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Electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) revealed the ion-electron transport mechanism of viologen electrodes is dependent on anion valency, specifically the divalent sulfate ion exhibited mixed ion movement. 

We show by extensive experimental characterization combined with molecular simulations that pH has a major impact on the assembly mechanism and properties of poly( l -lysine) (PLL) and poly( l -glutamic acid) (PGA) complexes. A combination of dynamic light scattering (DLS) and laser Doppler velocimetry (LDV) is used to assess the complexation, charge state, and other physical characteristics of the complexes, isothermal titration calorimetry (ITC) is used to examine the complexation thermodynamics, and circular dichroism (CD) is used to extract the polypeptides’ secondary structure. For enhanced analysis and interpretation of the data, analytical ultracentrifugation (AUC) is used to define the precise molecular weights and solution association of the peptides. Molecular dynamics simulations reveal the associated intra- and intermolecular binding changes in terms of intrinsic vs. extrinsic charge compensation, the role of hydrogen bonding, and secondary structure changes, aiding in the interpretation of the experimental data. We combine the data to reveal the pH dependency of PLL/PGA complexation and the associated molecular level mechanisms. This work shows that not only pH provides a means to control complex formation but also that the associated changes in the secondary structure and binding conformation can be systematically used to control materials assembly. This gives access to rational design of peptide materials via pH control. 

The storage of electric energy in a safe and environmentally friendly way is of ever-growing importance for a modern, technology-based society. With future pressures predicted for batteries that contain strategic metals, there is increasing interest in metal-free electrode materials. Among candidate materials, nonconjugated redox-active polymers (NC-RAPs) have advantages in terms of cost-effectiveness, good processability, unique electrochemical properties, and precise tuning for different battery chemistries. Here, we review the current state of the art regarding the mechanisms of redox kinetics, molecular design, synthesis, and application of NC-RAPs in electrochemical energy storage and conversion. Different redox chemistries are compared, including polyquinones, polyimides, polyketones, sulfur-containing polymers, radical-containing polymers, polyphenylamines, polyphenazines, polyphenothiazines, polyphenoxazines, and polyviologens. We close with cell design principles considering electrolyte optimization and cell configuration. Finally, we point to fundamental and applied areas of future promise for designer NC-RAPs. 

This perspective offers insights from discussions conducted during the Telluride Science meeting on organic mixed ionic and electronic conductors, outlining the challenges associated with understanding the behavior of this intriguing materials class.

 

Non-aqueous organic redox flow batteries (NAORFBs) are considered emerging large-scale energy storage systems due to their larger voltage window as compared to aqueous systems and their metal-free nature. However, low solubility, sustainability, and crossover of redox materials remain major challenges for the development of NAORFBs. Here, we report the use of redox active α-helical polypeptides suitable for NAORFBs. The polypeptides exhibit less crossover than small molecule analogs for both Daramic 175 separator and FAPQ 375 PP membrane, with FAPQ 375 PP preventing crossover most effectivley. Polypeptide NAORFBs assembled with a TEMPO-based polypeptide catholyte and viologen-based polypeptide anolyte exhibit low capacity fade ( ca. 0.1% per cycle over 500 cycles) and high coulombic efficiency (>99.5%). The polypeptide NAORFBs exhibit an output voltage of 1.1 V with a maximum capacity of 0.53 A h L −1 (39% of the theoretical capacity). After 500 charge–discharge cycles, 60% of the initial capacity was retained. Post cycling analysis using spectral and electrochemical methods demonstrate that the polypeptide backbone and the ester side chain linkages are stable during electrochemical cycling. Taken together, these polypeptides offer naturally-derived, deconstructable platforms for addressing the needs of metal-free energy storage. 

Abstract Porous MXene-polymer composites have gained attention due to their low density, large surface area, and high electrical conductivity, which can be used in applications such as electromagnetic interference shielding, sensing, energy storage, and catalysis. High internal phase emulsions (HIPEs) can be used to template the synthesis of porous polymer structures, and when solid particles are used as the interfacial agent, composites with pores lined with the particles can be realized. Here, we report a simple and scalable method to prepare conductive porous MXene/polyacrylamide structures via polymerization of the continuous phase in oil/water HIPEs. The HIPEs are stabilized by salt flocculated Ti 3 C 2 T x nanosheets, without the use of a co-surfactant. After polymerization, the polyHIPE structure consists of porous polymer struts and pores lined with Ti 3 C 2 T x nanosheets, as confirmed by scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. The pore size can be tuned by varying the Ti 3 C 2 T x concentration, and the interconnected Ti 3 C 2 T x network allows for electrical percolation at low Ti 3 C 2 T x loading; further, the electrical conductivity is stable for months indicating that in these composites, the nanosheets are stable to oxidation at ambient conditions. The polyHIPEs also exhibit rapid radio frequency heating at low power (10 °C s −1 at 1 W). This work demonstrates a simple approach to accessing electrically conductive porous MXene/polymer composites with tunable pore morphology and good oxidation stability of the nanosheets.