Electrochemical, Spectroscopic, and Thermal Investigations of LiSn2 ( PO4 ) 3 and Sn3 ( PO4 ) 2 Anodes during the First Discharge
Electrochemical, Spectroscopic, and Thermal Investigations of LiSn2 ( PO4 ) 3 and Sn3 ( PO4 ) 2 Anodes during the First Discharge
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LiSn2 (PO4) 3 和 Sn3 (PO4) 2 阳极首次放电期间的电化学、光谱和热研究
DOI：
10.1149/1.1914753
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发表时间：
2005
影响因子：
3.9
通讯作者：
R. Frech
中科院分区：
文献类型：
--
作者：
Christopher M. Burba;R. Frech
用红外光谱、差示扫描量热法(DSC)、X射线衍射仪(X射线衍射仪)和交流阻抗谱研究了晶态LiN2(PO4)3和Sn3(PO4)2的首次放电。在放电前，两种化合物在中红外和远红外都有丰富的振动结构；然而，当放电到1.00V时，这种结构完全被破坏。具体而言，PO3-4分子内伸缩振动和弯曲振动坍塌成宽带，晶格模消失。由此得到的中、远红外光谱与高度无序的Li3PO4的形成相一致。当其中一种化合物放电到1.00V时，在中红外光谱中出现碳酸盐谱带。这些谱带被归类为在这些电极中形成的金属锡催化的电解液分解反应的产物。红外光谱表明，Li+离子在Li-Sn合金化过程中与Li3PO4或Li2CO3没有强烈的相互作用。用X射线衍射仪和差示扫描量热仪检测了非合金金属锡的残留量。Sn3(PO4)2电极比LiNO2(PO4)3电极产生的残留锡量大得多。这些差异可以通过考虑每种化合物排放时产生的锡的相对浓度来解释。缓慢的Li+离子扩散可能导致较大聚集体中心的少量TiN保持未合金化。
The first discharge of crystalline LiSn 2 (PO 4 ) 3 and Sn 3 (PO 4 ) 2 is investigated with infrared spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and impedance spectroscopy. Prior to discharging, both compounds have a rich vibrational structure in the mid- and far-IR; however, discharging to 1.00 V completely destroys this structure. Specifically, the PO 3 - 4 intramolecular stretching and bending vibrations collapse into broad bands while the lattice modes vanish for both compounds. The resulting mid- and far-IR spectra are consistent with the formation of highly disordered Li 3 PO 4 . Carbonate bands appear in the mid-IR spectra when either compound is discharged to 1.00 V. These bands are assigned to the products of an electrolyte decomposition reaction catalyzed by the metallic tin that forms in these electrodes. The infrared spectra suggest that Li + ions do not strongly interact with the Li 3 PO 4 or Li 2 CO 3 during the Li-Sn alloying process. Residual amounts of unalloyed metallic tin are detected with XRD and DSC. The Sn 3 (PO 4 ) 2 electrodes result in considerably larger amounts of residual tin than LiSn 2 (PO 4 ) 3 . These differences may be explained by considering the relative concentration of tin produced when each compound is discharged. Slow Li + ion diffusion probably causes a small amount of tin in the center of the larger aggregates to remain unalloyed.
影响因子：
56.9
作者：
Idota, Y;Kubota, T;Miyasaka, T
通讯作者：
Miyasaka, T