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Conducting Polymers for Pseudocapacitive Energy Storage

Profile image of Julio D'ArcyJulio D'Arcy

2016, Chemistry of Materials

https://doi.org/10.1021/ACS.CHEMMATER.6B01762
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Abstract

Developing energy storage devices to be utilized within a rapidly advancing energy market requires a multipronged approach whereby material synthesis and engineering fundamentals combine to enable technological advances. These devices should be able to store a large amount of energy in a small, lightweight package, and should be able to distribute that energy quickly for high rate applications. Pseudocapacitors made from conducting polymers, which store charge via rapid reduction and oxidation reactions, are a particularly promising candidate. This perspective explores conductivity and charge storage mechanisms in conducting polymers and describes how synthetic strategies can affect these properties. We further develop chemical correlations that have been shown to enhance the performance of pseudocapacitive electrochemical capacitors fabricated from conducting polymers. Important device engineering strategies for improving the lifetime and applicability of pseudocapacitors are also discussed.

Figures (8)
‘Department of Chemistry, Washington University in St. Louis, St. Louis, Missouri 63130, United States
‘Department of Chemistry, Washington University in St. Louis, St. Louis, Missouri 63130, United States
Conducting polymers are composed of sp* conjugated carbon; in principle, they should be semimetallic like graphite or graphene. However, conducting polymer chains’ one- dimensionality allows for an energetically favorable Jahn— Teller-like relaxation to occur, known as a Peierls distortion, leading to the segregation between the filled and unfilled portions of the sp” band.** Graphene has also been shown to exhibit a band gap, but only when subjected to synthetically induced distortions.” To increase electronic conductivity in polymers, new energy levels must be added to the gap through doping (Figure 2). The formation of a charge island is a different doping mechanism than that of traditional semi-
Conducting polymers are composed of sp* conjugated carbon; in principle, they should be semimetallic like graphite or graphene. However, conducting polymer chains’ one- dimensionality allows for an energetically favorable Jahn— Teller-like relaxation to occur, known as a Peierls distortion, leading to the segregation between the filled and unfilled portions of the sp” band.** Graphene has also been shown to exhibit a band gap, but only when subjected to synthetically induced distortions.” To increase electronic conductivity in polymers, new energy levels must be added to the gap through doping (Figure 2). The formation of a charge island is a different doping mechanism than that of traditional semi-
Scheme 1. Chain Polymerization Mechanism of Pyrrole, Catalyzed by the Presence of an Acid
Scheme 1. Chain Polymerization Mechanism of Pyrrole, Catalyzed by the Presence of an Acid
Figure 3. Performance of an EC can be thought of as a separatory funnel that can only be charged through the bottom opening. If all devices have the same mass, the total volume of the funnel is the maximum specific energy (U) — the total amount of charge the device can store. The size of the hole in the stopcock is the maximum specific power (P), which dictates the maximum rate of charging and discharging. Power is a function of time whereas energy is an absolute metric. Device 1 has lowest energy and power whereas Device 2 has highest of both. Device 3 has similar performance to a capacitor, and Device 4 to a battery. The performance of electrochemical capacitors depends on the current density applied during charging and discharging, i., was enough time given to charge the funnel completely? At moderate power densities, Device 3 and 4 perform similarly.
Figure 3. Performance of an EC can be thought of as a separatory funnel that can only be charged through the bottom opening. If all devices have the same mass, the total volume of the funnel is the maximum specific energy (U) — the total amount of charge the device can store. The size of the hole in the stopcock is the maximum specific power (P), which dictates the maximum rate of charging and discharging. Power is a function of time whereas energy is an absolute metric. Device 1 has lowest energy and power whereas Device 2 has highest of both. Device 3 has similar performance to a capacitor, and Device 4 to a battery. The performance of electrochemical capacitors depends on the current density applied during charging and discharging, i., was enough time given to charge the funnel completely? At moderate power densities, Device 3 and 4 perform similarly.
Figure 4. Potential diagrams of fully charged and discharged states of (a) Type I, (b) Type II, (c) Type III and (d) Type IV electrochemical capacitor.
Figure 4. Potential diagrams of fully charged and discharged states of (a) Type I, (b) Type II, (c) Type III and (d) Type IV electrochemical capacitor.
Figure 6. Scanning electron micrograph of EVPP-PEDOT; (inset) X- ray photoelectron spectrum of EVPP-PEDOT, iron peak is due to reduced oxidant FeCl,. Our own work with conducting polymers shows that an oxidizing salt such as FeCl, also serves as a structure directing agent during nanostructure deposition from the vapor-phase (Figure 6). In evaporative vapor-phase polymerization (EVPP),
Figure 6. Scanning electron micrograph of EVPP-PEDOT; (inset) X- ray photoelectron spectrum of EVPP-PEDOT, iron peak is due to reduced oxidant FeCl,. Our own work with conducting polymers shows that an oxidizing salt such as FeCl, also serves as a structure directing agent during nanostructure deposition from the vapor-phase (Figure 6). In evaporative vapor-phase polymerization (EVPP),

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