Structure-Performance Relationships in Anthraquinone-Disulfonate Coordination Polymers for Li-Ion and Na-Ion Battery Cathodes

abstract

Coordination polymers (CPs) based on organic redox-active moieties offer a promising route to sustainable electrode materials for next-generation batteries. Herein, the synthesis, crystal structure determination, theoretical characterization, and electrochemical evaluation of a series of anthraquinone-disulfonate (AQDS) CPs incorporating Na+, Mg2+, and Cu2+ ions (AQDS-Na, AQDS-Mg, AQDS-Cu) as cathode materials for lithium-ion and sodium-ion storage are reported. Single-crystal X-ray diffraction reveals that AQDS-Na adopts a 3D framework, while AQDS-Mg and AQDS-Cu form 2D layered structures with coordinated water molecules. These structural differences significantly influence the electrochemical performance. For Li-ion storage, AQDS-Na delivers an initial capacity of 120 mAh g(-1), while AQDS-Mg and AQDS-Cu show lower initial capacities (95 mAh g(-1) and 106 mAh g(-1), respectively) and faster fading. For Na-ion storage, the performance divergence is even more pronounced: AQDS-Na achieves a stable capacity of 91 mAh g(-1) after 100 cycles, while AQDS-Mg and AQDS-Cu suffer from significant capacity loss (47 and 18 mAh g(-1) after 100 cycles, respectively), attributed to the presence of coordinated water molecules in the 2D frameworks. This study highlights the importance of structural dimensionality and coordination environment in designing high-performance cathode materials for battery systems.

keywords

COVALENT ORGANIC FRAMEWORKS; ELECTRODE MATERIALS; METAL; DICARBOXYLATE; STORAGE

subject category

Electrochemistry; Materials Science

authors

Ribeiro, C; Markowski, R; Mendes, RF; Fernández-Alarcón, A; Calbo, J; Rocha, J; Vlad, A; Souto, M

Groups

G1 - Porous Materials and Nanosystems
G3 - Electrochemical Materials, Interfaces and Coatings

Projects

CICECO - Aveiro Institute of Materials (UIDB/50011/2020)

CICECO - Aveiro Institute of Materials (UIDP/50011/2020)

Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)

Redox-active Metal-Organic Frameworks as Electrode Materials for Lithium-Ion Batteries (RedoxMOFs)

acknowledgements

This work has received funding from the European Research Council (ERC) under the European Union's Horizon Europe Framework Programme (ERC-2021-Starting Grant, grant agreement no. 101039748-ELECTROCOFS), from the FCT/MEC (CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020, LA/P/0006/2020), FCT (PTDC/QUI-ELT/2593/2021), from the Spanish Government (COFCAT, PID2023-152083OA-I00, PID2020-119748GA-I00 and TED2021-131255B-C44), and from the PRR-Plano de Recuperacao e Resiliencia (NextGenerationEU funds) through the scope of the Agenda for Business Innovation "New Generation Storage" (project no. 58 with the application C644936001-00000045). This work has also received financial support from the Xunta de Galicia (Centro singular de investigacion de Galicia accreditation 2023-2027, ED431G 2023/03) and the Oportunius program (Gain). A.F.-A. acknowledges Generalitat Valenciana for a postdoctoral contract (CIAPOS/2023/316). R.M. and A.V. acknowledge financial support from F.R.S.-FNRS through ASP PhD fellowship and Excellence of Science (EOS) program-ECOBAT [40007515], respectively.