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Infrared measurement on proton diffusion coefficients for crystalline phases of cesium hydrogen sulfate

硫酸氢铯晶相质子扩散系数的红外测量

基本信息

批准号：
17550091
负责人：
YAMAWAKI Hiroshi
金额：
$ 2.46万
依托单位：
National Institute of Advanced Industrial Science and Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-17550091/
关键词：
Infrared measurement proton conductor solid acid mutual diffsion coefficient high pressure deuterium ion

项目摘要

The purpose of this study was to clarify a correlation between the proton diffusion coefficients and the structures for various crystalline phases of cesium hydrogen sulfate (CsHSO_4), which is a representative solid-acid type proton conductor. CsHSO_4 have been shown to contain many polymorphs in the temperature-pressure phase diagram. The polymorphs all have the same chemical composition but show different proton conductivities for each crystal structure. At first, we examined the hydrogen bond states of CsHSO_4 crystal by infrared and Raman spectra, and determined a temperature-pressure phase diagram. Then, new phases HPHT1 and HPHT2 were found. These phases were stable at room temperature under high pressure. We succeeded in tracking the temporal change in the O-D distribution in the sample at high pressures using the infrared mapping measurement. We measured pressure dependence of a proton-deuteron mutual diffusion coefficient in a CsHSO_4/CsHSO_4 solid at 373 K. The coefficient for phase II was almost constant up to 1 GPa. Our results indicated that the influence of compression on the reorientation motion is small in phase II, although the ions should gather closely together. The diffusion coefficient decreased to 1×10^<-16> m^2/s at the transition from phase II to phase HPHT1 at 1.5 GPa, and showed similar values in phase HPHT2. The structural change from phase II to HPHT1 would cause a decrease in the mutual diffusion coefficient. The results showed that the reorientation motion of the HSO_4^￣ion was suppressed in both phases HPHT1 and HPHT2. Surface enhanced infrared absorption spectra of CsHSO_4 were obtained on a silver deposition plate. However, some problem (for example, thinning of tie sample, acid-resistance of plate) remains to apply the diffusion coefficient measurement.

本研究的目的是阐明具有代表性的固体-酸型质子导体——硫酸氢铯（CsHSO_4）的质子扩散系数与各晶相结构之间的关系。在温度-压力相图中发现CsHSO_4含有许多多晶。多晶体都具有相同的化学成分，但每种晶体结构的质子电导率不同。首先，利用红外光谱和拉曼光谱检测了CsHSO_4晶体的氢键态，并绘制了温度-压力相图。然后发现新的相HPHT1和HPHT2。这些相在室温高压下是稳定的。利用红外测图方法，成功地跟踪了高压下样品中O-D分布的时间变化。我们测量了CsHSO_4/CsHSO_4固体中质子-氘核相互扩散系数在373 K时的压强依赖性。第二阶段的系数几乎不变，直至1gpa。我们的结果表明，压缩对离子重定向运动的影响很小，尽管离子应该紧密聚集在一起。在1.5 GPa时，从II相到HPHT1相的扩散系数下降到1×10^<-16> m^2/s，在HPHT2相中也有类似的数值。从II相到HPHT1的结构变化会导致相互扩散系数降低。结果表明，HPHT1和HPHT2相均抑制了HSO_4^￣离子的重取向运动。在银沉积板上获得了CsHSO_4的表面增强红外吸收光谱。但是，应用扩散系数测量还存在一些问题（如试样变薄、板的耐酸性等）。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Vibrational spectra of CsHSO_4 at high pressure and high temperature

CsHSO_4高压高温振动谱

DOI：
发表时间：
2007
期刊：
Phys. Rev. B 75
影响因子：
0
作者：
K. Miura;G. Inoue;and A. Hosomi;三津勝清;三浦勝清;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki
通讯作者：
Hiroshi Yamawaki

Phase changes in CsHSO_4 under high temperature and high pressure

高温高压下CsHSO_4的相变

DOI：
发表时间：
2005
期刊：
影响因子：
0
作者：
K. Miura;G. Inoue;and A. Hosomi;三津勝清;三浦勝清;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;山脇浩;Hiroshi YAMAWAKI;山脇浩;Hiroshi YAMAWAKI
通讯作者：
Hiroshi YAMAWAKI

Protonic conductivity and structure of solid acid CsHSO_4 under high pressure

高压固体酸CsHSO_4的质子电导率和结构

DOI：
发表时间：
2005
期刊：
影响因子：
0
作者：
K. Miura;G. Inoue;and A. Hosomi;三津勝清;三浦勝清;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;山脇浩;Hiroshi YAMAWAKI;山脇浩;Hiroshi YAMAWAKI;山脇浩;Hiroshi YAMAWAKI
通讯作者：
Hiroshi YAMAWAKI

高圧下における固体酸CsHSO_4のプロトン伝導と構造

高压固体酸CsHSO_4的质子传导与结构

DOI：
发表时间：
2005
期刊：
影响因子：
0
作者：
K. Miura;G. Inoue;and A. Hosomi;三津勝清;三浦勝清;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;山脇浩;Hiroshi YAMAWAKI;山脇浩;Hiroshi YAMAWAKI;山脇浩
通讯作者：
山脇浩

高圧下におけるCsHSO_4のイオン伝導度測定

高压下CsHSO_4离子电导率测量

DOI：
发表时间：
2005
期刊：
影响因子：
0
作者：
K. Miura;G. Inoue;and A. Hosomi;三津勝清;三浦勝清;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroyuki Suga et al.;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;Hiroshi Yamawaki;山脇浩;Hiroshi YAMAWAKI;山脇浩;Hiroshi YAMAWAKI;山脇浩;Hiroshi YAMAWAKI;山脇浩
通讯作者：
山脇浩