Mg-Ion Conduction in Antiperovskite Solid Electrolytes Revealed by 25 Mg Ultrahigh Field NMR and First-Principles Calculations

Halat, David M. [University of California, Berkeley, CA (United States); Colorado School of Mines, Golden, CO (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000209191689); Liu, Haoyu [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000267417295); Kim, Kwangnam [University of Michigan, Ann Arbor, MI (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States). Laboratory for Energy Applications for the Future (LEAF)] (ORCID:0000000311491733); Alexander, Grant C. B. [University of Illinois, Chicago, IL (United States)]; Wang, Xiaoling [Florida State University, Tallahassee, FL (United States). National High Magnetic Field Laboratory (MagLab); California State University, East Bay, Hayward, CA (United States)]; Venkatesh, Amrit [Florida State University, Tallahassee, FL (United States). National High Magnetic Field Laboratory (MagLab)] (ORCID:0000000153199269); Altenhof, Adam R. [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)]; Mason, Harris E. [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000218400550); Lapidus, Saul H. [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000274864325); Yoon, Jeong Seop [University of Texas, Austin, TX (United States)] (ORCID:000000029002094X); Hung, Ivan [Florida State University, Tallahassee, FL (United States). National High Magnetic Field Laboratory (MagLab)] (ORCID:000000018916739X); Gan, Zhehong [Florida State University, Tallahassee, FL (United States). National High Magnetic Field Laboratory (MagLab)] (ORCID:0000000298555113); Cabana, Jordi [University of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000223535986); Siegel, Donald J. [University of Texas, Austin, TX (United States)] (ORCID:0000000179132513); Reimer, Jeffrey A. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)]; Key, Baris [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000219871629)

doi:10.1021/jacs.5c07442

DOE OSTI · 2575221

Mg-Ion Conduction in Antiperovskite Solid Electrolytes Revealed by 25 Mg Ultrahigh Field NMR and First-Principles Calculations

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Abstract

Magnesium-ion batteries hold the potential to outperform the energy density of lithium-ion batteries, given the divalent charge carried by each Mg 2+ cation, but remain in an early stage of development. Here, in this study, 25 Mg solid-state nuclear magnetic resonance (ssNMR) is used to gain insight into the local structure and Mg-ion dynamics of candidate Mg-ion solid electrolytes, the antiperovskites Mg 3 SbN and Mg 3 AsN. Using the highest available magnetic field (35.2 T) for high-resolution solid-state NMR, the largest 25 Mg quadrupole coupling constants (C Q ) yet measured of up to 22 MHz are reported and corroborated by first-principles calculations. Predicted C Q values are shown to correlate with the antiperovskite’s tolerance factor; thus, 25 Mg NMR linewidths can report on lattice distortions and phase stability of these antiperovskites. Variable-temperature 25 Mg NMR spectra demonstrate changes at elevated temperatures, ascribed to Mg-ion motional effects. 25 Mg T 1 relaxometry measurements at ultrahigh field reveal a lower activation energy for the more distorted Mg 3 AsN phase, matching computational predictions of a lower energy barrier for Mg 2+ ion migration and suggesting that additional scrutiny of antiperovskites as Mg-ion conductors is warranted. Given the inherent challenges of 25 Mg NMR, this work demonstrates the benefits of combining ultrahigh field NMR spectroscopy, advanced pulse sequences, modern signal processing, and first-principles calculations to facilitate NMR of quadrupolar nuclei as a tool to probe the local structure and ion dynamics in beyond-Li battery materials.

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Halat, David M. [University of California, Berkeley, CA (United States); Colorado School of Mines, Golden, CO (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000209191689), Liu, Haoyu [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000267417295), Kim, Kwangnam [University of Michigan, Ann Arbor, MI (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States). Laboratory for Energy Applications for the Future (LEAF)] (ORCID:0000000311491733), Alexander, Grant C. B. [University of Illinois, Chicago, IL (United States)], Wang, Xiaoling [Florida State University, Tallahassee, FL (United States). National High Magnetic Field Laboratory (MagLab); California State University, East Bay, Hayward, CA (United States)], Venkatesh, Amrit [Florida State University, Tallahassee, FL (United States). National High Magnetic Field Laboratory (MagLab)] (ORCID:0000000153199269), Altenhof, Adam R. [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)], Mason, Harris E. [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000218400550), Lapidus, Saul H. [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000274864325), Yoon, Jeong Seop [University of Texas, Austin, TX (United States)] (ORCID:000000029002094X), Hung, Ivan [Florida State University, Tallahassee, FL (United States). National High Magnetic Field Laboratory (MagLab)] (ORCID:000000018916739X), Gan, Zhehong [Florida State University, Tallahassee, FL (United States). National High Magnetic Field Laboratory (MagLab)] (ORCID:0000000298555113), Cabana, Jordi [University of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000223535986), Siegel, Donald J. [University of Texas, Austin, TX (United States)] (ORCID:0000000179132513), Reimer, Jeffrey A. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)], Key, Baris [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000219871629). 2025-07-24. Mg-Ion Conduction in Antiperovskite Solid Electrolytes Revealed by 25 Mg Ultrahigh Field NMR and First-Principles Calculations. https://doi.org/10.1021/jacs.5c07442

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