Ionically conductive thin film composite membranes for energy storage applications

Patent metadata

Field	Value
Publication number	US-2022134292-A1
Application number	US-202117389032-A
Country	US
Kind code	A1
Filing date	Jul 29, 2021
Priority date	Nov 4, 2020
Publication date	May 5, 2022
Grant date	—

Abstract

An ionically conductive thin film composite (TFC) membrane is described. The low cost, high performance TFC membrane comprises a micropous support membrane, and a hydrophilic ionomeric polymer coating layer on a surface of the microporous support membrane. The hydrophilic ionomeric polymer coating layer is ionically conductive. The ionomeric polymer can also be present in the micropores of the support membrane. Methods of making the membrane and redox flow battery system incorporating the TFC membrane are also described.

First claim

1 . An ionically conductive thin film composite (TFC) membrane comprising:
a microporous support membrane; a hydrophilic ionomeric polymer coating layer on a surface of the microporous support membrane, the hydrophilic ionomeric polymer coating layer is ionically conductive.

2 . The TFC membrane of claim 1 wherein the hydrophilic ionomeric polymer comprises a polyphosphoric acid-complexed polysaccharide polymer, a polyphosphoric acid and metal ion-complexed polysaccharide polymer, a metal ion-complexed polysaccharide polymer, a boric acid-complexed polysaccharide polymer, an alginate polymer, an alginic acid polymer, a hyaluronic acid polymer, a boric acid-complexed polyvinyl alcohol polymer, polyphosphoric acid-complexed polyvinyl alcohol polymer, a polyphosphoric acid and metal ion-complexed polyvinyl alcohol polymer, a metal ion-complexed polyvinyl alcohol polymer, a metal ion-complexed poly(acrylic acid) polymer, a boric acid-complexed poly(acrylic acid) polymer, a metal ion-complexed poly(methacrylic acid), a boric acid-complexed poly(methacrylic acid), or combinations thereof.

3 . The TFC membrane of claim 2 wherein the polysaccharide polymer comprises chitosan, sodium alginate, potassium alginate, calcium alginate, ammonium alginate, alginic acid, sodium hyaluronate, potassium hyaluronate, calcium hyaluronate, ammonium hyaluronate, hyaluronic acid, dextran, pullulan, carboxymethyl curdlan, sodium carboxymethyl curdlan, potassium carboxymethyl curdlan, calcium carboxymethyl curdlan, ammonium carboxymethyl curdlan, κ-carrageenan, λ-carrageenan, ι-carrageenan, carboxymethyl cellulose, sodium carboxymethyl cellulose, potassium carboxymethyl cellulose, calcium carboxymethyl cellulose, ammonium carboxymethyl cellulose, pectic acid, chitin, chondroitin, xanthan gum, or combinations thereof.

4 . The TFC membrane of claim 2 wherein metal ion is ferric ion, ferrous ion, or vanadium ion.

5 . The TFC membrane of claim 1 wherein the hydrophilic ionomeric polymer is a polyphosphoric acid-complexed chitosan polymer, a polyphosphoric acid and metal ion-complexed chitosan polymer, a metal ion-complexed alginic acid polymer, a sodium alginate polymer, an alginic acid polymer, a hyaluronic acid polymer, or combinations thereof.

6 . The TFC membrane of claim 5 wherein the metal ion is ferric ion, ferrous ion, or vanadium ion.

7 . The TFC membrane of claim 1 wherein the hydrophilic ionomeric polymer is a boric acid-complexed polyvinyl alcohol polymer, a boric acid-complexed alginic acid, or a blend of boric acid-complexed polyvinyl alcohol and alginic acid polymer.

8 . The TFC membrane of claim 1 wherein the support membrane comprises polyethylene, polypropylene, polyamide, polyacrylonitrile, polyethersulfone, sulfonated polyethersulfone, polysulfone, sulfonated polysulfone, poly(ether ether ketone), sulfonated poly(ether ether ketone), polyester, cellulose acetate, cellulose triacetate, polybenzimidazole, polyimide, polyvinylidene fluoride, polycarbonate, cellulose, or combinations thereof.

9 . The TFC membrane of claim 1 wherein the hydrophilic ionomeric polymer is present in the micropores of the support membrane.

10 . A method of preparing an ionically conductive thin film composite (TFC) membrane comprising:
applying a layer of an aqueous solution comprising a hydrophilic ionomeric polymer to one surface of a microporous support membrane; drying the coated membrane; and optionally complexing the hydrophilic ionomeric polymer using a complexing agent to form a cross-linked hydrophilic ionomeric polymer.

11 . The method of claim 10 wherein the hydrophilic ionomeric polymer on the coated membrane is dried before complexing the hydrophilic ionomeric polymer.

12 . The method of claim 10 wherein the coated membrane is dried after complexing the hydrophilic ionomeric polymer.

13 . The method of claim 10 wherein the complexing agent is selected from polyphosphoric acid, boric acid, a metal ion selected from ferric ion, ferrous ion, or vanadium ion, or combinations thereof.

14 . The method of claim 10 wherein complexing the hydrophilic ionomeric polymer comprises immersing the dried coated membrane in a second aqueous solution of polyphosphoric acid, boric acid, metal salt, hydrochloric acid, or combinations thereof.

15 . The method of claim 10 wherein complexing the hydrophilic ionomeric polymer comprises complexing the dried coated membrane with a complexing agent in situ in a redox flow battery cell.

16 . The method of claim 10 wherein the hydrophilic ionomeric polymer comprises a polysaccharide polymer, a poly(acrylic acid) polymer, a poly(methacrylic acid), or combinations thereof.

17 . The method of claim 16 wherein the polysaccharide polymer comprises chitosan, sodium alginate, potassium alginate, calcium alginate, ammonium alginate, alginic acid, sodium hyaluronate, potassium hyaluronate, calcium hyaluronate, ammonium hyaluronate, hyaluronic acid, dextran, pullulan, carboxymethyl curdlan, sodium carboxymethyl curdlan, potassium carboxymethyl curdlan, calcium carboxymethyl curdlan, ammonium carboxymethyl curdlan, κ-carrageenan, λ-carrageenan, ι-carrageenan, carboxymethyl cellulose, sodium carboxymethyl cellulose, potassium carboxymethyl cellulose, calcium carboxymethyl cellulose, ammonium carboxymethyl cellulose, pectic acid, chitin, chondroitin, xanthan gum, or combinations thereof.

18 . A redox flow battery system, comprising:
at least one rechargeable cell comprising a positive electrolyte, a negative electrolyte, and an ionically conductive thin film composite (TFC) membrane positioned between the positive electrolyte and the negative electrolyte, the positive electrolyte in contact with a positive electrode, and the negative electrolyte in contact with a negative electrode, wherein the TFC membrane comprises a microporous support membrane and a hydrophilic ionomeric polymer coating layer on a surface of the microporous support membrane, wherein the hydrophilic ionomeric polymer coating layer is ionically conductive.

19 . The redox flow battery system of claim 18 wherein the negative electrolyte, the positive electrolyte, or both the negative electrolyte and the positive electrolyte comprises a boric acid additive capable of complexing with a hydrophilic ionomeric polymer on the surface of the microporous support membrane to form a cross-linked hydrophilic ionomeric polymer coating layer.

20 . The redox flow battery system of claim 18 wherein the hydrophilic ionomeric polymer coating layer is formed in situ by complexing a hydrophilic ionomeric polymer on the surface of the microporous support membrane with a complexing agent in the negative electrolyte, the positive electrolyte, or both the negative electrolyte and the positive electrolyte.

Assignees

• Uop Llc

Inventors

• Liu Chunqing
• Dong Xueliang
• Ba Chaoyi

Classifications

• H01M8/188

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

• H01M8/1081

  starting from solutions, dispersions or slurries exclusively of polymers · CPC title

• H01M8/1053

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

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M8/1072

  by chemical reactions, e.g. in situ polymerisation or in situ crosslinking · CPC title