Designing High Performance Organic Batteries.

Organic redox‐active battery materials are an emerging alternative to their inorganic counterparts currently used in the commercialized battery technologies. The main advantages of organic batteries are the potential for low‐cost manufacturing, tunability of electrochemical properties through molecular engineering, and their environmental sustainability. The search for organic electroactive materials that could be used for energy storage in mobile and stationary applications is an active area of research. Computer simulations are used extensively to improve the understanding of the fundamental processes in the existing materials and to accelerate the discovery of new materials with improved performance. We will focus on two main types of redox‐active organic battery materials, that is, solid‐state organic electrode materials and organic electrolytes for redox flow batteries. Because organic materials are made of molecular building blocks, the molecular modeling methodology is usually the most appropriate to investigate their properties at the electronic and atomistic scales. After introducing the fundamentals of computational organic electrochemistry, we will survey its most recent applications in organic battery research and outline some of the remaining challenges for the development and applications of atomic‐scale modeling techniques in the organic battery context.This article is categorized under: Structure and Mechanism > Computational Materials Science Software > Molecular Modeling Electronic Structure Theory > Density Functional Theory

Organic batteries using redox-active polymers and small organic compounds have become promising candidates for next-generation energy storage devices due to the abundance, environmental benignity, and diverse nature of organic resources. To date, tremendous research efforts have been devoted to developing advanced organic electrode materials and understanding the material structure-performance correlation in organic batteries. In contrast, less attention was paid to the correlation between electrolyte structure and battery performance, despite the critical roles of electrolytes for the dissolution of organic electrode materials, the formation of the electrode-electrolyte interphase, and the solvation/desolvation of charge carriers. In this review, we discuss the prospects and challenges of organic batteries with an emphasis on electrolytes. The differences between organic and inorganic batteries in terms of electrolyte property requirements and charge storage mechanisms are elucidated. To provide a comprehensive and thorough overview of the electrolyte development in organic batteries, the electrolytes are divided into four categories including organic liquid electrolytes, aqueous electrolytes, inorganic solid electrolytes, and polymer-based electrolytes, to introduce different components, concentrations, additives, and applications in various organic batteries with different charge carriers, interphases, and separators. The perspectives and outlook for the future development of advanced electrolytes are also discussed to provide a guidance for the electrolyte design and optimization in organic batteries. We believe that this review will stimulate an in-depth study of electrolytes and accelerate the commercialization of organic batteries.

The integration of organic materials into electrode batteries, specifically lithium-ion batteries, has shown significant potential in enhancing battery performance. Organic materials offer several advantages, including abundant availability, environmental friendliness, and tunable properties, making them attractive alternatives to traditional inorganic materials. Research has demonstrated that organic compounds can improve the energy density, cycling stability, and overall efficiency of lithium-ion batteries. These materials contribute to better electrode flexibility, higher capacity retention, and faster charge-discharge rates. Innovations in the synthesis and design of organic electrode materials have led to the development of high-performance batteries with increased lifespan and reduced environmental impact. Challenges remain, such as ensuring long-term stability and addressing issues related to material degradation. However, ongoing advancements continue to drive the optimization of organic materials for lithium-ion batteries, promising a future with more sustainable and efficient energy storage solutions. This abstract highlights the transformative potential of organic materials in revolutionizing lithium-ion battery technology.

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.

Organic anode materials for lithium-ion battery have attracted widespread attention due to their diversity in organic linker functional species and the ability to tune their molecular levels. However, the rational design of advanced organic anodes with high reversible capacity and intentional organic molecular design requires a deep understanding of their mechanism for use in small-molecule organic rechargeable batteries. Herein, an optimized small-molecule-based organic anode material containing highly efficient active sites was developed for use in an organic lithium-ion battery. A small-molecule organic compound, 2,4,6-tris(pyrazinyl)-1,3,5-triazine (TPT), was formed by the trimerization of the 2-cyanopyrazine monomer. This molecule was rationally designed and evaluated as a lithium-ion battery organic anode material. TPT has a relatively small structure, but a superior reversible specific capacity was still achieved. Excitingly, TPT2 (liquid-phase synthetic) released a reversible capacity of 622 mAh g–1 at 100 mA g–1. Moreover, impressive long-term cycling performance was obtained, with a storage capacity of 541 mAh g–1 at 800 mA g–1 after 500 cycles. This demonstrated the durable cyclic stability of TPT2, which also achieved excellent rate performance at different current densities from 100 mA g–1 to 1.6 A g–1. The lithium storage mechanism of TPT was studied by theoretical calculations and ex situ Fourier transform infrared spectroscopy (FTIR) combined with X-ray photoelectron spectroscopy (XPS) characterization, which demonstrated that multiple active sites consisting of −C–N and −C═N groups were responsible for its superior lithium storage performance. This study provides a new understanding of the energy storage mechanism in small-molecule organic-based anode electrodes.

Ethynyl functionalized porphyrin complex as a new cathode for organic alkali metal batteries with excellent cycling stability

Recent advances in developing organic positive electrode materials for rechargeable aluminum-ion batteries

Novel organic anode based on o-benzene active material for high-performance lithium ion batteries

Aromatic carboxylic anhydrides are ubiquitous building blocks in organic materials chemistry and have received considerable attention in the synthesis of organic semiconductors, pigments, and battery electrode materials. Here we extend the family of aromatic carboxylic anhydrides with a unique new member, a conjugated cyclophane with four anhydride groups. The cyclophane is obtained in a three-step synthesis and can be functionalised efficiently, as shown by the conversion into tetraimides and an octacarboxylate. Crystal structures reveal the high degree of porosity achievable with the new building block. Excellent electrochemical properties and reversible reduction to the tetraanions are shown for the imides; NMR and EPR measurements confirm the global aromaticity of the dianions and evidence the global Baird aromaticity of the tetraanions. Considering the short synthesis and unique properties, we expect widespread use of the new building block in the development of organic materials.

Conjugated diketone-linked polyimide cathode material for organic lithium-ion batteries

Theory-inspired development of organic electro-optic materials

ABSTRACTPolyimides are being investigated as alternative, environmentally friendly and safe organic electrode materials for lithium and sodium batteries. However, further improvements need the proper chemical design of these polymers. In this paper, the effect of chemical structure of polyimides on their performance as cathodic materials in lithium batteries was investigated in detail. More in particular, we studied polyimides based on seven different diamine monomers in combination with best performing naphthalenic dianhydride monomer. The first set included the so‐called cardo diamines possessing additional redox‐active carbonyl group with the goal to enhance the theoretical capacity of the polymer. Second, several aromatic diamines including additional functionalities such as cyclic amides, anthrone, or quinolidinium groups were investigated. Finally, aliphatic diamines, containing oxyethylene moieties and thus capable to increase the ionic conductivity of the resulting polymer system, were explored. Among the different polyimides, the “cardo” one based on naphthalenic dianhydride and aromatic aniline phthalein with an additional carbonyl group showed the best results in terms of battery performance. Such polyimide was capable to deliver up to 130 mAhg−1 specific capacity (87% of the theoretical value) at 25 °C and at a current density of 250 mAg−1 during 100 charge/discharge cycles. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 714–723

<p indent="0mm">The pursuit of next-generation energy storage systems has intensified research on lithium-sulfur (Li-S) batteries, which offer high energy density and low cost. However, the practical application of Li-S batteries is hindered by issues such as the shuttle effect, low electrical conductivity of sulfur, and large volume changes during cycling. Organic electrode materials possess advantages such as safety, environmental friendliness, sustainability, design flexibility, and low cost, making them promising cathode materials for high-capacity lithium batteries. Among them, organosulfur has received increasing attention with the development of lithium-sulfur batteries. Similar to sulfur cathodes, organosulfur electrodes can provide a relatively high theoretical capacity based on the reversible breaking and formation of S–S bonds. However, inherent problems such as poor conductivity, sluggish redox kinetics, unsatisfactory cycling stability, and the solubility of cycling products seriously hinder the development of organosulfur cathode materials. Doping heteroatoms into organosulfur molecules to design and synthesize new organosulfur molecules is an effective strategy to improve the performance of organic sulfur cathodes. Heteroatom doping offers a versatile method to modify the electronic structure and chemical reactivity of organosulfur cathodes. By introducing elements such as oxygen (O), nitrogen (N), selenium (Se), tellurium (Te) and phosphorus (P), researchers aim to tailor the material’s properties to improve conductivity, accelerate redox reactions, stabilize electrode interfaces, and mitigate dissolution issues of reaction intermediates. Hybridized organosulfur cathode materials have received more and more attention due to their unique design strategy and flexible electrochemical modulation. Therefore, the research progress in heteroatom-containing organosulfur cathode materials is reviewed comprehensively in this paper, summarizing their applications in lithium battery systems. It primarily discusses heteroatom-containing small molecule organic sulfur and polymer organic sulfur materials, and concludes with the challenges and prospects for organic sulfur cathode materials. It covers synthetic strategies to incorporate heteroatoms, characterization techniques to elucidate their structural and electrochemical properties, and their performance as cathode materials in various battery configurations. The discussion encompasses mechanistic insights into how heteroatoms influence charge storage mechanisms, ion diffusion kinetics, and overall battery performance metrics. Despite the promising advances, challenges remain, including the precise control of heteroatom doping levels, maintaining structural integrity during cycling, and optimizing synthesis methods for scalability and cost-effectiveness. Furthermore, the environmental impact and recyclability of these materials are critical considerations for their sustainable application in energy storage technologies. Looking forward, the development of heteroatom-containing organic sulfur cathode materials holds significant potential to address current limitations and unlock new opportunities for next-generation rechargeable batteries. Future research directions focus on refining synthetic techniques, enhancing material stability and cycling performance, exploring novel heteroatom combinations, and integrating these materials into practical battery systems that meet the increasing demands for high-energy-density and sustainable energy storage solutions. In conclusion, heteroatom-doped organic sulfur cathode materials represent a significant advancement in the field of Li-S batteries. The synergistic effect of organic-inorganic hybridization, combined with the tunability of heteroatom doping, offers a promising avenue for the development of high-performance energy storage systems. Further research is needed to fully exploit the potential of these materials and to address the remaining challenges for their practical application.

Compared to inorganic electrodes, organic materials are regarded as promising electrodes for lithium-ion batteries (LIBs) due to the attractive advantages of light elements, molecular-level structural design, fast electron/ion transferring, favorable environmental impacts, and flexible feature, etc. Not only specific capacities but also working potentials of organic electrodes are reasonably tuned by polymerization, electron-donating/withdrawing groups, and multifunctional groups as well as conductive additives, which have attracted intensive attention. However, organic LIBs (OLIBs) are also facing challenges on capacity loss, side reactions, electrode dissolution, low electronic conductivity, and short cycle life, etc. Many strategies have been applied to tackle those challenges, and many inspiring results have been achieved in the last few decades. In this review, we have introduced the basic concepts of LIBs and OLIBs, followed by the typical cathode and anode materials with various physicochemical properties, redox reaction mechanisms, and evolutions of functional groups. Typical charge-discharge behaviors and molecular structures of organic electrodes are displayed. Moreover, effective strategies on addressing problems of organic electrodes are summarized to give some guidance on the synthesis of optimized organic electrodes for practical applications of OLIBs.

Due to abundant raw materials, low cost and high theoretical energy density, organic potassium ion batteries (OPIBs) have attracted more and more attention from researchers as next promising battery system. However, some challenges still need to be solved. For example, most small-molecule organic electrode materials faced serious dissolution problem in liquid electrolytes, resulting in poor cycle stability. In particular, there are relatively few reports on the current cathodes with really excellent comprehensive performance (such as: high specific capacity, high working voltage, long life-span and excellent rate performance) for OPIBs. In this article, two polyanthraquinoneimide polymers were successfully synthesized and used as organic cathode materials for potassium ion batteries. Attributed to the large molecular structure of the polymer, PPAQ and PNAQ both were successful to be insoluble in the electrolyte (1 mol/L KPF₆ in DME). After comparison, it was found that PNAQ exhibited better comprehensive electrochemical performance than PPAQ. At a current density of 100 mA/g, PNAQ achieved a stable discharge capacity of 138 mAh/g for 200 cycles and the retention rate was as high as 92%. At the same time, after 750 cycles at a high current density of 800 mA/g, the specific capacity of PNAQ still remained at 71 mAh/g with an average attenuation of only 0.03 mAh/g per cycle. Through an appropriate design process for the molecular structure, we proved that organic polymers could become excellent cathodes for potassium ion batteries.