Selective Blockage of Li-Ion Diffusion Pathways in Li10SnP2S12: Insights from Nuclear Magnetic Resonance
Selective Blockage of Li-Ion Diffusion Pathways in Li10SnP2S12: Insights from Nuclear Magnetic Resonance
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Li10SnP2S12 中锂离子扩散路径的选择性阻断：来自核磁共振的见解
DOI：
10.1021/acs.jpcc.1c09983
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发表时间：
2021-12
期刊：
影响因子：
--
通讯作者：
Feng Jiwen
中科院分区：
文献类型：
--
作者：
Liang Xinmiao;Yang Li;Lei Youyi;Qu Luyao;Wang Liying;Cai Wuyao;Xu Ke;Jiang Yangming;Liu Biaolan;Feng Jiwen
快离子导体Li10GeP2S12(LGPS)在室温下表现出极高的离子电导率，这归因于连接一维(1D)锂离子快速扩散隧道的二维(2D)路径。 Li离子的这些各向异性传输路径可以通过用Sn或Si等价取代Ge元素来调节。在这项工作中，我们使用多种7Li和31P固态核磁共振（ss-NMR）方法来研究Ge与Sn的取代对1D和2D锂离子动力学以及电导率的影响。与它的模拟 LGPS 一样，Li10SnP2S12(LSPS) 也表现出两种不同的锂离子扩散路径，即沿 c 轴的 1D 通道和 2Dab 平面扩散，其特征在于低温下的活化能为 0.17 eV，高温下的活化能为 0.13 eV。有趣的是，用 Sn 代替 Ge 会阻断 ab 平面中的大部分 Li(4)-Li(1) 扩散路径，平均只有约 10% 的 Li(4) 位点仍保持面内 Li 扩散活性。然而，这种元素替代并不能显着调节一维沟道内锂离子扩散。因此，这种取代引起的面内Li(4)-Li(1)离子扩散路径的严重阻塞是LSPS室温电导率降低的原因。我们的结果为理解结构-电导率关系和调节离子电导率的策略提供了新的见解。
The fast ionic conductor Li10GeP2S12(LGPS) exhibits exceptionally high ionic conductivity at room temperature, which is attributed to the two-dimensional (2D) pathways that connect the one-dimensional (1D) Li-ion fast diffusion tunnels. These anisotropic transport pathways for Li ions can be modulated by isovalent substitution of the Ge element by Sn or Si. In this work, we use multiple7Li and31P solid-state nuclear magnetic resonance (ss-NMR) methods to study the effects of Ge substitution with Sn on 1D and 2D Li-ion dynamics as well as conductivity. Like its analogue LGPS, Li10SnP2S12(LSPS) also exhibits two distinguishing Li-ion diffusion paths, i.e., a 1D channel along thec-axis and 2Dab-plane diffusion, characterized by activation energies of 0.17 eV at low temperatures and 0.13 eV at high temperatures. It is interestingly found that replacing Ge with Sn blocks most of the Li(4)–Li(1) diffusion pathways in theab-plane and only approximately 10% of the Li(4) sites on average remain active for in-plane Li diffusion. This element substitution, however, does not significantly modulate the 1D in-channel Li-ion diffusion. Such a substitution-induced heavy blockage of the in-plane Li(4)–Li(1) ion diffusion pathways is thus responsible for the reduced room-temperature conductivity of LSPS. Our results provide a new insight toward understanding the structure–conductivity relationship and the strategy of tuning the ionic conductivity.
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影响因子：
17.6
作者：
Bingkai Zhang;Luyi Yang;Lin-wang Wang;F. Pan
通讯作者：
Bingkai Zhang;Luyi Yang;Lin-wang Wang;F. Pan
影响因子：
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影响因子：
3.7
作者：
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影响因子：
41.2
作者：
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通讯作者：
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影响因子：
56.7
作者：
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通讯作者：
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