Electrochemical performance of M(dca)2pyz (M = Fe, Co and Ni) MOFs as sustainable anodes in lithium-ion batteries

Ciria-Ramos, Isabel (Universidad de Zaragoza) ; García-Fernández, Alberto ; Mayoral, Álvaro ; Orera, Alodia (Universidad de Zaragoza) ; Juarez-Perez, Emilio J. ; Haro, Marta (Universidad de Zaragoza)

Resumen: A family of Metal–Organic Frameworks (MOFs) based on the ligands pyrazine (pyz) and dicyanamide (dca) and the metal centers Fe, Co and Ni with the unit formula M(dca)2pyz has been studied as anodes for Li-Ion Batteries (LIBs). These compounds are analogs of transition metal nitrides (TMNs) but synthesized following an environmentally friendly process. Fe(dca)2pyz provides the best electrochemical performance with a specific capacity of 519 mA h g−1 and 375 mA h cm−3 after 450 cycles at 200 mA g−1 and a capacity retention of 90% with respect to the first cycle. This performance is better than most of the Fe nitrides reported to date, highlighting its potential as an anode for LIBs. The high capacity is due to the conversion and displacement reaction occurring with the Fe atoms and the insertion of Li+ into the ligands. In contrast, the specific capacities of Co(dca)2pyz and Ni(dca)2pyz are lower due to a partial reduction of the Co atoms in the first case, and to the oxidation of the Ni atoms which hinders the Li+ intercalation process in the second. As a result, the specific capacities after 450 cycles at 200 mA g−1 are 148 mA h g−1 for Co(dca)2pyz and 57 mA h g−1 for Ni(dca)2pyz. Powder-XRD and TEM characterizations after cycling of the three samples reveal that Fe(dca)2pyz and Co(dca)2pyz samples become amorphous while the Ni(dca)2pyz material does not. This suggests that the amorphization process is relevant for obtaining anodes with improved electrochemical performance. This study demonstrates that MOFs obtained by a cost-effective and environmentally friendly method can act as precursors for obtaining high performance anodes for LIBs without the need for an energy intensive carbonization process, since they undergo an in situ amorphization process, giving rise to AMorphous Organometallic (AMO) electrodes.

Idioma: Inglés

DOI: 10.1039/d4ta02137a

Año: 2024

Publicado en: Journal of Materials Chemistry A 12, 31 (2024), 20215-20228
ISSN: 2050-7488

Financiación: info:eu-repo/grantAgreement/ES/DGA/E13-23R
Financiación: info:eu-repo/grantAgreement/ES/DGA/E31-23R
Financiación: info:eu-repo/grantAgreement/ES/UZ-DGA/T57-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIU/CNS2023-144346
Financiación: info:eu-repo/grantAgreement/ES/MCIU/RYC-2018-024561-I
Financiación: info:eu-repo/grantAgreement/ES/MICINN-AEI/PID2019-107893RB-I00/AEI-10.13039-501100011033
Financiación: info:eu-repo/grantAgreement/ES/MICINN/CNS2023-145197
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2019-108247RA-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2022-140516OB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RYC-2018-025222-I

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Física (Dpto. Química Física)
Área (Departamento): Área Cienc.Mater. Ingen.Metal. (Dpto. Ciencia Tecnol.Mater.Fl.)