Electrochemical energy storage devices comprising self-compensating polymers

• US 9,882,215 B2
• Filed: 05/12/2015
• Issued: 01/30/2018
• Est. Priority Date: 05/13/2014
• Status: Active Grant

• Current Assignee: Arizona Board of Regents (University of Arizona)
• Original Assignee: Arizona Board of Regents (University of Arizona)
• Inventors: Johnson, Paul, Bautista-Martinez, Jose Antonio, Friesen, Cody, Switzer, Elise
• Primary Examiner(s): Huff, Mark F
• Assistant Examiner(s): Wills, Monique
• Application Number:
  US14/710,509
• Publication Number:
  US 20150333331A1
• Time in Patent Office: 994 Days
• CPC Class Codes: C08G 75/06 from cyclic thioethers
• CPC Class Codes: H01M 4/606 containing aromatic main chain polymers
• CPC Class Codes: H01M 4/608 containing heterocyclic rings
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The disclosed technology relates generally to devices comprising conductive polymers and more particularly to electrochemical devices comprising self-compensating conductive polymers. In one aspect, electrochemical energy storage device comprises a negative electrode comprising an active material including a redox-active polymer. The device additionally comprises a positive electrode comprising an active material including a redox-active polymer. The device further comprises an electrolyte material interposed between the negative electrode and positive electrode and configured to conduct mobile counterions therethrough between the negative electrode and positive electrode. At least one of the negative electrode redox-active polymer and the positive electrode redox-active polymer comprises a zwitterionic polymer unit configured to reversibly switch between a zwitterionic state in which the zwitterionic polymer unit has first and second charge centers having opposite charge states that compensate each other, and a non-zwitterionic state in which the zwitterionic polymer unit has one of the first and second charge centers whose charge state is compensated by mobile counterions.

Claims

1. An electrochemical energy storage device, comprising:

a negative electrode comprising a negative electrode redox-active polymer;

a positive electrode comprising a positive electrode redox-active polymer; and

an electrolyte material interposed between the negative electrode and the positive electrode,

wherein at least one of the positive and negative redox-active polymers comprises a zwitterionic polymer unit configured to reversibly switch between a zwitterionic state in which the zwitterionic polymer unit has first and second charge centers having opposite charge states that compensate each other, and a non-zwitterionic state in which the zwitterionic polymer unit has one of the first and second charge centers whose charge state is compensated by one or more mobile counterions.

2. The electrochemical energy storage device of claim 1, wherein the negative electrode redox-active polymer has a redox potential lower than a redox potential of the positive electrode redox-active polymer by greater than about 200 millivolts.

3. The electrochemical energy storage device of claim 1, wherein the negative electrode redox-active polymer has a redox potential lower than a redox potential of the positive electrode redox-active polymer by greater than about 1 volt.

4. The electrochemical energy storage device of claim 1, wherein each of the negative electrode redox-active polymer and the positive electrode redox-active polymer has an electrical conductivity greater than about 10⁻

6 S/cm.

5. The electrochemical energy storage device of claim 1, wherein each of the negative electrode redox-active polymer and the positive electrode redox-active polymer has an electrical conductivity greater than about 10⁻

4 S/cm.

6. The electrochemical energy storage device of claim 1, wherein the zwitterionic polymer unit comprises a repeating heterocyclic aromatic structure including at least one heteroatom, wherein each heteroatom is selected from the group consisting of oxygen (O), carbonyl, sulfur (S), nitrogen (N), and functionalized S or N.

7. The electrochemical energy storage device of claim 6, wherein the heterocyclic aromatic structure has two heteroatoms para to each other.

8. The electrochemical energy storage device of claim 6, wherein the heterocyclic aromatic structure further comprises a charge compensating substituent, such that the heteroatoms and the compensating substituent forms the first and second charge centers having opposite charge states that compensate each other.

9. The electrochemical energy storage device of claim 8, wherein the charge compensating substituent is selected to form a six-membered ring.

10. The electrochemical energy storage device of claim 8, wherein the charge compensating substituent is configured to form an anionic species, and wherein the charge compensating substituent has an oxidation potential from anionic to neutral state that is more positive than the redox potential corresponding to a transition of the heteroatom from neutral to cationic state.

11. The electrochemical energy storage device of claim 9, wherein the charge compensating substituent is configured to form a cationic species, and wherein the compensating substituent has a reduction potential from cationic to neutral state that is more negative than the redox potential corresponding to a transition of the heteroatom from neutral state to anionic state.

12. The electrochemical energy storage device of claim 1, wherein the at least one redox-active polymer comprises a structural group selected from the group consisting of quinones, phenothiazines, N-functionalized phenothiazines, thianthrenes, phenozines, phenoxazine, phenoxathiin, dihydrophenazine, dialkyldihydrophenazine, dibenzodioxin, benzofurans, benzodifurans, imides, phthalimides, N-substituted pthalimides, and their derivatives and combinations thereof.

13. The electrochemical energy storage device of claim 1, wherein the zwitterionic polymer unit comprises a structural group selected from the group consisting of

14. The electrochemical energy storage device of claim 1;

wherein the zwitterionic polymer unit comprises a structural group selected from the group consisting of;

15. The electrochemical energy storage device of claim 1, wherein the zwitterionic polymer unit comprises a structural group selected from the group consisting of:

16. The electrochemical energy storage device of claim 1, wherein the at least one of the negative electrode and the positive electrode further comprises a low dielectric constant additive configured to screen a zwitterionic charge.

17. The electrochemical energy storage device of claim 1, wherein the at least one of the negative electrode and the positive electrode further comprises a charge compensating polymer configured to screen a zwitterionic charge.

18. The electrochemical energy storage device of claim 1, wherein:

the negative electrode redox-active polymer is an n-type redox-active polymer configured to undergo a reversible redox reaction between a neutral state and a negatively charged state; and

the positive electrode redox-active polymer is a p-type redox-active polymer,

wherein the p-type redox-active polymer comprises a zwitterionic polymer unit configured to reversibly switch between a zwitterionic state in which the zwitterionic polymer unit has first and second charge centers having opposite charge states that compensate each other, and a non-zwitterionic state in which the zwitterionic polymer unit has one of the first and second charge centers whose charge state is compensated by a mobile cationic species in the anionic state.

19. The electrochemical energy storage device of claim 1, wherein:

the negative electrode redox-active polymer is an n-type redox-active polymer,

wherein the n-type redox-active polymer comprises a zwitterionic polymer unit configured to reversibly switch between a zwitterionic state in which the zwitterionic polymer unit has first and second charge centers having opposite charge states that compensate each other, and a non-zwitterionic state in which the zwitterionic polymer unit has one of the first and second charge centers whose charge state is compensated by a mobile anionic species in the cationic state; and

the positive electrode redox-active polymer is p-type redox-active polymer configured to undergo a reversible redox reaction between a neutral state and a positively charged state.

20. The electrochemical energy storage device of claim 1, wherein:

the negative electrode redox-active polymer is a p-type redox-active polymer,

wherein the negative redox-active polymer comprises a zwitterionic polymer unit configured to reversibly switch between a zwitterionic state in which the zwitterionic polymer unit has first and second charge centers having opposite charge states that compensate each other, and a non-zwitterionic state in which the zwitterionic polymer unit has one of the first and second charge centers whose charge state is compensated by a mobile cationic species in the anionic state; and

the positive electrode redox-active polymer is a p-type redox-active polymer,

wherein the positive redox-active polymer comprises a zwitterionic polymer unit configured to reversibly switch between a zwitterionic state in which the zwitterionic polymer unit has third and fourth charge centers having opposite charge states that compensate each other, and a non-zwitterionic state in which the zwitterionic polymer unit has one of the third and fourth charge centers whose charge state is compensated by the mobile cationic species in the anionic state.