Redox-Bipolar Polyimide Two-Dimensional Covalent Organic Framework Cathodes for Durable Aluminium Batteries.

Emerging rechargeable aluminium batteries (RABs) offer a sustainable option for next-generation energy storage technologies with low cost and exemplary safety. However, the development of RABs is restricted by the limited availability of high-performance cathode materials. Herein, we report two polyimide two-dimensional covalent organic frameworks (2D-COFs) cathodes with redox-bipolar capability in RAB. The optimal 2D-COF electrode achieves a high specific capacity of 132 mAh g-1 . Notably, the electrode presents long-term cycling stability (with a negligible ≈0.0007 % capacity decay per cycle), outperforming early reported organic RAB cathodes. 2D-COFs integrate n-type imide and p-type triazine active centres into the periodic porous polymer skeleton. With multiple characterizations, we elucidate the unique Faradaic reaction of the 2D-COF electrode, which involves AlCl2+ and AlCl4 - dual-ions as charge carriers. This work paves the avenue toward novel organic cathodes in RABs.

Liu Y ，Lu Y ，Hossain Khan A ，Wang G ，Wang Y ，Morag A ，Wang Z ，Chen G ，Huang S ，Chandrasekhar N ，Sabaghi D ，Li D ，Zhang P ，Ma D ，Brunner E ，Yu M ，Feng X ... -  《-》

p/n-Type Polyimide Covalent Organic Frameworks for High-Performance Cathodes in Sodium-Ion Batteries.

Jindal S ，Tian Z ，Mallick A ，Kandambeth S ，Liu C ，Bhatt PM ，Zhang X ，Shekhah O ，Alshareef HN ，Eddaoudi M ... -  《-》

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.

Luo LW ，Zhang C ，Ma W ，Han C ，Ai X ，Chen Y ，Xu Y ，Ji X ，Jiang JX ... -  《-》

Mesoporous Polyimide-Linked Covalent Organic Framework with Multiple Redox-Active Sites for High-Performance Cathodic Li Storage.

Covalent organic frameworks (COFs) are gaining increasing attention as renewable cathode materials for Li-ion batteries. However, COF electrodes reported so far still exhibit unsatisfying capacity due to their limited active site density and insufficient utilization. Herein, a new two-dimensional polyimide-linked COF, HATN-AQ-COF with multiple redox-active sites for storing Li+ ions, was designed and fabricated from a new module of 2,3,8,9,14,15-hexacarboxyl hexaazatrinaphthalene trianhydrides with a 2,6-diaminoanthraquinone linker. HATN-AQ-COF possessing excellent stability, good conductivity, and a large pore size of 3.8 nm enables the stable and fast ion transport. This, in combination with the abundant redox active sites, results in a high reversible capacity of 319 mAh g-1 at 0.5 C (1 C=358 mA g-1 ) for the HATN-AQ-COF electrode with a high active site utilization of 89 % and good cycle performance, representing one of the best performances among the reported COF electrodes.

Yang X ，Gong L ，Liu X ，Zhang P ，Li B ，Qi D ，Wang K ，He F ，Jiang J ... -  《-》

One-Dimensional Covalent Organic Framework as High-Performance Cathode Materials for Lithium-Ion Batteries.

Covalent organic frameworks (COFs) have emerged as a new class of cathode materials for energy storage in recent years. However, they are limited to two-dimensional (2D) or three-dimensional (3D) framework structures. Herein, this work reports designed synthesis of a redox-active one-dimensional (1D) COF and its composites with 1D carbon nanotubes (CNTs) via in situ growth. Used as cathode materials for Li-ion batteries, the 1D COF@CNT composites with unique dendritic core-shell structure can provide abundant and easily accessible redox-active sites, which contribute to improve diffusion rate of lithium ions and the corresponding specific capacity. This synergistic structural design enables excellent electrochemical performance of the cathodes, giving rise to 95% utilization of redox-active sites, high rate capability (81% capacity retention at 10 C), and long cycling stability (86% retention after 600 cycles at 5 C). As the first example to explore the application of 1D COFs in the field of energy storage, this study demonstrates the great potential of this novel type of linear crystalline porous polymers in battery technologies.

Jia C ，Duan A ，Liu C ，Wang WZ ，Gan SX ，Qi QY ，Li Y ，Huang X ，Zhao X ... -  《-》