A Physical Organic Chemistry Approach to Developing Cyclopropenium-Based Energy Storage Materials for Redox Flow Batteries.

ConspectusRedox flow batteries (RFBs) represent a promising modality for electrical energy storage. In these systems, energy is stored via paired redox reactions of molecules on opposite sides of an electrochemical cell. Thus, a central objective for the field is to design molecules with the optimal combination of properties to serve as energy storage materials in RFBs. The ideal molecules should undergo reversible redox reactions at relatively high potentials (for the molecule that is oxidized during battery charging, called the catholyte) or low potentials (for the species that is reduced during battery charging, called the anolyte). Furthermore, anolytes and catholytes must be highly soluble in the electrolyte solution and stable to extended electrochemical cycling in all battery-relevant redox states. The ideal candidates would undergo more than one reversible electron transfer event. Finally, the optimal structures should be resistant to crossover through a selective separator in order to maintain isolation of the two sides of the cell. This Account describes our design and optimization of organic molecules for this application. We first provide background for the metrics and experiments used to characterize anolytes/catholytes and to progress them toward deployment in flow batteries. We then use our studies of aminocyclopropenium-based catholytes to illustrate this workflow and approach.We identified tris(dimethylamino) cyclopropenium hexafluorophosphate as a first-generation catholyte for nonaqueous RFBs based on literature reports from the 1970s describing its reversible chemical and electrochemical oxidation. Cyclic voltammetry and electrochemical cycling experiments in acetonitrile/LiPF6 confirmed that this molecule undergoes oxidation at relatively high potential (0.86 V versus ferrocene/ferrocenium) and exhibits moderate stability toward charge-discharge cycling. Replacing the methyl groups with isopropyl substituents led to enhanced cycling stability but poor solubility of the radical dication (<0.1 M in acetonitrile). Solubility was optimized using quantitative structure-property relationship modeling, which predicted derivatives with ≥10-fold enhanced solubility. Cyclopropeniums with 300-500 mV higher redox potentials were identified by replacing one of the dialkylamino substituents with a less electron-donating thioalkyl or aryl group. Multielectron catholytes were developed by creating hybrid structures that contain a di(amino) cyclopropenium conjugated with a phenothiazine moeity. Finally, oligomeric tris(amino) cyclopropeniums were designed as crossover resistant catholytes. Optimization of their solubility enabled the deployment of these oligomers in high concentration asymmetric redox flow batteries with energy densities that are comparable to the state-of-the-art commercial aqueous inorganic systems.

Indolo[2,3-b]quinoxaline as a Low Reduction Potential and High Stability Anolyte Scaffold for Nonaqueous Redox Flow Batteries.

Redox flow batteries (RFBs) are a promising stationary energy storage technology for leveling power supply from intermittent renewable energy sources with demand. A central objective for the development of practical, scalable RFBs is to identify affordable and high-performance redox-active molecules as storage materials. Herein, we report the design, synthesis, and evaluation of a new organic scaffold, indolo[2,3-b]quinoxaline, for highly stable, low-reduction potential, and high-solubility anolytes for nonaqueous redox flow batteries (NARFBs). The mixture of 2- and 3-(tert-butyl)-6-(2-methoxyethyl)-6H-indolo[2,3-b]quinoxaline exhibits a low reduction potential (-2.01 V vs Fc/Fc+), high solubility (>2.7 M in acetonitrile), and remarkable stability (99.86% capacity retention over 49.5 h (202 cycles) of H-cell cycling). This anolyte was paired with N-(2-(2-methoxyethoxy)-ethyl)phenothiazine (MEEPT) to achieve a 2.3 V all-organic NARFB exhibiting 95.8% capacity retention over 75.1 h (120 cycles) of cycling.

Silver-Catalyzed, N-Formylation of Amines Using Glycol Ethers.

A silver-catalyzed protocol was found to afford the N-formylation of amines in moderate-to-good yields. Ethylene glycol-derived, oligomeric ethers were found to function as the formylating agent, with 1,4-dioxane affording the best results. This reaction does not require the use of stoichiometric activating reagents, and avoids the use of explosive reagents or toxic gases, such as CO, as the C1 synthon. Mechanistic studies indicate a single-electron transfer-based pathway. This work highlights the ability of silver to participate in unexpected reaction pathways.

Data science enabled discovery of a highly soluble 2,2'-bipyrimidine anolyte for application in a flow battery.

Development of non-aqueous redox flow batteries as a viable energy storage solution relies upon the identification of soluble charge carriers capable of storing large amounts of energy over extended time periods. A combination of metrics including number of electrons stored per molecule, redox potential, stability, and solubility of the charge carrier impact performance. In this context, we recently reported a 2,2'-bipyrimidine charge carrier that stores two electrons per molecule with reduction near -2.0 V vs. Fc/Fc+ and high stability. However, these first-generation derivatives showed a modest solubility of 0.17 M (0.34 M e-). Seeking to improve solubility without sacrificing stability, we harnessed the synthetic modularity of this scaffold to design a library of sixteen candidates. Using computed molecular descriptors and a single node decision tree, we found that minimization of the solvent accessible surface area (SASA) can be used to predict derivatives with enhanced solubility. This parameter was used in combination with a heatmap describing stability to de-risk a virtual screen that ultimately identified a 2,2'-bipyrimidine with significantly increased solubility and good stability metrics in the reduced states. This molecule was paired with a cyclopropenium catholyte in a prototype all-organic redox flow battery, achieving a cell potential up to 3 V.