The ion-ion correlations in organic ionic plastic crystal

Ahmed, Md. Dipu; Martins, Murillo L.; Abdullah, Mohanad; Singh, Harmandeep; Zheng, Allen; Greenbaum, Steven; Sokolov, Alexei P.; Popov, Ivan

doi:10.20517/energymater.2024.209

Title: The ion-ion correlations in organic ionic plastic crystal

Journal Article · 27 March 2025 · Energy Materials

DOI: https://doi.org/10.20517/energymater.2024.209 · OSTI ID:2549306

Ahmed, Md. Dipu ^[1]; Martins, Murillo L. ^[2]; Abdullah, Mohanad ^[1]; Singh, Harmandeep ^[2]; Zheng, Allen ^[3]; Greenbaum, Steven ^[3];

^[2];

^[1]

University of Tennessee, Knoxville, TN (United States)
University of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Hunter College of the City University of New York, NY (United States)

Organic ionic plastic crystals (OIPCs) are emerging as promising electrolyte materials for solid-state batteries. However, despite the fast ionic diffusion, OIPCs exhibit relatively low DC conductivity in solid phases caused by strong ion-ion correlations that suppress charge transport. To understand the origin of this suppression, we performed a study of ion dynamics in the OIPC 1-Ethyl-1-methylpyrrolidinium bis (trifluoromethyl sulfonyl) imide [P₁₂][TFSI] utilizing dielectric spectroscopy, light scattering, and Nuclear Magnetic Resonance diffusometry. Comparison of the results obtained in this study with the published earlier results on an OIPC with a completely different structure (Diethyl(methyl)(isobutyl)phosphonium Hexafluorophosphate [P_1,2,2,4][PF₆]) revealed strong similarities in ion dynamics in both systems. Unlike DC conductivity, which may drop more than ten times between melted and solid phases, diffusion of anions and cations remains high and does not show strong changes at phase transition. The conductivity spectra in the broad frequency range demonstrate unusual shapes in solid phases with an additional step separating fast local ion motions from suppressed long-range charge diffusion controlling DC conductivity. We suggested that in solid phases, anions and cations can jump only between the specific ion sites defined by the crystalline structure. These constraints lead to strong cation-cation and anion-anion correlations strongly suppressing long-range charge transport.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Case Western Reserve University, Cleveland, OH (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019409

OSTI ID:: 2549306

Journal Information:: Energy Materials, Journal Name: Energy Materials Journal Issue: 7 Vol. 5; ISSN 2770-5900

Publisher:: OAECopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Plastic Crystal Electrolyte Materials: New Perspectives on Solid State Ionics MacFarlane, D. R.; Forsyth, M. Advanced Materials, Vol. 13, Issue 12-13 https://doi.org/10.1002/1521-4095(200107)13:12/13<957::aid-adma957>3.0.co;2-#	journal	July 2001
Organic Ionic Plastic Crystals as Hole Transporting Layer for Stable and Efficient Perovskite Solar Cells Sonigara, Keval K.; Shao, Zhipeng; Prasad, Jyoti Advanced Functional Materials, Vol. 30, Issue 28 https://doi.org/10.1002/adfm.202001460	journal	May 2020
Unexpected Energy Applications of Ionic Liquids Matuszek, Karolina; Piper, Samantha L.; Brzęczek‐Szafran, Alina Advanced Materials, Vol. 36, Issue 23 https://doi.org/10.1002/adma.202313023	journal	March 2024
Mixed Phase Solid-State Plastic Crystal Electrolytes Based on a Phosphonium Cation for Sodium Devices Makhlooghiazad, Faezeh; Gunzelmann, Daniel; Hilder, Matthias Advanced Energy Materials, Vol. 7, Issue 2 https://doi.org/10.1002/aenm.201601272	journal	September 2016
Ionic Liquids and Organic Ionic Plastic Crystals: Advanced Electrolytes for Safer High Performance Sodium Energy Storage Technologies Basile, Andrew; Hilder, Matthias; Makhlooghiazad, Faezeh Advanced Energy Materials, Vol. 8, Issue 17 https://doi.org/10.1002/aenm.201703491	journal	May 2018
Quantitative Phase Analysis Madsen, Ian C.; Scarlett, Nicola V. Y.; Webster, Nathan A. S. Uniting Electron Crystallography and Powder Diffraction https://doi.org/10.1007/978-94-007-5580-2_19	book	January 2012
Development of new solid-state electrolytes based on a hexamethylguanidinium plastic crystal and lithium salts Biernacka, Karolina; Al-Masri, Danah; Yunis, Ruhamah Electrochimica Acta, Vol. 357 https://doi.org/10.1016/j.electacta.2020.136863	journal	October 2020
Unveiling the dynamic change in the ionic conductivity of a solid-state binary mixture comprising an organic ionic plastic crystal and LiBF4 Ueda, Hiroyuki; Saito, Naoto; Nakanishi, Azusa Materials Today Physics, Vol. 43 https://doi.org/10.1016/j.mtphys.2024.101395	journal	April 2024
New insights into ordering and dynamics in organic ionic plastic crystal electrolytes Forsyth, M.; Chen, F.; O'Dell, L. A. Solid State Ionics, Vol. 288 https://doi.org/10.1016/j.ssi.2015.11.025	journal	May 2016
Organic Ionic Plastic Crystals as Solid-State Electrolytes Zhu, Haijin; MacFarlane, Douglas R.; Pringle, Jennifer M. Trends in Chemistry, Vol. 1, Issue 1 https://doi.org/10.1016/j.trechm.2019.01.002	journal	April 2019
Solid state lithium ion conduction in pyrrolidinium imide–lithium imide salt mixtures Huang, J. Solid State Ionics, Vol. 136-137, Issue 1-2 https://doi.org/10.1016/s0167-2738(00)00450-1	journal	November 2000
Self-Diffusion Coefficients and Related Transport Properties for a Number of Fragile Ionic Liquids Harris, Kenneth R.; Kanakubo, Mitsuhiro Journal of Chemical & Engineering Data, Vol. 61, Issue 7 https://doi.org/10.1021/acs.jced.6b00021	journal	June 2016
Effect of Ion Mass on Dynamic Correlations in Ionic Liquids Ahmed, Md. Dipu; Zhu, Zhenghao; Khamzin, Airat The Journal of Physical Chemistry B, Vol. 127, Issue 48 https://doi.org/10.1021/acs.jpcb.3c05568	journal	November 2023
Can the Transport Properties of Molten Salts and Ionic Liquids Be Used To Determine Ion Association? Harris, Kenneth R. The Journal of Physical Chemistry B, Vol. 120, Issue 47 https://doi.org/10.1021/acs.jpcb.6b08381	journal	November 2016
Mechanism of Conductivity Relaxation in Liquid and Polymeric Electrolytes: Direct Link between Conductivity and Diffusivity Gainaru, C.; Stacy, E. W.; Bocharova, V. The Journal of Physical Chemistry B, Vol. 120, Issue 42 https://doi.org/10.1021/acs.jpcb.6b08567	journal	October 2016
Strongly Correlated Ion Dynamics in Plastic Ionic Crystals and Polymerized Ionic Liquids Popov, Ivan; Biernacka, Karolina; Zhu, Haijin The Journal of Physical Chemistry C, Vol. 124, Issue 33 https://doi.org/10.1021/acs.jpcc.0c03297	journal	July 2020
Investigation of Unusual Conductivity Behavior and Ion Dynamics in Hexamethylguanidinium Bis(fluorosulfonyl)imide-Based Electrolytes for Sodium Batteries Biernacka, Karolina; Makhlooghiazad, Faezeh; Popov, Ivan The Journal of Physical Chemistry C, Vol. 125, Issue 23 https://doi.org/10.1021/acs.jpcc.1c01777	journal	June 2021
Collective Ion Dynamics in Ionic Plastic Crystals: The Origin of Conductivity Suppression Popov, Ivan; Zhu, Haijin; Khamzin, Airat The Journal of Physical Chemistry C, Vol. 127, Issue 32 https://doi.org/10.1021/acs.jpcc.3c03590	journal	August 2023
Ion Mobilities, Transference Numbers, and Inverse Haven Ratios of Polymeric Ionic Liquids Zhang, Zidan; Wheatle, Bill K.; Krajniak, Jakub ACS Macro Letters, Vol. 9, Issue 1 https://doi.org/10.1021/acsmacrolett.9b00908	journal	December 2019
Charge Transport and Glassy Dynamics in Ionic Liquids Sangoro, Joshua R.; Kremer, Friedrich Accounts of Chemical Research, Vol. 45, Issue 4 https://doi.org/10.1021/ar2001809	journal	November 2011
Evaluation of velocity correlation coefficients from experimental transport data in electrolytic systems Schoenert, Hans Juergen The Journal of Physical Chemistry, Vol. 88, Issue 15 https://doi.org/10.1021/j150659a045	journal	July 1984
Structure and Transport Properties of a Plastic Crystal Ion Conductor: Diethyl(methyl)(isobutyl)phosphonium Hexafluorophosphate Jin, Liyu; Nairn, Kate M.; Forsyth, Craig M. Journal of the American Chemical Society, Vol. 134, Issue 23 https://doi.org/10.1021/ja301175v	journal	May 2012
Pulsed-Gradient Spin−Echo ¹ H and ¹⁹ F NMR Ionic Diffusion Coefficient, Viscosity, and Ionic Conductivity of Non-Chloroaluminate Room-Temperature Ionic Liquids Noda, Akihiro; Hayamizu, Kikuko; Watanabe, Masayoshi The Journal of Physical Chemistry B, Vol. 105, Issue 20 https://doi.org/10.1021/jp004132q	journal	May 2001
Physicochemical Properties and Structures of Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in Imidazolium Cation Tokuda, Hiroyuki; Hayamizu, Kikuko; Ishii, Kunikazu The Journal of Physical Chemistry B, Vol. 109, Issue 13 https://doi.org/10.1021/jp044626d	journal	April 2005
Physicochemical Properties and Structures of Room Temperature Ionic Liquids. 1. Variation of Anionic Species Tokuda, Hiroyuki; Hayamizu, Kikuko; Ishii, Kunikazu The Journal of Physical Chemistry B, Vol. 108, Issue 42 https://doi.org/10.1021/jp047480r	journal	October 2004
Physicochemical Properties and Structures of Room-Temperature Ionic Liquids. 3. Variation of Cationic Structures Tokuda, Hiroyuki; Ishii, Kunikazu; Susan, Md. Abu Bin Hasan The Journal of Physical Chemistry B, Vol. 110, Issue 6 https://doi.org/10.1021/jp053396f	journal	February 2006
How Ionic Are Room-Temperature Ionic Liquids? An Indicator of the Physicochemical Properties Tokuda, Hiroyuki; Tsuzuki, Seiji; Susan, Md. Abu Bin Hasan The Journal of Physical Chemistry B, Vol. 110, Issue 39 https://doi.org/10.1021/jp064159v	journal	October 2006
Relations between the Fractional Stokes−Einstein and Nernst−Einstein Equations and Velocity Correlation Coefficients in Ionic Liquids and Molten Salts Harris, Kenneth R. The Journal of Physical Chemistry B, Vol. 114, Issue 29 https://doi.org/10.1021/jp102687r	journal	July 2010
How Is Charge Transport Different in Ionic Liquids and Electrolyte Solutions? Kashyap, Hemant K.; Annapureddy, Harsha V. R.; Raineri, Fernando O. The Journal of Physical Chemistry B, Vol. 115, Issue 45 https://doi.org/10.1021/jp204182c	journal	November 2011
Dynamic Heterogeneity and Ionic Conduction in an Organic Ionic Plastic Crystal and the Role of Vacancies Chen, Fangfang; de Leeuw, Simon W.; Forsyth, Maria The Journal of Physical Chemistry Letters, Vol. 4, Issue 23 https://doi.org/10.1021/jz402222j	journal	November 2013
Lithium-doped plastic crystal electrolytes exhibiting fast ion conduction for secondary batteries MacFarlane, Douglas R.; Huang, Junhua; Forsyth, Maria Nature, Vol. 402, Issue 6763 https://doi.org/10.1038/45514	journal	December 1999
Ionic liquids and their solid-state analogues as materials for energy generation and storage MacFarlane, Douglas R.; Forsyth, Maria; Howlett, Patrick C. Nature Reviews Materials, Vol. 1, Issue 2 https://doi.org/10.1038/natrevmats.2015.5	journal	January 2016
Lithium doped N-methyl-N-ethylpyrrolidinium bis(trifluoromethanesulfonyl)amide fast-ion conducting plastic crystals Forsyth, Maria; Huang, Junhua; MacFarlane, Douglas R. Journal of Materials Chemistry, Vol. 10, Issue 10 https://doi.org/10.1039/b003168m	journal	January 2000
On the concept of ionicity in ionic liquids MacFarlane, Douglas R.; Forsyth, Maria; Izgorodina, Ekaterina I. Physical Chemistry Chemical Physics, Vol. 11, Issue 25 https://doi.org/10.1039/b900201d	journal	January 2009
Organic ionic plastic crystals: recent advances Pringle, Jennifer M.; Howlett, Patrick C.; MacFarlane, Douglas R. Journal of Materials Chemistry, Vol. 20, Issue 11 https://doi.org/10.1039/b920406g	journal	January 2010
Recent progress in the development and use of organic ionic plastic crystal electrolytes Pringle, Jennifer M. Phys. Chem. Chem. Phys., Vol. 15, Issue 5 https://doi.org/10.1039/c2cp43267f	journal	January 2013
Proton transport behaviour and molecular dynamics in the guanidinium triflate solid and its mixtures with triflic acid Zhu, Haijin; Rana, Usman ali; Ranganathan, Vijayraghavan J. Mater. Chem. A, Vol. 2, Issue 3 https://doi.org/10.1039/c3ta13344c	journal	January 2014
Structure and dynamics in an organic ionic plastic crystal, N-ethyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl) amide, mixed with a sodium salt Forsyth, Maria; Chimdi, Tarekegn; Seeber, Aaron J. Mater. Chem. A, Vol. 2, Issue 11 https://doi.org/10.1039/c3ta15153k	journal	January 2014
New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid–solid phase transitions Romanenko, Konstantin; Pringle, Jennifer M.; O'Dell, Luke A. Physical Chemistry Chemical Physics, Vol. 17, Issue 29 https://doi.org/10.1039/c5cp03294f	journal	January 2015
Exploration of phase diagram, structural and dynamic behavior of [HMG][FSI] mixtures with NaFSI across an extended composition range Biernacka, Karolina; Makhlooghiazad, Faezeh; Popov, Ivan Physical Chemistry Chemical Physics, Vol. 24, Issue 27 https://doi.org/10.1039/d2cp01910h	journal	January 2022
Organic ionic plastic crystals: flexible solid electrolytes for lithium secondary batteries Thomas, Morgan L.; Hatakeyama-Sato, Kan; Nanbu, Shinkoh Energy Advances, Vol. 2, Issue 6 https://doi.org/10.1039/d3ya00078h	journal	January 2023
Defect-assisted conductivity in organic ionic plastic crystals Pas, Steven J.; Huang, Junhua; Forsyth, Maria The Journal of Chemical Physics, Vol. 122, Issue 6 https://doi.org/10.1063/1.1845397	journal	January 2005
The random free‐energy barrier model for ac conduction in disordered solids Dyre, Jeppe C. Journal of Applied Physics, Vol. 64, Issue 5 https://doi.org/10.1063/1.341681	journal	September 1988
Atomistic simulation of structure and dynamics of the plastic crystal diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate Chen, F.; Jin, L.; de Leeuw, S. W. The Journal of Chemical Physics, Vol. 138, Issue 24 https://doi.org/10.1063/1.4811179	journal	June 2013
Fundamental questions relating to ion conduction in disordered solids Dyre, Jeppe C.; Maass, Philipp; Roling, Bernhard Reports on Progress in Physics, Vol. 72, Issue 4 https://doi.org/10.1088/0034-4885/72/4/046501	journal	March 2009
Electrode polarization in dielectric measurements: a review Ishai, Paul Ben; Talary, Mark S.; Caduff, Andreas Measurement Science and Technology, Vol. 24, Issue 10 https://doi.org/10.1088/0957-0233/24/10/102001	journal	August 2013
Nonstandard relaxation behavior in ionically conducting materials Maass, Philipp; Meyer, Martin; Bunde, Armin Physical Review B, Vol. 51, Issue 13 https://doi.org/10.1103/physrevb.51.8164	journal	April 1995
Ion transport in glass: Influence of glassy structure on spatial extent of nonrandom ion hopping Roling, B.; Martiny, C.; Brückner, S. Physical Review B, Vol. 63, Issue 21 https://doi.org/10.1103/physrevb.63.214203	journal	May 2001
ac Hopping Conduction at Extreme Disorder Takes Place on the Percolating Cluster Schrøder, Thomas B.; Dyre, Jeppe C. Physical Review Letters, Vol. 101, Issue 2 https://doi.org/10.1103/physrevlett.101.025901	journal	July 2008
Quantitative phase analysis using the Rietveld method Bish, D. L.; Howard, S. A. Journal of Applied Crystallography, Vol. 21, Issue 2 https://doi.org/10.1107/s0021889887009415	journal	April 1988

Similar Records

Dynamics of fluorinated imide-based ionic liquids using nuclear magnetic resonance techniques

Journal Article · 2025 · Physical Chemistry Chemical Physics · OSTI ID:2997389

Pranto, Tawhid; Fraenza, Carla C.; Philippi, Frederik; +5 more

Supercapacitive properties of micropore- and mesopore-rich activated carbon in ionic liquid electrolytes with various constituent ions

Journal Article · 2018 · ChemSusChem · OSTI ID:1493121

Nguyen, Quoc Dat; Patra, Jagabandhu; Hsieh, Chien-Te; +3 more

Ion Dynamics in Ionic-Liquid-Based Li-Ion Electrolytes Investigated by Neutron Scattering and Dielectric Spectroscopy

Journal Article · 2018 · ChemSusChem · OSTI ID:1479749

Jafta, Charl J.; Bridges, Craig; Haupt, Leon; +10 more

Related Subjects

36 MATERIALS SCIENCE
Organic ionic plastic crystal
ion conductivity
ion-ion correlations

Title: The ion-ion correlations in organic ionic plastic crystal

Citation Formats

References (50)

Similar Records

Related Subjects