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| Main Authors: | , , , , , , , , , , , , , , |
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| Format: | Preprint |
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2025
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| Subjects: | |
| Online Access: | https://arxiv.org/abs/2512.05841 |
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| _version_ | 1866912801371455488 |
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| author | Miura, Akira Baek, Woohyeon Fujii, Yuta Tadanaga, Kiyoharu Hossain, Rana Yamashita, Aichi Mizuguchi, Yoshikazu Moriyoshi, Chikako Kobayashi, Shintaro Kawaguchi, Shogo Ding, Jiong Mori, Shigeo Sakuda, Atsushi Hayashi, Akitoshi Sun, Wenhao |
| author_facet | Miura, Akira Baek, Woohyeon Fujii, Yuta Tadanaga, Kiyoharu Hossain, Rana Yamashita, Aichi Mizuguchi, Yoshikazu Moriyoshi, Chikako Kobayashi, Shintaro Kawaguchi, Shogo Ding, Jiong Mori, Shigeo Sakuda, Atsushi Hayashi, Akitoshi Sun, Wenhao |
| contents | $α$-Li$_3$PS$_4$ is a promising solid-state electrolyte with the highest ionic conductivity among its polymorphs. However, its formation presents a thermodynamic paradox: the $α$-phase is the equilibrium phase at high temperature and transforms to the stable $γ$-Li$_3$PS$_4$ polymorph when cooled to room temperature; however, $α$-Li$_3$PS$_4$ can be synthesized and quenched in a metastable state via rapid heating at relatively low temperatures. The origin of this synthesizability and anomalous stability has remained elusive. Here, we resolve this paradox by establishing a comprehensive time-temperature-transformation (TTT) diagram, constructed from a computational temperature-size phase diagram and experimental high-time-resolution isothermal measurements. Our density functional theory calculations reveal that at the nanoscale, the $α$-phase is stabilized by its low surface energy, which drastically lowers the nucleation barrier across a wide temperature range. This size-dependent stabilization is directly visualized using in-situ synchrotron X-ray diffraction and electron microscopy, capturing the rapid nucleation of nano-sized $α$-phase and its subsequent slow transformation. This work presents a generalizable framework that integrates thermodynamic and kinetic factors for understanding nucleation and phase transformation mechanisms, providing a rational strategy for the targeted synthesis of functional metastable materials. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2512_05841 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Time-Temperature-Transformation (TTT) Diagrams to rationalize the nucleation and quenchability of metastable $α$-Li$_3$PS$_4$ Miura, Akira Baek, Woohyeon Fujii, Yuta Tadanaga, Kiyoharu Hossain, Rana Yamashita, Aichi Mizuguchi, Yoshikazu Moriyoshi, Chikako Kobayashi, Shintaro Kawaguchi, Shogo Ding, Jiong Mori, Shigeo Sakuda, Atsushi Hayashi, Akitoshi Sun, Wenhao Materials Science $α$-Li$_3$PS$_4$ is a promising solid-state electrolyte with the highest ionic conductivity among its polymorphs. However, its formation presents a thermodynamic paradox: the $α$-phase is the equilibrium phase at high temperature and transforms to the stable $γ$-Li$_3$PS$_4$ polymorph when cooled to room temperature; however, $α$-Li$_3$PS$_4$ can be synthesized and quenched in a metastable state via rapid heating at relatively low temperatures. The origin of this synthesizability and anomalous stability has remained elusive. Here, we resolve this paradox by establishing a comprehensive time-temperature-transformation (TTT) diagram, constructed from a computational temperature-size phase diagram and experimental high-time-resolution isothermal measurements. Our density functional theory calculations reveal that at the nanoscale, the $α$-phase is stabilized by its low surface energy, which drastically lowers the nucleation barrier across a wide temperature range. This size-dependent stabilization is directly visualized using in-situ synchrotron X-ray diffraction and electron microscopy, capturing the rapid nucleation of nano-sized $α$-phase and its subsequent slow transformation. This work presents a generalizable framework that integrates thermodynamic and kinetic factors for understanding nucleation and phase transformation mechanisms, providing a rational strategy for the targeted synthesis of functional metastable materials. |
| title | Time-Temperature-Transformation (TTT) Diagrams to rationalize the nucleation and quenchability of metastable $α$-Li$_3$PS$_4$ |
| topic | Materials Science |
| url | https://arxiv.org/abs/2512.05841 |