Hybrid Hexagonal Perovskite Ba3Ti0.7Mo1.3O8.3: Integrating High Cationic Disordering with Enhanced Tetrahedral Proportion to Achieve High Oxide Ionic Conductivity

Zien Cheng; Liyang Zhang; Yuling An; Ivan da Silva; Joerg C. Neuefeind; Zhengyang Zhou; Congling Yin; Rihong Cong; Tao Yang; Pengfei Jiang

doi:10.1021/acs.chemmater.5c00101

Hybrid Hexagonal Perovskite Ba₃Ti_0.7Mo_1.3O_8.3: Integrating High Cationic Disordering with Enhanced Tetrahedral Proportion to Achieve High Oxide Ionic Conductivity

Zien Cheng
, Liyang Zhang
, Yuling An
, Ivan da Silva
, Joerg C. Neuefeind
, Zhengyang Zhou
, Congling Yin
, Rihong Cong
, Tao Yang
, Pengfei Jiang

Research output: Contribution to journal › Article › peer-review

Abstract

The advancement of crystalline solid-state oxide-ion conductors is essential for the development of clean energy applications, particularly in the context of solid-oxide fuel cells. Although numerous oxide-ion conducting materials exist, there is a pressing need for electrolyte materials that exhibit high oxide ionic conductivity at intermediate temperatures (300-600 °C). Herein, we report a fast oxide ionic conductor Ba₃Ti_0.7Mo_1.3O_8.3, which possesses a hybrid perovskite identified by three-dimensional electron diffraction, neutron powder diffraction, neutron pair distribution functions, and in situ synchrotron X-ray diffraction. Ba₃Ti_0.7Mo_1.3O_8.3 exhibits the highest degree of M-site disordering among the Ba₃M′M″O_{8.5 ± δ} hexagonal perovskite family while simultaneously maintaining a high proportion of the tetrahedral coordination geometry within the structure. The high level of M-site disordering and the high tetrahedral percentage in Ba₃Ti_0.7Mo_1.3O_8.3 facilitate oxide-ion diffusion along the c-axis and ab-plane, respectively, thereby resulting in a high bulk conductivity of 1.4 mS/cm at 500 °C, which is significantly higher than those of the Ba₃M′M″O_{8.5 ± δ} family members and other oxide ionic conductors. Our findings demonstrate that achieving a balance between M-site disordering and tetrahedral percentage is an effective strategy for improving the oxide ionic conductivity of Ba₃M′M″O_{8.5 ± δ}-type conductors.

Original language	English
Pages (from-to)	4629-4638
Number of pages	10
Journal	Chemistry of Materials
Volume	37
Issue number	13
DOIs	https://doi.org/10.1021/acs.chemmater.5c00101
State	Published - Jul 8 2025
Externally published	Yes

Funding

This work is financially supported by the National Natural Science Foundation of China (nos. 22271030, 22171031, and 22171032) and the Fundamental Research Funds for the Central Universities (project no. 2024CDJXY010). A portion of this research used resources at Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beamtime was allocated to NOMAD on Proposal Number IPTS-27837. J.C.N. is supported by contract no. DE-AC05-00OR22725 with the U.S. Department of Energy (DOE). We also acknowledge the support from the sharing fund of large-scale equipment of Chongqing University (202403150085).

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Cheng, Z., Zhang, L., An, Y., da Silva, I., Neuefeind, J. C., Zhou, Z., Yin, C., Cong, R., Yang, T., & Jiang, P. (2025). Hybrid Hexagonal Perovskite Ba₃Ti_0.7Mo_1.3O_8.3: Integrating High Cationic Disordering with Enhanced Tetrahedral Proportion to Achieve High Oxide Ionic Conductivity. Chemistry of Materials, 37(13), 4629-4638. https://doi.org/10.1021/acs.chemmater.5c00101

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title = "Hybrid Hexagonal Perovskite Ba3Ti0.7Mo1.3O8.3: Integrating High Cationic Disordering with Enhanced Tetrahedral Proportion to Achieve High Oxide Ionic Conductivity",

abstract = "The advancement of crystalline solid-state oxide-ion conductors is essential for the development of clean energy applications, particularly in the context of solid-oxide fuel cells. Although numerous oxide-ion conducting materials exist, there is a pressing need for electrolyte materials that exhibit high oxide ionic conductivity at intermediate temperatures (300-600 °C). Herein, we report a fast oxide ionic conductor Ba3Ti0.7Mo1.3O8.3, which possesses a hybrid perovskite identified by three-dimensional electron diffraction, neutron powder diffraction, neutron pair distribution functions, and in situ synchrotron X-ray diffraction. Ba3Ti0.7Mo1.3O8.3 exhibits the highest degree of M-site disordering among the Ba3M′M″O8.5 ± δ hexagonal perovskite family while simultaneously maintaining a high proportion of the tetrahedral coordination geometry within the structure. The high level of M-site disordering and the high tetrahedral percentage in Ba3Ti0.7Mo1.3O8.3 facilitate oxide-ion diffusion along the c-axis and ab-plane, respectively, thereby resulting in a high bulk conductivity of 1.4 mS/cm at 500 °C, which is significantly higher than those of the Ba3M′M″O8.5 ± δ family members and other oxide ionic conductors. Our findings demonstrate that achieving a balance between M-site disordering and tetrahedral percentage is an effective strategy for improving the oxide ionic conductivity of Ba3M′M″O8.5 ± δ-type conductors.",

author = "Zien Cheng and Liyang Zhang and Yuling An and \{da Silva\}, Ivan and Neuefeind, \{Joerg C.\} and Zhengyang Zhou and Congling Yin and Rihong Cong and Tao Yang and Pengfei Jiang",

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doi = "10.1021/acs.chemmater.5c00101",

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Cheng, Z, Zhang, L, An, Y, da Silva, I, Neuefeind, JC, Zhou, Z, Yin, C, Cong, R, Yang, T & Jiang, P 2025, 'Hybrid Hexagonal Perovskite Ba₃Ti_0.7Mo_1.3O_8.3: Integrating High Cationic Disordering with Enhanced Tetrahedral Proportion to Achieve High Oxide Ionic Conductivity', Chemistry of Materials, vol. 37, no. 13, pp. 4629-4638. https://doi.org/10.1021/acs.chemmater.5c00101

TY - JOUR

T1 - Hybrid Hexagonal Perovskite Ba3Ti0.7Mo1.3O8.3

T2 - Integrating High Cationic Disordering with Enhanced Tetrahedral Proportion to Achieve High Oxide Ionic Conductivity

AU - Cheng, Zien

AU - Zhang, Liyang

AU - An, Yuling

AU - da Silva, Ivan

AU - Neuefeind, Joerg C.

AU - Zhou, Zhengyang

AU - Yin, Congling

AU - Cong, Rihong

AU - Yang, Tao

AU - Jiang, Pengfei

PY - 2025/7/8

Y1 - 2025/7/8

N2 - The advancement of crystalline solid-state oxide-ion conductors is essential for the development of clean energy applications, particularly in the context of solid-oxide fuel cells. Although numerous oxide-ion conducting materials exist, there is a pressing need for electrolyte materials that exhibit high oxide ionic conductivity at intermediate temperatures (300-600 °C). Herein, we report a fast oxide ionic conductor Ba3Ti0.7Mo1.3O8.3, which possesses a hybrid perovskite identified by three-dimensional electron diffraction, neutron powder diffraction, neutron pair distribution functions, and in situ synchrotron X-ray diffraction. Ba3Ti0.7Mo1.3O8.3 exhibits the highest degree of M-site disordering among the Ba3M′M″O8.5 ± δ hexagonal perovskite family while simultaneously maintaining a high proportion of the tetrahedral coordination geometry within the structure. The high level of M-site disordering and the high tetrahedral percentage in Ba3Ti0.7Mo1.3O8.3 facilitate oxide-ion diffusion along the c-axis and ab-plane, respectively, thereby resulting in a high bulk conductivity of 1.4 mS/cm at 500 °C, which is significantly higher than those of the Ba3M′M″O8.5 ± δ family members and other oxide ionic conductors. Our findings demonstrate that achieving a balance between M-site disordering and tetrahedral percentage is an effective strategy for improving the oxide ionic conductivity of Ba3M′M″O8.5 ± δ-type conductors.

AB - The advancement of crystalline solid-state oxide-ion conductors is essential for the development of clean energy applications, particularly in the context of solid-oxide fuel cells. Although numerous oxide-ion conducting materials exist, there is a pressing need for electrolyte materials that exhibit high oxide ionic conductivity at intermediate temperatures (300-600 °C). Herein, we report a fast oxide ionic conductor Ba3Ti0.7Mo1.3O8.3, which possesses a hybrid perovskite identified by three-dimensional electron diffraction, neutron powder diffraction, neutron pair distribution functions, and in situ synchrotron X-ray diffraction. Ba3Ti0.7Mo1.3O8.3 exhibits the highest degree of M-site disordering among the Ba3M′M″O8.5 ± δ hexagonal perovskite family while simultaneously maintaining a high proportion of the tetrahedral coordination geometry within the structure. The high level of M-site disordering and the high tetrahedral percentage in Ba3Ti0.7Mo1.3O8.3 facilitate oxide-ion diffusion along the c-axis and ab-plane, respectively, thereby resulting in a high bulk conductivity of 1.4 mS/cm at 500 °C, which is significantly higher than those of the Ba3M′M″O8.5 ± δ family members and other oxide ionic conductors. Our findings demonstrate that achieving a balance between M-site disordering and tetrahedral percentage is an effective strategy for improving the oxide ionic conductivity of Ba3M′M″O8.5 ± δ-type conductors.

UR - https://www.scopus.com/pages/publications/105008984836

U2 - 10.1021/acs.chemmater.5c00101

DO - 10.1021/acs.chemmater.5c00101

M3 - Article

AN - SCOPUS:105008984836

SN - 0897-4756

VL - 37

SP - 4629

EP - 4638

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 13

ER -

Hybrid Hexagonal Perovskite Ba₃Ti_0.7Mo_1.3O_8.3: Integrating High Cationic Disordering with Enhanced Tetrahedral Proportion to Achieve High Oxide Ionic Conductivity

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