A Total Organic Aqueous Redox Flow Battery Employing a Low Cost and Sustainable Methyl Viologen Anolyte and 4‐HO‐TEMPO Catholyte

Increasing worldwide energy demands and rising CO₂ emissions have motivated a search for new technologies to take advantage of renewables such as solar and wind energies. Redox flow batteries (RFBs) with their high power density, high energy efficiency, scalability (up to MW and MWh), and safety features are one suitable option for integrating such energy sources and overcoming their intermittency. However, resource limitation and high system costs of current RFB technologies impede wide implementation. Here, a total organic aqueous redox flow battery (OARFB) is reported, using low‐cost and sustainable methyl viologen (MV, anolyte) and 4‐hydroxy‐2,2,6,6‐tetramethylpiperidin‐1‐oxyl (4‐HO‐TEMPO, catholyte), and benign NaCl supporting electrolyte. The electrochemical properties of the organic redox active materials are studied using cyclic voltammetry and rotating disk electrode voltammetry. The MV/4‐HO‐TEMPO ARFB has an exceptionally high cell voltage, 1.25 V. Prototypes of the organic ARFB can be operated at high current densities ranging from 20 to 100 mA cm², and deliver stable capacity for 100 cycles with nearly 100% Coulombic efficiency. The MV/4‐HO‐TEMPO ARFB displays attractive technical merits and thus represents a major advance in ARFBs.     

All‐Organic Battery Composed of Thianthrene‐ and TCAQ‐Based Polymers

An all‐organic battery consisting of two redox‐polymers, namely poly(2‐vinylthianthrene) and poly(2‐methacrylamide‐TCAQ) is assembled. This all‐organic battery shows excellent performance characteristics, namely flat discharge plateaus, an output voltage exceeding 1.3 V, and theoretical capacities of both electrodes higher than 100 mA h g^?1. Both organic electrode materials are synthesized in two respective three synthetic steps using the free‐radical polymerization technique. Li‐organic batteries manufactured from these polymers prove their suitability as organic electrode materials. The cathode material poly(2‐vinylthianthrene) (3) displays a discharging plateau at 3.95 V versus Li⁺/Li and a discharge capacity of 105 mA h g^?1, corresponding to a specific energy of about 415 mW h g^?1. The anode material poly(2‐methacrylamide‐TCAQ) (7) exhibits an initial discharge capacity of 130 mA h g^?1, corresponding to 94% material activity. The combination of both materials results in an all‐organic battery with a discharge voltage of 1.35 V and an initial discharge capacity of 105 mA h g^?1 (95% material activity).     

Fast and Reversible Four‐Electron Storage Enabled by Ethyl Viologen for Rechargeable Magnesium Batteries

Magnesium (Mg) batteries are the most promising “post‐lithium‐ion” energy storage technologies owing to their high theoretical energy density, low cost, and intrinsic safety with air and moisture. However, the development of Mg batteries has been limited to cathode materials leading to low power, low reversible energy density, and poor cycle life. Here, a new Mg cathode is reported based on ethyl viologen (EV), which not only has a fast redox couple EV²⁺/EV⁰ but also is capable of coupling with redox‐active anions, such as iodide (I^?), achieving a total four‐electron storage. The EV²⁺/EV⁰ redox couple demonstrates a superior rate performance (10 C) and stable cycle life (500 cycles) owing to intrinsic fast electrode kinetics. A high material utilization (>80%) can be achieved at 1.0 C under a high areal loading of 5 mg cm^?2. When coupling with iodide I^?, a reversible four‐electron storage is achieved with a high energy density (304.2 Wh kg^?1) and a stable cycle life (>100 cycles). This study provides effective strategies for designing reversible multielectron storage for high‐rate and high‐energy rechargeable Mg batteries.     

Metal‐Organic Framework‐Derived Carbons for Battery Applications

The applications of carbon and carbon‐based materials with high porosity, high surface area, and functionalities based on metal‐organic framework precursors and/or templates have attracted significant research interest in recent years, particularly in the field of batteries. The chemical and physical properties of carbon and carbon‐based materials obtained by the heat treatment of various metal‐organic framework precursors or templates are improved to a certain extent. In this comprehensive review, the synthetic methods and electrochemical performance of carbon materials derived from metal‐organic frameworks (metal/carbon, metal oxide/carbon, nitrogen‐doped carbon, porous carbon, etc.) along with their applications in batteries are outlined.     

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.     

Covalent–Organic Frameworks: Advanced Organic Electrode Materials for Rechargeable Batteries

Covalent–organic frameworks (COFs), featuring structural diversity, framework tunability and functional versatility, have emerged as promising organic electrode materials for rechargeable batteries and garnered tremendous attention in recent years. The adjustable pore configuration, coupled with the functionalization of frameworks through pre‐ and post‐synthesis strategies, enables a precise customization of COFs, which provides a novel perspective to deepen the understanding of the fundamental problems of organic electrode materials. In this review, a summary of the recent research into COFs electrode materials for rechargeable batteries including lithium‐ion batteries, sodium‐ion batteries, potassium‐ion batteries, and aqueous zinc batteries is provided. In addition, this review will also cover the working principles, advantages and challenges, strategies to improve electrochemical performance, and applications of COFs in rechargeable batteries.     

Single‐Step Spray Printing of Symmetric All‐Organic Solid‐State Batteries Based on Porous Textile Dye Electrodes

A symmetric solid‐state battery based on organic porous electrodes is fabricated using scalable spray‐printing. The active electrode material is based on a textile dye (disperse blue 134 anthraquinone) and is capable of forming divalent cations and anions in oxidation and reduction processes. The resulting molecule can be used in both negative and positive electrode reactions. After spray printing an inter‐connected pore honeycomb electrode, a solid‐state electrolyte (σ_Li: × 10^?4 S cm^?1) based on a polymeric ionic liquid is spray‐printed as a second layer and infiltrated through the porous electrodes. A symmetric all‐organic battery is then formed with the addition of another identical set of electrode and electrolyte layers. Both density functional theory calculations and charge‐discharge profiles show that the potentials for the negative and positive electrode reactions are amongst the lowest (≈2.0 V vs Li) and the highest (≈3.5 V vs Li), respectively, for quinone‐type molecules. Over the C‐rate range 0.2 to 5 C, the battery has a discharge cell voltage of more than 1 V even up to 250 charge‐discharge cycles and capacities are in the range 50–80 mA h g^?1 at 0.5 C.     

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.     

Carbonyls: Powerful Organic Materials for Secondary Batteries

The application of organic carbonyl compounds as high performance electrode materials in secondary batteries enables access to metal‐free, low‐cost, environmental friendly, flexible, and functional rechargeable energy storage systems. Organic compounds have so far not received much attention as potential active materials in batteries, mainly because of the success of inorganic materials in both research and commercial applications. However, new requirements in secondary batteries such as flexibility accompanied with low production costs and environmental friendliness, in particular for portable devices, reach the limit of inorganic electrode materials. Organic carbonyl compounds represent the most promising materials to satisfy these needs. Here, recent efforts of the research in the field of organic carbonyl materials for secondary batteries are summarized, and the working principle and the structural design of different groups of carbonyl material is presented. Finally, the influence of conductive additives and binders on the cell performance is closely evaluated for each class of materials.     

Development of Active Organic and Polymeric Materials for Batteries and Solar Cells: Introduction to Essential Characterization Techniques

Establishing renewable energy sources is currently one of the major scientific topics. Two aspects are most crucial: energy conversion and energy storage. Thus, the development of efficient solar‐cell devices and high‐capacity, high‐current rechargeable battery systems turns out to be of great importance. In particular, the design of active materials and their characterization using electrochemical and spectroscopic means represent essential elements in the development process. Here, a concise overview of both methods and key properties with regard to the characterization of organic and polymeric active materials with a focus on energy conversion/storage is provided. Benefits and limitations of complementary techniques are presented to enable a consistent and comprehensive characterization procedure.     

Stable Li–Organic Batteries with Nafion‐Based Sandwich‐Type Separators

Similar to Li–S batteries, Li–organic batteries have also been plagued by the dissolution of active materials and the resulting shuttle effect for many years. An effective strategy to eliminate the shuttle effect is adopting solid electrolytes or Li–ion permselective separators to prohibit the dissolved electroactive species from migrating to the Li anode. A polypropylene/Nafion/polypropylene (PNP) sandwich‐type separator is reported with many advantages in comparison with previously reported LISICON, polymer electrolyte, and other Nafion utilization forms. The physical and chemical properties of PNP separators are studied in detail by cross‐section scanning electron microscopy (SEM), infrared spectroscopy (IR), and electrochemical impedance spectroscopy. 1,1′‐Iminodianthraquinone (IDAQ), a novel organic cathode, is taken as an example to quantitatively investigate the function of PNP separators. In the presence of PNP5 with the most appropriate Nafion loading of 0.5 mg cm^–2, IDAQ is able to achieve dramatically improved cycling stability with capacity retention of 76% after 400 cycles and Coulombic efficiency above 99.6%, which reaches the highest level for reported soluble organic electrode materials. Besides Li–organic batteries, such kind of Nafion‐based sandwich‐type separators are also promising for Li–S batteries and other new battery designs involving dissolved electroactive species.     

Zwitterions for Organic/Perovskite Solar Cells,Light‐Emitting Devices,and Lithium Ion Batteries: Recent Progress and Perspectives

Zwitterions, a class of materials that contain covalently bonded cations and anions, have been extensively studied in the past decades owing to their special features, such as excellent solubility in polar solvents, for solution processing and dipole formation for the transfer of carriers and ions. Recently, zwitterions have been developed as electrode modifiers for organic solar cells (OSCs), perovskite solar cells (PVSCs), and organic light‐emitting devices (OLEDs), as well as electrolyte additives for lithium ion batteries (LIBs). With the rapid advances of zwitterionic materials, high‐performance devices have been constructed with enhanced efficiencies by introducing them as interface layers and electrolyte additives. In this review, recent progress in OSCs, PVSCs, OLEDs, and LIBs by using zwitterions is highlighted. The authors also elaborate the role of various zwitterionic materials as interfacial layers and additives for highly efficient OSCs, PVSCs, OLEDs, and LIBs. This article presents an overview of device performance of zwitterionic materials. The structure–property relationship is also discussed. Finally, the prospects of zwitterion materials are also addressed.     

Comparison of Quinone‐Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long‐Term Stability with Tetrasubstituted Quinones

Quinones are appealing targets as organic charge carriers for aqueous redox flow batteries (RFBs), but their utility continues to be constrained by limited stability under operating conditions. The present study evaluates the stability of a series of water‐soluble quinones, with redox potentials ranging from 605–885 mV versus NHE, under acidic aqueous conditions (1 m H₂SO₄). Four of the quinones are examined as cathodic electrolytes in an aqueous RFB, paired with anthraquinone‐2,7‐disulfonate as the anodic electrolyte. The RFB data complement other solution stability tests and show that the most stable electrolyte is a tetrasubstituted quinone containing four sulfonated thioether substituents. The results highlight the importance of substituting all C–H positions of the quinone in order to maximize the quinone stability and set the stage for design of improved organic electrolytes for aqueous RFBs.     

Anthraquinone Derivatives in Aqueous Flow Batteries

Anthraquinone derivatives are being considered for large scale energy storage applications because of their chemical tunability and rapid redox kinetics. The authors investigate four anthraquinone derivatives as negative electrolyte candidates for an aqueous quinone‐bromide redox flow battery: anthraquinone‐2‐sulfonic acid (AQS), 1,8‐dihydroxyanthraquinone‐2,7‐disulfonic acid (DHAQDS), alizarin red S (ARS), and 1,4‐dihydroxyanthraquinone‐2,3‐dimethylsulfonic acid (DHAQDMS). The standard reduction potentials are all lower than that of anthraquinone‐2,7‐disulfonic acid (AQDS), the molecule used in previous quinone‐bromide batteries. DHAQDS and ARS undergo irreversible reactions on contact with bromine, which precludes their use against bromine but not necessarily against other electrolytes. DHAQDMS is apparently unreactive with bromine but cannot be reversibly reduced, whereas AQS is stable against bromine and stable upon reduction. The authors demonstrate an AQS‐bromide flow cell with higher open circuit potential and peak galvanic power density than the equivalent AQDS‐bromide cell. This study demonstrates the use of chemical synthesis to tailor organic molecules for improving flow battery performance.