Probing local structure and hydrogen incorporation in solution-processed thin-film solid electrolytes
10 affiliations
- 1Electrochemical Innovation Lab, Department of Chemical Engineering
- 2University College London
- 3Advanced Propulsion Lab
- 4Institute of Physical Chemistry, University of Munster, Corrensstrasse 28/30, Mu nster, Germany, 48149
- 5International Graduate School for Battery Chemistry, Characterization, Analysis, Recycling and Application (BACCARA, Universita t Mu nster, Mu nster, Germany, 48149
- 6Institute of Inorganic and Analytical Chemistry, University of Munster, Corrensstrasse 28, Mu nster, Germany, 48149
- 7Advanced Technology Institute
- 8University of Surrey
- 9Department of Energy Conversion and Storage
- 10Technical University of Denmark
Abstract
Solution processing of functional thin films offers significant benefits, yet characterising their local structure and bulk composition remains challenging. Here, we investigate the composition-structure-property relationships of nanocomposite Na-Al-P-O (NAPO) thin-film solid electrolytes using impedance spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and time-of-flight elastic recoil detection analysis (ToF-ERDA). An invariant activation energy of ≈0.8 eV across NAPO compositions was observed despite a ≈20-fold variation in ionic conductivity, suggesting that these differences arise primarily from changes in the concentration of mobile Na⁺ in the amorphous matrix. NMR measurements revealed highly disordered Al environments that were correlated with increased conductivity, evidence for multiple Na environments with differing mobilities, as well as a reduced local energy barrier to Na + hopping of ≈0.5 eV for two compositions. ToF-ERDA measurements showed that the elemental distributions were homogeneous, alongside significant H incorporation, identified as hydroxyl groups bound to Al and P via NMR. The H content increased as the ionic conductivity decreased in the NAPO system. Comparison with related, but ionically insulating compositions showed that H is a universal component of solution-processed materials. Although the protons were not mobile in these systems, H is proposed to occupy mobile sites within the framework that would otherwise host mobile ions such as Na + . Thus, our work suggests that promoting local disorder and minimising H incorporation are key design strategies for enhancing ionic conductivity in solution-processed amorphous solid electrolytes.
Related
- Impact of Perchloric Acid on the Thermodynamic Stability of THF, CH4/THF, and H2/THF Hydrates and Hydrogen Incorporation into H2/THF Hydrates
- Growth and crystallization of solution-processed TIPSpentacene on ultra-thin ferroelectric HZO gate dielectrics
- Direct Synthesis of Ag-In-Zn-S Quantum Dot Inks for Solution-Processed Optoelectronics
- Solution-Processed Ge25S75 and Ge25Se75 Thin Films─Influence of the Solution Preparation Pathway
- Olympic-patterned pentaboron emitter featuring highly distorted geometry enables efficient solution-processed ultrapure green OLEDs
BibTeX
@misc{gill2026probing,
title = {{Probing local structure and hydrogen incorporation in solution-processed thin-film solid electrolytes}},
author = {Thomas E. Gill and Leon Hensmann and Jędrzej Kondek and Matthew K. Sharpe and Callum D. McAleese and Michael Ryan Hansen and Yaoguang Song and Alexander J. E. Rettie},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009950/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009950/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Probing local structure and hydrogen incorporation in solution-processed thin-film solid electrolytes
AU - Thomas E. Gill
AU - Leon Hensmann
AU - Jędrzej Kondek
AU - Matthew K. Sharpe
AU - Callum D. McAleese
AU - Michael Ryan Hansen
AU - Yaoguang Song
AU - Alexander J. E. Rettie
PY - 2026
DA - 2026/10/05
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009950/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009950/v1
AB - Solution processing of functional thin films offers significant benefits, yet characterising their local structure and bulk composition remains challenging. Here, we investigate the composition-structure-property relationships of nanocomposite Na-Al-P-O (NAPO) thin-film solid electrolytes using impedance spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and time-of-flight elastic recoil detection analysis (ToF-ERDA). An invariant activation energy of ≈0.8 eV across NAPO compositions was observed despite a ≈20-fold variation in ionic conductivity, suggesting that these differences arise primarily from changes in the concentration of mobile Na⁺ in the amorphous matrix. NMR measurements revealed highly disordered Al environments that were correlated with increased conductivity, evidence for multiple Na environments with differing mobilities, as well as a reduced local energy barrier to Na + hopping of ≈0.5 eV for two compositions. ToF-ERDA measurements showed that the elemental distributions were homogeneous, alongside significant H incorporation, identified as hydroxyl groups bound to Al and P via NMR. The H content increased as the ionic conductivity decreased in the NAPO system. Comparison with related, but ionically insulating compositions showed that H is a universal component of solution-processed materials. Although the protons were not mobile in these systems, H is proposed to occupy mobile sites within the framework that would otherwise host mobile ions such as Na + . Thus, our work suggests that promoting local disorder and minimising H incorporation are key design strategies for enhancing ionic conductivity in solution-processed amorphous solid electrolytes.
ER -