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Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte Na3PS4
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-10-15 , DOI: 10.1021/jacs.0c06668 Theodosios Famprikis 1, 2, 3, 4 , Ö. Ulaş Kudu 1 , James A. Dawson 2, 5 , Pieremanuele Canepa 6 , François Fauth 7 , Emmanuelle Suard 8 , Mohamed Zbiri 8 , Damien Dambournet 4, 9 , Olaf J. Borkiewicz 10 , Houssny Bouyanfif 11 , Steffen P. Emge 12 , Sorina Cretu 1 , Jean-Noël Chotard 1 , Clare P. Grey 3, 12 , Wolfgang G. Zeier 13 , M. Saiful Islam 2, 3 , Christian Masquelier 1, 3, 4
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-10-15 , DOI: 10.1021/jacs.0c06668 Theodosios Famprikis 1, 2, 3, 4 , Ö. Ulaş Kudu 1 , James A. Dawson 2, 5 , Pieremanuele Canepa 6 , François Fauth 7 , Emmanuelle Suard 8 , Mohamed Zbiri 8 , Damien Dambournet 4, 9 , Olaf J. Borkiewicz 10 , Houssny Bouyanfif 11 , Steffen P. Emge 12 , Sorina Cretu 1 , Jean-Noël Chotard 1 , Clare P. Grey 3, 12 , Wolfgang G. Zeier 13 , M. Saiful Islam 2, 3 , Christian Masquelier 1, 3, 4
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Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na3PS4 are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg and pair distribution function), spectroscopy (impedance, Raman, NMR and INS), and ab initio simulations aimed at elucidating the synthesis-property relationships in Na3PS4. We consolidate previously reported interpretations regarding the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na+ migration in Na3PS4, which is ∼30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na3PS4 to ∼10-4 S/cm can be reproduced by applying external pressure on a sample from conventional high-temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain, and activation volume.
中文翻译：
压力下：机械化学对钠离子固体电解质 Na3PS4 结构和离子传导的影响
快离子导体对固态电池的发展至关重要。导致原型钠离子导体 Na3PS4 中离子电导率增加的机械化学合成的影响尚不完全清楚。我们在此基于衍射（布拉格和对分布函数）、光谱学（阻抗、拉曼、NMR 和 INS）以及旨在阐明 Na3PS4 中合成-性质关系的从头算模拟进行综合分析。我们巩固了先前报道的关于球磨样品局部结构的解释，强调了钠无序，并表明局部四方框架比最初提出的立方框架更准确地描述了结构。通过变压阻抗谱测量，我们首次报告了 Na3PS4 中 Na+ 迁移的激活体积，对于球磨样品来说，它高出约 30%。此外，我们表明，球磨对将 Na3PS4 的离子电导率提高到 10-4 S/cm 的影响可以通过对来自常规高温陶瓷合成的样品施加外部压力来重现。我们得出结论，机械化学合成对固体电解质性质的关键影响可以从压力、应变和活化体积方面进行分析和理解。
更新日期：2020-10-15
中文翻译：
压力下：机械化学对钠离子固体电解质 Na3PS4 结构和离子传导的影响
快离子导体对固态电池的发展至关重要。导致原型钠离子导体 Na3PS4 中离子电导率增加的机械化学合成的影响尚不完全清楚。我们在此基于衍射（布拉格和对分布函数）、光谱学（阻抗、拉曼、NMR 和 INS）以及旨在阐明 Na3PS4 中合成-性质关系的从头算模拟进行综合分析。我们巩固了先前报道的关于球磨样品局部结构的解释，强调了钠无序，并表明局部四方框架比最初提出的立方框架更准确地描述了结构。通过变压阻抗谱测量，我们首次报告了 Na3PS4 中 Na+ 迁移的激活体积，对于球磨样品来说，它高出约 30%。此外，我们表明，球磨对将 Na3PS4 的离子电导率提高到 10-4 S/cm 的影响可以通过对来自常规高温陶瓷合成的样品施加外部压力来重现。我们得出结论，机械化学合成对固体电解质性质的关键影响可以从压力、应变和活化体积方面进行分析和理解。
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