PH controlled electrochemical deposition of polyelectrolyte complex films

Patent metadata

Field	Value
Publication number	US-10604648-B2
Application number	US-201815901024-A
Country	US
Kind code	B2
Filing date	Feb 21, 2018
Priority date	Feb 22, 2017
Publication date	Mar 31, 2020
Grant date	Mar 31, 2020

Abstract

Methods for forming a polyelectrolyte complex (PEC) film are provided. In embodiments, the method comprises applying a potential between a working electrode and a counter electrode, the electrodes in contact with an aqueous polyelectrolyte solution characterized by a bulk pH. The aqueous polyelectrolyte solution comprises a pH sensitive PEC pair comprising an unmodified anionic polymer and a cationic species, an electrochemical pH agent other than water, and a salt. The applied potential induces an electrochemical reaction of the electrochemical pH agent to generate OH − or H + at the working electrode without inducing water electrolysis in the aqueous polyelectrolyte solution, thereby forming a PEC film from the unmodified anionic polymer and the cationic species on a surface of the working electrode.

First claim

What is claimed is:

1. A method for forming a polyelectrolyte complex (PEC) film, the method comprising applying a potential between a working electrode and a counter electrode, the electrodes in contact with an aqueous polyelectrolyte solution having a bulk pH, the aqueous polyelectrolyte solution comprising
a pH sensitive PEC pair comprising an unmodified anionic polymer and a cationic species,
an electrochemical pH agent other than water, and
a salt,
wherein the applied potential induces an electrochemical reaction of the electrochemical pH agent to generate OH − or H + at the working electrode without inducing water electrolysis in the aqueous polyelectrolyte solution, thereby forming a PEC film from the unmodified anionic polymer and the cationic species on a surface of the working electrode.

2. The method of claim 1 , wherein the unmodified anionic polymer and the cationic species are provided as two distinct compounds.

3. The method of claim 1 , wherein the unmodified anionic polymer comprises carboxylic acid groups, phosphoric acid groups, or sulfonic acid groups.

4. The method of claim 3 , wherein the unmodified anionic polymer comprises carboxylic acid groups.

5. The method of claim 1 , wherein the cationic species is an unmodified cationic polymer.

6. The method of claim 5 , wherein the unmodified cationic polymer comprises amine groups.

7. The method of claim 1 , wherein the unmodified anionic polymer comprises carboxylic acid groups, phosphoric acid groups or sulfonic acid groups, and the cationic species is an unmodified cationic polymer.

8. The method of claim 7 , wherein the unmodified cationic polymer comprises amine groups.

9. The method of claim 1 , wherein the electrochemical pH agent is not hydroquinone.

10. The method of claim 1 , wherein the electrochemical pH agent is hydrogen peroxide.

11. The method of claim 10 , wherein the hydrogen peroxide is present at a concentration in a range of from about 1 mM to about 150 mM.

12. The method of claim 1 , wherein the aqueous polyelectrolyte solution comprises a dye, a pigment, or both.

13. The method of claim 1 , wherein the surface of the working electrode is non-planar.

14. The method of claim 1 , wherein the PEC film is characterized by a thickness of at least about 1 μm after about 5 minutes.

15. The method of claim 14 , wherein the thickness is at least about 5 μm.

16. A method for forming a polyelectrolyte complex (PEC) film, the method comprising applying a potential between a working electrode and a counter electrode, the electrodes in contact with an aqueous polyelectrolyte solution having a bulk pH, the aqueous polyelectrolyte solution comprising
a pH sensitive PEC pair comprising an unmodified anionic polymer and an unmodified cationic polymer, the unmodified anionic polymer and the unmodified cationic polymer being two distinct compounds,
an electrochemical pH agent other than water or hydroquinone, and
a salt,
wherein the applied potential induces an electrochemical reaction of the electrochemical pH agent to generate OH − or H + at the working electrode without inducing water electrolysis in the aqueous polyelectrolyte solution, thereby forming a PEC film from the unmodified anionic polymer and the cationic species on a surface of the working electrode.

17. The method of claim 16 , wherein the unmodified anionic polymer comprises carboxylic acid groups, phosphoric acid groups, or sulfonic acid groups.

18. The method of claim 17 , wherein the unmodified cationic polymer comprises amine groups.

19. The method of claim 16 , wherein the electrochemical pH agent is hydrogen peroxide.

20. The method of claim 18 , wherein the electrochemical pH agent is hydrogen peroxide.

Assignees

• Univ Northwestern

Inventors

• Shull Kenneth R
• Sadman Kazi
• Wang Qifeng

Classifications

• H01M8/1032

  having sulfur, e.g. sulfonated-polyethersulfones [S-PES] · CPC title

• C08L41/00

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Compositions of derivatives of such polymers · CPC title

• H01M4/9016

  Oxides, hydroxides or oxygenated metallic salts · CPC title

• C08L2203/16

  used for films · CPC title

• C09D139/00

  Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers · CPC title