Construction and dynamic property of the lithium in conductor having rock salt structure

岩盐结构导体中锂的结构及动态特性

• 批准号: 15550121
• 负责人: YAMADA Koji
• 金额: $ 1.79万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550121/
• 关键词: Lithium ion conductor; Rock salt structure; 7Li NMR; 115In NMR; Conductivity; Powder X-ray diffraction; Order-disorder phase transition; 固体NMR; 岩塩型イオン伝導体; X繰回折; ナトリウムイオン伝導体

Li_3InBr_6 is one of the promising compounds for the construction of an all solid-state lithium ion battery. This compound undergoes a phase transition to a superionic phase having rock-salt structure and the conductivity is as high as 2^*10^<-2>Scm just above the superionic phase transition. In order to understand this high conductivity, firstly we tried to synthesize a series of similar compounds and searched new superionic conductors. Secondary we discussed the conduction mechanism by means of various measurements. Following points have become apparent from these experiments.1.The ionic radius of In^<3+> is quite similar to that of Li^+. This fact is most important for the appearance of the superionic phase in the LiX-InX_3 system.2.Na_3InCl_6 did not show high conductivity like Li_3InBr_6. However, we could determine the conduction path of the Na^+ by means of X-ray diffraction and NMR.3.Li_3InBr_6 at the superionic phase was isomorphous with Li_3InCl_6, in which not only Li^+ but In^<3+> are disordered state.4.^7LiNMR suggested that ca 15% of the Li^+ contributed to the conductivity just above the phase transition.5.With increasing temperature the X-ray diffraction pattern changed gradually to a simple one which was characteristic to a rock salt structure. This suggests the appearance of the averaged structure as a result of the rapid cationic diffusion.

Li_3InBr_6 是用于构建全固态锂离子电池的有前途的化合物之一。该化合物经历相变到具有岩盐结构的超离子相，并且电导率高达2^*10^-2Scm，刚好高于超离子相变。为了理解这种高电导率，我们首先尝试合成一系列类似的化合物并寻找新的超离子导体。其次，我们通过各种测量讨论了传导机制。从这些实验中可以看出以下几点：1.In^<3+>的离子半径与Li^+的离子半径非常相似。这一事实对于LiX-InX_3体系中超离子相的出现最为重要。2.Na_3InCl_6没有像Li_3InBr_6那样表现出高电导率。然而，我们可以通过X射线衍射和NMR确定Na^+的传导路径。3.超离子相的Li_3InBr_6与Li_3InCl_6是同晶的，其中不仅Li^+而且In^<3+>都是无序态。4.^7LiNMR表明约15%的Li^+对相变上方的电导率做出了贡献。5.随着温度的升高，X射线 衍射图案逐渐变为简单的衍射图案，这是岩盐结构的特征。这表明由于快速阳离子扩散而出现平均结构。

项目成果

Conduction path of the sodium ion in Na3InCl6 studied by X-ray diffraction and 23Na and 115In NMR

• DOI: 10.1016/j.ssi.2004.10.016
• 发表时间: 2005-02
• 期刊: Solid State Ionics
• 影响因子: 3.2
• 作者: Koji Yamada;Keiji Kumano;T. Okuda

Structural phase transition of the two dimensional fluoride ion conductor KSn_2F_5 Studied by X-ray diffraction.

X射线衍射研究二维氟离子导体KSn_2F_5的结构相变。

• 发表时间: 2004
• 期刊: Solid State Ionics 167
• 作者: M.Hashimoto;F.Tajima;K.Eda;K.Yamamura;T.Okazaki;Kimiaki Yamamura;K.Yamada et al.;K.Yamada et al.;K.Yamada et al.;Y.Tomita et al.;K.Yamada et al.;K.Yamada et al.
• 通讯作者: K.Yamada et al.

M.M.Ahmad et al.: "Fluoride ion dynamics and relaxation in KSn_2F_5 studies by ^<19>F NMR and impedance spectroscopy"J.Phys.Condens.Matter. 15. 5341-5352 (2003)

M.M.Ahmad等人：“通过 19 F NMR和阻抗谱研究KSn_2F_5中的氟离子动力学和弛豫”J.Phys.Condens.Matter。

Superprotonic conductor CsH2PO4 studied by 1H, 31P NMR and X-ray diffraction

• DOI: 10.1016/j.ssi.2004.03.042
• 发表时间: 2004-11-30
• 期刊: SOLID STATE IONICS
• 影响因子: 3.2
• 作者: Yamada, K;Sagara, T;Okuda, T
• 通讯作者: Okuda, T

Li ion conductivity of solid electrolyte, Li_<3-2x>M_xInBr_6(M=Mg,Ca,St,Ba)

固体电解质的Li离子电导率，Li_<3-2x>M_xInBr_6(M=Mg,Ca,St,Ba)

• 发表时间: 2004
• 期刊: Solid State Ionics 174
• 作者: M.Hashimoto;F.Tajima;K.Eda;K.Yamamura;T.Okazaki;Kimiaki Yamamura;K.Yamada et al.;K.Yamada et al.;K.Yamada et al.;Y.Tomita et al.;K.Yamada et al.;K.Yamada et al.;K.Yamada et al.;Y.Tomita et al.;K.Yamada et al.;H.Morooka et al.;K.Yamada et al.;K.Yamada et al.;Y.Tomita et al.
• 通讯作者: Y.Tomita et al.