Reversibly reducible materials and use thereof

Patent metadata

Field	Value
Publication number	US-2018099917-A1
Application number	US-201715730428-A
Country	US
Kind code	A1
Filing date	Oct 11, 2017
Priority date	Oct 11, 2016
Publication date	Apr 12, 2018
Grant date	—

Abstract

Provided herein are a reversibly reducible material and a method of forming a reversibly reducible material. The reversibly reducible material includes the molecular formula:

wherein each of R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of hydrogen, oxygen, alkyl, cycloalkyl, O-alkyl, amine, quaternary ammonium, and sulfonate; R 5 is selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, and amine; X is selected from the group consisting of hydrogen, branched or un-branched alkyl chain having 1-8 atoms containing 0-3 oxygen or nitrogen atoms, and substituted or unsubstituted aryl; and Z is selected from the group consisting of branched or un-branched alkyl chain having 1-8 atoms containing 0-3 oxygen or nitrogen atoms, and substituted or unsubstituted aryl. The method of forming a reversibly reducible material comprising reacting a quinone with an amine in an ethereal solvent. Also provided herein is a negolyte.

First claim

What is claimed is:

1 . A reversibly reducible material comprising the molecular formula:

wherein each of R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of hydrogen, oxygen, alkyl, cycloalkyl, O-alkyl, amine, quaternary ammonium, and sulfonate;
wherein R 5 is selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, and amine;
wherein X is selected from the group consisting of hydrogen, branched or un-branched alkyl chain having 1-8 atoms containing 0-3 oxygen or nitrogen atoms, and substituted or unsubstituted aryl; and
wherein Z is selected from the group consisting of branched or un-branched alkyl chain having 1-8 atoms containing 0-3 oxygen or nitrogen atoms, and substituted or unsubstituted aryl.

2 . The material of claim 1 , wherein X and Z are connected by an alkyl or heteroalkyl chain containing O, S, or N.

3 . The material of claim 1 , wherein X, Z, and the N to which they are bound form an aromatic heterocycle selected from the group consisting of a carbazole, phenothiazine, pyrrole, and imidazole.

4 . The material of claim 1 , wherein R 1 , R 2 , R 3 , and R 4 comprise an alkyl, O-alkyl, or amine system.

5 . The material of claim 4 , wherein at least one of R 1 and R 2 , R 2 and R 3 , and R 3 and R 4 are linked together to form a ring structure consisting of 3-6 atoms.

6 . The material of claim 1 , wherein the molecular formula is selected from the group consisting of:

7 . A method of forming a reversibly reducible material comprising reacting a quinone with an amine in an ethereal solvent.

8 . The method of claim 7 , wherein the quinone comprises 1,4-naphthoquinone and the solvent comprises tetrahydrofuran according to the following reaction:

9 . The method of claim 7 , wherein the ethereal solvent is selected from the group consisting of dioxane, diethyl ether, glyme, and combinations thereof.

10 . The method of claim 7 , further comprising triethylamine or Hünig's base.

11 . The method of claim 7 , further comprising a three-fold excess of the amine.

12 . A negolyte comprising:
a reversibly reducible material; a redox flow battery solvent; and a soluble electrolyte.

13 . The negolyte of claim 12 , wherein the reversibly reducible material is arranged and disposed to reversibly accept up to two electrons.

14 . The negolyte of claim 12 , wherein the reversibly reducible material comprises the molecular formula:

wherein each of R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of hydrogen, oxygen, alkyl, cycloalkyl, O-alkyl, amine, quaternary ammonium, and sulfonate;
wherein R 5 is selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, and amine;
wherein X is selected from the group consisting of hydrogen, branched or un-branched alkyl chain having 1-8 atoms containing 0-3 oxygen or nitrogen atoms, and substituted or unsubstituted aryl; and
wherein Z is selected from the group consisting of branched or un-branched alkyl chain having 1-8 atoms containing 0-3 oxygen or nitrogen atoms, and substituted or unsubstituted aryl.

15 . The negolyte of claim 14 , wherein X and Z are connected by an alkyl or heteroalkyl chain containing O, S, or N.

16 . The negolyte of claim 14 , wherein X, Z, and the N to which they are bound form an aromatic heterocycle selected from the group consisting of a carbazole, phenothiazine, pyrrole, and imidazole.

17 . The negolyte of claim 14 , wherein R 1 , R 2 , R 3 , and R 4 comprise an alkyl, O-alkyl, or amine system.

18 . The negolyte of claim 17 , wherein at least one of R 1 and R 2 , R 2 and R 3 , and R 3 and R 4 are linked together to form a ring structure consisting of 3-6 atoms.

19 . The negolyte of claim 14 , wherein the molecular formula is selected from the group consisting of:

20 . The negolyte of claim 12 , wherein the solvent is selected from the group consisting of acetonitrile, propylene glycol, propylene carbonate, dimethyl acetamide, and dimethyl formamide; and wherein the electrolyte is selected from the group consisting of tetraalkylammonium hexafluorophosphate, perchlorate, tetrafluoroborate, triflate, perfluorobutylsulfonate, and corresponding lithium salts thereof.

Assignees

• Univ Kentucky Res Found

Inventors

• Anthony John
• Odom Susan A

Classifications

• C07C211/42

  with six-membered aromatic rings being part of the condensed ring systems · CPC title

• C07C211/57

  having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M8/188

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

• C07C50/12 Primary

  Naphthoquinones, i.e. C10H6O2 · CPC title