Oxygen Vacancy in Magnéli Phases and Its Effect on Thermoelectric Performances

Magnéli phases exhibit significant potential for applications in electronic materials in energy conversion due to their high electrical conductivity and excellent thermal stability. In this study, single-phase Ti<sub>n</sub>O<sub>2n−1</sub> (<i>n</i> = 4, 5, 6) bu...

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Main Authors: Zhou Guan, Chuangshi Feng, Hongquan Song, Lingxu Yang, Xin Wang, Huijun Liu, Jiawei Zhang, Fanqian Wei, Xin Yuan, Hengyong Yang, Yu Tang, Fuxiang Zhang
Format: Article
Language:English
Published: MDPI AG 2025-04-01
Series:Nanomaterials
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Online Access:https://www.mdpi.com/2079-4991/15/9/684
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author Zhou Guan
Chuangshi Feng
Hongquan Song
Lingxu Yang
Xin Wang
Huijun Liu
Jiawei Zhang
Fanqian Wei
Xin Yuan
Hengyong Yang
Yu Tang
Fuxiang Zhang
author_facet Zhou Guan
Chuangshi Feng
Hongquan Song
Lingxu Yang
Xin Wang
Huijun Liu
Jiawei Zhang
Fanqian Wei
Xin Yuan
Hengyong Yang
Yu Tang
Fuxiang Zhang
author_sort Zhou Guan
collection DOAJ
description Magnéli phases exhibit significant potential for applications in electronic materials in energy conversion due to their high electrical conductivity and excellent thermal stability. In this study, single-phase Ti<sub>n</sub>O<sub>2n−1</sub> (<i>n</i> = 4, 5, 6) bulk materials were successfully prepared by a combination of the carbothermal reduction of nano-sized rutile TiO<sub>2</sub> and hot-press sintering methods. The relationships between the phase evolution, microstructural features, and thermoelectric performance were investigated systematically. Synchrotron X-ray diffraction (SXRD) and scanning electron microscopy (SEM) analyses revealed that the Ti<sub>4</sub>O<sub>7</sub> and Ti<sub>5</sub>O<sub>9</sub> materials had single-phase structures with high densities (relative density > 97%) and no obvious grain boundary holes or microcracks. We tested the thermoelectric properties of the Magnéli phases in the temperature range of 300–1100 K. The Magnéli phases exhibited a significant temperature dependence, with peak zT values of 0.17, 0.18, and 0.14 for Ti<sub>4</sub>O<sub>7</sub>, Ti<sub>5</sub>O<sub>9</sub>, and Ti<sub>6</sub>O<sub>11</sub>, respectively, at 1100 K. This variation in thermoelectric performance was mainly attributed to the synergistic effect of the oxygen vacancy concentration and the shear surface density on the carrier concentration and lattice thermal conductivity. Furthermore, the Fermi energy levels and electronic thermal conductivity of the Magnéli phases were calculated using the single parabolic band (SPB) model.
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spelling doaj-art-329452c615014b45a74565b2b6050b012025-08-20T02:59:15ZengMDPI AGNanomaterials2079-49912025-04-0115968410.3390/nano15090684Oxygen Vacancy in Magnéli Phases and Its Effect on Thermoelectric PerformancesZhou Guan0Chuangshi Feng1Hongquan Song2Lingxu Yang3Xin Wang4Huijun Liu5Jiawei Zhang6Fanqian Wei7Xin Yuan8Hengyong Yang9Yu Tang10Fuxiang Zhang11Songshan Lake Materials Laboratory, Dongguan 523808, ChinaSongshan Lake Materials Laboratory, Dongguan 523808, ChinaCollege of Physics and Telecommunication Engineering, Zhoukou Normal University, Zhoukou 466001, ChinaSchool of Ocean Engineering, Guangzhou Maritime University, Guangzhou 510330, ChinaSongshan Lake Materials Laboratory, Dongguan 523808, ChinaSongshan Lake Materials Laboratory, Dongguan 523808, ChinaSongshan Lake Materials Laboratory, Dongguan 523808, ChinaSongshan Lake Materials Laboratory, Dongguan 523808, ChinaSongshan Lake Materials Laboratory, Dongguan 523808, ChinaSongshan Lake Materials Laboratory, Dongguan 523808, ChinaSongshan Lake Materials Laboratory, Dongguan 523808, ChinaSongshan Lake Materials Laboratory, Dongguan 523808, ChinaMagnéli phases exhibit significant potential for applications in electronic materials in energy conversion due to their high electrical conductivity and excellent thermal stability. In this study, single-phase Ti<sub>n</sub>O<sub>2n−1</sub> (<i>n</i> = 4, 5, 6) bulk materials were successfully prepared by a combination of the carbothermal reduction of nano-sized rutile TiO<sub>2</sub> and hot-press sintering methods. The relationships between the phase evolution, microstructural features, and thermoelectric performance were investigated systematically. Synchrotron X-ray diffraction (SXRD) and scanning electron microscopy (SEM) analyses revealed that the Ti<sub>4</sub>O<sub>7</sub> and Ti<sub>5</sub>O<sub>9</sub> materials had single-phase structures with high densities (relative density > 97%) and no obvious grain boundary holes or microcracks. We tested the thermoelectric properties of the Magnéli phases in the temperature range of 300–1100 K. The Magnéli phases exhibited a significant temperature dependence, with peak zT values of 0.17, 0.18, and 0.14 for Ti<sub>4</sub>O<sub>7</sub>, Ti<sub>5</sub>O<sub>9</sub>, and Ti<sub>6</sub>O<sub>11</sub>, respectively, at 1100 K. This variation in thermoelectric performance was mainly attributed to the synergistic effect of the oxygen vacancy concentration and the shear surface density on the carrier concentration and lattice thermal conductivity. Furthermore, the Fermi energy levels and electronic thermal conductivity of the Magnéli phases were calculated using the single parabolic band (SPB) model.https://www.mdpi.com/2079-4991/15/9/684Magnéli phaseoxygen vacancythermoelectric performancesingle parabolic band
spellingShingle Zhou Guan
Chuangshi Feng
Hongquan Song
Lingxu Yang
Xin Wang
Huijun Liu
Jiawei Zhang
Fanqian Wei
Xin Yuan
Hengyong Yang
Yu Tang
Fuxiang Zhang
Oxygen Vacancy in Magnéli Phases and Its Effect on Thermoelectric Performances
Nanomaterials
Magnéli phase
oxygen vacancy
thermoelectric performance
single parabolic band
title Oxygen Vacancy in Magnéli Phases and Its Effect on Thermoelectric Performances
title_full Oxygen Vacancy in Magnéli Phases and Its Effect on Thermoelectric Performances
title_fullStr Oxygen Vacancy in Magnéli Phases and Its Effect on Thermoelectric Performances
title_full_unstemmed Oxygen Vacancy in Magnéli Phases and Its Effect on Thermoelectric Performances
title_short Oxygen Vacancy in Magnéli Phases and Its Effect on Thermoelectric Performances
title_sort oxygen vacancy in magneli phases and its effect on thermoelectric performances
topic Magnéli phase
oxygen vacancy
thermoelectric performance
single parabolic band
url https://www.mdpi.com/2079-4991/15/9/684
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