Supercapacitors Based on Polymeric Dioxypyrroles and Single Walled Carbon Nanotubes

Abstract

This paper reports a novel supercapacitor electrode design based on poly(3,4-propylenedioxypyrrole) (PProDOP) electropolymerized onto thin films of single walled carbon nanotubes (SWNTs) on glass substrates. This permits the electropolymerization of thicker PProDOP films than can be deposited onto flat gold-coated Kapton electrodes and a correspondingly greater capacitance per unit area. A pyrene functionalized polyfluorene, designated Sticky-PF, was designed and used as an effective monolayer interfacial adhesion modifier between the SWNT films and PProDOP via noncovalent self-assembly onto the SWNT film surfaces before polymer electrodeposition. The thickness of the electrodeposited PProDOP was found to be self-limiting at thicknesses characteristic of each substrate electrode. Optimized areal capacitance values for PProDOP on flat gold and Sticky-PF coated SWNT films were measured to be 8.1 mF/cm 2 and 16.4 mF/cm 2 , respectively, with the twofold enhancement due to the thicker films possible on the SWNT electrode. The specific capacitance of PProDOP on gold and Sticky-PF|SWNT film substrates were found to be similar at 141 F/g and 122 F/g, respectively, indicating the capacitance to be due to the electroactive polymer. The areal capacitance values of the corresponding supercapacitor devices constructed with Au/Kapton substrates was 3.2 mF/cm 2 , whereas a significantly greater value of 8.8 mF/cm 2 was measured for the Sticky-PF|SWNT film substrates. The supercapacitors prepared using the Au/Kapton substrates were highly stable, retaining 80% of their electroactivity after 32 700 nonstop charge/discharge cycles (100% depth of discharge). Supercapacitors made using the Sticky-PF|SWNT substrates showed a steady loss of capacitance to about 57% of the original value (to 5.0 mF/cm 2 ) after 32 700 charge/discharge cycles, which was still 38% larger than the initial capacitance of the gold electrode devices.

Metallocene/carbon hybrids prepared by a solution process for supercapacitor applications

“…1,2,5 Recently, heterogeneous nanostructured materials have emerged as promising systems for electrochemical energy storage, due to the combined benefits of reduced inherent structure size of the bulk materials (e.g., enhanced specific surface area and reduced ion diffusion length) and synergy of the properties of the individual components (e.g., improved electron transport efficiency and mechanical stability). 6,7 Hybrid nanostructures have been created by controlled assembly of different capacitive materials, such as conducting polymer/carbon, [8][9][10][11][12][13][14] conducting polymer/metal oxide, 15 metal oxide/carbon, [16][17][18] metal oxide/metal oxide, 19 and metal oxide/metal, [20][21][22] and have been reported to exhibit extremely high capacitances as well as improved energy and power densities. When constructing these heterogeneous systems, the ability to manipulate their composition and nanoscale architecture, and to assemble the individual components in a way that does not impair their respective advantageous features (e.g., preservation of intrinsically high conductivity of the conducting component), plays a key role in the optimization of their electrocapacitive performance.…”

“…When constructing these heterogeneous systems, the ability to manipulate their composition and nanoscale architecture, and to assemble the individual components in a way that does not impair their respective advantageous features (e.g., preservation of intrinsically high conductivity of the conducting component), plays a key role in the optimization of their electrocapacitive performance. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] Low-cost, high-throughput, and readily scalable solution processes have been exploited to deposit various nanomaterials on appropriate substrates for large-scale applications, including solar cells, 23,24 thin-film transistors, [25][26][27] lithium-ion batteries, 28,29 and single-component supercapacitor devices. 29,30 However, it is very difficult to employ solution processes to construct heterogeneous nanomaterials based on well-studied pseudo-capacitive materials (i.e., metal oxides and conducting polymers), especially those with controlled morphology and electrocapacitive properties.…”

“…31,32 Thus, in general, different capacitive materials cannot form stable complexes in solvents, and it is difficult to generate well-dispersed, high-quality heterogeneous "inks" for solution processing. The common techniques for integrating conducting polymers [8][9][10][11][12][13]15 or metal oxides 15,[17][18][19][20][21][22] with other components rely heavily on electrochemical deposition or co-deposition of their precursors (i.e., solublized monomers or metal ions, respectively). These methods use electrochemical synthesis conditions to manipulate the nanostructures and thus electrocapacitive properties of the resulting heterogeneous materials.…”

Highly conductive poly(3,4-ethylenedioxypyrrole) and poly(3,4-ethylenedioxythiophene) enwrapped Sb2S3nanorods for flexible supercapacitors

“…19 In a previous report, flexible, uniform graphene-poly(pyrrole) composite films prepared by a pulsed electro-polymerization technique exhibited a specific capacitance of 237 F g À1 and a power density of 1184 W kg…”

Szerkezeti tényezők hatása a vezető polimerek termoelektromos tulajdonságaira

“…Ebből kifolyólag, a polimer tömege helyett a rétegek geometriai felületére normálva 1-3 F cm -2 közötti értékek adódnak, messze meghaladva a hasonló, de mikrométeres nagyságrendbe eső magasságú rendszerekre meghatározottakat. [149][150][151] A legnagyobb fajlagos kapacitású kompozit stabilitását hosszú távú mérések segítségé- …”