Coprecipitation Temperature Effects of Morphology-Controlled Nickel Hexacyanoferrate on the Electrochemical Performance in Aqueous Sodium-Ion Batteries.

Coprecipitation effortlessly fabricated nickel hexacyanoferrate (NiHCF) with outstanding rate capability and stability for aqueous batteries. Citrate-aided coprecipitation decelerated the crystallization, assembling cubic-shaped powder based on separation between nucleation and growth. This study revealed that coprecipitation temperature determined the electrochemical performance. With lower temperatures, smaller particles with more water were formed by predominant nucleation, resulting in low crystallinity and capacity of 58 mAh g-1 . Expanded surface area reduced electrode/electrolyte interface charge-transfer resistance and showed excellent rate capability (79 % of initial capacity at 100 C-rate). However, poor cyclability was obtained. At elevated temperatures, nuclei growth and dehydration occurred, and thus highly crystalline large particles were formed. In turn, NiHCF delivered excellent capacity of 76 mAh g-1 at 1 C-rate but exhibited inferior rate performance because of longer diffusional path. Meanwhile, normal coprecipitation at 70 °C induced irregular-shaped tiny particles, presenting 93 % retention of initial capacity at 100 C-rate.

Facile synthesis of Mn-doped NiCo2O4 nanoparticles with enhanced electrochemical performance for a battery-type supercapacitor electrode.

We report the synthesis of manganese-doped nickel cobalt oxide (Mn-doped NiCo2O4) nanoparticles (NPs) by an efficient hydrothermal and subsequent calcination route. The material exhibits a homogeneous distribution of the Mn dopant and a battery-type behavior when tested as a supercapacitor electrode material. Mn-doped NiCo2O4 NPs show an excellent specific capacity of 417 C g-1 at a scan rate of 10 mV s-1 and 204.3 C g-1 at a current density of 1 A g-1 in a standard three-electrode configuration, ca. 152-466% higher than that of pristine NiCo2O4 or MnCo2O4. In addition, Mn-doped NiCo2O4 NPs showed an excellent capacitance retention of 99% after 1000 charge-discharge cycles at a current density of 2 A g-1. The symmetric solid-state supercapacitor device assembled using this material delivered an energy density of 0.87 µW h cm-2 at a power density of 25 µW h cm-2 and 0.39 µW h cm-2 at a high power density of 500 µW h cm-2. The cost-effective synthesis and high electrochemical performance suggest that Mn-doped NiCo2O4 is a promising material for supercapacitors.

Efficient Charge Storage in Dual-Redox Electrochemical Capacitors through Reversible Counterion-Induced Solid Complexation.

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.

Evidence of Porphyrin-Like Structures in Natural Melanin Pigments Using Electrochemical Fingerprinting.

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.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge.

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.

High Energy Density Aqueous Electrochemical Capacitors with a KI-KOH Electrolyte.

We report a new electrochemical capacitor with an aqueous KI-KOH electrolyte that exhibits a higher specific energy and power than the state-of-the-art nonaqueous electrochemical capacitors. In addition to electrical double layer capacitance, redox reactions in this device contribute to charge storage at both positive and negative electrodes via a catholyte of IOx-/I- couple and a redox couple of H2O/Had, respectively. Here, we, for the first time, report utilizing IOx-/I- redox couple for the positive electrode, which pins the positive electrode potential to be 0.4-0.5 V vs Ag/AgCl. With the positive electrode potential pinned, we can polarize the cell to 1.6 V without breaking down the aqueous electrolyte so that the negative electrode potential could reach -1.1 V vs Ag/AgCl in the basic electrolyte, greatly enhancing energy storage. Both mass spectroscopy and Raman spectrometry confirm the formation of IO3- ions (+5) from I- (-1) after charging. Based on the total mass of electrodes and electrolyte in a practically relevant cell configuration, the device exhibits a maximum specific energy of 7.1 Wh/kg, operates between -20 and 50 °C, provides a maximum specific power of 6222 W/kg, and has a stable cycling life with 93% retention of the peak specific energy after 14,000 cycles.

Catechol-mediated reversible binding of multivalent cations in eumelanin half-cells.

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.

Biologically derived melanin electrodes in aqueous sodium-ion energy storage devices.

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(+)-loaded melanin anodes exhibit specific capacities of 30.4 ± 1.6 mAhg(-1). Full cells composed of natural melanin anodes and λ-MnO2 cathodes exhibit an initial potential of 1.03 ± 0.06 V with a maximum specific capacity of 16.1 ± 0.8 mAhg(-1). Natural melanin anodes exhibit higher specific capacities compared with synthetic melanins due to a combination of beneficial chemical, electrical, and physical properties exhibited by the former. Taken together, these results suggest that melanin pigments may serve as a naturally occurring biologically derived charge storage material to power certain types of medical devices.

Self-deployable current sources fabricated from edible materials.

Flexible biodegradable electronics have the potential to serve as the centerpiece for temporary electronically active medical implants. Biodegradable electronics may exhibit many advantages over traditional chronic implants. Two important long-term goals for biodegradable electronics are (1) supplying sufficient power and (2) reducing the invasiveness of device deployment. Edible electronic devices are capable of addressing both challenges. Here, we introduce electrochemical electronic power sources that are compatible with non-invasive deployment strategies and are composed entirely of edible materials and naturally occurring precursors that are consumed in common diets. The current sources developed herein are powered by onboard sodium ion electrochemical cells. Potentials up to 0.6 V and currents in the range of 5-20 µA can be generated routinely. These devices could serve as an enabling platform technology for edible electronics used in non-invasive sensing and stimulation of tissues within the human body.

Electrochemically active nitrogen-enriched nanocarbons with well-defined morphology synthesized by pyrolysis of self-assembled block copolymer.

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.