Crown Ether Electrolyte Additive Enables High-Rate and Stable Polyviologen Cathode Material for Chloride Ion Batteries.

A variety of inorganic and inorganic cathode materials for chloride ion storage are reported. However, their application in chloride ion batteries (CIB) is hindered by poor rate capability and cycling stability. Herein, an organic poly(butyl viologen dichloride) (PBVCl2) cathode material with significantly enhanced rate and cycling performance in the CIB is achieved using a crown ether (18-Crown-6) additive in the tributylmethylammonium chloride-based electrolyte. The as-prepared PBVCl2 cathodes exhibit impressive capacity increases from 149.4 to 179.1 mAh g-1 at 0.1 C and from 57.8 to 111.9 mAh g-1 at 10 C, demonstrating the best rate performance with the highest energy density among those of various reported cathodes for CIBs. This impressive performance improvement is a result of the great boosts in charge transfer, ion transport, and interface stability of the battery by the use of 18-Crown-6, which also contributes to a more than twofold increase in capacity retention after 120 cycles. The electrode reaction mechanism of the CIB based on highly reversible chloride ion transfer is revealed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.

Recent Progress of the Cathode Material Design for Aqueous Zn-Organic Batteries.

Aqueous zinc-ion batteries (ZIBs) have emerged as the most promising candidate for large-scale energy storage due to their inherent safety, environmental friendliness, and cost-effectiveness. Simultaneously, the utilization of organic electrode materials with renewable resources, environmental compatibility, and diverse structures has sparked a surge in research and development of aqueous Zn-organic batteries (ZOBs). A comprehensive review is warranted to systematically present recent advancements in design principles, synthesis techniques, energy storage mechanisms, and zinc-ion storage performance of organic cathodes. In this review article, we comprehensively summarize the energy storage mechanisms employed by aqueous ZOBs. Subsequently, we categorize organic cathode materials into small-molecule compounds and high-molecular polymers respectively. Novel polymer materials such as conjugated polymers (CPs), conjugated microporous polymers (CMPs), and covalent organic frameworks (COFs) are highlighted with an overview of molecular design strategies and structural optimization based on organic cathode materials aimed at enhancing the performance of aqueous ZOBs. Finally, we discuss the challenges faced by aqueous ZOBs along with future prospects to offer insights into their practical applications.

Dynamically Ion-Coordinated Bipolar Organodichalcogenide Cathodes Enabling High-Energy and Durable Aqueous Zn Batteries.

Bipolar organic cathode materials (OCMs) implementing cation/anion storage mechanisms are promising for high-energy aqueous Zn batteries (AZBs). However, conventional organic functional group active sites in OCMs usually fail to sufficiently unlock the high-voltage/capacity merits. Herein, we initially report dynamically ion-coordinated bipolar OCMs as cathodes with chalcogen active sites to solve this issue. Unlike conventional organic functional groups, chalcogens bonded with conjugated group undergo multielectron-involved positive-valence oxidation and negative-valence reduction, affording higher redox potentials and reversible capacities. With phenyl diselenide (PhSe-SePh, PDSe) as a proof of concept, it exhibits a conversion pathway from (PhSe)- to (PhSe-SePh)0 and then to (PhSe)+ as unveiled by characterization and theoretical simulation, where the diselenide bonds are periodically broken and healed, dynamically coordinating with ions (Zn2+ and OTF-). When confined into ordered mesoporous carbon (CMK-3), the dissolution of PDSe intermediates is greatly inhibited to obtain an ultralong lifespan without voltage/capacity compromise. The PDSe/CMK-3 || Zn batteries display high reversibility capacity (621.4 mAh gPDSe -1), distinct discharge plateau (up to 1.4 V), high energy density (578.3 Wh kgPDSe -1), and ultralong lifespan (12 000 cycles) at 10 A g-1, far outperforming conventional bipolar OCMs. This work sheds new light on conversion-type active site engineering for high-voltage/capacity bipolar OCMs towards high-energy AZBs.

Effect of Synthesis Temperature on Performance of Phenazine-based Cathode for Sodium Dual-ion Batteries.

Organic materials have attracted much attention in the field of electrochemical energy storage due to their ecological sustainability, abundant resources and structural designability. However, low electrical conductivity and severe agglomeration of organic materials lead to poor discharge capacity and reaction kinetics in batteries. Herein, the morphology of the phenazine-based organic polymer poly(5,10-diphenylphenazine) (PDPPZ) was modified by varying the synthesis temperature. PDPPZ-165 °C with an exceptional porous structure provides abundant reaction channels for rapid charge transfer and diffusion that improves the reaction kinetics in sodium dual-ion batteries. Therefore, PDPPZ-165 °C cathode possesses excellent rapid charge-discharge capability delivering a specific capacity of 119.2 mAh g-1 at 40 C. Furthermore, a high specific capacity of 124.7 mAh g-1 can be provided even at a high loading of 16 mg cm-2 at 0.5 C with a capacity retention of 86.4% after 500 cycles. This work could afford new insights for optimizing the performance of organic cathode materials in sodium dual-ion batteries.

Facile Synthesis of Diazaanthraquinone Dimers as High-Capacity Organic Cathode Materials for Rechargeable Lithium Batteries.

Organic cathode materials (OCMs) have tremendous potential to construct sustainable and highly efficient batteries beyond conventional Li-ion batteries. Thereinto, quinone/pyrazine hybrids show significant advantages in material availability, energy density, and cycling stability. Herein, we propose a facile method to synthesize quinone/pyrazine hybrids, i.e., the condensation reaction between ortho-diamine and bromoacetyl groups. Based on it, we have successfully synthesized three 1,4-diazaanthraquinone (DAAQ) dimers, including 2,2'-bi(1,4-diazaanthraquinone) (BDAAQ) with an exceptional theoretical capacity of 512 mAh g-1 based on the eight-electron reaction. It can be fully utilized in Li batteries in a wide voltage range of 0.8-3.8 V, at the cost of inferior cycling stability. In an optimal voltage range of 1.4-3.8 V, BDAAQ exhibits one of the best comprehensive electrochemical performances for small-molecule OCMs, including a high specific capacity of 366 mAh g-1, an average discharge voltage of 2.26 V, as well as a respectable capacity retention of 59% after 500 cycles. Moreover, the in-depth investigations reveal the redox reaction mechanisms based on C═O and C═N groups as well as the capacity fading mechanisms based on dissolution-redeposition behaviors. In brief, this work provides an instructive synthesis method and mechanism understanding of high-performance OCMs based on a quinone/pyrazine hybrid structure.

Cost-Effective Rechargeable Magnesium Battery Based on a Fluorinated Alkoxyaluminate Electrolyte and a Carbonyl Polymer Cathode.

Rechargeable magnesium batteries (RMBs) are one of the most promising "post-lithium" battery technologies, but the electrochemical performance is still far from expectation due to the sluggish reaction kinetics of divalent Mg2+ ions. Herein, we report a low-cost, high-performance Mg-organic battery based on the combination of a fluorinated alkoxyaluminate electrolyte and a carbonyl polymer cathode material. First, the one-pot synthesized Mg[Al(HFIP)4]2 (HFIP = hexafluoro-2-propanol) is proved superior to the Mg[B(HFIP)4]2 analogue in both Mg anode compatibility and electrochemical window, as the electrolyte salt in the G2-DME (G2 = diethylene glycol dimethyl ether; DME = 1,2-dimethoxyethane) mixture solvent. Second, a simple wet grinding method is proposed to effectively improve the dispersion uniformity of the poly(benzoquinone-pyrrole) (PBQPy) active material in the cathode. Third, the elaborate Mg-PBQPy battery exhibits superior electrochemical performance within 0.4-3.0 V, including a high reversible capacity of 197 mA h g-1, a high average discharge voltage of 1.6 V, and a high capacity retention of 71% after 500 cycles. Finally, based on various electrochemical analysis and ex situ characterization results, we propose a general microscopic structure evolution model to reveal the electrochemical behaviors of carbonyl polymer cathode in RMBs, including the swelling of polymer active material, trapping of Mg2+ ions, and reversible redox reaction.

Small-molecule organic electrode materials on carbon-coated aluminum foil for high-performance sodium-ion batteries.

Organic molecular electrode materials are promising candidates in batteries. However, direct application of small molecule materials usually suffers from drastic capacity decay and inefficient utilization of active materials because of their high solubility in organic electrolytes and low electrical conductivity. Herein, a simple strategy is found to address the above issues through coating the small-molecule organic materials on a commercialized carbon-coated aluminum foil (CCAF) as the enhanced electrode. Both the experimental and calculation results confirm that the relatively rough carbon coating on the aluminum foil not only exhibits superior adsorption capacity of small-molecule organic electrode materials with a tight contact interface but also provides continuous electronic conduction channels for the facilitated charge transfer and accelerated reaction kinetics. In addition, the carbon coating also inhibits Al corrosion in electrochemical process. As a result, by using the tetrahydroxy quinone-fused aza-phenazine (THQAP) molecule as an example, the THQAP-CCAF electrode exhibits an excellent rate performance with a high capacity of 220 and 180 mAh g-1 at 0.1 and 2 A/g, respectively, and also a remarkable cyclability with a capacity retention of 77.3% even after 1700 cycles in sodium-ion batteries. These performances are much more superior than that of batteries with the THQAP on bare aluminum foil (THQAP-AF). This work provides a substantial step in the practical application of the small-molecule organic electrode materials for future sustainable batteries.

Regulating the Double-Way Traffic of Cations and Anions in Ambipolar Polymer Cathodes for High-Performing Aluminum Dual-Ion Batteries.

The strong Coulombic interactions between Al3+ and traditional inorganic crystalline cathodes present a significant obstacle in developing high-performance rechargeable aluminum batteries (RABs) that hold promise for safe and sustainable stationary energy storage. While accommodating chloroaluminate ions (AlCl4 -, AlCl2+, etc.) in redox-active organic compounds offers a promising solution for RABs, the issues of dissolution and low ionic/electronic conductivities plague the development of organic cathodes. Herein, electron donors are synthetically connected with acceptors to create crosslinked, bipolar-conjugated polymer cathodes. These cathodes exhibit overlapped redox potential ranges for both donors and acceptors in highly concentrated AlCl3-based ionic liquid electrolytes. This approach strategically enables on-site doping of the polymer backbones during redox reactions involving both donor and acceptor units, thereby enhancing the electron/ion transfer kinetics within the resultant polymer cathodes. Based on the optimal donor/acceptor combination, the bipolar polymer cathodes can deliver a high specific capacity of 205 mAh g-1 by leveraging the co-storage of AlCl4 - and AlCl2+. The electrodes exhibit excellent rate performance, a stable cycle life of 60 000 cycles, and function efficiently at high mass loadings, i.e., 100 mg cm-2, and at low temperatures, i.e., -30 °C. The findings exemplify the exploration of high-performing conjugated polymer cathodes for RABs through rational structural design.

Phenothiazine Derivatives as Small-Molecule Organic Cathodes with Adjustable Dropout Voltage and Cycle Performance.

Compared with conventional inorganic materials, organic electrodes are competitive candidates for secondary battery cathodes due to their resourcefulness, environmental friendliness, and cost-effectiveness. Much effort is devoted at the level of chemical structure, while ignoring the impact of molecular aggregation on battery behavior. Herein, this work designs a series of organic molecules with two electrochemically active phenothiazine groups linked by different lengths of alkyl chain to regulate molecular symmetry and crystallinity. The results emphasize the equally important role of molecular aggregation and chemical structure for battery performance. Among them, 2PTZ-C7H14|Li cell exhibits the most impressive cycle and rate performance. At the high rate of 50 C, it can still deliver a capacity of 63.4 mA h g-1 and 74.5% capacity retention after 10 000 cycles. Besides, the dropout voltage of 2PTZ-C9H18|Li cell is only 52 mV, which is among the lowest reported for lithium-organic batteries to the best of the author's knowledge.

Stable Hexaazatrinaphthalene-Based Planar Polymer Cathode Material for Organic Lithium-Ion Batteries.

Organic materials have garnered intensive focus as a new group of electrodes for lithium-ion batteries (LIBs). However, many reported organic electrodes so far still exhibit unsatisfying cycling stability because of the dissolution in the electrolytes. Herein, a novel azo-linked hexaazatrianphthalene (HATN)-based polymer (AZO-HATN-AQ) is designed and fabricated by the polymerization of trinitrodiquinoxalino[2,3-a:2',3'-c]phenazine (HATNTN) and 2,6-diaminoanthraquinone (DAAQ). The abundant redox-active sites, extended π-conjugated planar conformation, and low energy gap endow the AZO-HATN-AQ electrode with high theoretical capacity, excellent solubility resistance, and fast Li-ion transport. In particular, the fully lithiated AZO-HATN-AQ still keeps the planar structure, contributing to the excellent cycling stability. As a result, AZO-HATN-AQ cathodes show high specific capacity (240 mAh g-1 at 0.05 A g-1), prominent rate capability (98 mAh g-1 at 8 A g-1), and outstanding cycling stability (120 mAh g-1 after 2000 cycles at 4 A g-1 with 85.7% capacity retention) simultaneously. This study demonstrates that rational structure design of the polymer electrodes is an effective approach to achieving excellent comprehensive electrochemical performance.

A Nitro-Rich Small-Molecule-Based Organic Cathode Material for Effective Rechargeable Lithium Batteries.

Organic cathode materials have attracted extensive research interest for rechargeable lithium-ion batteries (LIBs) because of their diverse structures and tunable properties. However, the preparation of organic cathode materials with high capacities, long cycling life, and high energy densities still remains a big challenge. To address these issues, we designed and synthesized a novel multinitro-decorated organic small molecule, N4,N4''-bis(2,4-dinitrophenyl)-5'-(4-((2,4-dinitrophenyl)amino)phenyl)-[1,1':3',1''-terphenyl]-4,4''-diamine (TAPB-6NO2), where the unique electronic character of nitro group should enable TAPB-6NO2 to be a promising cathode candidate for LIBs. We found that the introduction of multiple nitro groups could efficiently reduce the solubility of TAPB-6NO2 in organic electrolytes, resulting in a high specific capacity of around 180 mAh g-1 and stable cycling with a capacity retention of 91% after 1100 cycles at 1000 mA g-1. This work suggests that attaching multiple nitro groups on a small molecule is an effective approach to construct high-performance organic cathode materials for stable and sustainable rechargeable LIBs.

Organic Cathode with Dual-Type Multielectron Reaction Centers for High-Energy-Density Lithium Primary Batteries.

Organic electrode materials are composed of abundant elements, have diverse and designable molecular structures, and are relatively easily synthesized, promising a bright future for low-cost and large-scale energy storage. However, they are facing low specific capacity and low energy density. Herein, we report a high-energy-density organic electrode material, 1,5-dinitroanthraquinone, which is composed of two kinds of electrochemically active sites of nitro and carbonyl groups. They experience six- and four-electron reduction and are transformed into amine and methylene groups, respectively, in the presence of fluoroethylene carbonate (FEC) in the electrolyte. Drastically increased specific capacity and energy density are demonstrated with an ultrahigh specific capacity of 1321 mAh g-1 and a high voltage of ∼2.62 V, corresponding to a high energy density of 3400 Wh kg-1. This surpasses the electrode materials in commercial lithium batteries. Our findings provide an effective strategy to design high-energy-density and novel lithium primary battery systems.

High-Performance Poly(1-naphthylamine)/Mesoporous Carbon Cathode for Lithium-Ion Batteries with Ultralong Cycle Life of 45000 Cycles at -15 °C.

Organic electrode materials for lithium-ion batteries have attracted significant attention in recent years. Polymer electrode materials, as compared to small-molecule electrode materials, have the advantage of poor solubility, which is beneficial for achieving high cycling stability. However, the severe entanglement of polymer chains often leads to difficulties in preparing nanostructured polymer electrodes, which is vital for achieving fast reaction kinetics and high utilization of active sites. This study demonstrates that these problems can be solved by the in situ electropolymerization of electrochemically active monomers in nanopores of ordered mesoporous carbon (CMK-3), combining the advantages of the nano-dispersion and nano-confinement effects of CMK-3 and the insolubility of the polymer materials. The as-prepared nanostructured poly(1-naphthylamine)/CMK-3 cathode exhibits a high active site utilization of 93.7%, ultrafast rate capability of 60 A g-1 (≈320 C), and an ultralong cycle life of 10000 cycles at room temperature and 45000 cycles at -15 °C. The study herein provides a facile and effective method that can simultaneously solve both the dissolution problem of small-molecule electrode materials and the inhomogeneous dispersion issue of polymer electrode materials.

Double-layer Composite Gel Polymer Electrolyte for Organic Sodium-Metal Batteries.

Organic cathode materials have the advantages of abundant raw materials, high theoretical specific capacity, controllable structure and easy recycling. Pyrene-4,5,9,10-tetraone (PTO), as one of the typical organic cathode materials, achieves efficient storage and release of Na+ . However, its good solubility in traditional organic liquid electrolytes is detrimental to the cyclic stability of batteries. To address this issue, the double-layer composite gel polymer electrolyte (DLCGPE) consisting of poly (ionic liquid) gel polymer electrolyte and plastic crystal electrolyte was developed and applied to organic sodium-metal batteries. This as-prepared DLCGPE displays an ionic conductivity of 2.17×10-4  S cm-1 and an electrochemical window of 4.8 V. The as-fabricated sodium-symmetric batteries maintain interfacial stability after 500 h of cycling. Furthermore, the PTO/Na batteries could also retain a specific capacity of 201 mAh g-1 after 300 cycles, confirming that DLCGPE achieves the purpose of inhibiting PTO dissolution and maintaining batteries stability. This work broadens the application of asymmetric electrolytes in organic secondary battery.

Organic Cathode Materials for Rechargeable Zinc Batteries: Mechanisms, Challenges, and Perspectives.

Energy and environmental issues have given rise to the development of advanced energy-storage devices worldwide. Electrochemical energy technologies, such as rechargeable batteries, are considered to be the most reliable and efficient candidates. Compared with other batteries, zinc-based batteries seem promising due to their advantages, including inherent safety, cost-effectiveness, and environmentally friendliness. As potential alternatives to conventional inorganic cathodes, organic cathodes for Zn-organic batteries have become a hot topic for research, owing to their favorable characteristics, such as easy structure design, controllable synthesis, and environmental benignancy. Herein, a systematic overview on the fundamentals of organic cathode materials for zinc batteries, including material design, electrochemical mechanisms, technical advances, and challenging analysis, is provided. Furthermore, perspectives and corresponding research directions are offered to facilitate the future development of organic cathode materials for zinc batteries toward practical applications.

Conjugated Carbonyl Polymer-Based Flexible Cathode for Superior Lithium-Organic Batteries.

Conjugated carbonyl compounds are deemed as high theoretical capacity and green electrode materials for lithium-ion batteries (LIBs) but are limited by their high dissolution and poor electronic conductivity. In this paper, we have successfully synthesized a series of multicarbonyl conjugated polymers using the coupling polymerization reaction and then constructed carbonyl-conjugated polymer/carbon nanotube hybrid films by a vacuum-filtration method. Importantly, the hybrid films could serve as a flexible, binder-free, and free-standing organic cathode for LIBs, which could deliver a high reversible discharge capacity of 142.3 mAh g-1 at 50 mA g-1, good cycling stability with a capacity retention of 74.6% at 500 mA g-1 after 300 cycles, and excellent rate capability of 120.6 mAh g-1 at 1000 mA g-1. In addition, the theoretical calculation has proved that the symmetrical conjugated structure can well accommodate four Li+ ions during the electrochemical reaction. Interestingly, the assembled full cell and flexible battery can power the small devices, suggesting its potential to use in bendable or wearable energy-storages devices.