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TEMPO has been widely explored as one of the most promising catholyte redox scaffolds in aqueous redox flow batteries, but the often-observed performance degradation raises concern with respect to its chemical instability. In this work, we demonstrate that the charged TEMPO species (i.e., TEMPO+) lack sufficient stability and also determine the major decomposition pathways. The decay products of TEMPO+ are experimentally analyzed using combined tools including nuclear magnetic resonance and mass spectroscopy. Reductive conversion to 2,2,6,6-tetramethylpiperidine (TEMPH) is commonly observed for a variety of 4-O-substituted TEMPO derivatives. The general detection of alkene and related carbonyl signals, in conjunction with the electrolyte acidification, reveals a deprotonation-initiated ring opening route that proceeds towards TEMPO decay. The protons on the β carbon are susceptible to chemical extraction by nucleophilic agents such as hydroxyl and the formed piperidine. This finding highlights the intrinsic structural factors for TEMPO degradation and will shed light on the potential stabilization strategies to afford long-cycling TEMPO-based flow batteries. 

The inexpensive sulfur raw material is promising to enable cost-effective redox flow batteries for long duration energy storage. But the catastrophic through-membrane crossover of polysulfides remains a severe challenge resulting in irreversible performance degradation and short cycle life. In this work, we demonstrate that use of a permselective cation exchange membrane yields a two orders of magnitude enhancement in polysulfide retention compared to the benchmark Nafion membrane. Combined physico-chemical, spectroscopic, and microscopic analyses suggest more disordered sidechain structures, which lead to the more hydrophobic nature and smaller hydrophilic domains in the membrane. The microstructural features contribute to the effective mitigation of polysulfide crossover. As a result, the cycle life of polysulfide/ferricyanide flow cells is boosted over a substantially extended test time. This finding sheds light on the fundamental membrane factors that cause polysulfide permeation and can provide feasible directions in the development of permselective membranes for polysulfide flow batteries. 

Redox flow batteries have demonstrated attractive attributes in large-scale stationary energy storage, but practical applications are impeded by high capital cost. Polysulfides are exceedingly cost-effective candidates of redox-active materials for achieving cost reduction, and a recent revival has been witnessed. But the slow conversion kinetics and irreversible crossover loss of polysulfides are daunting challenges that have caused severe technoeconomic stress and even system failure. Solutions to these issues capitalize on the innovations of powerful electrocatalysts and permselective membranes. To inspire viable development strategies and further advance polysulfide redox, this Review presents a critical overview of the state of the art of electrocatalysts and membranes, highlighting their working mechanisms, design protocols, and performance metrics. We briefly describe the complicated processes of the polysulfide reaction and the major spectroscopic methods for polysulfide speciation. Next, we point out the specific characteristics of polysulfide redox and summarize the metallic, metal sulfide, and molecular electrocatalysts to elucidate the fundamental requirements for imparting strong catalytic effects. We then discuss the possible origins of polysulfide crossover and outline the major families of membrane chemistries targeting polysulfide retention. Finally, the remaining challenges and the future perspectives for potential considerations are provided, aiming to realize efficient, durable polysulfide flow batteries. 

Redoxmers are organic molecules that serve as charge carriers in redox flow batteries. While these materials are affordable and easy to source, insufficient stability of their charged states (radical ions) remains a challenge. A common reaction of these species is their disproportionation. This reversible reaction yields unstable multiply charged states, shifting the overall charge transfer equilibrium toward the decomposition products. Here we show how kinetic controls can be engineered into a redoxmer molecule to suppress these unwanted charge transfer reactions. This approach is used to transform Wurster’s blue, which is historically the first example of a stable radical ion in organic chemistry, into an exceptionally durable redoxmer molecule that persists over thousands of electrochemical cycles. 

Redox-active molecules, or redoxmers, in nonaqueous redox flow batteries often suffer from membrane crossover and low electrochemical stability. Transforming inorganic polyionic redoxmers established for aqueous batteries into nonaqueous candidates is an attractive strategy to address these challenges. Here we demonstrate such tailoring for hexacyanoferrate (HCF) by pairing the anions with tetra-n-butylammonium cation (TBA+). TBA3HCF has good solubility in acetonitrile and >1 V lower redox potential vs the aqueous counterpart; thus, the familiar aqueous catholyte becomes a new nonaqueous anolyte. The lowering of redox potential correlates with replacement of water by acetonitrile in the solvation shell of HCF, which can be traced to H-bond formation between water and cyanide ligands. Symmetric flow cells indicate exceptional stability of HCF polyanions in nonaqueous electrolytes and Nafion membranes completely block HCF crossover in full cells. Ion pairing of metal complexes with organic counterions can be effective for developing promising redoxmers for nonaqueous flow batteries. 

Nonaqueous flow batteries hold promise given their high cell voltage and energy density, but their performance is often plagued by the crossover of redox compounds. In this study, we used permselective lithium superionic conducting (LiSICON) ceramic membranes to enable reliable long-term use of organic redox molecules in nonaqueous flow cells. With different solvents on each side, enhanced cell voltages were obtained for a flow battery using viologen-based negolyte and TEMPO-based posolyte molecules. The thermoplastic assembly of the LiSICON membrane realized leakless cell sealing, thus overcoming the mechanical brittleness challenge. As a result, stable cycling was achieved in the flow cells, which showed good capacity retention over an extended test time. 

Due to their almost unlimited scalability, redox flow batteries can make versatile and affordable energy storage systems. Redox active materials (redoxmers) in these batteries largely define their electrochemical performance, including the life span of the battery that depends on the stability of charged redoxmers. In this study, we examine the effects of expanding the π-system in the arene rings on the chemical stability of dialkoxyarene redoxmers that are used to store positive charge in RFBs. When 1,4-dimethoxybenzene is π-extended to 1,4-dimethoxynaphthalene, a lower redox potential, improved kinetic stability, and longer cycling life are observed. However, when an additional ring is fused to make 9,10-dimethoxyanthracene, the radical cation undergoes rapid O-dealkylation possibly due to increased steric strain that drives methoxy out of the arene plane thus breaking the π-conjugation with O 2p orbitals. On the other hand, the planar structure of 1,4-dimethoxynaphthalene may facilitate second-order reactions of radical cations leading to their neutralization in the bulk. Our study suggests that extending the π-system changes reactivity in multiple (sometimes, opposite) ways, so lowering the oxidation potential through π-conjugation to improve redoxmer stability should be pursued with caution. 

We have developed a novel molecular design that enables six-electron redox activity in fused phenazine-based organic scaffolds. Combined electrochemical and spectroscopic tests successfully confirm the two-step 6e − redox mechanism. This work offers an opportunity for achieving energy-dense redox flow batteries, on condition that the solubility and stability issues are addressed.