AROMATIC POLYMER ION EXCHANGE MEMBRANES, ITS COMPOSITE MEMBRANCE, AND ITS APPLICATION IN ACIDIC ELECTROLYTE FLOW BATTERY

• US 20120196188A1
• Filed: 06/25/2010
• Published: 08/02/2012
• Est. Priority Date: 10/16/2009
• Status: Active Grant

• Current Assignee: Dalian Rongke Power Co., Ltd.
• Original Assignee: Dalian Institute of Chemical Physics Chinese Academy of Sciences (Chinese Academy of Sciences), Dalian Rongke Power Co., Ltd.
• Inventors: Zhang, Huamin, Li, Xianfeng, Dai, Hua, Bi, Cheng
• Granted Patent: US 9,276,282 B2
• Time in Patent Office: Days
• US Class Current: 429/309
• CPC Class Codes: C08G 73/18 Polybenzimidazoles
• CPC Class Codes: H01M 8/1027 having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
• CPC Class Codes: H01M 8/103 having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
• CPC Class Codes: H01M 8/1032 having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
• CPC Class Codes: H01M 8/1048 Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
• CPC Class Codes: H01M 8/1051 Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
• CPC Class Codes: H01M 8/188 by recharging of redox couples containing fluids; Redox flow type batteries
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A polymer ion exchange membrane for acidic electrolyte flow battery. The membrane is nitrogen heterocycles aromatic polymer, especially polybenzimidazole type polymer. A nitrogen heterocycles in the membrane interact with acid in the electrolyte to form donor-receptor proton transport network, so as to keep the proton transport performance of the membrane. The preparation condition for the membrane is mild, and the process is simplicity. The preparation method is suitable for mass production. The membrane is used in acidic electrolyte flow battery, especially in vanadium flow energy storage battery. The membrane has excellent mechanical stability and thermostability. In vanadium redox flow battery, the membrane has excellent proton conduct performance and excellent resistance to the permeation of vanadium ions.

Claims

1. Applications of aromatic polymeric ion exchange membranes and its composite membrane in acidic electrolyte flow battery, characterized in that:

the aromatic polymers comprises nitrogen heterocycles, said polymer is a homopolymer or copolymer of one or more chosen from benzimidazole, vinyl imidazole, pyridine, vinyl pyridine;

pyrazole, pyrimidine, thiazole, benzothiazole, oxazole, benzoxazole, oxadiazole, quinoline, quinoxaline, thiadiazole, and purine.

2. The application according to claim 1, characterized in that the aromatic polymeric ion exchange membrane is made from one or more ion exchange membranes chosen from polybenzimidazole, poly(vinyl imidazole), polypyridine, poly(vinyl pyridine), polypyrazole, polypyrimidine, polythiazole, polybenzothiazole, polyoxazole, polybezoxazole, polyoxadiazole, polyquinoline, polyquinoxaline, polythiadiazole, and polypurine.

3. The application according to claim 1, characterized in that:

the aromatic polymer is a homopolymer of polybenzimidazole having the following structural formula;

4. The application according to claim 1, wherein the aromatic polymer is a polybenzimidazole homopolymer having a structural formula as follows:

5. The application according to claim 3, the polybenzimidazole copolymer comprises a pyridine functional group having structural formula as follows:

6. The application according to claim 1, the resulting ion exchange membrane has a thickness of 10 to 200 μ

m, and is immersed in strong acid like HCl, HNO₃, phosphoric acid and sulfuric acid for 0.05 to 1000 hours at 5-100°

C. The concentration range of the acid is between 0.1-25 mol/L.

7. The application according to the claim 1, wherein the composite membrane is a inorganic-organic blend membrane. The inorganic phase can be SiO₂, TiO₂, ZrO₂, ZrPO₃ nanoparticles or their blend. The content of the nanoparticles is in the range of 0.1˜

40 wt %. Wherein the thickness of the composite membrane is in the range of 0.1˜

200 micrometer, and the composite membrane is immersed in strong acid like HCl, HNO3, phosphoric acid and sulfuric acid for 0.05 to 1000 hours at 5-100°

C. The concentration range of the acid is between 0.1-25 mol/L.

8. The application according claim 7, wherein the organic-inorganic composite ion exchange membrane comprises an organic phase and an inorganic phase, a weight ratio between the inorganic phase and the organic phase is in the range of 2:

100 to 30;

100. The organic phase can be polybenzimidazole with following structure.

9. The application according to claim 1, wherein the composite membranes is an aromatic polymer ion exchange membrane comprising one or more sulfonated polymers chosen from perfluorinated sulfonic acid polymer, sulfonated polysulfone, sulfonated polypropylene, sulfonated polyether sulfone, sulfonated poly (ether sulfone), sulfonated poly aryl sulfone, sulfonated polyphenylene ether, sulfonatedpolyether ether ketone, and sulfonated poly (aryl ether ketone), The weight ratio of sulfonated polymeris in the range of 0.1-50% of the aromatic polymer. The thickness of the membrane is in the range of 0.1-200 μ

m. The membranes are treated with 0.1-25 mol/L strong acid solutions. The acid can be phosphoric acid, chloride acid and sulfuric acid etc.

10. The application according to claim 1, wherein the membrane is used in a redox flow battery with an acidic electrolyte, including vanadium flow battery, Fe—

Cr flow battery, Zn—

Br flow battery, Zn—

Cr flow battery, and sodium polysulfide-Br flow battery.