In operando visualization of redox flow battery in membrane-free microfluidic platform.

Redox flow batteries (RFBs) are attractive large-scale energy storage techniques, achieving remarkable progress in performance enhancement for the last decades. Nevertheless, an in-depth understanding of the reaction mechanism still remains challenging due to its unique operation mechanism, where electrochemistry and hydrodynamics simultaneously govern battery performance. Thus, to elucidate the precise reactions occurring in RFB systems, an appropriate analysis technique that enables the real-time observation of electrokinetic phenomena is indispensable. Herein, we report in operando visualization and analytical study of RFBs by employing a membrane-free microfluidic platform, that is, a membrane-free microfluidic RFB. Using this platform, the electrokinetic investigations were carried out for the 5,10-bis(2-methoxyethyl)-5,10-dihydrophenazine (BMEPZ) catholyte, which has been recently proposed as a high-performance multiredox organic molecule. Taking advantage of the inherent colorimetric property of BMEPZ, we unravel the intrinsic electrochemical properties in terms of charge and mass transfer kinetics during the multiredox reaction through in operando visualization, which enables theoretical study of physicochemical hydrodynamics in electrochemical systems. Based on insights on the electrokinetic limitations in RFBs, we verify the validity of electrode geometry design that can suppress the range of the depletion region, leading to enhanced cell performance.

Versatile Redox-Active Organic Materials for Rechargeable Energy Storage.

With the ever-increasing demand on energy storage systems and subsequent mass production, there is an urgent need for the development of batteries with not only improved electrochemical performance but also better sustainability-related features such as environmental friendliness and low production cost. To date, transition metals that are sparse have been centrally employed in energy storage devices ranging from portable lithium ion batteries (e.g., cobalt and nickel) to large-scale redox flow batteries (e.g., vanadium). Toward the sustainable battery chemistry, there are ongoing efforts to replace the transition metal-based electrode materials in these systems to redox-active organic materials (ROMs). Most ROMs are composed of the earth abundant elements (e.g., carbon, nitrogen, oxygen, sulfur), thus are less restrained by the resource, and their production does not require high-energy consuming processes. Furthermore, the structural diversity and chemical tunability of organic compounds make them more attractive for the versatile design of future energy storage systems. Accordingly, the timely development of high-performance ROM-based electrodes would expedite the shift from the current resource-limited battery chemistry to more sustainable energy solutions.In this Account, we provide an overview of the endeavors to employ and develop ROMs as high-performance active materials for various battery systems. Diverse approaches will be introduced starting from the new ROM design mimicking the energy carrying molecules in biological metabolism to the chemical modifications to tailor the properties for specific battery systems. The molecular redesign of ROM, for example, can be carried out by substituting heteroatoms in the redox center, which leads to the enhancement of the redox potential by the inductive effect. Or, tailoring the ROM molecule by removing redox-inactive functionals results in a reduced molecular weight, thereby an increased specific capacity. The intrinsic limitations of ROMs, such as the low electrical conductivity and the dissolving nature, have been under extensive scrutiny; however, they can be partly addressed through efforts including intermolecular fusion and/or nanoscale hybridization with a conducting scaffold. On the other hand, this problematic dissolving nature of ROMs makes them appealing for some new battery configurations such as redox flow batteries that employ the liquid-state active materials. The high solubility and the stability of the ROM were found to be beneficial in attaining the enhanced energy density and the cycle stability of flow batteries, which could be further optimized by the chemical modifications of ROMs. Besides the role of active materials, the redox activity of ROMs has also enabled their use as catalysts to promote the electrode reaction in metal-air batteries. The redox capability of the ROM was often proven to be effective in the solution-based redox mediation that facilitates both the charging and discharging reaction in metal-air batteries. Finally, we conclude this account by proposing the future research directions regarding the fundamental electrochemistry and the further practical development of ROMs for the sustainable rechargeable energy storage.

Pyrrolinium-Substituted Persistent Zwitterionic Ferrocenate Derivative Enabling the Application of Ferrocene Anolyte.

Here, we report the imidazolium-/pyrrolinium-substituted persistent zwitterionic ferrocenate derivatives, which were characterized by electron paramagnetic resonance (EPR) and 57Fe Mössbauer spectroscopy. Additional theoretical studies on these zwitterionic ferrocenate derivatives clearly explain the origin of their thermal stability and the orbital interactions between iron and imidazolium-/pyrrolinium-substituted zwitterionic cyclopentadienyl ligand. Exploiting the facile Fe(II/I) redox chemistry, we successfully demonstrated that the pyrrolinium-substituted ferrocene derivative can be applied as an example of derivatized ferrocene anolyte for redox-flow batteries. These zwitterionic ferrocenate derivatives will not only deepen our understanding of the intrinsic chemistry of ferrocenate but have the potential to open the way for the rational design of metallocenate derivatives for various applications.

Tunable Redox-Active Triazenyl-Carbene Platforms: A New Class of Anolytes for Non-Aqueous Organic Redox Flow Batteries.

Non-aqueous all organic redox flow batteries (NORFBs) are one of the promising options for large-scale renewable energy storage systems owing to their scalability with energy and power along with the affordability. The discovery of new redox-active organic molecules (ROMs) for the anolyte/catholyte would bring them one step closer to the practical application, thus it is highly demanded. Here, we report a new class of ROMs based on cationic triazenyl systems supported by N-heterocyclic carbenes (NHCs) and demonstrate, for the first time, that the triazenyl can serve as a new redox motif for ROMs and could be significantly stabilized for the use in NORFBs by the coupling with NHCs even at radical states. A series of NHC-triazenyl ROM families were successfully synthesized via the reaction of a synthon, N-heterocyclic carbene azido cation, with various Lewis bases including NHCs. Remarkably, it is revealed that NHCs substituted on the triazenyl fragments can serve as a versatile platform for tailoring the electrochemical activity and stability of triazenyl-based compounds, introducing various ROMs exploiting triazenyl redox motif, as demonstrated in the full cell of NORFBs for an anolyte.

Biological Nicotinamide Cofactor as a Redox-Active Motif for Reversible Electrochemical Energy Storage.

Nicotinamide adenine dinucleotide (NAD+ ) is one of the most well-known redox cofactors carrying electrons. Now, it is reported that the intrinsically charged NAD+ motif can serve as an active electrode in electrochemical lithium cells. By anchoring the NAD+ motif by the anion incorporation, redox activity of the NAD+ is successfully implemented in conventional batteries, exhibiting the average voltage of 2.3 V. The operating voltage and capacity are tunable by altering the anchoring anion species without modifying the redox center itself. This work not only demonstrates the redox capability of NAD+ , but also suggests that anchoring the charged molecules with anion incorporation is a viable new approach to exploit various charged biological cofactors in rechargeable battery systems.

Recent Progress in Organic Electrodes for Li and Na Rechargeable Batteries.

Organic rechargeable batteries, which use organics as electrodes, are excellent candidates for next-generation energy storage systems because they offer design flexibility due to the rich chemistry of organics while being eco-friendly and potentially cost efficient. However, their widespread usage is limited by intrinsic problems such as poor electronic conductivity, easy dissolution into liquid electrolytes, and low volumetric energy density. New types of organic electrode materials with various redox centers or molecular structures have been developed over the past few decades. Moreover, research aimed at enhancing electrochemical properties via chemical tuning has been at the forefront of organic rechargeable batteries research in recent years, leading to significant progress in their performance. Here, an overview of the current developments of organic rechargeable batteries is presented, with a brief history of research in this field. Various strategies for improving organic electrode materials are discussed with respect to tuning intrinsic properties of organics using molecular modification and optimizing their properties at the electrode level. A comprehensive understanding of the progress in organic electrode materials is provided along with the fundamental science governing their performance in rechargeable batteries thus a guide is presented to the optimal design strategies to improve the electrochemical performance for next-generation battery systems.