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

• US 10,482,367 B2
• Filed: 03/12/2019
• Issued: 11/19/2019
• 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 B., Bautista-Martinez, Jose Antonio, Friesen, Cody A., Switzer, Elise
• Primary Examiner(s): Paik, Steven S
• Assistant Examiner(s): Taylor, April A
• Application Number:
  US16/299,884
• Publication Number:
  US 20190205717A1
• Time in Patent Office: 252 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. An active tag apparatus, comprising:

an electrochemical energy storage device comprising;

a first electrode layer comprising a first redox-active polymer having mobile ions and mobile electrons, the first electrode layer having a first redox potential;

a second electrode layer comprising a second redox-active polymer having mobile ions and mobile electrons, the second electrode layer having a second redox potential higher than the first redox potential and wherein at least one of the first electrode layer and the second electrode layer further comprises a dielectric constant additive configured to screen a zwitterionic charge; and

an electrolyte layer interposed between the first electrode layer and the second electrode layer, the electrolyte layer comprising a conductive polymer film configured to conduct ionic current by passing mobile ions therethrough between the first electrode layer and the second electrode layer, the conductive polymer film further configured to not conduct a substantial amount of electronic current;

wherein at least one of the first redox-active polymer and the second redox-active polymer is a self-compensating polymer; and

a load device operatively coupled to the storage device.

2. The active tag apparatus of claim 1, wherein under a charge condition, the storage device is configured to be charged through an ionic current flowing through the electrolyte layer between the first and second electrode layers.

3. The active tag apparatus of claim 1, wherein under a discharge condition, the first electrode layer is configured to be oxidized and the second electrode layer is configured to be reduced such that an electronic current flows through the load device.

4. The active tag apparatus of claim 1, wherein the load device comprises at least one of an electromagnetic wave transmission device and an electroluminescent device.

5. The active tag apparatus of claim 1, wherein at least one of the first electrode layer and the second electrode layer further comprises a charge compensating polymer configured to screen a zwitterionic charge.

6. The active tag apparatus of claim 1, wherein at least one of the first redox-active polymer and the second redox-active polymer comprises a zwitterionic polymer unit.

7. The active tag apparatus of claim 1, wherein:

the first redox-active polymer is an n-type redox-active polymer;

the second redox-active polymer is a p-type redox-active polymer; and

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.

8. The active tag apparatus of claim 1, wherein:

the first redox-active polymer is an n-type redox-active polymer;

the second redox-active polymer is a p-type redox-active polymer; and

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.

9. The active tag apparatus of claim 1, wherein:

the first redox-active polymer is an n-type redox-active polymer;

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 cationic species in the anionic state;

the second redox-active polymer is a p-type redox-active polymer; and

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 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.

10. An active tag apparatus, comprising:

a conductive structure having a first terminal and a second terminal and configured to receive an electromagnetic signal therebetween, the conductive structure comprising a redox-active polymer film;

a conversion circuit configured to convert the electromagnetic signal into a DC voltage; and

a storage device comprising;

a first electrode layer and a second electrode layer configured to receive the DC voltage, wherein at least one of the first electrode layer and the second electrode layer comprises a self-compensating polymer and wherein at least one of the first electrode layer and the second electrode layer further comprises a dielectric constant additive configured to screen a zwitterionic charge; and

an electrolyte layer interposed between the first electrode layer and the second electrode layer, the electrolyte layer comprising a conductive polymer film configured to conduct ionic current by passing mobile ions therethrough between the first electrode layer and the second electrode layer, the conductive polymer film further configured to not conduct a substantial amount of electronic current;

wherein the storage device is configured to be charged in response to the DC voltage developed by mobile ions passing between the first and second electrode layers in response to the DC voltage.

11. The active tag apparatus of claim 10, wherein the redox-active polymer film comprises mobile ions and mobile electrons configured to conduct an electrical current generated by the mobile ions and the mobile electrons in response to the electromagnetic signal.

12. The active tag apparatus of claim 10, wherein the conductive structure and at least one of the first electrode layer and the second electrode layer comprise a continuous layer of the same redox-active polymer film.

13. The active tag apparatus of claim 10, wherein the active tag apparatus comprises a radio frequency identification (RFID) tag.

14. A method of manufacturing an active tag apparatus, comprising:

providing an electrochemical energy storage device, the storage device comprising;

a first electrode layer comprising a first redox-active polymer having mobile ions and mobile electrons, the first electrode layer having a first redox potential;

a second electrode layer comprising a second redox-active polymer having mobile ions and mobile electrons, the second electrode layer having a second redox potential higher than the first redox potential, and wherein at least one of the first redox-active polymer and the second redox-active polymer is a self-compensating polymer, and wherein at least one of the first electrode layer and the second electrode layer further comprises a dielectric constant additive configured to screen a zwitterionic charge; and

an electrolyte layer interposed between the first electrode layer and the second electrode layer, the electrolyte layer comprising a conductive polymer film configured to conduct ionic current by passing mobile ions therethrough between the first electrode layer and the second electrode layer, the conductive polymer film further configured to not conduct a substantial amount of electronic current;

providing a load device; and

operatively coupling the load device to the storage device.

15. The method of claim 14, further comprising discharging the storage device through the load device by oxidizing the first electrode layer and reducing the second electrode layer such that an electronic current flows through the load device.

16. The method of claim 14, further comprising charging the storage device by passing an ionic current flowing through the electrolyte layer between the first and second electrode layers.