Real-time visualization of Zn metal plating/stripping in aqueous batteries with high areal capacities

Zinc aqueous batteries have attracted great attention due to the earth abundance and the low redox potential of Zn metal. Utilizing Zn metal as an anode, however, causes low coulombic efficiency stemming from a dendritic Zn plating and formation of byproducts such as hydrogen gas, solid zinc hydroxide and salt-related compounds. One effective way of mitigating the issues is to modify the solvation structure of the electrolyte to increase the energy barrier of the water molecules for hydrolysis and electrolysis. Nevertheless, Zn aqueous batteries still indiscriminately utilize several types of electrolytes without elucidating the correlation between electrolyte composition and the electrochemistry of Zn metal. Here, we use operando optical microscopy to visualize the microstructural evolution of Zn metal, which strongly affects the electrochemical reversibility. In ZnSO4 electrolyte, large Zn platelets grow and form loose agglomerates vulnerable to unexpected delamination from the electrodes. In Zn(OTf)(2) electrolyte, Zn platelets nucleate more homogeneously and grow smaller, which forms denser agglomerates enabling more stable cycling. We further reveal that the formation of a stable solidelectrolyte interphase layer holds the key to the excellent performance of acetonitrile-hybrid water-in-salt electrolytes. Our results show the necessity of designing proper electrolytes to develop long-life Zn aqueous batteries.

Utilizing Latent Multi-Redox Activity of p-Type Organic Cathode Materials toward High Energy Density Lithium-Organic Batteries

Organic electrode materials hold great potential due to their cost-efficiency, eco-friendliness, and possibly high theoretical capacity. Nevertheless, most organic cathode materials exhibit a trade-off relationship between the specific capacity and the voltage, failing to deliver high energy density. Herein, it is shown that the trade-off can be mitigated by utilizing the multi-redox capability of p-type electrodes, which can significantly increase the specific capacity within a high-voltage region. The molecular structure of 5,10-dihydro-5,10-dimethylphenazine is modified to yield a series of phenoxazine and phenothiazine derivatives with elevated redox potentials by substitutions. Subsequently, the feasibility of the multi-redox capability is scrutinized for these high-voltage p-type organic cathodes, achieving one of the highest energy densities. It is revealed that the seemingly impractical second redox reaction is indeed dependent on the choice of the electrolyte and can be reversibly realized by tailoring the donor number and the salt concentration of the electrolyte, which places the voltage of the multi-redox reaction within the electrochemical stability window. The results demonstrate that high-energy-density organic cathodes can be practically achieved by rational design of multi-redox p-type organic electrode materials and the compatibility consideration of the electrolyte, opening up a new avenue toward advanced organic rechargeable batteries.

Bio-inspired Molecular Redesign of a Multi-redox Catholyte for High-Energy Non-aqueous Organic Redox Flow Batteries

Redox-active organic materials (ROMs) have recently attracted significant attention for redox flow batteries (RFBs) to achieve green and cost-efficient energy storage. In particular, multi-redox ROMs have shown great promise, and further tailoring of these ROMs would yield RFB technologies with the highest possible energy density. Here, we present a phenazine-based catholyte material, 5,10-bis(2-methoxyethyl)-5,10-dihydrophenazine (BMEPZ), that undergoes two single-electron redox reactions at high redox potentials (-0.29 and 0.50 V versus Fc/Fc(+)) with enhanced solubility (0.5 M in acetonitrile), remarkable chemical stability, and fast kinetics. Moreover, an all-organic flow battery exhibits cell voltages of 1.2 and 2.0 V when coupled with 9-fluorenone (FL) as an anolyte. It shows capacity retention of 99.94% per cycle over 200 cycles and 99.3% per cycle with 0.1 M and 0.4 M BMEPZ catholyte, respectively. Notably, the BMEPZ/FL couple results in the highest energy density (similar to 17 Wh L-1) among the non-aqueous all- organic RFBs reported to date

Redox-Active Organic Compounds for Future Sustainable Energy Storage System

Utilizing redox-active organic compounds for future energy storage system (ESS) has attracted great attention owing to potential cost efficiency and environmental sustainability. Beyond enriching the pool of organic electrode materials with molecular tailoring, recent scientific efforts demonstrate the innovations in various cell chemistries and configurations. Herein, recent major strategies to build better organic batteries, are highlighted: diversifying charge-carrying ions, modifying electrolytes, and utilizing liquid-type organic electrodes. Each approach is summarized along with their advantages over Li-ion batteries (LIBs). An outlook is also provided on the practical realization of organic battery systems, which hints at possible solutions for future sustainable ESSs.

Multi-electron redox phenazine for ready-to-charge organic batteries

Organic redox compounds represent an emerging class of cathode materials in rechargeable batteries for low-cost and sustainable energy storage. However, the low operating voltage (<3 V) and necessity of using lithium-containing anodes have significantly limited their practical applicability to battery systems. Here, we introduce a new class of p-type organic redox centers based on N,N'-substituted phenazine (NSPZ) to build ready-to-charge organic batteries. In the absence of lithium-containing anodes, NSPZ cathodes facilitate reversible two-electron transfer at 3.7 and 3.1 V accompanying anion association, which results in a specific energy of 622 Wh kg(-1) in dual-ion batteries.

Exploiting Biological Systems: Toward Eco-Friendly and High-Efficiency Rechargeable Batteries

To meet the ever-increasing energy demands and sustainability requirements, next-generation battery systems must provide superior energy densities while employing eco-friendly components. Transition metal oxide-based materials have served as important high-energy-density battery electrodes over the past few decades; however, their further development is challenging as we approach the theoretical limits arising from their crystal structures and constituting elements. Exploiting materials from biological systems, or bio-inspiration, offers an alternative strategy to overcome the conventional energy storage mechanism through the chemical diversity, highly efficient biochemistry, sustainability, and natural abundance provided by these materials. Here, we overview recent progress in biomimetic research focused on novel electrode material design for rechargeable batteries, exploiting redox-active molecules involved in the biometabolism and diverse bioderived materials with various morphologies. Successful demonstrations of energy storage using biomimetic materials that simultaneously exhibit outstanding performance and sustainability would provide insight toward the development of an eco-friendly and high-efficiency energy storage system.11scopu

Utilizing Latent Multi‐Redox Activity of p‐Type Organic Cathode Materials toward High Energy Density Lithium‐Organic Batteries

Organic electrode materials hold great potential due to their cost-efficiency, eco-friendliness, and possibly high theoretical capacity. Nevertheless, most organic cathode materials exhibit a trade-off relationship between the specific capacity and the voltage, failing to deliver high energy density. Herein, it is shown that the trade-off can be mitigated by utilizing the multi-redox capability of p-type electrodes, which can significantly increase the specific capacity within a high-voltage region. The molecular structure of 5,10-dihydro-5,10-dimethylphenazine is modified to yield a series of phenoxazine and phenothiazine derivatives with elevated redox potentials by substitutions. Subsequently, the feasibility of the multi-redox capability is scrutinized for these high-voltage p-type organic cathodes, achieving one of the highest energy densities. It is revealed that the seemingly impractical second redox reaction is indeed dependent on the choice of the electrolyte and can be reversibly realized by tailoring the donor number and the salt concentration of the electrolyte, which places the voltage of the multi-redox reaction within the electrochemical stability window. The results demonstrate that high-energy-density organic cathodes can be practically achieved by rational design of multi-redox p-type organic electrode materials and the compatibility consideration of the electrolyte, opening up a new avenue toward advanced organic rechargeable batteries.N

Highly persistent triphenylamine-based catholyte for durable organic redox flow batteries

Organic redox flow batteries (ORFBs) have recently drawn significant attention as cost-effective and scalable energy storage systems, utilizing the distinct features of redox-active organic materials (ROMs), which offer chemical diversity and potential mass-scalability. Nevertheless, their inferior cycle performance compared with that of conventional inorganic-based RFBs is one of the major drawbacks limiting their practical application, which is often attributable to the chemical instability of charged ROMs during long-term operation. Herein, we present an ultra-stable triphenylamine-based molecule, tris(4-methoxyphenyl)amine or 3MTPA, which exhibits a highly stable redox reaction and rapid kinetics as a catholyte in non-aqueous media. It is demonstrated that the 3MTPA catholyte exhibits exceptionally robust radical cation stability, enabling its retention of near the theoretical capacity even after 168 h of high temperature storage in a fully charged state, while most known ROMs have not been able to achieve it and suffer from the significant degradation. Moreover, a flow cell exploiting 3MTPA is capable of delivering an unprecedentedly high capacity retention of 99.998% per cycle over 1400 cycles, opening up a new pathway toward highly durable ORFBs.

Abnormal self-discharge in lithium-ion batteries

Lithium-ion batteries are expected to serve as a key technology for large-scale energy storage systems (ESSs), which will help satisfy recent increasing demands for renewable energy utilization. Besides their promising electrochemical performance, the low self-discharge rate (<5% of the stored capacity over 1 month) of lithium-ion batteries is one of their most significant advantages for ESSs. Herein, contrary to conventional belief, we report that the self-discharge of LIBs can be abnormally accelerated when the battery has been exposed even to a routine short-term thermal exposure. We demonstrate that this thermal 'history' in addition to the temperature itself is memorized in the battery and accelerates the self-discharge rate. The series of characterizations performed in our work reveal that the electrolyte salt acts as a strong oxidizing agent by vigorously damaging the surface of the cathode, producing an internal 'parasitic' lithium source that continuously supplies lithium for the self-discharge. Although it is widely known that battery operation at elevated temperature generally induces faster degradation of capacity over multiple cycles, the key finding here is that not only the operation temperature but also the 'thermal history' of the battery should be carefully considered because this history remains and continues to affect the self-discharge rate afterwards. The self-discharge of LIBs has remained largely neglected; however, our findings suggest that close attention must be paid to the self-discharge of LIBs applied to large-scale ESSs, which, unlike mobile electronic devices, will be exposed to various outdoor temperature conditions.

Zirconia Toughened Alumina-Based Separator Membrane for Advanced Alkaline Water Electrolyzer

Hydrogen is nowadays considered a favorable and attractive energy carrier fuel to replace other fuels that cause global warming problems. Water electrolysis has attracted the attention of researchers to produce green hydrogen mainly for the accumulation of renewable energy. Hydrogen can be safely used as a bridge to successfully connect the energy demand and supply divisions. An alkaline water electrolysis system owing to its low cost can efficiently use renewable energy sources on large scale. Normally organic/inorganic composite porous separator membranes have been employed as a membrane for alkaline water electrolyzers. However, the separator membranes exhibit high ionic resistance and low gas resistance values, resulting in lower efficiency and raised safety issues as well. Here, in this study, we report that zirconia toughened alumina (ZTA)–based separator membrane exhibits less ohmic resistance 0.15 Ω·cm2 and low hydrogen gas permeability 10.7 × 10−12 mol cm−1 s−1 bar−1 in 30 wt.% KOH solution, which outperforms the commercial, state-of-the-art Zirfon® PERL separator. The cell containing ZTA and advanced catalysts exhibit an excellent performance of 2.1 V at 2000 mA/cm2 at 30 wt.% KOH and 80 °C, which is comparable with PEM electrolysis. These improved results show that AWEs equipped with ZTA separators could be superior in performance to PEM electrolysis