Short range order structrures of lithium oxy-thiosilicophosphate glasses
Short range order structrures of lithium oxy-thiosilicophosphate glasses
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硫代硅磷酸锂玻璃的短程有序结构
DOI：
10.1016/j.nocx.2023.100198
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发表时间：
2023
影响因子：
--
通讯作者：
Martin, Steve W.
中科院分区：
文献类型：
--
作者：
Hu, Guantai;Torres, Victor M.;Martin, Steve W.
在这项工作中，制备了硫化物和混合氧硫化物 (MOS) 玻璃 0.56Li2S + 0.44[(0.33-x)PS5/2+ xPO5/2+ 0.67SiS2] 的组成系列，其中 0 ≤ x ≤ 0.33，并研究了它们的短程有序 (SRO) 结构和热性能。粉末 X 射线衍射 (XRD) 证实 MOS 玻璃没有结晶，仅在 x = 0 玻璃中观察到非常小的衍射峰。使用傅立叶变换红外(FT-IR)、拉曼、29Si和31P魔角旋转(MAS)NMR光谱来鉴定这些玻璃中存在的SRO结构。这些光谱揭示了合成过程中氧从 P 迁移到 Si。尽管氧以氧化磷的形式引入，但这些玻璃中的大部分氧最终与硅结合，从而形成以磷为中心的富硫SRO和以硅为中心的MOS SRO。进一步发现 P-S SRO 物质主要是带电非桥联硫 (NBS)。 Si SRO物种由中性桥氧（BO）和带电非桥氧（NBO）以及中性桥硫（BS）和带电非桥硫组成，其中中性BO和BS物种的分数大于NBO和NBS。这些结果表明，这些玻璃中移动的Li+阳离子的优势位于带负电的P中心附近，而不是带中性的Si中心附近。 P0SRO 结构的平均负电荷为 ∼−3.0，P0SRO 中约 97% 的磷物质，而 Si SRO 结构的平均负电荷为 -2.3。与 P 上产生大量 NBS 以及 Si 上产生更多 BO 和 BS 一致，这些值分别比成分预期平均值 -2.55 更负和更正。差示扫描量热法 (DSC) 测量其玻璃化转变 (Tg) 和结晶 (Tc) 温度表明，这些玻璃的 Tg 高于 300 °C，其工作范围 ΔT ≡ Tc – Tg 约为 100 °C。
In this work, the compositional series of sulfide and mixed oxysulfide (MOS) glasses 0.56Li2S + 0.44[(0.33-x)PS5/2+ xPO5/2+ 0.67SiS2] was prepared, where 0 ≤ x ≤ 0.33, and their short range order (SRO) structures and their thermal properties have been investigated. Powder x-ray diffraction (XRD) confirmed that the MOS glasses were free from crystallization, with only very minor diffraction peaks in the x = 0 glass being observed. Fourier transform infrared (FT-IR), Raman, and29Si and31P magic angle spinning (MAS) NMR spectroscopies were used to identify the SRO structures present in these glasses. These spectra revealed oxygen migration from P to Si during synthesis. Although oxygen was introduced in the form of phosphorus oxide, the majority of the oxygen in these glasses ends up being bonded to silicon, thereby creating sulfur-rich SROs centered by phosphorus and MOS SROs centered by silicon. It was further found that the P-S SRO species were predominantly charged non-bridging sulfurs (NBS). The Si SRO species were comprised of neutral bridging oxygens (BOs) and charged non-bridging oxygens (NBOs) and neutral bridging sulfurs (BS) and charged non-bridging sulfurs with the neutral BO and BS species being larger in fraction than the NBO and NBS. These results suggest that the preponderance of the mobile Li+cations in these glasses are located near the more negatively charged P centers and not near the more neutrally charged Si centers. The average negative charge of the P SRO structures was found to be ∼ − 3.0 with ∼97% of the phosphorous species in the P0SRO while the average negative charge of the Si SRO structures was found to be −2.3. Consistent with the creation of the large numbers of NBS on the P and more BOs and BSs on the Si, these values are more negative and more positive, respectively, than the compositionally expected average value of −2.55. Differential scanning calorimetry (DSC) measurements of their glass transition (Tg) and crystallization (Tc) temperatures showed that the Tgs of these glasses are higher than 300 °C and their working ranges, ΔT ≡ Tc – Tg, are ∼100 °C.
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