Buchberger Dominika A, Garbacz Piotr, Słupczyński Krzysztof, Brzezicki Artur, Boczar Maciej, Czerwiński Andrzej
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland.
Adamed Pharma SA, 05-152 Pieńków, Poland.
ACS Appl Mater Interfaces. 2023 Nov 22;15(46):53417-53428. doi: 10.1021/acsami.3c10857. Epub 2023 Nov 3.
In this study, the activation energy and ionic conductivity of the LiPSCl material for all-solid-state batteries were investigated using solid-state nuclear magnetic resonance (NMR) spectroscopy and electrochemical impedance spectroscopy (EIS). The results show that the activation energy values estimated from nuclear relaxation rates are significantly lower than those obtained from impedance measurements. The total ionic conductivities for long-range lithium diffusion in LiPSCl calculated from EIS studies depend on the crystal size and unit cell parameter. The study also presents a new sample preparation method for measuring activation energy using temperature-dependent EIS and compares the results with the solid-state NMR data. The activation energy for a thin-film sample is equivalent to the long-range lithium dynamics estimated from NMR measurements, indicating the presence of additional limiting processes in thick pellets. Additionally, a theoretical model of Li-ion hopping based on results obtained using density-functional theory methods in comparison with experimental findings was discussed. Overall, the study emphasizes the importance of sample preparation methods in determining accurate activation energy and ionic conductivity values for solid-state lithium batteries and the significance of solid-state electrolyte thickness in new solid-state battery design for faster Li-ion diffusion.
在本研究中，使用固态核磁共振（NMR）光谱和电化学阻抗谱（EIS）研究了全固态电池用LiPSCl材料的活化能和离子电导率。结果表明，由核弛豫速率估算的活化能值显著低于由阻抗测量获得的值。通过EIS研究计算得出的LiPSCl中长程锂扩散的总离子电导率取决于晶体尺寸和晶胞参数。该研究还提出了一种使用与温度相关的EIS测量活化能的新样品制备方法，并将结果与固态NMR数据进行了比较。薄膜样品的活化能与通过NMR测量估算的长程锂动力学相当，这表明厚颗粒中存在额外的限制过程。此外，还讨论了基于密度泛函理论方法获得的结果并与实验结果相比较的锂离子跳跃理论模型。总体而言，该研究强调了样品制备方法在确定固态锂电池准确活化能和离子电导率值方面的重要性，以及固态电解质厚度在新型固态电池设计中实现更快锂离子扩散的重要性。
