Designing Highly Conductive Sodium-Based Metal Hydride Nanocomposites: Interplay between Hydride and Oxide Properties

Laura M. de Kort; Oscar E. Brandt Corstius; Valerio Gulino; Andrei Gurinov; Marc Baldus; Peter Ngene

doi:10.1002/adfm.202209122

Designing Highly Conductive Sodium-Based Metal Hydride Nanocomposites: Interplay between Hydride and Oxide Properties

Laura M. de Kort, Oscar E. Brandt Corstius, Valerio Gulino, Andrei Gurinov, Marc Baldus, Peter Ngene^*

^*Corresponding author for this work

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

Abstract

Sodium-based complex hydrides have recently gained interest as electrolytes for all-solid-state batteries due to their light weight and high electrochemical stability. Although their room temperature conductivities are not sufficiently high for battery application, nanocomposite formation with metal oxides has emerged as a promising approach to enhance the ionic conductivity of complex hydrides. This enhancement is generally attributed to the formation of a space charge layer at the hydride-oxide interface. However, in this study it is found that the conductivity enhancement results from interface reactions between the metal hydride and the oxide. Highly conductive NaBH₄ and NaNH₂/oxide nanocomposites are obtained by optimizing the interface reaction, which strongly depends on the interplay between the surface chemistry of the oxides and the reactivity of the metal hydrides. Notably, for NaBH₄, the best performance is obtained with Al₂O₃, while NaNH₂/SiO₂ is the most conductive NaNH₂/oxide nanocomposite with conductivities of, respectively, 4.7 × 10⁻⁵ and 2.1 × 10⁻⁵ S cm⁻¹ at 80 °C. Detailed structural characterization reveals that this disparity originates from the formation of different tertiary interfacial compounds, and is not only a space charge effect. These results provide useful insights for the preparation of highly conductive nanocomposite electrolytes by optimizing interface interactions.

Original language	English
Article number	2209122
Number of pages	15
Journal	Advanced Functional Materials
Volume	33
Issue number	13
DOIs	https://doi.org/10.1002/adfm.202209122
Publication status	Published - 23 Mar 2023

Bibliographical note

Funding Information:
The authors greatly appreciate funding from the NWO materials for sustainability (739.017.009) grant, as well as the NWO ECHO (712.015.005) grant. A.G. and the NMR experiments conducted at 950 MHz were supported by uNMR‐NL, the National Roadmap Large‐Scale NMR Facility of the Netherlands (NWO grant 184.032.207). Furthermore, the authors thank Sander Lambregts, Silvia Zanoni, and Suzan Schoemaker for physisorption measurements, Matt Peerlings and Maaike van Ittersum for Py‐IR measurements, Mies van Steenbergen for low temperature DSC measurements, and Johan van der Zwan for additional NMR measurements. Jan Willem de Rijk and Dennie Wezendonk are thanked for their technical support, and Petra de Jongh for fruitful discussions about the results.

Publisher Copyright:
© 2023 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.

Funding

The authors greatly appreciate funding from the NWO materials for sustainability (739.017.009) grant, as well as the NWO ECHO (712.015.005) grant. A.G. and the NMR experiments conducted at 950 MHz were supported by uNMR-NL, the National Roadmap Large-Scale NMR Facility of the Netherlands (NWO grant 184.032.207). Furthermore, the authors thank Sander Lambregts, Silvia Zanoni, and Suzan Schoemaker for physisorption measurements, Matt Peerlings and Maaike van Ittersum for Py-IR measurements, Mies van Steenbergen for low temperature DSC measurements, and Johan van der Zwan for additional NMR measurements. Jan Willem de Rijk and Dennie Wezendonk are thanked for their technical support, and Petra de Jongh for fruitful discussions about the results. The authors greatly appreciate funding from the NWO materials for sustainability (739.017.009) grant, as well as the NWO ECHO (712.015.005) grant. A.G. and the NMR experiments conducted at 950 MHz were supported by uNMR‐NL, the National Roadmap Large‐Scale NMR Facility of the Netherlands (NWO grant 184.032.207). Furthermore, the authors thank Sander Lambregts, Silvia Zanoni, and Suzan Schoemaker for physisorption measurements, Matt Peerlings and Maaike van Ittersum for Py‐IR measurements, Mies van Steenbergen for low temperature DSC measurements, and Johan van der Zwan for additional NMR measurements. Jan Willem de Rijk and Dennie Wezendonk are thanked for their technical support, and Petra de Jongh for fruitful discussions about the results.

Funders	Funder number
Petra de Jongh
Nederlandse Organisatie voor Wetenschappelijk Onderzoek	184.032.207, 712.015.005, 739.017.009

Keywords

complex hydride electrolytes
interfacial ion conduction
nanocomposite solid electrolytes
nanoconfined electrolytes
sodium-ion conductors

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Adv Funct Materials - 2023 - Kort - Designing Highly Conductive Sodium‐Based Metal Hydride Nanocomposites InterplayFinal published version, 3.81 MBLicence: CC BY

Cite this

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title = "Designing Highly Conductive Sodium-Based Metal Hydride Nanocomposites: Interplay between Hydride and Oxide Properties",

abstract = "Sodium-based complex hydrides have recently gained interest as electrolytes for all-solid-state batteries due to their light weight and high electrochemical stability. Although their room temperature conductivities are not sufficiently high for battery application, nanocomposite formation with metal oxides has emerged as a promising approach to enhance the ionic conductivity of complex hydrides. This enhancement is generally attributed to the formation of a space charge layer at the hydride-oxide interface. However, in this study it is found that the conductivity enhancement results from interface reactions between the metal hydride and the oxide. Highly conductive NaBH4 and NaNH2/oxide nanocomposites are obtained by optimizing the interface reaction, which strongly depends on the interplay between the surface chemistry of the oxides and the reactivity of the metal hydrides. Notably, for NaBH4, the best performance is obtained with Al2O3, while NaNH2/SiO2 is the most conductive NaNH2/oxide nanocomposite with conductivities of, respectively, 4.7 × 10−5 and 2.1 × 10−5 S cm−1 at 80 °C. Detailed structural characterization reveals that this disparity originates from the formation of different tertiary interfacial compounds, and is not only a space charge effect. These results provide useful insights for the preparation of highly conductive nanocomposite electrolytes by optimizing interface interactions.",

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author = "{de Kort}, {Laura M.} and {Brandt Corstius}, {Oscar E.} and Valerio Gulino and Andrei Gurinov and Marc Baldus and Peter Ngene",

note = "Funding Information: The authors greatly appreciate funding from the NWO materials for sustainability (739.017.009) grant, as well as the NWO ECHO (712.015.005) grant. A.G. and the NMR experiments conducted at 950 MHz were supported by uNMR‐NL, the National Roadmap Large‐Scale NMR Facility of the Netherlands (NWO grant 184.032.207). Furthermore, the authors thank Sander Lambregts, Silvia Zanoni, and Suzan Schoemaker for physisorption measurements, Matt Peerlings and Maaike van Ittersum for Py‐IR measurements, Mies van Steenbergen for low temperature DSC measurements, and Johan van der Zwan for additional NMR measurements. Jan Willem de Rijk and Dennie Wezendonk are thanked for their technical support, and Petra de Jongh for fruitful discussions about the results. Publisher Copyright: {\textcopyright} 2023 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.",

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AU - Gulino, Valerio

AU - Gurinov, Andrei

AU - Baldus, Marc

AU - Ngene, Peter

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Designing Highly Conductive Sodium-Based Metal Hydride Nanocomposites: Interplay between Hydride and Oxide Properties

Abstract

Bibliographical note

Funding

Keywords

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