Proton (deuteron) conductivity in Cs1.5Li1.5H(SO4)2 and Cs1.5Li1.5D(SO4)2 single crystals

B. V. Merinov; C. R I Chisholm; D. A. Boysen; S. M. Haile

doi:10.1016/S0167-2738(01)00954-7

Proton (deuteron) conductivity in Cs_1.5Li_1.5H(SO₄)₂ and Cs_1.5Li_1.5D(SO₄)₂ single crystals

B. V. Merinov^*, C. R I Chisholm, D. A. Boysen, S. M. Haile

^*Corresponding author for this work

Materials Science and Engineering

Research output: Contribution to journal › Conference article › peer-review

5 Scopus citations

Abstract

Calorimetric (DSC), NMR and electrical studies of Cs_1.5Li_1.5X(SO₄)₂ (X = H, D) single crystals have been performed in the temperature range from 300 to 533 K. No phase transitions are observed upon heating and the conductivity follows an Arrhenius temperature dependence to the point of decomposition at ∼ 470 K. Despite the high protonic conductivity of Cs_1.5Li_1.5X(SO₄)₂ (σ ∼ 10^-3 S cm^-1) at high temperature, these compounds cannot be classified as superprotonic because of the large value of the activation energy (E_a ∼ 1 eV). The proton NMR studies confirmed that two crystallographic proton sites exist in Cs_1.5Li_1.5H(SO₄)₂, presumably corresponding to two minima in the single, crystallographically distinct (and asymmetric) hydrogen bond. A measurable isotope effect in the conductivity data confirmed that protons/deuterons, as opposed to lithium ions, are the mobile species. The high activation energy for proton transport in Cs_1.5Li_1.5X(SO₄)₂ most probably results from the asymmetry of the hydrogen bonds, and from electrostatic repulsion between the protons and the Li⁺ ions which likely hinders reorientation of XSO₄^- groups.

Original language	English (US)
Pages (from-to)	185-189
Number of pages	5
Journal	Solid State Ionics
Volume	145
Issue number	1-4
DOIs	https://doi.org/10.1016/S0167-2738(01)00954-7
State	Published - Dec 1 2001
Event	10th International Conference on Solid State (SSPC10) - Montpellier, France Duration: Sep 24 2000 → Sep 28 2000

Keywords

CsH(SO)
CsHSO
CsLiH(SO)
Proton conductivity

ASJC Scopus subject areas

Chemistry(all)
Materials Science(all)
Condensed Matter Physics

Access to Document

10.1016/S0167-2738(01)00954-7

Cite this

@article{615a85db8975490aabd5e6cb0fa6aa69,

title = "Proton (deuteron) conductivity in Cs1.5Li1.5H(SO4)2 and Cs1.5Li1.5D(SO4)2 single crystals",

abstract = "Calorimetric (DSC), NMR and electrical studies of Cs1.5Li1.5X(SO4)2 (X = H, D) single crystals have been performed in the temperature range from 300 to 533 K. No phase transitions are observed upon heating and the conductivity follows an Arrhenius temperature dependence to the point of decomposition at ∼ 470 K. Despite the high protonic conductivity of Cs1.5Li1.5X(SO4)2 (σ ∼ 10-3 S cm-1) at high temperature, these compounds cannot be classified as superprotonic because of the large value of the activation energy (Ea ∼ 1 eV). The proton NMR studies confirmed that two crystallographic proton sites exist in Cs1.5Li1.5H(SO4)2, presumably corresponding to two minima in the single, crystallographically distinct (and asymmetric) hydrogen bond. A measurable isotope effect in the conductivity data confirmed that protons/deuterons, as opposed to lithium ions, are the mobile species. The high activation energy for proton transport in Cs1.5Li1.5X(SO4)2 most probably results from the asymmetry of the hydrogen bonds, and from electrostatic repulsion between the protons and the Li+ ions which likely hinders reorientation of XSO4- groups.",

keywords = "CsH(SO), CsHSO, CsLiH(SO), Proton conductivity",

author = "Merinov, {B. V.} and Chisholm, {C. R I} and Boysen, {D. A.} and Haile, {S. M.}",

note = "Funding Information: The authors would like to thank the National Science Foundation for funding this research. Dr. Sonjong Hwang kindly assisted with the NMR data collection and analysis.; 10th International Conference on Solid State (SSPC10) ; Conference date: 24-09-2000 Through 28-09-2000",

year = "2001",

month = dec,

day = "1",

doi = "10.1016/S0167-2738(01)00954-7",

language = "English (US)",

volume = "145",

pages = "185--189",

journal = "Solid State Ionics",

issn = "0167-2738",

publisher = "Elsevier",

number = "1-4",

}

TY - JOUR

T1 - Proton (deuteron) conductivity in Cs1.5Li1.5H(SO4)2 and Cs1.5Li1.5D(SO4)2 single crystals

AU - Merinov, B. V.

AU - Chisholm, C. R I

AU - Boysen, D. A.

AU - Haile, S. M.

N1 - Funding Information: The authors would like to thank the National Science Foundation for funding this research. Dr. Sonjong Hwang kindly assisted with the NMR data collection and analysis.

PY - 2001/12/1

Y1 - 2001/12/1

N2 - Calorimetric (DSC), NMR and electrical studies of Cs1.5Li1.5X(SO4)2 (X = H, D) single crystals have been performed in the temperature range from 300 to 533 K. No phase transitions are observed upon heating and the conductivity follows an Arrhenius temperature dependence to the point of decomposition at ∼ 470 K. Despite the high protonic conductivity of Cs1.5Li1.5X(SO4)2 (σ ∼ 10-3 S cm-1) at high temperature, these compounds cannot be classified as superprotonic because of the large value of the activation energy (Ea ∼ 1 eV). The proton NMR studies confirmed that two crystallographic proton sites exist in Cs1.5Li1.5H(SO4)2, presumably corresponding to two minima in the single, crystallographically distinct (and asymmetric) hydrogen bond. A measurable isotope effect in the conductivity data confirmed that protons/deuterons, as opposed to lithium ions, are the mobile species. The high activation energy for proton transport in Cs1.5Li1.5X(SO4)2 most probably results from the asymmetry of the hydrogen bonds, and from electrostatic repulsion between the protons and the Li+ ions which likely hinders reorientation of XSO4- groups.

AB - Calorimetric (DSC), NMR and electrical studies of Cs1.5Li1.5X(SO4)2 (X = H, D) single crystals have been performed in the temperature range from 300 to 533 K. No phase transitions are observed upon heating and the conductivity follows an Arrhenius temperature dependence to the point of decomposition at ∼ 470 K. Despite the high protonic conductivity of Cs1.5Li1.5X(SO4)2 (σ ∼ 10-3 S cm-1) at high temperature, these compounds cannot be classified as superprotonic because of the large value of the activation energy (Ea ∼ 1 eV). The proton NMR studies confirmed that two crystallographic proton sites exist in Cs1.5Li1.5H(SO4)2, presumably corresponding to two minima in the single, crystallographically distinct (and asymmetric) hydrogen bond. A measurable isotope effect in the conductivity data confirmed that protons/deuterons, as opposed to lithium ions, are the mobile species. The high activation energy for proton transport in Cs1.5Li1.5X(SO4)2 most probably results from the asymmetry of the hydrogen bonds, and from electrostatic repulsion between the protons and the Li+ ions which likely hinders reorientation of XSO4- groups.

KW - CsH(SO)

KW - CsHSO

KW - CsLiH(SO)

KW - Proton conductivity

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U2 - 10.1016/S0167-2738(01)00954-7

DO - 10.1016/S0167-2738(01)00954-7

M3 - Conference article

AN - SCOPUS:0035546191

SN - 0167-2738

VL - 145

SP - 185

EP - 189

JO - Solid State Ionics

JF - Solid State Ionics

IS - 1-4

T2 - 10th International Conference on Solid State (SSPC10)

Y2 - 24 September 2000 through 28 September 2000

ER -