Structure and Ionic Conductivity in the Mixed-Network Former Chalcogenide Glass System [Na2S]2/3[(B2S3)x(P2S5)1–x]1/3
Structure and Ionic Conductivity in the Mixed-Network Former Chalcogenide Glass System [Na2S]2/3[(B2S3)x(P2S5)1–x]1/3
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混合网络前硫属化物玻璃体系的结构和离子电导率 [Na2S]2/3[(B2S3)x(P2S5)1âx]1/3
DOI：
10.1021/jp3068365
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发表时间：
2012
影响因子：
3.7
通讯作者：
S. W. Martin
中科院分区：
文献类型：
--
作者：
D. Larink;H. Eckert;S. W. Martin
采用熔体淬冷法制备了[Na2S]2/3[(B2S3)x(P2S5)1-x]1/3(0.0≤x≤1.0)系统玻璃，并用热分析和交流阻抗谱对其性能进行了表征。用拉曼光谱和11B、31P和23Na高分辨固态魔角自旋(MAS)核磁共振技术对其原子级结构进行了全面表征。31P魔角自旋核磁共振峰的归属是通过同核J分辨和重聚焦不充分技术检测到的31P-31P间接自旋-自旋相互作用的存在或不存在来确定的。用31P{11B}和11B{31P}旋转回波双共振谱定量了B-S-P在玻璃网络中的连接程度。结果表明，网络改性剂碱性硫化物Na2S在两个网络前组份B和P之间并不成比例地共享，相反，硫代磷酸盐(P)组分吸引的网络改性剂物种的浓度往往比本体组成预测的要大，这导致了P2S74-，焦硫代磷酸盐，Na/P=2：1，基团转化为PS43-，正硫代磷酸盐，Na/P=3：1基团。电荷平衡是通过形成共价桥硫(BS)单元来增加硫代硼(B)单元的净聚合度来维持的，B-S-B。对11B MAS核磁共振谱的详细检查表明，形成了多个硫代硼酸盐单元，从中性的BS3/2基团一直到完全解聚的正硫硼酸(BS33-)物种。在这些结果的基础上，建立了一个全面的、定量的玻璃结构模型，在此基础上，可以合理地确定玻璃的玻璃化转变温度(Tg)和离子电导率的组成趋势。在x=0.4时，主导过程可用网络反应方程式P1+B1⇆P0+B4来简化描述，其中上标表示各个网络前物种的BS原子数。Abovex=0.4时，所有硫代磷酸盐单元均为P0型，且焦化(B1)和正硫硼酸(B0)物种对网络结构的贡献均随着x的增大而增大。与钠硼磷酸盐玻璃的情况形成鲜明对比的是，四配位硫代硼酸盐物种的丰度通常较低，并且似乎不存在B-S-P异原子键。在此结构信息的基础上，讨论了离子电导率的组成趋势与电荷补偿阴离子物种的性质和电荷载流子的空间分布有关。
Glasses in the system [Na2S]2/3[(B2S3)x(P2S5)1–x]1/3(0.0 ≤x≤ 1.0) were prepared by the melt quenching technique, and their properties were characterized by thermal analysis and impedance spectroscopy. Their atomic-level structures were comprehensively characterized by Raman spectroscopy and11B,31P, and23Na high resolution solid state magic-angle spinning (MAS) NMR techniques.31P MAS NMR peak assignments were made by the presence or absence of homonuclear indirect31P–31P spin–spin interactions as detected using homonuclear J-resolved and refocused INADEQUATE techniques. The extent of B–S–P connectivity in the glassy network was quantified by31P{11B} and11B{31P} rotational echo double resonance spectroscopy. The results clearly illustrate that the network modifier alkali sulfide, Na2S, is not proportionally shared between the two network former components, B and P. Rather, the thiophosphate (P) component tends to attract a larger concentration of network modifier species than predicted by the bulk composition, and this results in the conversion of P2S74–, pyrothiophosphate, Na/P = 2:1, units into PS43–, orthothiophosphate, Na/P = 3:1, groups. Charge balance is maintained by increasing the net degree of polymerization of the thioborate (B) units through the formation of covalent bridging sulfur (BS) units, B–S–B. Detailed inspection of the11B MAS NMR spectra reveals that multiple thioborate units are formed, ranging from neutral BS3/2groups all the way to the fully depolymerized orthothioborate (BS33–) species. On the basis of these results, a comprehensive and quantitative structural model is developed for these glasses, on the basis of which the compositional trends in the glass transition temperatures (Tg) and ionic conductivities can be rationalized. Up tox= 0.4, the dominant process can be described in a simplified way by the net reaction equation P1+ B1⇆ P0+ B4, where the superscripts denote the number of BS atoms for the respective network former species. Abovex= 0.4, all of the thiophosphate units are of the P0type and both pyro- (B1) and orthothioborate (B0) species make increasing contributions to the network structure with increasingx. In sharp contrast to the situation in sodium borophosphate glasses, four-coordinated thioborate species are generally less abundant and heteroatomic B–S–P linkages appear to not exist. On the basis of this structural information, compositional trends in the ionic conductivities are discussed in relation to the nature of the charge-compensating anionic species and the spatial distribution of the charge carriers.
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