Novel nanoporous nitrogen-enriched carbon materials were prepared through a simple carbonization procedure of well-defined block copolymer precursors containing the source of carbon, i.e., polyacrylonitrile (PAN), and a sacrificial block, i.e., poly(n-butyl acrylate) (PBA). The preparation of nitrogen-enriched nanocarbons with hierarchical pore structure was enabled by the high fidelity preservation of the initial phase-separated nanostructure between two polymer blocks upon carbonization. Supercapacitors fabricated from the prepared carbons exhibited unusually high capacitance per unit surface area (>30 μF/cm(2)) which was attributed to the pseudocapacitance resulting from the high nitrogen content originating from the PAN precursor. Electrochemical availability of the nitrogen species was also evident from the results of oxygen reduction experiments. The hierarchical pore structure and the high nitrogen content in such materials make them particularly promising for use in supercapacitor and electrocatalyst applications.

Biodegradable electronics represents an attractive and emerging paradigm in medical devices by harnessing simultaneous advantages afforded by electronically active systems and obviating issues with chronic implants. Integrating practical energy sources that are compatible with the envisioned operation of transient devices is an unmet challenge for biodegradable electronics. Although high-performance energy storage systems offer a feasible solution, toxic materials and electrolytes present regulatory hurdles for use in temporary medical devices. Aqueous sodium-ion charge storage devices combined with biocompatible electrodes are ideal components to power next-generation biodegradable electronics. Here, we report the use of biologically derived organic electrodes composed of melanin pigments for use in energy storage devices. Melanins of natural (derived from Sepia officinalis) and synthetic origin are evaluated as anode materials in aqueous sodium-ion storage devices. Na

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg−1 based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30–50 Wh kg−1 is possible with optimization.

Electrochemical storage systems that utilize divalent cations such as Mg2+ can improve the volumetric charge storage capacities compared to those that use monovalent ions. Here, a cathode based on naturally derived melanin pigments is used in secondary Mg2+ batteries. Redox active catechol groups in melanins permit efficient and reversible exchange of divalent Mg2+ cations to preserve charge storage capacity in biopolymer cathodes for more than 500 cycles.

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COMMUNICATIONScheme 1 Envisioned deployment and operation of edible current sources.

Eumelanins are extended heterogeneous biopolymers composed of molecular subunits with ambiguous macromolecular topology. Here, an electrochemical fingerprinting technique is described, which suggests that natural eumelanin pigments contain indole-based tetramers that are arranged into porphyrin-like domains. Spectroscopy and density functional theory calculations suggest that sodium ions undergo occupancy-dependent stepwise insertion into the core of porphyrin-like tetramers in natural eumelanins at discrete potentials.

The performance of redox-enhanced electrochemical capacitors (redox ECs) is substantially improved when oxidized catholyte (bromide) and reduced anolyte (viologen) are retained within the porous electrodes through reversible counterion-induced solid complexation. Investigation of the mechanism illustrates design principles and identifies pentyl viologen/bromide (PV/Br) as a new high-performance electrolyte. The symmetric PV/Br redox EC produces a specific energy of 48.5 W·h/kgdry at 0.5 A/gdry (0.44 kW/kgdry) with 99.7% Coulombic efficiency, maintains stability over 10 000 cycles, and functions identically when operated with reversed polarity.