Molecular Engineering of Quinone-Based Nickel Complexes and Polymers for All-Organic Li-Ion Batteries (original) (raw)
Recent Progress in Organic Electrodes for Li and Na Rechargeable Batteries
Advanced Materials, 2018
Organic rechargeable batteries, which use organics as electrodes, are excellent candidates for next‐generation energy storage systems because they offer design flexibility due to the rich chemistry of organics while being eco‐friendly and potentially cost efficient. However, their widespread usage is limited by intrinsic problems such as poor electronic conductivity, easy dissolution into liquid electrolytes, and low volumetric energy density. New types of organic electrode materials with various redox centers or molecular structures have been developed over the past few decades. Moreover, research aimed at enhancing electrochemical properties via chemical tuning has been at the forefront of organic rechargeable batteries research in recent years, leading to significant progress in their performance. Here, an overview of the current developments of organic rechargeable batteries is presented, with a brief history of research in this field. Various strategies for improving organic el...
Advanced Functional Materials, 2020
Rechargeable sodium‐ion batteries (SIBs) are considered attractive alternatives to lithium‐ion batteries for next‐generation sustainable and large‐scale electrochemical energy storage. Organic sodium‐ion batteries (OSIBs) using environmentally benign organic materials as electrodes, which demonstrate high energy/power density and good structural designability, have recently attracted great attention. Nevertheless, the practical applications and popularization of OSIBs are generally restricted by the intrinsic disadvantages related to organic electrodes, such as their low conductivity, poor stability, and high solubility in electrolytes. Here, the latest research progress with regard to electrode materials of OSIBs, ranging from small molecules to organic polymers, is systematically reviewed, with the main focus on the molecular structure design/modification, the electrochemical behavior, and the corresponding charge‐storage mechanism. Particularly, the challenges faced by OSIBs and ...
Recent research on emerging organic electrode materials for energy storage
Energy Materials, 2021
Due to the growth of the demand for rechargeable batteries in intelligent terminals, electric vehicles, energy storage, and other markets, electrode materials, as the essential of batteries, have attracted tremendous attention. The research of emerging organic electrode materials in batteries has been boosted recently to their advantages of low cost, environmental friendliness, biodegradability, and designability. This manuscript highlights and classifies several recent studies on organic electrode materials and lists their potential applications in various battery systems. Finally, the challenge and perspective of organic electrode materials are also summarized.
Energy Materials, 2022
Electroactive organics have attracted significant attention as electrode materials for next-generation rechargeable batteries because of their structural diversity, molecular adjustability, abundance, flexibility, environmental friendliness and low cost. To date, a large number of organic materials have been applied in a variety of energy storage devices. However, the inherent problems of organic materials, such as their dissolution in electrolytes and low electronic conductivity, have restricted the development of organic electrodes. In order to solve these problems, many groups have carried out research and remarkable progress has been made. Nevertheless, most reviews of organic electrodes have focused on the positive electrode rather than the negative electrode. This review first provides an overview of the recent work on organic anodes for Li- and Na-ion batteries. Six categories of organic anodes are summarized and discussed. Many of the key factors that influence the electrochemical performance of organic anodes are highlighted and their prospects and remaining challenges are evaluated.
Recent Progress on Organic Electrodes Materials for Rechargeable Batteries and Supercapacitors
Materials
Rechargeable batteries are essential elements for many applications, ranging from portable use up to electric vehicles. Among them, lithium-ion batteries have taken an increasing importance in the day life. However, they suffer of several limitations: safety concerns and risks of thermal runaway, cost, and high carbon footprint, starting with the extraction of the transition metals in ores with low metal content. These limitations were the motivation for an intensive research to replace the inorganic electrodes by organic electrodes. Subsequently, the disadvantages that are mentioned above are overcome, but are replaced by new ones, including the solubility of the organic molecules in the electrolytes and lower operational voltage. However, recent progress has been made. The lower voltage, even though it is partly compensated by a larger capacity density, may preclude the use of organic electrodes for electric vehicles, but the very long cycling lives and the fast kinetics reached r...
Angewandte Chemie-international Edition, 2010
Li-ion batteries are considered very promising energy-storage devices for a variety of applications including large-scale batteries. Given the large quantities of energy to be stored in such applications, the amount of cathode materials will be in the order kilograms per battery unit. This will not only raise concerns about the finite quantity of some resources on the earth and its environmental intolerance but also about overall CO 2 management. To overcome such problems efficiently, Armand, Chen, and co-workers recently suggested a new class of sustainable lithium batteries based on organic compounds. The other available literature mainly reports on the use of polymers as possible electroactive materials in Liion batteries or totally organic polymer based rechargeable batteries. Indeed, certain redox active centers of organic molecules (and also polymers) offer almost unlimited combinations of atomic arrangements and many possibilities for substitutions; this allows for fine tuning of the desired properties. Herein, our primary focus is the use of "monomer" organic molecules as an active material for Li-ion batteries. The reversible capacity of certain organic compounds, such as Li x C 6 O 6 , can reach values as high as 580 mA h g À1 , but their operating voltage is typically quite low (about 2 V vs. Li). However, the most critical problem associated with utilization of organic materials in batteries is the high solubility of many interesting organic molecules in the aprotic electrolytes commonly used in the Li-ion batteries. Although soluble molecules can act as a charge carrier, the operation of a battery using such molecules is diffusionlimited. Besides that, the use of soluble organic molecules in a long-term cycling process may be questionable. Herein we propose, for the first time, that this problem can be overcome by grafting (anchoring) of soluble electroactive organic molecules onto the surface of an appropriate insoluble substrate. The essence of this approach is the strong attach-
Electrochemistry Communications, 2017
Two N-substituted naphthalene tetracarboxylic diimide (NTCDI) ionic compounds, carboxylic and sulfonic sodium salts, were prepared and used as positive electrode active materials in lithium-half cells. The aim of this investigation was to assess the solubility-suppressing effect of two different negatively charged substituent groups on a redox-active organic backbone using a carbonate-based liquid electrolyte. NTCDI derivatives were obtained in high yields from reaction of naphthalene tetracarboxylic dianhydride with neutralized glycine or with neutralized taurine. They were mixed with carbon black and cycled in galvanostatic mode against lithium metal using 1 M LiPF 6 EC/DMC liquid electrolyte. These two NTCDI derivatives exhibit a quite stable electrochemical activity upon cycling at an average potential of 2.3 V vs. Li + /Li 0 giving rise to specific capacity values of 147 mAh•g −1 and 113 mAh•g −1 for the dicarboxylate and the disulfonate derivative, respectively. This study clearly supports the useful effect of such grafted permanent charges as a general rule on the electrochemical stability of crystallized organic materials based on the assembly of small redox-active units.
Organic batteries free of toxic metal species could lead to a new generation of consumer energy storage devices that are safe and environmentally benign. However, the conventional organic electrodes remain problematic because of their structural instability, slow ion-diffusion dynamics, and poor electrical conductivity. Here, we report on the development of a redox-active, crystalline, mesoporous covalent organic framework (COF) on carbon nanotubes for use as electrodes; the electrode stability is enhanced by the covalent network, the ion transport is facilitated by the open meso-channels, and the electron conductivity is boosted by the carbon nanotube wires. These effects work synergistically for the storage of energy and provide lithium-ion batteries with high efficiency, robust cycle stability, and high rate capability. Our results suggest that redox-active COFs on conducting carbons could serve as a unique platform for energy storage and may facilitate the design of new organic electrodes for high-performance and environmentally benign battery devices.
Review: Overview of Organic Cathode Materials in Lithium-Ion Batteries and Supercapacitors
MDPI, 2025
Organic materials have emerged as promising candidates for cathode materials in lithium-ion batteries and supercapacitors, offering unique properties and advantages over traditional inorganic counterparts. This review investigates the use of organic compounds as cathode materials in energy storage devices, focusing on their application in lithium-ion batteries and supercapacitors. The review covers various types of organic materials, organosulfur compounds, organic free radical compounds, organic carbonyl compounds, conducting polymers, and imine compounds. The advantages, challenges, and ongoing developments in this area are examined and the potential of organic cathode materials to achieve higher energy density, improved cycling stability, and environmental sustainability is highlighted. The comprehensive analysis of organic cathode materials provides insights into their electrochemical performance, electrode reaction mechanisms, and design strategies such as molecular structure modification, hybridization with inorganic components, porous architectures, conductive additives, electrolyte optimization, binder selection, and electrode architecture to improve their efficiency and performance. In addition, future research in the field of organic cathode materials should focus on addressing current limitations such as low energy density, cycling stability, poor discharge capability, potential safety concerns and improving their performance. To do this, it will be necessary to improve structural stability, conductivity, cycle life, and capacity fading, explore new redox-active organic compounds, and pave the way for the next generation of high-performance energy storage devices. For organic cathode materials to be commercially viable, it is also essential to develop scalable and economical manufacturing processes.
Electrochemical Mechanism of Al Metal–Organic Battery Based on Phenanthrenequinone
Energy Material Advances
Al metal-organic batteries are a perspective high-energy battery technology based on abundant materials. However, the practical energy density of Al metal-organic batteries is strongly dependent on its electrochemical mechanism. Energy density is mostly governed by the nature of the aluminium complex ion and utilization of redox activity of the organic group. Although organic cathodes have been used before, detailed study of the electrochemical mechanism is typically not the primary focus. In the present work, electrochemical mechanism of Al metal-phenanthrenequinone battery is investigated with a range of different analytical techniques. Firstly, its capacity retention is optimized through the preparation of insoluble cross-coupled polymer, which exemplifies extremely low capacity fade and long-term cycling stability. Ex situ and operando ATR-IR confirm that reduction of phenanthrenequinone group proceeds through the two-electron reduction of carbonyl groups, which was previously b...
Voltage Gain in Lithiated Enolate-Based Organic Cathode Materials by Isomeric Effect
ACS Applied Materials & Interfaces, 2014
Li-ion batteries (LIBs) appear nowadays as flagship technology able to power an increasing range of applications starting from small portable electronic devices to advanced electric vehicles. Over the past two decades, the discoveries of new metal-based host structures, together with substantial technical developments, have considerably improved their electrochemical performance, particularly in terms of energy density. To further promote electrochemical storage systems while limiting the demand on metal-based raw materials, a possible parallel research to inorganic-based batteries consists in developing efficient and low-polluting organic electrode materials. For a long time, this class of redoxactive materials has been disregarded mainly due to stability issues but, in recent years, progress has been made demonstrating that organics undeniably exhibit considerable assets. On the basis of our ongoing research aiming at elaborating lithiated organic cathode materials, we report herein on a chemical approach that takes advantage of the positive potential shift when switching from para to ortho-position in the dihydroxyterephthaloyl system. In practice, dilithium (2,3-dilithium-oxy)-terephthalate compound (Li 4 C 8 H 2 O 6 ) was first produced through an eco-friendly synthesis scheme based on CO 2 sequestration, then characterized, and finally tested electrochemically as lithiated cathode material vs. Li. This new organic salt shows promising electrochemical performance, notably fast kinetics, good cycling stability and above all an average operating potential of 2.85 V vs. Li + /Li 0 (i.e., +300 mV in comparison with its para-regioisomer), verifying the relevance of the followed strategy.
Electrochemically stabilised quinone based electrode composites for Li-ion batteries
Lancet
In order to improve the stability and kinetics of organic materials for lithium batteries, composites between a quinone derivative of calyx[4]arene and carbon black were prepared. Two different approaches were used, the first relying on covalent grafting and the second on electrochemical grafting of the quinone derivatives on the carbon black support. The properties of prepared composites were investigated using XRD, FTIR, TGA and NMR, while their electrochemical stability was studied using classical galvanostatical cycling. It was found that the efficiency of the electrochemical stabilisation of organic molecules depends on the surface properties of the substrate. Interestingly, within the same compositional range, the covalently and electrochemically grafted quinone derivatives of calyx[4]arene showed similar cycling stability. Composites with approximately 20 wt.% of active organic material showed excellent cycling stability within 100 cycles with a delivered capacity of about 60 mAh g -1 of composite (more than 300 mAh g -1 per quinone).