Double Paddle‐Wheel Enhanced Sodium Ion Conduction in an Antiperovskite Solid Electrolyte

Tsai, Ping‐Chun; Mair, Sunil; Smith, Jeffrey; Halat, David M.; Chien, Po‐Hsiu; Kim, Kwangnam; Zhang, Duhan; Li, Yiliang; Yin, Liang; Liu, Jue; Lapidus, Saul H.; Reimer, Jeffrey A.; Balsara, Nitash P.; Siegel, Donald J.; Chiang, Yet‐Ming

doi:10.1002/aenm.202203284

Title: Double Paddle‐Wheel Enhanced Sodium Ion Conduction in an Antiperovskite Solid Electrolyte

Journal Article · 27 December 2022 · Advanced Energy Materials

DOI: https://doi.org/10.1002/aenm.202203284 · OSTI ID:1907132

Tsai, Ping‐Chun ^[1];

^[2]; Smith, Jeffrey ^[3]; Halat, David M. ^[4]; Chien, Po‐Hsiu ^[5]; Kim, Kwangnam ^[3]; Zhang, Duhan ^[2]; Li, Yiliang ^[2]; Yin, Liang ^[6]; Liu, Jue ^[5]; Lapidus, Saul H. ^[6]; Reimer, Jeffrey A. ^[4]; Balsara, Nitash P. ^[4]; Siegel, Donald J. ^[7];

^[2]

National Taiwan University of Science and Technology Taipei City 10607 Taiwan, Massachusetts Institute of Technology Cambridge MA 02139 USA
Massachusetts Institute of Technology Cambridge MA 02139 USA
University of Michigan Ann Arbor MI 48103 USA
University of California Berkeley CA 94720 USA
Oak Ridge National Laboratory Oak Ridge TN 37830 USA
Argonne National Laboratory Lemont IL 60439 USA
University of Texas at Austin Austin TX 78712 USA

Abstract Antiperovskite structure compounds (X ₃ AB, where X is an alkali cation and A and B are anions) have the potential for highly correlated motion between the cation and a cluster anion on the A or B site. This so‐called “paddle‐wheel” mechanism may be the basis for enhanced cation mobility in solid electrolytes. Through combined experiments and modeling, the first instance of a double paddle‐wheel mechanism, leading to fast sodium ion conduction in the antiperovskite Na ₃₋ _x O ₁₋ _x (NH ₂ ) _x (BH ₄ ), is shown. As the concentration of amide (NH ₂ ⁻ ) cluster anions is increased, large positive deviations in ionic conductivity above that predicted from a vacancy diffusion model are observed. Using electrochemical impedance spectroscopy, powder X‐ray diffraction, synchrotron X‐ray diffraction, neutron diffraction, ab initio molecular dynamics simulations, and NMR, the cluster anion rotational dynamics are characterized and it is found that cation mobility is influenced by the rotation of both NH ₂ ⁻ and BH ₄ ⁻ species, resulting in sodium ion conductivity a factor of 10 ² higher at x = 1 than expected for the vacancy mechanism alone. Generalization of this phenomenon to other compounds could accelerate fast ion conductor exploration and design.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Ministry of Science and Technology of Taiwan (MOST); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1907132

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 7 Vol. 13; ISSN 1614-6832

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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