from 1 mol L −1 to 2 mol L −1 .

12 . The flow battery according to claim 10 , wherein in the flow battery electrolyte, the flow battery electrolyte consists of the bromine ions, the amine compound with the electron-withdrawing group at the ortho-position of the amino group, and the supporting electrolyte; when the amine compound with the electron-withdrawing group at the ortho-position of the amino group carries the ion-conducting group, the flow battery electrolyte does not comprise the supporting electrolyte.

13 . The flow battery according to claim 10 , wherein in the flow battery electrolyte, the bromine ions, and the amine compound with the electron-withdrawing group at the ortho-position of the amino group are used as a positive active material;
the bromine ions, and the amine compound with the electron-withdrawing group at the ortho-position of the amino group undergo an oxidation reaction and/or a reduction reaction during a cycling process of the flow battery.

14 . The flow battery according to claim 10 , wherein in the flow battery electrolyte, the bromine ions comprise at least one of hydrobromic acid, sodium bromide, potassium bromide, the zinc bromide, ammonium bromide, and other salts containing the bromide ions.

15 . The flow battery according to claim 10 , wherein in the flow battery electrolyte, the amine compound comprises at least one of sulfamic acid, sodium sulfamate, potassium sulfamate, ammonium sulfamate, sulfonamide, succinimide, acetamide, phthalimide, saccharin, sodium pyrrolidonecarboxylate, barbituric acid, dicyandiamide, methanesulfonamide, cyanuric acid, trifluoromethanesulfonamide, and 2-aminopyrimidine.

16 . The flow battery according to claim 10 , wherein in the flow battery electrolyte, the supporting electrolyte comprises at least one of sulfuric acid, acetic acid, glycolic acid, bromoacetic acid, potassium chloride, potassium acetate, sodium chloride, sodium acetate, and sodium sulfate.

17 . The flow battery according to claim 10 , wherein in the flow battery electrolyte, the flow battery electrolyte is an aqueous solution comprising the bromine ions, the amine compound with the electron-withdrawing group at the ortho-position of the amino group, and the supporting electrolyte; and
wherein a concentration of the bromine ions is from 0.1 mol L −1 to 5 mol L −1 ; a concentration of the amine compound is from 0.1 mol L −1 to 5 mol L −1 ; a concentration of the supporting electrolyte is from 0.1 mol L −1 to 4 mol L −1 .

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Li Xianfeng
• Xu Yue
• Xie Congxin

Classifications

• H01M2300/0005

  Acid electrolytes · CPC title

• H01M8/188 Primary

  by recharging of redox couples containing fluids; Redox flow type batteries · CPC title

• H01M2300/0002

  Aqueous electrolytes · CPC title

• H01M2300/0091

  in the form of mixtures · CPC title

• Y02E60/50

  Fuel cells · CPC title