Understanding the Li-Ion storage mechanism of h-Zn2GeO4 nanoparticles: Experimental and theoretical studies
Por:
Cosio-Aguilar G., Rodríguez J.R., Belman-Rodríguez C., Ponce-Pérez R., Guerrero-Sánchez J., Guadalupe-Moreno M., Vilchis R., Aguirre S.B., Martínez-Carreón M.J., Camacho-López S.
Publicada:
1 ene 2025
Resumen:
Interesting conversion and alloying anode materials have been developed because of their ability to store a lot of Li-ions. However, some important issues must be fully understood to improve their cycle performance such as Li-ion storage mechanisms, volumetric expansion, kinetics and diffusion pathways. In this direction, h-Zn2GeO4 (h-ZGO) nanoparticles with willemite structure were studied by electrochemical methods to understand the origin of its high charge capacity of 567 mAh g-1 at 200 mA g-1 with an efficiency >99 % after 400 cycles. Also, DFT calculations were carried out to understand the lithiation mechanism, which revealed that the h-ZGO primitive cell can store 84 Li-ions per unit cell, approximately 14 Li-ions per molecule (theoretical capacity of 1443 mAh g-1) with a stable formation energy of -0.8 eV and a volumetric expansion of 177 % after full lithiation. Also, the minimum energy pathway for Li diffusion through the h-ZGO structure takes place from the Wyckoff positions 3a to 9d with an activation energy barrier of 1.42 eV. Additionally, AIMD calculations corroborated the rupture of Ge-O and Zn-O bonds, allowing the formation of different secondary phases at anode as LiZn, Li2O and Li3.7Ge. © 2025 Elsevier Ltd
Filiaciones:
Cosio-Aguilar G.:
Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, BC, Ensenada, 22860, Mexico
Centro de Investigación Científica y de Educación Superior de Ensenada, BC, Ensenada, 22860, Mexico
Rodríguez J.R.:
Centro de Investigación Científica y de Educación Superior de Ensenada, BC, Ensenada, 22860, Mexico
Belman-Rodríguez C.:
Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, BC, Ensenada, 22860, Mexico
Ponce-Pérez R.:
Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, BC, Ensenada, 22860, Mexico
Guerrero-Sánchez J.:
Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, BC, Ensenada, 22860, Mexico
Guadalupe-Moreno M.:
Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, BC, Ensenada, 22860, Mexico
Vilchis R.:
Centro Conjunto de Investigación en Química Sustentable, UAEM-UNAM, EM, Toluca, 50120, Mexico
Aguirre S.B.:
Facultad de Ingeniería, Arquitectura y Diseño, Universidad Autónoma de Baja California, BC, Ensenada, 22860, Mexico
Martínez-Carreón M.J.:
Facultad de Ciencias Físico Matemáticas, Universidad Autónoma de Nuevo León, San Nicolás de los Garza, Nuevo León, 66455, Mexico
Camacho-López S.:
Centro de Investigación Científica y de Educación Superior de Ensenada, BC, Ensenada, 22860, Mexico
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