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Enhancing Pseudocapacitive Charge Storage in Polymer Templated Mesoporous Materials

Accounts of Chemical Research2013Vol. 46(5), pp. 1113–1124

Citations Over TimeTop 10% of 2013 papers

Iris E. Rauda, Veronica Augustyn, Bruce Dunn, Sarah H. Tolbert

Abstract

Growing global energy demands coupled with environmental concerns have increased the need for renewable energy sources. For intermittent renewable sources like solar and wind to become available on demand will require the use of energy storage devices. Batteries and supercapacitors, also known as electrochemical capacitors (ECs), represent the most widely used energy storage devices. Supercapacitors are frequently overlooked as an energy storage technology, however, despite the fact that these devices provide greater power, much faster response times, and longer cycle life than batteries. Their limitation is that the energy density of ECs is significantly lower than that of batteries, and this has limited their potential applications. This Account reviews our recent work on improving pseudocapacitive energy storage performance by tailoring the electrode architecture. We report our studies of mesoporous transition metal oxide architectures that store charge through surface or near-surface redox reactions, a phenomenon termed pseudocapacitance. The faradaic nature of pseudocapacitance leads to significant increases in energy density and thus represents an exciting future direction for ECs. We show that both the choice of material and electrode architecture is important for producing the ideal pseudocapacitor device. Here we first briefly review the current state of electrode architectures for pseudocapacitors, from slurry electrodes to carbon/metal oxide composites. We then describe the synthesis of mesoporous films made with amphiphilic diblock copolymer templating agents, specifically those optimized for pseudocapacitive charge storage. These include films synthesized from nanoparticle building blocks and films made from traditional battery materials. In the case of more traditional battery materials, we focus on using flexible architectures to minimize the strain associated with lithium intercalation, that is, the accumulation of lithium ions or atoms between the layers of cathode or anode materials that occurs as batteries charge and discharge. Electrochemical analysis of these mesoporous films allows for a detailed understanding of the origin of charge storage by separating capacitive contributions from traditional diffusion-controlled intercalation processes. We also discuss methods to separate the two contributions to capacitance: double-layer capacitance and pseudocapacitance. Understanding these contributions should allow the selection of materials with an optimized architecture that maximize the contribution from pseudocapacitance. From our studies, we show that nanocrystal-based nanoporous materials offer an architecture optimized for high levels of redox or surface pseudocapacitance. Interestingly, in some cases, materials engineered to minimize the strain associated with lithium insertion can also show intercalation pseudocapacitance, which is a process where insertion processes become so kinetically facile that they appear capacitive. Finally, we conclude with a summary of simple design rules that should result in high-power, high-energy-density electrode architectures. These design rules include assembling small, nanosized building blocks to maximize electrode surface area; maintaining an interconnected, open mesoporosity to facilitate solvent diffusion; seeking flexibility in electrode structure to facilitate volume expansion during lithium insertion; optimizing crystalline domain size and orientation; and creating effective electron transport pathways.

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Abstract

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