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Polymorphism and Fast Potassium‐Ion Conduction in the T5 Supertetrahedral Phosphidosilicate KSi(2)P(3)

The all‐solid‐state battery (ASSB) is a promising candidate for electrochemical energy storage. In view of the limited availability of lithium, however, alternative systems based on earth‐abundant and inexpensive elements are urgently sought. Besides well‐studied sodium compounds, potassium‐based sy...

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Autores principales: Haffner, Arthur, Hatz, Anna‐Katharina, Zeman, Otto E. O., Hoch, Constantin, Lotsch, Bettina V., Johrendt, Dirk
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8252096/
https://www.ncbi.nlm.nih.gov/pubmed/33734533
http://dx.doi.org/10.1002/anie.202101187
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author Haffner, Arthur
Hatz, Anna‐Katharina
Zeman, Otto E. O.
Hoch, Constantin
Lotsch, Bettina V.
Johrendt, Dirk
author_facet Haffner, Arthur
Hatz, Anna‐Katharina
Zeman, Otto E. O.
Hoch, Constantin
Lotsch, Bettina V.
Johrendt, Dirk
author_sort Haffner, Arthur
collection PubMed
description The all‐solid‐state battery (ASSB) is a promising candidate for electrochemical energy storage. In view of the limited availability of lithium, however, alternative systems based on earth‐abundant and inexpensive elements are urgently sought. Besides well‐studied sodium compounds, potassium‐based systems offer the advantage of low cost and a large electrochemical window, but are hardly explored. Here we report the synthesis and crystal structure of K‐ion conducting T5 KSi(2)P(3) inspired by recent discoveries of fast ion conductors in alkaline phosphidosilicates. KSi(2)P(3) is composed of SiP(4) tetrahedra forming interpenetrating networks of large T5 supertetrahedra. The compound passes through a reconstructive phase transition from the known T3 to the new tetragonal T5 polymorph at 1020 °C with enantiotropic displacive phase transitions upon cooling at about 155 °C and 80 °C. The potassium ions are located in large channels between the T5 supertetrahedral networks and show facile movement through the structure. The bulk ionic conductivity is up to 2.6×10(−4) S cm(−1) at 25 °C with an average activation energy of 0.20 eV. This is remarkably high for a potassium ion conductor at room temperature, and marks KSi(2)P(3) as the first non‐oxide solid potassium ion conductor.
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spelling pubmed-82520962021-07-07 Polymorphism and Fast Potassium‐Ion Conduction in the T5 Supertetrahedral Phosphidosilicate KSi(2)P(3) Haffner, Arthur Hatz, Anna‐Katharina Zeman, Otto E. O. Hoch, Constantin Lotsch, Bettina V. Johrendt, Dirk Angew Chem Int Ed Engl Communications The all‐solid‐state battery (ASSB) is a promising candidate for electrochemical energy storage. In view of the limited availability of lithium, however, alternative systems based on earth‐abundant and inexpensive elements are urgently sought. Besides well‐studied sodium compounds, potassium‐based systems offer the advantage of low cost and a large electrochemical window, but are hardly explored. Here we report the synthesis and crystal structure of K‐ion conducting T5 KSi(2)P(3) inspired by recent discoveries of fast ion conductors in alkaline phosphidosilicates. KSi(2)P(3) is composed of SiP(4) tetrahedra forming interpenetrating networks of large T5 supertetrahedra. The compound passes through a reconstructive phase transition from the known T3 to the new tetragonal T5 polymorph at 1020 °C with enantiotropic displacive phase transitions upon cooling at about 155 °C and 80 °C. The potassium ions are located in large channels between the T5 supertetrahedral networks and show facile movement through the structure. The bulk ionic conductivity is up to 2.6×10(−4) S cm(−1) at 25 °C with an average activation energy of 0.20 eV. This is remarkably high for a potassium ion conductor at room temperature, and marks KSi(2)P(3) as the first non‐oxide solid potassium ion conductor. John Wiley and Sons Inc. 2021-05-07 2021-06-07 /pmc/articles/PMC8252096/ /pubmed/33734533 http://dx.doi.org/10.1002/anie.202101187 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Communications
Haffner, Arthur
Hatz, Anna‐Katharina
Zeman, Otto E. O.
Hoch, Constantin
Lotsch, Bettina V.
Johrendt, Dirk
Polymorphism and Fast Potassium‐Ion Conduction in the T5 Supertetrahedral Phosphidosilicate KSi(2)P(3)
title Polymorphism and Fast Potassium‐Ion Conduction in the T5 Supertetrahedral Phosphidosilicate KSi(2)P(3)
title_full Polymorphism and Fast Potassium‐Ion Conduction in the T5 Supertetrahedral Phosphidosilicate KSi(2)P(3)
title_fullStr Polymorphism and Fast Potassium‐Ion Conduction in the T5 Supertetrahedral Phosphidosilicate KSi(2)P(3)
title_full_unstemmed Polymorphism and Fast Potassium‐Ion Conduction in the T5 Supertetrahedral Phosphidosilicate KSi(2)P(3)
title_short Polymorphism and Fast Potassium‐Ion Conduction in the T5 Supertetrahedral Phosphidosilicate KSi(2)P(3)
title_sort polymorphism and fast potassium‐ion conduction in the t5 supertetrahedral phosphidosilicate ksi(2)p(3)
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8252096/
https://www.ncbi.nlm.nih.gov/pubmed/33734533
http://dx.doi.org/10.1002/anie.202101187
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