Donor–Acceptor Covalent Organic Framework Enables Ambipolar Charge Storage in Aluminum-Ion Energy Storage
Abstract
The development of sustainable high-performance energy storage systems (ESS) beyond lithium-ion technology has become a global priority due to lithium's geopolitical and supply-chain constraints. Among emerging alternatives, aluminum-ion ESS (Al-ESS) offer remarkable advantages, including aluminum's natural abundance, high theoretical volumetric capacity, and intrinsic safety. However, progress in Al-ESS is hindered by the scarcity of effective cathode materials capable of reversible Al-ion storage. In this context, covalent organic frameworks (COFs) offer tunable structures and abundant redox-active sites, which enable multi-electron reactions and fast ion transport. However, their practical implementation is often undermined by poor electronic conductivity and limited accessibility of redox centers. Herein, 2D donor–acceptor COF integrating electron-rich tetrakis(4-aminophenyl)-1,4-phenylenediamine (TPA) and electron-deficient naphthalenediimide (NDI) units is reported as an ambipolar cathode for Al-ESS. The highly crystalline, microporous framework exhibits intrinsic charge-transport pathways, enabling operation without conductive carbon-nanotube additives. COF TPA-NDI delivers a high specific capacity of 270 mAh/g, a specific energy of 447 Wh/kg, and exceptional cycling stability. Ex situ analyses reveal a reversible multi-electron redox process involving amine, imine, and carbonyl sites coordinating both cationic and anionic species. These findings demonstrate that donor–acceptor engineering in COFs can yield intrinsically conductive organic cathodes, providing a new design paradigm for next-generation Al-ESS.
Related
- Atomic Chalcogen Substitution Modulates Photophysical Properties and Electronic Structure in Donor–Acceptor Covalent Organic Frameworks
- Low-threshold Deep-red Organic Laser Dye Based on a Vinylene-bridged Benzothiadiazole Dimer in a Donor–Acceptor–π–Acceptor–Donor Framework
- 非可逆偶氮共价有机骨架用于水中2，5-二氯-1，4-苯醌的吸附 Irreversible azo covalent organic framework for adsorption of 2，5-dichloro-1，4-benzoquinone from water
- Dual Breaking the Geometric and Electronic Symmetry of Covalent Organic Framework for Enhanced H 2 O 2 Photosynthesis
- Metal-organic and covalent organic frameworks for precision drug delivery: a precision-by-design evidence framework for biologically accountable nanomedicine.
BibTeX
@article{valentini2026donoracceptor,
title = {{Donor–Acceptor Covalent Organic Framework Enables Ambipolar Charge Storage in Aluminum-Ion Energy Storage}},
author = {Cataldo Valentini and Verónica Montes‐garcía and Wojciech Kukułka and Saira Sarwar and Michał Bielejewski and Mateusz Wlazło and Rossella Greco and Viktorija Pankratova and Ignacio Pérez‐juste and Dawid Pakulski and Paolo Samorì and Artur Ciesielski},
journal = {Advanced Energy Materials},
year = {2026},
month = sep,
doi = {10.1002/aenm.71198},
url = {https://univoak.hal.science/hal-05740256v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Donor–Acceptor Covalent Organic Framework Enables Ambipolar Charge Storage in Aluminum-Ion Energy Storage
AU - Cataldo Valentini
AU - Verónica Montes‐garcía
AU - Wojciech Kukułka
AU - Saira Sarwar
AU - Michał Bielejewski
AU - Mateusz Wlazło
AU - Rossella Greco
AU - Viktorija Pankratova
AU - Ignacio Pérez‐juste
AU - Dawid Pakulski
AU - Paolo Samorì
AU - Artur Ciesielski
PY - 2026
DA - 2026/09/02
JO - Advanced Energy Materials
DO - 10.1002/aenm.71198
UR - https://univoak.hal.science/hal-05740256v1
AB - The development of sustainable high-performance energy storage systems (ESS) beyond lithium-ion technology has become a global priority due to lithium's geopolitical and supply-chain constraints. Among emerging alternatives, aluminum-ion ESS (Al-ESS) offer remarkable advantages, including aluminum's natural abundance, high theoretical volumetric capacity, and intrinsic safety. However, progress in Al-ESS is hindered by the scarcity of effective cathode materials capable of reversible Al-ion storage. In this context, covalent organic frameworks (COFs) offer tunable structures and abundant redox-active sites, which enable multi-electron reactions and fast ion transport. However, their practical implementation is often undermined by poor electronic conductivity and limited accessibility of redox centers. Herein, 2D donor–acceptor COF integrating electron-rich tetrakis(4-aminophenyl)-1,4-phenylenediamine (TPA) and electron-deficient naphthalenediimide (NDI) units is reported as an ambipolar cathode for Al-ESS. The highly crystalline, microporous framework exhibits intrinsic charge-transport pathways, enabling operation without conductive carbon-nanotube additives. COF TPA-NDI delivers a high specific capacity of 270 mAh/g, a specific energy of 447 Wh/kg, and exceptional cycling stability. Ex situ analyses reveal a reversible multi-electron redox process involving amine, imine, and carbonyl sites coordinating both cationic and anionic species. These findings demonstrate that donor–acceptor engineering in COFs can yield intrinsically conductive organic cathodes, providing a new design paradigm for next-generation Al-ESS.
SN - 1614-6832
SN - 1614-6840
ER -