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Herein we report that organic compounds comprising planar C6 ring structures and carboxylate groups can function as an excellent anode material for sodium-organic batteries. Systematic comparisons of different electrode materials including the multi-ring aromatic compounds with or without carboxylate groups are carried out, the Na insertion mechani...
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... The study also explored the concept of sodium insertion on carbon-carbon double bonds, suggesting the potential for a mechanism involving the reduction of sodium ions into carbon-sodium bonds. However, this mechanism is still in its nascent stages of development and requires further validation for practical application in SIBs [11,12]. The realm of anion insertion compounds was also probed, revealing compounds capable of reversibly incorporating or releasing anions from the electrolyte. ...
This review presents a comprehensive perspective on the evolution of biodegradable battery materials within the context of sustainable energy storage, emphasizing their burgeoning significance. The exploration encompasses the transition towards paper-based batteries, a pivotal step towards ecologically friendly, lightweight, and cost-effective energy storage systems, alongside the introduction of novel sodium-ion hybrid electrolyte batteries that address growing environmental concerns through replaceable components. Moreover, the promise of organic sodium electrodes, derived from renewable biomass resources, potentially revolutionizes battery technology with materials that align with environmental principles. Furthermore, the review elucidates the potential of biodegradable organic materials within sodium-based batteries, underscoring their capacity to mitigate environmental impact. Drawing from these diverse sources, this review serves as a comprehensive exploration of the evolving landscape of biodegradable battery materials, illuminating their role in shaping a sustainable energy future.
... To provide context for comparison, the properties of previously reported Na + storage materials are listed in Fig. 3d. Generally, small molecules (below the red dashed line) display high capacity but poor stability [8, 14,16,[56][57][58][59]. However, the supramolecular polymer PMCDI here showed excellent performance in terms of stability while maintaining high capacity, even comparable to many polymers and COFs (above the red dashed line) [13,53,[60][61][62][63][64]. ...
Organic electrodes possess numerous advantages of structure designability, high capacity, and accommodating large cations. However, the capacity of organic electrode materials in sodium-ion batteries remains low, and their solubility in organic electrolytes leads to a shortened lifespan. Researchers are thus concerned about enhancing their performance through compound design. In this study, we successfully improved both the capacity and cycling stability by simply grafting amino acids onto organic compounds (PMCDI). Firstly, the introduction of amino acids facilitated the formation of a more stable layered structure of PMCDI through hydrogen bonding. Additionally, the amino acid groups promoted intermolecular interactions between the organic electrode material and the carboxymethyl cellulose binder, thereby reducing interfacial resistance and significantly enhancing the cycling stability for over 2000 cycles. Secondly, both experimental and computational results revealed that the non-conjugated carboxylic acid group provided Na+ transport pathways and an additional reversible storage site, leading to an improvement in specific capacity (~300 mA h g−1). The strategy employed in this work sheds light on the design of organic molecules for future sodium-ion batteries.
... Before that, PTCDA had been extensively applied as an active material for NIBs and LIBs. [60][61][62][63] The electrochemical mechanism of PTCDA is that C O in PTCDA is converted to C O M (M represents Li + , Na + , K + , etc.) during metal ion insertion and will be reversibly converted back to C O during deinsertion. 64,65 According to a previous report, organic PTCDA could provide a specific capacity of $140 mAh/g at 10 mA/g in NIBs and a discharge capacity of 100 mAh/g after the 200th cycle at 200 mA/g. ...
Potassium‐ion batteries (KIBs) with many technical advantages have attracted much attention. However, it is difficult to find a host material with a large interlayer spacing and stable framework to accommodate K⁺ with a large radius, resulting in the slower development of inorganic electrode materials for KIBs. Organic electrode materials have the advantages of structural diversity and adjustability, and their electrochemical performance depends on the conversion reaction between K⁺ and active functional groups, which ignores the steric hindrance effect caused by the large radius of K⁺. The research progress of organic KIBs is summarized from four aspects: organic cathode materials, organic anode materials, electrolyte optimization, and full batteries. The compositions, structures, reaction mechanisms, electrochemical performances, and development strategies of organic materials with various functional groups are presented. This paper can provide inspiration for researchers to develop high‐performance organic KIBs and realize the application of organic KIBs.
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... Han et al. [29] reported that 1,4,5,8naphthalenetetracarboxylic dianhydride (NTCDA) has a Li-ion insertion capacity of up to nearly 2000 mA h g -1 , which was ascribed to the fact that each C 6 ring can reversibly accept six Li ions to form a 1:1 Li/C complex [ Figure 3A]. The lithium storage capability of the C 6 ring was also verified by Yang et al. [30] . They reported that a 2,9-dimethylquinacridone (2,9-DMQA) anode can deliver a high capacity of 1150 mA h g -1 at 0.1 A g -1 and suggested that the carbonyl groups in 2,9-DMQA and the intermediate with 20 π-electrons enable reversible store a total of 22 Li ions [ Figure 3B]. ...
... Schematic of proposed reversible electrochemical redox mechanism of (A) NTCDA [29] , Reproduced from Ref. [29] with permission from John Wiley and Sons. (B) 2,9-DMQA [30] , Reproduced from Ref. [30] with permission from Elsevier. (C) PTCDA and NaPTCDA [31] . ...
... Schematic of proposed reversible electrochemical redox mechanism of (A) NTCDA [29] , Reproduced from Ref. [29] with permission from John Wiley and Sons. (B) 2,9-DMQA [30] , Reproduced from Ref. [30] with permission from Elsevier. (C) PTCDA and NaPTCDA [31] . ...
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.
... Conjugated carbonyl compounds are typical n-type electrode materials with good electrochemical properties (high capacity, high efficiency, extended cycle capacity, etc.) as the battery's cathode. [64][65][66][67][68] They mainly included quinone compounds, imide, and polyimide compounds ( Figure 4A). 30,[69][70][71] The redox reaction of conjugated carbonyl compound is an enolization and metal coordination process, and the fast kinetics of renovation usually results in higher electrochemical reversibility of carbonyl compounds. ...
The quest for advanced energy storage devices with cheaper, safer, more resource‐abundant storage has triggered intense research into zinc ion batteries (ZIBs). Among them, organic materials as cathode materials for ZIBs have attracted great interest due to their flexible structure designability, high theoretical capacity, environmental friendliness, and sustainability. Although numerous organic electrode materials have been studied and different redox mechanisms have been proposed in the past decade, their electrochemical performance still needs further improvement, and the mechanisms require further exploration. This paper provides a systematical overview of three types of organic materials (bipolar‐type conductive polymer, n‐type conjugated carbonyl compounds, and p‐type material) on the energy storage mechanisms and distinct characteristics. We then focus on discussing the design strategies to improve electrochemical performance. Furthermore, the challenges and future research directions are discussed to provide a foundation for further developing organic‐based ZIBs. As cathode materials for zinc‐ion batteries, organic materials have attracted great interests due to their flexible structure designability, high theoretical capacity, environmental friendliness, and sustainability. A systematical overview of three types of organic materials is presented to summarize their structures and performances, propose the strategies for their performance enhancement, expound the current challenges and perspectives.
... The introduction of ionic groups is a way to reduce solubility. [17] For example, the specific capacity of Li terephthalate (Li 2 C 8 H 4 O 4 ) remains 234.00 mAh g À 1 after 50 cycles, much better than that of general neutral organic redox compounds. [18] (c) The density of redox units of organic redox compounds is usually low, which limits their specific capacity for battery application. ...
Organic electrode materials are one of potential energy storage materials for the next generation lithium batteries. Herein, carboxylate groups are installed to conjugated tetrathiafulvalene (TTF) platform to yield two compounds, namely lithium tetrathiafulvalene‐dicarboxylate (TTF‐Li2) and lithium tetrathiafulvalene‐tetracarboxylate (TTF‐Li4), as stable anode materials for lithium batteries. The low solubility in electrolyte brought about by the carboxylate groups and high rechargeablity ensured by the conjugated TTF platform lead to excellent battery performance. After cycling at a current density of 0.5 C for 120 cycles, a net specific capacity of 108.19 mAh g‐1 and 217.55 mAh g‐1 is obtained for the TTF‐Li2 and TTF‐Li4 anodes containing 70 wt.% of active materials, respectively, corresponding to 61.4% and 82.0% of their theoretical capacities, respectively. The density functional theory (DFT) calculation confirms the well‐delocalized charge for both TTF‐Li2 and TTF‐Li4. Therefore, the TTF‐Li2 and TTF‐Li4 are promising anode materials for lithium batteries.
... (a) Calculated HOMO plots of compound x with different uptake amounts of sodium[66] (b) HOMO plots of compound x by using selected molecules/anions with different extents of reduction calculated at the B3LYP/6-31G(d) level[43] 图 4. (a) 计算了化合物 x 在不同钠吸收量下的 HOMO 图[66]。 (b) 在 B3LYP/6-31G(d) 水平上计算不同还原程度的选定分子/阴离子，得到化合物 x 的 HOMO 图谱[43] PI，它们相互连接电化学二酐，如 PMDA、NTCDA 和 PTCDA (图 5(a)) [44]。如上所述， 将芳香体系由 PMDA 转变为 NTCDA 和 PTCDA 可以降低 LUMO 能量， 从而提高平均放电电压(图 5(b))。 此外，缩短烷基链可以增加重量容量(图 5(c))。重要的是，将二酐结构掺入聚合物框架极大地抑制了电解 质中不必要的溶解，从而提高了稳定性。因此，基于 PTCDA 的 PI 在 5000 次循环后表现出超长的循环稳 定性，且没有明显的衰减，比功率为 20.99 kW•kg −1 ，比能量为 285 Wh•kg −1 (图 5(d))。显然，用烷基链连 接氧化还原活性羰基化合物可以有效抑制严重的容量衰退，但烷基链是不氧化还原的，这可能导致固有 的电化学负担和较低的理论容量。因此，有必要缩短连接链，以增加理论容量。因此，用短链联氨连接 PTCDA 合成 PI，其可逆容量为 126 mAh•g −1 ，容量保持良好。有趣的是，当这种类型的 PI 与对苯二甲酸 钠耦合时，实现了全有机钠离子全电池，其初始容量为 73 mAh•g −1 ，平均电池电压为 1.35 V。为了进一 步降低电化学自重，提高理论容量，提出并应用了羰基小分子自连接策略。例如，Xu 等以 2,6-二氨基蒽 醌为链连接 PMDA 和 NTCDA， 合成了两种基于蒽醌的 PI， 其可逆容量分别高达 165 和 192 mAh•g −1 [70]。 随后， Xu 等人以 1,5-二氨基蒽醌为链连接 NTCDA， 同样合成了聚蒽醌酰亚胺， 其可逆容量为 190 mAh•g −1 李舒冰，费奔 DOI: 10.12677/ms.2021.116083 725 材料科学 [71]。与预期的一样，使用自链接策略合成的所有 PI 都具有良好的循环稳定性。除了 PI，多巴胺(PDA) 也被证明是 SIB 的电极材料事实上，从多巴胺到 PDA 的聚合机制是复杂且有争议的，但毫无疑问，它具 有与氧化还原活性醌基相似的分子结构。因此，PDA 可以作为电极材料，甚至是阳极和阴极材料。例如， Sun 等人受到生理过程的启发，选择 PDA 作为阳极材料，其表现出优异的电化学性能[72] (a) Chemical structures of tailored polyimides. ...
... Rate performance of this composition was stable and significant capacity of 133 mAh g -1 even for cycling at a rate of 5 C. A more detailed study on multi-ring aromatic systems was reported by Zhang and co-workers. [60] The authors chose 3,4,9,10-perylene tetracarboxylic dianhydride (PTD) and its tetrasodiated form (Na4PTC). The central molecule was chosen with the motivation of extremely low solubilities of perylene derivatives and the presence of a planar conjugated π-electron network. ...
... The compound delivered a high specific capacity with significant stability. Unlike the sodium analog (Na4PTC), [60] the authors observed that the MOF could activate the perylene ring and up to 8 ions could be inserted. This was attributed to the presence of a wavy open framework and local structure arrangement. ...
Electrochemical energy storage (EES) devices are gaining ever greater prominence in the quest for global energy security. With increasing applications and widening scope, rechargeable battery technology is gradually finding avenues for more abundant and sustainable systems such as Na‐ion (NIB) and K‐ion batteries (KIB). Development of suitable electrode materials lies at the core of this transition. Organic redox‐active molecules are attractive candidates as negative electrode materials owing to their low redox potentials and the fact that they can be obtained from biomass. Also, the rich structural diversity allows integration into several solid‐state polymeric materials. Research in this domain is increasingly focused on deploying molecular engineering to address specific electrochemical limitations that hamper competition with rival materials. This Minireview aims to summarize the advances in both the electrochemical properties and the materials development of organic anode materials.
... Based on the FTIR spectra, we can identify the functional groups produced, at wave numbers 1774 cm -1 (s) and 1302 cm -1 (s) identified as stretching vibrations of closed chain (cyclic) C=O anhydride groups in PTCDA no longer appearing on the Na 4 -PTC FTIR spectrum. In the Na 4 -PTC FTIR spectrum shows the absorption that appears at wave numbers 1594 cm -1 (s) and 1435 cm -1 (s) which are identified as stretching vibrations of the group (-COO-), confirming that there is a sodium carboxylic group which is conjugated to the perylene ring [10]. Stretching vibration -C=O carboxylic at wave numbers 1725-1700 cm -1 does not appear in the IR La-MOFs spectrum. ...
Lanthanum-Metal Organic Frameworks (La-MOFs) have been successfully synthesized based on perylene-3,4,9,10-tetracarboxylic dyes and ion lanthanum (La³⁺) as metal organic linkers using solvothermal methods. The absence of absorption at wavenumber 1700 cm⁻¹ as vibration stretching v(C = O) from La-MOFs, indicates that the oxygen atom from ligand can coordinate with the lanthanum metal ion. This indicates that La-MOFs has been successfully formed. Peak intensity of strong and sharp from X-ray diffraction indicates the high crystallinity of La-MOFs. La-MOFs possesses a HOMO-LUMO band gap of 2.686 eV determined by UV-Vis spectroscopy with absorbed edge at 462 nm, which present effective photocatalytic activity for hydrogen gas production in the process of water splitting under UV-Vis irradiation. The results of cyclic voltammetry from La-MOFs obtained a reduction potential value (LUMO) of - 2.0735 V vs. NHE which is more negative than the H⁺/H2 reduction potential, it can be concluded that La-MOFs have potential thermodynamic requirements for the reduction of H⁺/H2. The production of hydrogen gas obtained from La-MOFs reached 4112.784 µmol in 4 hours.
... [28,29] Besides, the swelling effect between solvent molecules and the polymeric network might also benefit the penetration of the electrolyte. [30] The voltage tailoring of dihydrophenazine derivatives could be readily realized by the copolymerization of PZ-OMe, PZ and PZ-CN monomers with distinct redox potential as schematically shown in Figure 3a. Figure 3b and 3c show the cyclic voltammetry (CV) profiles of p-PZ-OMe, p-PZ, p-PZ-CN and copolymerized p-PZ-X. The three polymers polymerized through their corresponding monomers showed two pairs of symmetric cathodic/anodic peaks with large peak separation of ca. ...
... AgCl/Ag) at a sweep rate of 10 mV · s À 1 . Koutecký-Levich plots at the reciprocal of the current at low over potential (5,10,15,20,30,40, 60 and 80 mV) were fitted a straight linearly relationship with the reciprocal of the square root of the rotation rate. The y-intercept give the reciprocal of i k , the current in the absence of mass transport limitations (the extrapolation to infinite rotation rate). ...
Redox‐active organics based on a multi‐electron mechanism are of great interest in battery electrode materials as they are capable of delivering high capacity per molecular weight. However, most of such organics shows huge voltage gap that is inherited from their stepwise redox reactions occurring in the same conjugated redox moiety. This study focuses on the voltage tailoring of polymeric dihydrophenazine derivative which shows high specific capacity as a cathode electrode material and decent cycling stability, but suffers huge voltage gap of ca. 0.8 V. We demonstrate a strategy to modify the voltage gap of dihydrophenazine derivatives through the incorporation of functional groups with different electron affinity near the redox moiety. The as‐designed dihydrophenazine derivatives are further copolymerized to yield a polymeric material with significantly smoothened charge‐discharge profiles and good capacity retention. We further demonstrate through theoretical calculation based on density‐functional theory that the substitute site and types of functional groups are of great importance in voltage tailoring as well as structural stability of the dihydrophenazine derivatives.
