Membranes for aqueous redox flow batteries

Patent metadata

Field	Value
Publication number	US-2021013536-A1
Application number	US-202016914012-A
Country	US
Kind code	A1
Filing date	Jun 26, 2020
Priority date	Jun 29, 2018
Publication date	Jan 14, 2021
Grant date	—

Abstract

The present invention provides a membrane comprising a polyamine polymer. In another embodiment, the present invention provides an electrochemical cell comprising a membrane of the present invention; a positive electrode; and a negative electrode. In another embodiment, the present invention provides a composition comprising a polyamine polymer of Formula J, I or II.

First claim

1 . A membrane comprising a polyamine polymer.

2 . The membrane of claim 1 , wherein the polyamine polymer is a zwitterionic quaternary polyamine polymer.

3 . The membrane of claim 1 , wherein the membrane allows monoatomic and monovalent ions and/or the acid/base dissociation products of water to permeate the membrane such that the conductivity of the membrane is at least 0.01 mS/cm and the diffusive permeability of polyvalent ions and/or ionic transition metal complexes is limited to less than 1×10 −8 cm 2 /s.

4 . The membrane of claim 3 , wherein the monoatomic and monovalent ions are independently H + , Li + , Na + , K + , F − , Cl − , Br − , or I − .

5 . The membrane of claim 3 , wherein the polyvalent ions are independently S 2 2− , S 4 2− , S 8 2− , MnO 4 − , or MnO 4 2− .

6 . The membrane of claim 1 , wherein the membrane filters aqueous or non-aqueous electrolytes in electrochemical applications.

7 . The membrane of claim 1 , wherein the polyamine polymer comprises a Tröger's base polymer or copolymer thereof.

8 . The membrane of claim 1 , wherein the polyamine polymer comprises a repeat unit of Formula J:

wherein:
Y is absent or —CH 2 —;
R 1a and R 1b are each independently absent, hydrogen, C 1-6 alkyl, -L 1 -S(O) 2 O − , -L 1 -C(O)O − , or -L 1 -P(O) 2 O − , such that at least one of R 1a and R 1b is C 1-6 alkyl, -L 1 -S(O) 2 O − , -L 1 -C(O)O − , or -L 1 -P(O) 2 O − ;
each L 1 is independently C 1-6 alkylene;
alternatively, R 1a and R 1b on different polymers can combine to form a crosslinker;
R 2a and R 2b are each independently C 1-6 alkyl or C(O)O − ;
alternatively, R 2a and R 2b on different polymers can combine to form a crosslinker; and
A is a bond, optionally substituted C 1-6 alkylene, urethane, amide, sulfone, ester, ether, a linker, or combined with the adjacent rings to form an optionally substituted C 6-20 bicyclic cycloalkyl.

9 . The membrane of claim 8 , wherein:
R 1a and R 1b are each independently absent, hydrogen, C 1-3 alkyl, or -L 1 -S(O) 2 O − , and L 1 is a C 2-4 alkylene; alternatively, R 1a and R 1b on different polymers can combine to form a crosslinker, wherein the crosslinker is C 3-10 alkylene or C 3-10 haloalkylene.

10 . The membrane of claim 8 , wherein:
R 1a and R 1b are each independently absent, hydrogen, methyl, or —CH 2 CH 2 CH 2 S(O) 2 O − ; alternatively, R 1a and R 1b on different polymers can combine to form a crosslinker, wherein the crosslinker is

11 . The membrane of claim 8 , wherein:
R 1a and R 1b on different polymers can combine to form a crosslinker, wherein the crosslinker is

and
wherein R is C 2-10 alkylene, poly(ethylene glycol), arylene or heteroarylene.

12 . The membrane of claim 8 , wherein
R 1a and R 1b are each independently hydrogen, methyl, or —CH 2 CH 2 CH 2 S(O) 2 O − ; alternatively, R 1a and R 1b on different polymers can combine to form a crosslinker, wherein the crosslinker is

wherein n=1-12.

13 . The membrane of claim 8 , wherein:
R 2a and R 2b are each independently C 1-3 alkyl; alternatively, R 2a and R 2b on different polymers can combine to form a crosslinker, wherein the crosslinker is C 3-10 alkylene, C 3-10 haloalkylene,

14 . The membrane of claim 8 , wherein:
R 2a and R 2b are each independently methyl; alternatively, R 2a and R 2b on different polymers can combine to form a crosslinker, wherein the crosslinker is

15 . The membrane of claim 8 , wherein A is a bond, methylene, ethylene, propylene, butylene, urethane, amide, sulfone, ester, ether,

wherein R is a C 1-12 alkylene, and n is 0 to 20.

16 . The membrane of claim 8 , wherein A is a bond, sulfone, ester, ether,

and
wherein R is a C 1-12 alkylene, and n is 0 to 20.

17 . The membrane of claim 1 , wherein the polyamine polymer is

wherein:
X is

 and
X′ is

18 . The membrane of claim 1 , wherein the polyamine polymer is

19 . The membrane of claim 1 , wherein the polyamine polymer is

20 . The membrane of claim 1 , wherein the polyamine polymer is

wherein
X is

 and
X′ is

21 . The membrane of claim 1 , wherein the polyamine polymer is

22 . The membrane of claim 1 , wherein the polyamine polymer is

23 . The membrane of claim 1 , wherein the polyamine polymer membrane is a composite with a metal oxide.

24 . The membrane of claim 1 , wherein the polyamine polymer membrane is a composite with manganese dioxide.

25 . A composition comprising a polyamine polymer of Formula J:

wherein:
Y is absent or —CH 2 —;
R 1a and R 1b are each independently absent, hydrogen, C 1-6 alkyl, -L 1 -S(O) 2 O − , -L 1 -C(O)O − , or -L 1 -P(O) 2 O − , such that at least one of R 1a and R 1b is C 1-6 alkyl, -L 1 -S(O) 2 O − , -L 1 -C(O)O − , or -L 1 -P(O) 2 O − ;
each L 1 is independently C 1-6 alkylene;
alternatively, R 1a and R 1b on different polymers can combine to form a crosslinker;
R 2a and R 2b are each independently C 1-6 alkyl or C(O)O − ;
alternatively, R 2a and R 2b on different polymers can combine to form a crosslinker; and
A is a bond, optionally substituted C 1-6 alkylene, urethane, amide, sulfone, ester, ether, a linker, or combined with the ad

Assignees

• Sepion Tech Inc
• Form Energy Inc

Inventors

• Golden Jessica H
• Frischmann Peter David
• Helms Brett Anthony
• Ripley Katelyn
• Silver Jessa
• Xie Wei

Classifications

• H01M8/188 Primary

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

• C08G73/024 Primary

  Polyamines containing oxygen in the form of ether bonds in the main chain · CPC title

• H01M8/103

  having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh] · CPC title

• H01M8/1053

  consisting of layers of polymers with at least one layer being ionically conductive · CPC title

• Y02E60/50

  Fuel cells · CPC title