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Quantum‐Chemical Study of the FeNCN Conversion‐Reaction Mechanism in Lithium‐ and Sodium‐Ion Batteries
Author(s) -
Chen Kaixuan,
Fehse Marcus,
Laurita Angelica,
Arayamparambil Jeethu Jiju,
Sougrati Moulay Tahar,
Stievano Lorenzo,
Dronskowski Richard
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201914760
Subject(s) - lithium (medication) , ion , ternary operation , battery (electricity) , chemistry , lithium ion battery , chemical physics , materials science , computational chemistry , thermodynamics , organic chemistry , medicine , power (physics) , physics , computer science , programming language , endocrinology
We report a computational study on 3d transition‐metal (Cr, Mn, Fe, and Co) carbodiimides in Li‐ and Na‐ion batteries. The obtained cell voltages semi‐quantitatively fit the experiments, highlighting the practicality of PBE+U as an approach for modeling the conversion‐reaction mechanism of the FeNCN archetype with lithium and sodium. Also, the calculated voltage profiles agree satisfactorily with experiment both for full (Li‐ion battery) and partial (Na‐ion battery) discharge, even though experimental atomistic knowledge is missing up to now. Moreover, we rationalize the structural preference of intermediate ternaries and their characteristic lowering in the voltage profile using chemical‐bonding and Mulliken‐charge analysis. The formation of such ternary intermediates for the lithiation of FeNCN and the contribution of at least one ternary intermediate is also confirmed experimentally. This theoretical approach, aided by experimental findings, supports the atomistic exploration of electrode materials governed by conversion reactions.