Conformational Dynamics in an Organic Ionic Plastic Crystal

Liyu Jin; Kate M. Nairn; Chris D. Ling; Haijin Zhu; Luke A. O'Dell; Jiaye Li; Fangfang Chen; Adriano F. Pavan; Louis A. Madsen; Patrick C. Howlett; Douglas R. Macfarlane; Maria Forsyth; Jennifer M. Pringle

doi:10.1021/acs.jpcb.7b02780

Conformational Dynamics in an Organic Ionic Plastic Crystal

Liyu Jin^*, Kate M. Nairn, Chris D. Ling, Haijin Zhu, Luke A. O'Dell, Jiaye Li, Fangfang Chen, Adriano F. Pavan, Louis A. Madsen, Patrick C. Howlett, Douglas R. Macfarlane, Maria Forsyth, Jennifer M. Pringle

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

Understanding the short-range molecular motions of organic ionic plastic crystals is critical for the application of these materials as solid-state electrolytes in electrochemical devices such as lithium batteries. However, the theory of short-range-motions was originally developed for simple molecular plastic crystals and does not take account of strong interionic interactions that are present in organic ionic plastic crystals. Here we report a fundamental investigation of the dynamic behavior of an archetypal example triethyl(methyl)phosphonium bis(fluorosulfonyl)amide ([P₁₂₂₂][FSI]) through calorimetry, impedance spectroscopy, synchrotron X-ray diffraction, and solid-state NMR and Raman spectroscopies. For the first time, we show the presence of conformational dynamics in the solid state for the FSI anion. We relate the dynamics to a unique second-order displacive phase transition of [P₁₂₂₂][FSI]. This detailed analysis suggests a new disorder mechanism involving cooperative motion between the cation and FSI anion in the plastic crystal due to strong interionic interactions.

Original language	English
Pages (from-to)	5439-5446
Number of pages	8
Journal	Journal of Physical Chemistry B
Volume	121
Issue number	21
DOIs	https://doi.org/10.1021/acs.jpcb.7b02780
State	Published - 1 Jun 2017
Externally published	Yes

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title = "Conformational Dynamics in an Organic Ionic Plastic Crystal",

abstract = "Understanding the short-range molecular motions of organic ionic plastic crystals is critical for the application of these materials as solid-state electrolytes in electrochemical devices such as lithium batteries. However, the theory of short-range-motions was originally developed for simple molecular plastic crystals and does not take account of strong interionic interactions that are present in organic ionic plastic crystals. Here we report a fundamental investigation of the dynamic behavior of an archetypal example triethyl(methyl)phosphonium bis(fluorosulfonyl)amide ([P1222][FSI]) through calorimetry, impedance spectroscopy, synchrotron X-ray diffraction, and solid-state NMR and Raman spectroscopies. For the first time, we show the presence of conformational dynamics in the solid state for the FSI anion. We relate the dynamics to a unique second-order displacive phase transition of [P1222][FSI]. This detailed analysis suggests a new disorder mechanism involving cooperative motion between the cation and FSI anion in the plastic crystal due to strong interionic interactions.",

author = "Liyu Jin and Nairn, {Kate M.} and Ling, {Chris D.} and Haijin Zhu and O'Dell, {Luke A.} and Jiaye Li and Fangfang Chen and Pavan, {Adriano F.} and Madsen, {Louis A.} and Howlett, {Patrick C.} and Macfarlane, {Douglas R.} and Maria Forsyth and Pringle, {Jennifer M.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.jpcb.7b02780",

language = "英语",

volume = "121",

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T1 - Conformational Dynamics in an Organic Ionic Plastic Crystal

AU - Jin, Liyu

AU - Nairn, Kate M.

AU - Ling, Chris D.

AU - Zhu, Haijin

AU - O'Dell, Luke A.

AU - Li, Jiaye

AU - Chen, Fangfang

AU - Pavan, Adriano F.

AU - Madsen, Louis A.

AU - Howlett, Patrick C.

AU - Macfarlane, Douglas R.

AU - Forsyth, Maria

AU - Pringle, Jennifer M.

PY - 2017/6/1

Y1 - 2017/6/1

N2 - Understanding the short-range molecular motions of organic ionic plastic crystals is critical for the application of these materials as solid-state electrolytes in electrochemical devices such as lithium batteries. However, the theory of short-range-motions was originally developed for simple molecular plastic crystals and does not take account of strong interionic interactions that are present in organic ionic plastic crystals. Here we report a fundamental investigation of the dynamic behavior of an archetypal example triethyl(methyl)phosphonium bis(fluorosulfonyl)amide ([P1222][FSI]) through calorimetry, impedance spectroscopy, synchrotron X-ray diffraction, and solid-state NMR and Raman spectroscopies. For the first time, we show the presence of conformational dynamics in the solid state for the FSI anion. We relate the dynamics to a unique second-order displacive phase transition of [P1222][FSI]. This detailed analysis suggests a new disorder mechanism involving cooperative motion between the cation and FSI anion in the plastic crystal due to strong interionic interactions.

AB - Understanding the short-range molecular motions of organic ionic plastic crystals is critical for the application of these materials as solid-state electrolytes in electrochemical devices such as lithium batteries. However, the theory of short-range-motions was originally developed for simple molecular plastic crystals and does not take account of strong interionic interactions that are present in organic ionic plastic crystals. Here we report a fundamental investigation of the dynamic behavior of an archetypal example triethyl(methyl)phosphonium bis(fluorosulfonyl)amide ([P1222][FSI]) through calorimetry, impedance spectroscopy, synchrotron X-ray diffraction, and solid-state NMR and Raman spectroscopies. For the first time, we show the presence of conformational dynamics in the solid state for the FSI anion. We relate the dynamics to a unique second-order displacive phase transition of [P1222][FSI]. This detailed analysis suggests a new disorder mechanism involving cooperative motion between the cation and FSI anion in the plastic crystal due to strong interionic interactions.

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DO - 10.1021/acs.jpcb.7b02780

M3 - 文章

C2 - 28460174

AN - SCOPUS:85021648492

SN - 1520-6106

VL - 121

SP - 5439

EP - 5446

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

IS - 21

ER -

Conformational Dynamics in an Organic Ionic Plastic Crystal

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