Liquid-circulating battery

• US 5,759,711 A
• Filed: 02/14/1997
• Issued: 06/02/1998
• Est. Priority Date: 02/19/1996
• Status: Expired due to Term

• Current Assignee: Sumitomo Electric Industries Limited (Sumitomo Corporation)
• Original Assignee: Kashima-Kita Electric Power Corporation
• Inventors: Sekiguchi, Sumie, Sato, Kanji, Furusato, Kouichi, Miyabayashi, Mitsutaka, Nakajima, Masato
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US08/801,115
• Time in Patent Office: 473 Days
• Field of Search: 429/101, 429/105, 429/15, 429/50-52, 429/249, 429/254, 429/14, 429/17, 429/72, 29/623.1, 204/296
• US Class Current: 429/51
• CPC Class Codes: H01M 50/414 Synthetic resins, e.g. thermoplastics or thermosetting resins
• CPC Class Codes: H01M 50/417 Polyolefins
• CPC Class Codes: H01M 50/426 Fluorocarbon polymers
• CPC Class Codes: H01M 50/489 Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• CPC Class Codes: H01M 50/497 Ionic conductivity
• CPC Class Codes: H01M 8/0289 Means for holding the electrolyte solid polymer electrolytes H01M8/1018
• CPC Class Codes: H01M 8/188 by recharging of redox couples containing fluids; Redox flow type batteries
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

The present invention provides a liquid-circulating battery including a positive electrode, a negative electrode, a permeable membrane interposed between the positive and negative electrodes to hold the same in separated relation to each other and to partition the same into a positive chamber and a negative chamber, two porous liquid-permeable carbon electrodes disposed respectively in the positive and negative electrolytic solutions being circulated respectively into the positive and negative chambers such that an oxidation-reduction reaction occurs and causes charging and discharging, wherein the permeable membrane is an ion-exchange me membrane including as an ion exchanger layer a polymeric pellicle which results from crosslinking of a halogenated alkylated product of an aromatic polysulfone type polymer with use of a polyamine and which has an ion exchange capacity of 0.3 to 8.0 milliequivalent/gram of dry resin and a thickness 0.1 to 120 μm, said polysulfone type polymer having as a recurring unit a group represented at least by the following formula (I); and ##STR1## and wherein each of said positive and negative electrolytic solutions is an electrolytic solution having a vanadium ion concentration of 0.5 to 8 mols/liter.

Claims

1. A liquid-circulating battery comprising:

a positive electrode chamber;

a negative electrode chamber;

a permeable membrane interposed between said positive and negative electrode chambers to separate said positive chamber and said negative chamber;

a first and a second porous liquid-permeable carbon electrodes disposed respectively in said positive and negative chambers; and

a positive and a negative electrolytic solutions, said positive and negative electrolytic solutions being circulated respectively into said positive and negative chambers such that an oxidation-reduction reaction occurs and causes charging and discharging, wherein said permeable membrane is defined by the following requirement (a), and each of said positive and negative electrolytic solutions is defined by the following requirement (b);

(a) an ion-exchange membrane including as an ion-exchanger layer a polymeric pellicle which results from crosslinking of a halogenated alkylated product of an aromatic polysulfone polymer with use of a polyamine and which has an ion exchange capacity of 0.3 to 8.0 milliequivalent/gram of dry resin and a thickness of 0.1 to 120 μ

m, said polysulfone polymer having as a recurring unit at least a group represented by the following formula (I); and

##STR8## (b) an electrolytic solution having a vanadium ion concentration of 0.5 to 8 mols/liter.

2. The battery according to claim 1, wherein each of said positive and negative electrolytic solutions has a sulfate group contained in a concentration of 0.5 to 9.0 mols/liter.

3. The battery according to claim 1 or 2, wherein said ion exchanger layer is disposed on a substrate layer formed substantially free from ion exchange groups and having a thickness of 1.0 to 250 μ

m.

4. The battery according to claim 3, wherein said ion exchanger layer is disposed on a porous substrate layer formed of a polyolefin or a polyfluoroolefin and having a porosity of 20 to 90%.

5. The battery according to claim 3, wherein said ion exchanger layer is disposed on a nonwoven fabric formed of a polyolefin.

6. The battery according to claim 3, wherein said ion exchanger layer is disposed on a translucent film having ionic conductivity.

8. The battery according to claim 1, which further includes at least one cell structure having two current collectors positioned respectively on a side of said first and second porous liquid-permeable carbon electrode near to said permeable membrane and on the opposite side of the former electrode remote from the latter membrane, said porous carbon electrode being interposed between and by said permeable membrane and said current collectors and has a thickness of 0.3 to 10 mm.

9. A method of making the liquid-circulating battery of claim 1 comprising:

separating said positive electrode chamber from said negative electrode chamber by placing said permeable membrane between said positive and said negative electrode chambers.

10. The method of making the liquid-circulating battery of claim 9, further comprising:

placing said first porous liquid-permeable carbon electrode in said positive electrode chamber and said second porous liquid-permeable carbon electrode in said negative electrode chamber.

11. The method of making the liquid-circulating battery of claim 10, further comprising:

filling said positive electrode chamber with said positive electrolytic solution and said negative electrode chamber with said negative electrolytic solution.

12. A liquid-circulating battery of claim 1 prepared by a process comprising:

filling said positive electrode chamber with said positive electrolytic solution and said negative electrode chamber with said negative electrolytic solution.

13. The liquid-circulating battery of claim 12, wherein said process further comprises:

separating said positive electrode chamber from said negative electrode chamber by placing said permeable membrane between said positive and the negative electrode chambers.

14. The liquid-circulating battery of claim 13, wherein said process further comprises:

placing said first porous liquid-permeable carbon electrode in said positive electrode chamber and said second porous liquid-permeable carbon electrode in said negative electrode chamber.

7. The battery according to claim I, wherein each of said first and second porous liquid-permeable carbon electrodes has a bulk density of 0.04 to 0.8 g/cc.

15. A battery comprising:

a positive electrode chamber,

a negative electrode chamber,

a permeable membrane interposed between said positive and negative electrode chambers to separate said positive chamber and said negative chamber,

a first and a second porous liquid-permeable carbon electrodes disposed respectively in said positive and negative chambers;

wherein said permeable membrane is an ion-exchange membrane comprising a polymeric pellicle as an ion-exchanger layer which results from crosslinking of a halogenated alkylated product of an aromatic polysulfone polymer with use of a polyamine, wherein the ion-exchange membrane has an ion exchange capacity of 0.3 to 0.8 milliequivalent/gram of dry resin and a thickness of 0.1 to 120 μ

m and,

said polysulfone polymer has as a recurring unit at least a group represented by the following formula (I);

##STR9##

16. The battery according to claim 15, wherein said ion exchanger layer is disposed on a substrate layer formed substantially free from ion exchange groups and having a thickness of 1.0 to 250 μ

m.

17. The battery according to claim 15, wherein said ion exchanger layer is disposed on a porous substrate layer formed of a polyolefin or a polyfluoroolefin and having a porosity of 20 to 90%.

18. The battery according to claim 15, wherein said ion exchanger layer is disposed on a nonwoven fabric formed of a polyolefin.

19. The battery according to claim 15, wherein said ion exchanger layer is disposed on a translucent film having ionic conductivity.

20. The battery according to claim 15, wherein each of said first and second porous liquid-permeable carbon electrodes has a bulk density of 0.4 to 0.8 g/cc.