Development and Application of Lithium lon Conducting Glasses Utilized of Mixed Anion Effect

利用混合阴离子效应的锂离子导电玻璃的研制与应用

• 批准号: 06555270
• 负责人: TATSUMISAGO Masahiro
• 金额: $ 4.03万
• 依托单位: University of Osaka Prefecture
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06555270/
• 关键词: Oxysulfide glass; Rapid quenching; Lithium ion conduction; Solid electrolyte; Solid lithium battery; Glass structure; Mixed anion effect; Solid state NMR

(1) Glasses in the systems Li_2S-SiS_2-Li_xMO_y (Li_xMO_y = Li_3PO_4, Li_4SiO_4, Li_4GeO_4, Li_2SO_4, Li_2WO_4) were prepared by using twin-roller rapid quenching. The doping of Li_3PO_4 Provided the most extended glass-forming region.(2) The difference between Tg and Tc, which is one of the measures of the glass stability, was maximized at the composition with 5 mol% Li_xMO_y.(3) The glasses with 5 mol% Li_xMO_y exhibited high conductivities of about 10^<-3> Scm^<-1>.(4) ^<29> MAS-NMR spectra revealed that a large number of silicon atoms in the glasses were coordinated with both sulfur and oxygen atoms.(5) The fraction of the SiO_nS^<4-n> in the oxysulfide glasses was larger in the order of Li_4GeO_4 < Li_4SiO_4 < Li_3PO_4 as dopants.(6) The combination of bridging oxygen atoms and non-bridging sulfur atoms may result in the enhancement of lithium ion mobility.

(1)采用双辊快速淬火技术制备了Li_2S-SiS_2-Li_xMO_y(Li_xMO_y=Li_3PO_4、Li_4SiO_4、Li_4GeO_4、Li_2SO_4、Li_2WO_4)体系玻璃。 Li_3PO_4 的掺杂提供了最大扩展的玻璃形成区域。(2) Tg 和 Tc 之间的差异（玻璃稳定性的衡量标准之一）在 Li_xMO_y 含量为 5 mol% 时达到最大。(3) 玻璃5 mol% Li_xMO_y 表现出约 10^<-3> Scm^<-1> 的高电导率。(4) ^<29> MAS-NMR 谱显示(5)硫氧化物玻璃中SiO_nS^<4-n>的比例较大,掺杂剂为Li_4GeO_4 < Li_4SiO_4 < Li_3PO_4 (6)桥接氧原子和非桥接硫原子的组合可以导致锂离子迁移率的增强。

项目成果

M.Takahashi: "Solid State NMR Spectra of Rapidly Quenched Superionic Glasses Composed of Two Lithium Ortho-oxosales" Solid State Ionics. (in press). (1996)

M.Takahashi：“由两个正氧化锂组成的快速淬火超离子玻璃的固态核磁共振谱”固态离子。

M.Takahashi: "Structural Investigation of Rapidly Quenched Li_3BO_3-Li_4GeO_4 Glasses" J.Mat.Sci. 29. 5703-5708 (1994)

M.Takahashi：“快速淬火Li_3BO_3-Li_4GeO_4 玻璃的结构研究”J.Mat.Sci。

Y.Kowada: "Electronic States of Modifier Ions in Silicate Glasses" J.Non-Cryst.Solids. 177. 286-292 (1995)

Y.Kowada：“硅酸盐玻璃中改性剂离子的电子状态”J.Non-Cryst.Solids。

Y.Kowada: "Electronic States of Transition Metal Ions in Silicate Glasses" J.Non-Cryst.Solids,. (in press.). (1995)

Y.Kowada：“硅酸盐玻璃中过渡金属离子的电子态”J.Non-Cryst.Solids，。

K.Hirai: "Thermal and Electrical Properties of Rapidly Quenched Glasses in the Systems Li_2S-SiS_2-Li_xMO_y(Li_xMO_y=Li_4SiO_4,Li_2SO_4)" Solid State Ionics. 78. 269-273 (1995)

K.Hirai：“Li_2S-SiS_2-Li_xMO_y(Li_xMO_y=Li_4SiO_4,Li_2SO_4)系统中快速淬火玻璃的热电性能”固态离子学。