Person:

Kerr, Emily

This communication describes the use of uncoated cellophane (regenerated cellulose films) for the fabrication of microplates, and the use of coated cellophane for the fabrication of open-channel microfluidic devices. The microplates based on uncoated cellophane are particularly interesting for applications that require high transparency in the ultraviolet (UV) regime, and offer a low-cost alternative to expensive quartz-well plates. Uncoated cellophane is also resistant to damage by various solvents. The microfluidic devices, based on coated cellophane, can have features with dimensions as small as 500 μm, and complex, non-planar geometries. Electrodes can be printed on the surface of the coated cellophane, and embedded in microfluidic devices, to develop resistive heaters and electroanalytical devices for flow injection analysis, and continuous flow electrochemiluminescence (ECL) applications. These open-channel devices are appropriate for applications where optical transparency (especially in the visible regime), resistance to damage by water, biocompatibility and biodegradability are important. Cellophane microfluidic systems complement existing cellulose-based paper microfluidic systems, and provide an alternative to other materials used in microfluidics, such as synthetic polymers or glass. Cellulose films are plausible materials for uses in integrated microfluidic systems for diagnostics, analyses, cell-culture, and MEMS.

A highly stable phosphonate‐functionalized anthraquinone is introduced as the redox‐active material in a negative potential electrolyte (negolyte) for aqueous redox flow batteries operating at nearly neutral pH. The design and synthesis of 2,6‐DPPEAQ, (((9,10‐dioxo‐9,10‐dihydroanthracene‐2,6‐diyl)bis(oxy))bis(propane‐3,1‐diyl))bis(phosphonic acid), which has a high solubility at pH 9 and above, is described. Chemical stability studies demonstrate high stability at both pH 9 and 12. By pairing 2,6‐DPPEAQ with a potassium ferri/ferrocyanide positive electrolyte across an inexpensive, nonfluorinated permselective polymer membrane, this near‐neutral quinone flow battery exhibits an open‐circuit voltage of 1.0 V and a capacity fade rate of 0.00036% per cycle and 0.014% per day, which is the lowest ever reported for any flow battery in the absence of rebalancing processes. It is further demonstrated that the negolyte pH drifts upward upon atmospheric oxygen penetration but, when oxygen is excluded, oscillates reversibly between 9 and 12 during cycling. These results enhance the suitability of aqueous‐soluble redox‐active organics for use in large‐scale energy storage, potentially enabling massive penetration of intermittent renewable electricity.

Microbatteries with safe, non-corrosive electrolyte chemistries can have an immediate positive impact on modern life applications, such as ingestible electronic pills and system-on-chip bioelectronics. Here a safe, non-corrosive and non-flammable microbattery is reported. A natural agarose hydrogel is the electrolyte-supporting matrix, and organic and organometallic molecules are the redox-active species. This device can safely meet the needs of ingestible medical microdevices as a primary battery. Additionally, this redox gel system can be used as a secondary battery for on-chip electronics applications, potentially enabling safe and cost-effective small-scale energy storage.

Water‐soluble redox‐active organic molecules have attracted extensive attention as electrical energy storage alternatives to redox‐active metals that are low in abundance and high in cost. Here an aqueous zinc–organic hybrid redox flow battery (RFB) is reported with a positive electrolyte comprising a functionalized 1,4‐hydroquinone bearing four (dimethylamino)methyl groups dissolved in sulfuric acid. By utilizing a three‐electrolyte, two‐membrane configuration this acidic positive electrolyte is effectively paired with an alkaline negative electrolyte comprising a Zn/[Zn(OH)4]2− redox couple and a hybrid RFB is operated at a high operating voltage of 2.0 V. It is shown that the electrochemical reversibility and kinetics of the organic redox species can be enhanced by an electrocatalyst, leading to a cyclic voltammetry peak separation as low as 35 mV and enabling an enhanced rate capability.

Quinones can undergo thermodynamically reversible proton-coupled electron transfer reactions and are being applied as electroactive compounds in aqueous organic batteries. However, the electrochemical reversibility of these compounds is affected not only by their molecular structure but also by the properties of a carbon-based electrode surface. This study combines experimental and theoretical approaches to understand this dependence. We study the electron transfer kinetics of two synthesized quinone derivatives and two commercially available ones with a glassy carbon, a highly ordered pyrolytic graphite, and a high-edge-density graphite electrode (HEDGE). The electrochemical reversibility is notably improved on the HEDGE, which shows a higher density of defects and presents oxygenated functional groups at its surface. The electron transfer kinetics are controlled by adsorbed species onto the HEDGE. Molecular dynamics simulation and quantum mechanics calculations suggest defects with oxygen-containing functional groups, such as C–O and C═O, on HEDGE surfaces drive the interaction with the functional groups of the molecules, during physisorption from van der Waals forces. The presence of sulfonic acid side groups and a greater number of aromatic rings in the molecular structure may contribute to a higher stabilization of quinone derivatives on HEDGEs. We propose that high-performance carbon-based electrodes can be obtained without catalysts for organic batteries, by the engineering of carbon-based surfaces with edge-like defects and oxygenated functional groups.

We demonstrate the electrochemical oxidation of an anthracene derivative to a redox-active anthraquinone at room temperature in a flow cell without the use of hazardous oxidants or noble metal catalysts. The anthraquinone, generated in situ, was used as the active species in a flow battery electrolyte without further modification or purification. This potentially scalable, safe, green, and economical electrosynthetic method is also applied to another anthracene-based derivative and may be extended to other redox-active aromatics.

Monolithically integrated solar flow batteries (SFBs) hold promise as compact stand‐alone energy systems for off‐grid solar electrification. Although considerable research is devoted to studying and improving the round‐trip efficiency of SFBs, little attention is paid to the device lifetime. Herein, a neutral pH aqueous electrolyte SFB with robust organic redox couples and inexpensive silicon‐based photoelectrodes is demonstrated. Enabled by the excellent stability of both electrolytes and protected photoelectrodes, this SFB device exhibits not only unprecedented stable continuous cycling performance over 200 h but also a capacity utilization rate higher than 80%. Moreover, through comprehensive study on the working mechanisms of SFBs, a new theory based on instantaneous solar‐to‐output electricity efficiency toward more optimized device design is developed and a significantly improved solar‐to‐output electricity efficiency of 5.4% from single‐junction silicon photoelectrodes is realized. The design principles presented in this work for extending device lifetime and boosting round trip energy efficiency will make SFBs more competitive for off‐grid applications.

Water‐soluble redox‐active organic molecules have attracted extensive attention as electrical energy storage alternatives to redox‐active metals that are low in abundance and high in cost. Here an aqueous zinc–organic hybrid redox flow battery (RFB) is reported with a positive electrolyte comprising a functionalized 1,4‐hydroquinone bearing four (dimethylamino)methyl groups dissolved in sulfuric acid. By utilizing a three‐electrolyte, two‐membrane configuration this acidic positive electrolyte is effectively paired with an alkaline negative electrolyte comprising a Zn/[Zn(OH)4]2− redox couple and a hybrid RFB is operated at a high operating voltage of 2.0 V. It is shown that the electrochemical reversibility and kinetics of the organic redox species can be enhanced by an electrocatalyst, leading to a cyclic voltammetry peak separation as low as 35 mV and enabling an enhanced rate capability.

Aqueous organic redox flow batteries (AORFBs) have recently gained significant attention as a potential candidate for grid-scale electrical energy storage. Successful implementation of this technology will require redox-active organic molecules with many desired properties. Here we introduce a naphthoquinone dimer, bislawsone, as the redox-active material in a negative potential electrolyte (negolyte) for an AORFB. This novel dimerization strategy substantially improves the performance of the electrolyte vs. that of the lawsone monomer in terms of solubility, stability, reversible capacity, permeability and cell voltage. An AORFB pairing bislawsone with a ferri/ferrocyanide positive electrolyte delivers an open-circuit voltage of 1.05 V and cycles at a current density of 300 mA/cm2 with a negolyte concentration of 2 M electrons in alkaline solution. We determined the degradation mechanism for the naphthoquinone-based electrolyte using chemical analysis, and predict theoretically electrolytes based on naphthoquinones that will be even more stable.