Orthoquinone-Based Covalent Organic Frameworks with Ordered Channel Structures for Ultrahigh Performance Aqueous Zinc-Organic Batteries.

Elaborate molecular design on cathodes is of great importance for rechargeable aqueous zinc-organic batteries' performance elevation. Herein, we design a novel orthoquinone-based covalent organic framework with an ordered channel structures (BT-PTO COF) cathode for an ultrahigh performance aqueous zinc-organic battery. The ordered channel structure facilitates ions transfer and makes the COF follow a redox pseudocapacitance mechanism. Thus, it delivers a high reversible capacity of 225 mAh g-1 at 0.1 A g-1 and an exceptional long-term cyclability (retention rate 98.0 % at 5 A g-1 (≈18 C) after 10 000 cycles). Moreover, a co-insertion mechanism with Zn2+ first followed by two H+ is uncovered for the first time. Significantly, this co-insertion behaviour evolves to more H+ insertion routes at high current density and gives the COF ultra-fast kinetics thus it achieves unprecedented specific power of 184 kW kg-1 (COF) and a high energy density of 92.4 Wh kg-1 (COF) . Our work reports a superior organic material for zinc batteries and provides a design idea for future high-performance organic cathodes.

Organic Positive Materials for Magnesium Batteries: A Review.

Magnesium batteries, like lithium-ion batteries, with higher abundance and similar efficiency, have drawn great interest for large-scale applications such as electric vehicles, grid energy storage and many more. On the other hand, the use of organic electrode materials allows high energy-performance, metal-free, environmentally friendly, versatile, lightweight, and economically efficient magnesium storage devices. In particular, the structural diversity and the simple activity of organic molecules make redox properties, and hence battery efficiency, easy to monitor. While organic magnesium batteries still in their infancy, this field becomes more and more promising because significant results were reported. To summarize the achievements in studies on organic cathodes for magnesium systems, their synthesis is discussed, combined with electrode design to provide the basis for controlling the electrochemical properties. Moreover, the techniques to synthesize organic materials with high-yield are mentioned. Finally, potential problems and prospects are explored to further improve organic cathodes.

Revisit of Polyaniline as a High-Capacity Organic Cathode Material for Li-Ion Batteries.

Polyaniline (PANI) has long been explored as a promising organic cathode for Li-ion batteries. However, its poor electrochemical utilization and cycling instability cast doubt on its potential for practical applications. In this work, we revisit the electrochemical performance of PANI in nonaqueous electrolytes, and reveal an unprecedented reversible capacity of 197.2 mAh g-1 (244.8 F g-1) when cycled in a wide potential range of 1.5 to 4.4 V vs. Li+/Li. This ultra-high capacity derives from 70% -NH- transformed to =NH+- during deep charging/discharging process. This material also demonstrates a high average coulombic efficiency of 98%, an excellent rate performance with 73.5 mAh g-1 at 1800 mA g-1, and retains 76% of initial value after 100 cycles, which are among the best reported values for PANI electrodes in battery applications.

Electropolymerization of a Carbonyl-Modified Dihydropyrazine Derivative for Aqueous Zinc Batteries with Ultrahigh Cycling Stability.

The design of aqueous zinc-ion batteries (ZIBs) that have high specific capacity and long-term stability is essential for future large-scale energy storage systems. Cathode materials with extended π-conjugation and abundant active sites are desirable to enhance the charge storage performance and the cycling stability of the aqueous ZIB. Based on this concept, 6,9-dihydropyrazino[2,3-g]quinoxaline-2,3,7,8(1H,4H)-tetrone was chosen as the monomer to be electropolymerized onto carbon cloth (PDHPQ-Tetrone/CC). When used as the cathode material for aqueous ZIBs, an exceptional cycling life (>20,000 cycles) at a current density of 10 A g-1 was achieved, with the specific capacity maintained at 82.8% and with the Coulombic efficiency at around 100% throughout cycling. At the charge-discharge current density of 0.1 A g-1, the ZIB with PDHPQ-Tetrone/CC achieved a high specific capacity of 248 mAh g-1. Kinetic analyses showed that both surface-capacitive-controlled processes and semi-infinite diffusion-controlled processes contribute to the stored charge. The charge storage mechanism was investigated with ex situ characterizations and involves the redox processes of carbonyl/hydroxyl and amino/imino groups coupled with insertion and extraction of both Zn2+ and H+.

The Compatibility of COFs Cathode and Optimized Electrolyte for Ultra-Long Lifetime Rechargeable Aqueous Zinc-Ion Battery.

Rechargeable aqueous zinc-ion batteries (RAZIBs) are attractive due to their affordability, safety, and eco-friendliness. However, their potential is limited by the lack of high-capacity cathodes and compatible electrolytes needed for reliable performance. Herein, we have presented a compatibility strategy for the development of a durable and long-lasting RAZIBs. The covalent organic frameworks (COFs) based on anthraquinone (DAAQ-COF) is created and utilized as the cathode, with zinc metal serving as the anode. The electrolyte is made up of an aqueous solution containing zinc salts at various concentrations. The COF cathode has been designed to be endowed with a rich array of redox-active groups, enhancing its electrochemical properties. Meanwhile, the electrolyte is formulated using triflate anions, which have exhibited superiority over sulfate anions. This strategy lead to the development of an optimized COF cathode with fast charging capability, high Coulombic efficiency (nearly 100 %) and long-term cyclability (retention rate of nearly 100 % at 1 A g-1 after 10000 cycles). Moreover, through experimental analysis, a co-insertion mechanism involving Zn2+ and H+ in this cathode is discovered for the first time. These findings represent a promising path for the advancement of organic cathode materials in high-performance and sustainable RAZIBs.

Benzoquinone-Pyrrole Polymers as Cost-Effective Cathodes toward Practical Organic Batteries.

Organic cathode materials (OCMs) for rechargeable Li and Na batteries show great advantages in resource sustainability and huge potential in electrochemical performance but suffer from dissolution problems and costly synthesis. Herein, for the first time, we investigated the copolymer of benzoquinone (BQ) and pyrrole (Py), namely, poly(benzoquinone-pyrrole) (PBQPy), as an OCM for Li batteries. The low-cost raw materials and solvent-free synthesis provide PBQPy much brighter prospects in large-scale production compared to other carbonyl-based polymer cathode materials. Nevertheless, PBQPy showed one of the best electrochemical performances among all OCMs, including excellent energy density (2.32 V × 255 mAh g-1 = 592 Wh kg-1), rate capability (79%@2000 mA g-1), and cycling stability (81%@1000th cycle). By introducing poly(benzoquinone-methyl pyrrole) for comparison, as well as employing density functional theory calculations and various characterizations for in-depth understanding, the synthesis mechanism, polymer structure, electrochemical behavior, and redox mechanism were clearly clarified. It is believed that this work will encourage more efforts to develop cost-effective OCMs toward practical organic batteries.

Constructing Extended π-Conjugated Molecules with o-Quinone Groups as High-Energy Organic Cathode Materials.

Although organic cathode materials with sustainability and structural designability have great potential for rechargeable lithium batteries, the dissolution issue presents a huge challenge to meet the demands of cycling stability and energy density simultaneously. Herein, we have designed and successfully synthesized two novel small-molecule organic cathode materials (SMOCMs) by the same innovative route, namely 7,14-diazabenzo[a]tetracene-5,6,8,13-tetraone (DABTTO) and 7,9,16,18-tetraazadibenzo[a,l]pentacene-5,6,8,14,15,17-hexaone (TADBPHO). The integrated p-quinone, o-quinone, and pyrazine groups provide these SMOCMs with attractive theoretical capacities of 473 and 568 mAh g-1 based on 6- and 10-electron reactions, respectively, which were almost fully utilized within 0.8-3.8 V vs Li+/Li. The extended aromatic nucleus of TADBPHO makes it much less soluble than DABTTO and thus able to achieve the highest level of cycling stability (66% @ 500th cycle) for SMOCMs in addition to the exceptional energy density (364 mAh g-1 × 2.56 V = 932 Wh kg-1) within 1.5-3.8 V. In addition to the excellent electrochemical performance, the redox reaction and capacity fading mechanisms have been also investigated in detail. The novel approach to construct extended π-conjugated molecules with o-quinone groups is enlightening for the development of high-energy and stable OCMs for future efficient and sustainable energy storage devices.

Revisiting the Structure and Electrochemical Performance of Poly(o-phenylenediamine) as an Organic Cathode Material.

Poly(o-phenylenediamine) (PoPDA) has been recognized as a low-cost electroactive organic material and studied as a cathode for aqueous zinc batteries or as an anode for nonaqueous lithium batteries. However, there remains a lot of confusion about its synthesis, structure, and electrochemical application. Especially, the previously studied PoPDA samples were mostly synthesized at room temperature, which were proved by us to be just a dimer, that is, 2,3-diaminophenazine (DAPZ). By various characterization methods including elemental analysis and mass spectrometry, we verified that the product synthesized at high temperature, PoPDA-H, was a polymer based on DAPZ as the structural repeat unit and with some imperfect substitutes (OH and NH3+CH3COO-). Based on the reversible redox reaction of phenazine units and the stable polymer structure within 1.3-3.8 V vs Li+/Li, PoPDA-H was more appropriate to be applied as a cathode rather than as an anode for lithium batteries. It achieved a high energy density of 490 Wh kg-1 (2.12 V × 231 mAh g-1) at 50 mA g-1 and a high cycling stability (79%@1000th cycle) at 500 mA g-1, both of which were comparable to previously reported expensive pyrazine- and carbonyl-based polymers. This work clarifies many misunderstandings of PoPDA, which is important to its further development toward practical application in energy-storage devices.

First-Principle Insights Into Molecular Design for High-Voltage Organic Electrode Materials for Mg Based Batteries.

Low cost, scalability, potentially high energy density, and sustainability make organic magnesium (ion) battery (OMB) technologies a promising alternative to other rechargeable metal-ion battery solutions such as secondary lithium ion batteries (LIB). However, most reported OMB cathode materials have limited performance due to, in particular, low voltages often smaller than 2 V vs. Mg2+/Mg and/or low specific capacities compared to other competing battery technologies, e.g., LIB or sodium ion batteries. While the structural diversity of organic compounds and the large amount of possible chemical modifications potentially allow designing high voltage/capacity OMB electrode materials, the large search space requires efficient exploration of potential molecular-based electrode materials by rational design strategies on an atomistic scale. By means of density functional theory (DFT) calculations, we provide insights into possible strategies to increase the voltage by changes in electronic states via functionalization, by strain, and by coordination environment of Mg cations. A systematic analysis of these effects is performed on explanatory systems derived from selected prototypical building blocks: five- and six-membered rings with redox-active groups. We demonstrate that voltage increase by direct bandstructure modulation is limited, that strain on the molecular scale can in principle be used to modulate the voltage curve and that the coordination/chemical environment can play an important role to increase the voltage in OMB. We propose molecular structures that could provide voltages for Mg insertion in excess of 3 V.