TY - JOUR
T1 - Tuning the Electronic, Ion Transport, and Stability Properties of Li-rich Manganese-based Oxide Materials with Oxide Perovskite Coatings
T2 - A First-Principles Computational Study
AU - Zhou, Zizhen
AU - Chu, Dewei
AU - Gao, Bo
AU - Momma, Toshiyuki
AU - Tateyama, Yoshitaka
AU - Cazorla, Claudio
N1 - Funding Information:
Z.Z. and Y.T. thank the financial support by MEXT as “Program for Promoting Research on the Supercomputer Fugaku” grant number JPMXP1020200301, JSPS KAKENHI grant number JP19H05815, and JST COI-NEXT grant number JPMJPF2016. The calculations were performed on the NIMS supercomputer and the supercomputer Fugaku at the RIKEN through the HPCI System Research Projects (project IDs: hp210173 and hp220177). C.C. acknowledges support from the Spanish Ministry of Science, Innovation, and Universities under the ″Ramon y Cajal″ fellowship RYC2018-024947-I. D.C. acknowledges financial support from the Australian Research Council (LP1900113).
Funding Information:
Z.Z. and Y.T. thank the financial support by MEXT as “Program for Promoting Research on the Supercomputer Fugaku” grant number JPMXP1020200301, JSPS KAKENHI grant number JP19H05815 and JST COI-NEXT grant number JPMJPF2016. The calculations were performed on the NIMS supercomputer and the supercomputer Fugaku at the RIKEN through the HPCI System Research Projects (project IDs: hp210173 and hp220177). C.C. acknowledges support from the Spanish Ministry of Science, Innovation, and Universities under the ″Ramon y Cajal″ fellowship RYC2018-024947-I. D.C. acknowledges financial support from the Australian Research Council (LP1900113).
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/8/17
Y1 - 2022/8/17
N2 - Lithium-rich manganese-based oxides (LRMO) are regarded as promising cathode materials for powering electric applications due to their high capacity (250 mAh g-1) and energy density (∼900 Wh kg-1). However, poor cycle stability and capacity fading have impeded the commercialization of this family of materials as battery components. Surface modification based on coating has proven successful in mitigating some of these problems, but a microscopic understanding of how such improvements are attained is still lacking, thus impeding systematic and rational design of LRMO-based cathodes. In this work, first-principles density functional theory (DFT) calculations are carried out to fill out such a knowledge gap and to propose a promising LRMO-coating material. It is found that SrTiO3 (STO), an archetypal and highly stable oxide perovskite, represents an excellent coating material for Li1.2Ni0.2Mn0.6O2 (LNMO), a prototypical member of the LRMO family. An accomplished atomistic model is constructed to theoretically estimate the structural, electronic, oxygen vacancy formation energy, and lithium-transport properties of the LNMO/STO interface system, thus providing insightful comparisons with the two integrating bulk materials. It is found that (i) electronic transport in the LNMO cathode is enhanced due to partial closure of the LNMO band gap (∼0.4 eV) and (ii) the lithium ions can easily diffuse near the LNMO/STO interface and within STO due to the small size of the involved ion-hopping energy barriers. Furthermore, the formation energy of oxygen vacancies notably increases close to the LNMO/STO interface, thus indicating a reduction in oxygen loss at the cathode surface and a potential inhibition of undesirable structural phase transitions. This theoretical work therefore opens up new routes for the practical improvement of cost-affordable lithium-rich cathode materials based on highly stable oxide perovskite coatings.
AB - Lithium-rich manganese-based oxides (LRMO) are regarded as promising cathode materials for powering electric applications due to their high capacity (250 mAh g-1) and energy density (∼900 Wh kg-1). However, poor cycle stability and capacity fading have impeded the commercialization of this family of materials as battery components. Surface modification based on coating has proven successful in mitigating some of these problems, but a microscopic understanding of how such improvements are attained is still lacking, thus impeding systematic and rational design of LRMO-based cathodes. In this work, first-principles density functional theory (DFT) calculations are carried out to fill out such a knowledge gap and to propose a promising LRMO-coating material. It is found that SrTiO3 (STO), an archetypal and highly stable oxide perovskite, represents an excellent coating material for Li1.2Ni0.2Mn0.6O2 (LNMO), a prototypical member of the LRMO family. An accomplished atomistic model is constructed to theoretically estimate the structural, electronic, oxygen vacancy formation energy, and lithium-transport properties of the LNMO/STO interface system, thus providing insightful comparisons with the two integrating bulk materials. It is found that (i) electronic transport in the LNMO cathode is enhanced due to partial closure of the LNMO band gap (∼0.4 eV) and (ii) the lithium ions can easily diffuse near the LNMO/STO interface and within STO due to the small size of the involved ion-hopping energy barriers. Furthermore, the formation energy of oxygen vacancies notably increases close to the LNMO/STO interface, thus indicating a reduction in oxygen loss at the cathode surface and a potential inhibition of undesirable structural phase transitions. This theoretical work therefore opens up new routes for the practical improvement of cost-affordable lithium-rich cathode materials based on highly stable oxide perovskite coatings.
KW - Li-rich manganese-based cathode
KW - density functional theory
KW - interface modeling
KW - ionic diffusion
KW - lithium battery
KW - oxide perovskite
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U2 - 10.1021/acsami.2c07560
DO - 10.1021/acsami.2c07560
M3 - Article
C2 - 35930401
AN - SCOPUS:85136073107
SN - 1944-8244
VL - 14
SP - 37009
EP - 37018
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 32
ER -