Redox active polymer devices and methods of using and manufacturing the same

• US 9,990,578 B2
• Filed: 05/12/2015
• Issued: 06/05/2018
• 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): Le, Thien M
• Assistant Examiner(s): TAYLOR, APRIL ALICIA
• Application Number:
  US14/710,367
• Publication Number:
  US 20150332141A1
• Time in Patent Office: 1,120 Days
• CPC Class Codes: C08G 2261/142 Side-chains containing oxygen
• CPC Class Codes: C08G 2261/143 Side-chains containing nitrogen
• CPC Class Codes: C08G 2261/1452 containing sulfonyl or sulfonate-groups
• CPC Class Codes: C08G 2261/147 Side-chains with other heteroatoms in the side-chain
• CPC Class Codes: C08G 2261/312 Non-condensed aromatic systems, e.g. benzene
• CPC Class Codes: C08G 2261/3221 containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
• CPC Class Codes: C08G 2261/3223 containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• CPC Class Codes: C08G 2261/3241 containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
• CPC Class Codes: C08G 2261/3243 containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
• CPC Class Codes: C08G 2261/3246 containing nitrogen and sulfur as heteroatoms
• CPC Class Codes: C08G 2261/516 ion-conductive
• CPC Class Codes: C08G 2261/90 Applications
• CPC Class Codes: C08G 2261/92 TFT applications
• CPC Class Codes: C08G 61/122 derived from five- or six-membered heterocyclic compounds, other than imides
• CPC Class Codes: C08G 61/123 derived from five-membered heterocyclic compounds
• CPC Class Codes: G06K 19/0702 the arrangement including a battery
• CPC Class Codes: G06K 19/0717 the sensor being capable of sensing environmental conditions such as temperature history or pressure
• CPC Class Codes: G06K 19/0723 the record carrier comprising an arrangement for non-contact communication, e.g. wireless communication circuits on transponder cards, non-contact smart cards or RFIDs
• CPC Class Codes: G06K 19/07743 External electrical contacts
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/608 : containing heterocyclic rings
• CPC Class Codes: Y10T 29/49018 : with other electrical component

Abstract

The disclosed technology relates generally to apparatus comprising conductive polymers and more particularly to tag and tag devices comprising a redox-active polymer film, and method of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

Claims

1. A tag apparatus, comprising:

a substrate;

a conductive structure formed on the substrate and comprising a layer of redox-active polymer having mobile ions and mobile electrons, the conductive structure further comprising a first terminal and a second terminal configured to receive an electrical signal therebetween,

wherein the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the mobile electrons in response to the electrical signal; and

a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure,

wherein the layer of 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 that migrate in and out of the zwitterionic polymer unit.

2. The tag apparatus 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 tag apparatus 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 tag apparatus 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 tag apparatus 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 tag apparatus 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 tag apparatus of claim 6, wherein the heterocyclic aromatic structure has two heteroatoms para to each other.

8. The tag apparatus of claim 7, 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 tag apparatus of claim 8, wherein the charge compensating substituent is selected to form a six-membered ring.

10. The tag apparatus 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 tag apparatus 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 tag apparatus of claim 1, wherein the layer of 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 tag apparatus of claim 1, wherein the zwitterionic polymer unit comprises a structural group selected from the group consisting of

14. The tag apparatus of claim 1, wherein the zwitterionic polymer unit comprises a structural group selected from the group consisting of:

15. The tag apparatus of claim 1, wherein the zwitterionic polymer unit comprises a structural group selected from the group consisting of:

16. The tag apparatus 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 tag apparatus 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 tag apparatus of claim 1, wherein:

the negative electrode redox-active polymer is an n-type redox-active polymer; 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 tag apparatus 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.

20. The tag apparatus 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.