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Journal of Advanced Ceramics 2023, 12(9): 1742-1757 https://doi.org/10.26599/JAC.2023.9220783
Research Article | Open Access | Issue | Published: 05 September 2023

Enhanced conductivity and stability of Co0.98CuxMn2.02−xO4 ceramics with dual phases and twin structures

Show Author's Information Chengjian Maa( ),  Longhua Heb,  Lei Bic,  Hong Gaod,  Jianxiang Dinge
Analytical and Testing Center, Yancheng Institute of Technology, Yancheng 224051, China
School of Materials Science and Engineering, Yancheng Institute of Technology, Yancheng 224051, China
School of Resource Environment and Safety Engineering, University of South China, Hengyang 421001, China
School of Mathematics and Physics, Yancheng Institute of Technology, Yancheng 224051, China
School of Materials Science and Engineering, Anhui University of Technology, Ma’anshan 243002, China
Keywords:
negative temperature coefficient (NTC) ceramics, first-principles calculation, Cu-containing spinel, high electrical stability, twin structure, electron-exchange interaction
Cite this article:
Ma C, He L, Bi L, et al. Enhanced conductivity and stability of Co0.98CuxMn2.02−xO4 ceramics with dual phases and twin structures. Journal of Advanced Ceramics, 2023, 12(9): 1742-1757. https://doi.org/10.26599/JAC.2023.9220783
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Abstract Full text About this article

Semiconductor materials with heterogeneous interfaces and twin structures generally demonstrate a higher concentration of carriers and better electrical stability. A variety of Cu-doped Co0.98CuxMn2.02−xO4 (0 ≤ x ≤ 0.5) negative temperature coefficient (NTC) ceramics with dual phases and twin structures were successfully prepared in this study. Rietveld refinement indicates that the content of a cubic spinel phase increases with increasing Cu content. The addition of Cu can promote grain growth and densification. Atomic-level structural characterization reveals the evolution of twin morphology from large lamellae with internal fine lamellae (LIT lamellae) to large lamellae without internal fine lamellae (L lamellae) and the distribution of twin boundary defects. First-principles calculations reveal that the dual phases and twin structures have lower oxygen-vacancy formation energy than those in the case of the pure tetragonal and cubic spinel, thereby enhancing the transmission of carriers. Additionally, the three-dimensional charge-density difference shows that metal ions at the interface lose electrons and dwell in high valence states, thereby enhancing electrical stability of the NTC ceramics. Furthermore, the additional Cu ions engage in electron-exchange interactions with Mn and Co ions, thereby reducing resistivity. In comparison to previous Cu-containing systems, the Co0.98CuxMn2.02−xO4 series exhibit superior stability (aging value ≤ 2.84%), tunable room-temperature resistivity (ρ), and material constant (B) value (17.5 Ω·cm ≤ ρ ≤ 7325 Ω·cm, 2836 K ≤ B ≤ 4315 K). These discoveries lay a foundation for designing and developing new NTC ceramics with ultra-high performance.


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About this article

Enhanced conductivity and stability of Co0.98CuxMn2.02−xO4 ceramics with dual phases and twin structures

Show Author's information Chengjian Maa( ), Longhua Heb, Lei Bic, Hong Gaod, Jianxiang Dinge
Analytical and Testing Center, Yancheng Institute of Technology, Yancheng 224051, China
School of Materials Science and Engineering, Yancheng Institute of Technology, Yancheng 224051, China
School of Resource Environment and Safety Engineering, University of South China, Hengyang 421001, China
School of Mathematics and Physics, Yancheng Institute of Technology, Yancheng 224051, China
School of Materials Science and Engineering, Anhui University of Technology, Ma’anshan 243002, China

Abstract

Semiconductor materials with heterogeneous interfaces and twin structures generally demonstrate a higher concentration of carriers and better electrical stability. A variety of Cu-doped Co0.98CuxMn2.02−xO4 (0 ≤ x ≤ 0.5) negative temperature coefficient (NTC) ceramics with dual phases and twin structures were successfully prepared in this study. Rietveld refinement indicates that the content of a cubic spinel phase increases with increasing Cu content. The addition of Cu can promote grain growth and densification. Atomic-level structural characterization reveals the evolution of twin morphology from large lamellae with internal fine lamellae (LIT lamellae) to large lamellae without internal fine lamellae (L lamellae) and the distribution of twin boundary defects. First-principles calculations reveal that the dual phases and twin structures have lower oxygen-vacancy formation energy than those in the case of the pure tetragonal and cubic spinel, thereby enhancing the transmission of carriers. Additionally, the three-dimensional charge-density difference shows that metal ions at the interface lose electrons and dwell in high valence states, thereby enhancing electrical stability of the NTC ceramics. Furthermore, the additional Cu ions engage in electron-exchange interactions with Mn and Co ions, thereby reducing resistivity. In comparison to previous Cu-containing systems, the Co0.98CuxMn2.02−xO4 series exhibit superior stability (aging value ≤ 2.84%), tunable room-temperature resistivity (ρ), and material constant (B) value (17.5 Ω·cm ≤ ρ ≤ 7325 Ω·cm, 2836 K ≤ B ≤ 4315 K). These discoveries lay a foundation for designing and developing new NTC ceramics with ultra-high performance.

Keywords: negative temperature coefficient (NTC) ceramics, first-principles calculation, Cu-containing spinel, high electrical stability, twin structure, electron-exchange interaction

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Publication history

Received: 09 April 2023
Revised: 07 June 2023
Accepted: 26 June 2023
Published: 05 September 2023
Issue date: September 2023

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© The Author(s) 2023.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 52002347), and Natural Science Foundation of the Jiangsu Higher Education Institutions of China (Grant No. 19KJB430039). The authors would like to thank Shiyanjia Lab (www.shiyanjia. com) for the language editing service.

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