Molecular insights: structure and dynamics of a Li ion doped organic ionic plastic crystal

Jin, Liyu; Leeuw, Simon de; Koudriachova, Marina V.; Pringle, Jennifer M.; Howlett, Patrick C.; Chen, Fang Fang; Forsyth, Maria

doi:10.1039/c3cp53604a

Cited by 11 publications

(12 citation statements)

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“…In addition to the overall structure of the matrix ions, the structure immediately surrounding the alkali metal ions was also investigated–in particular, the interactions with the PF 6 – anion. Both Li + or Na + ions incorporated within an electrolyte system will have a coordination sphere of counterion species, such as is observed in RTILs, with the precise speciation being dependent on the nature of both cation and anion. ,, In a recent MD study of a Li-doped N,N,N,N -tetramethylammonium dicyanamide ([TMA][DCA]) system, the formation of a coordination complex between a Li + dopant and several neighboring [DCA] − anions was reported. This was suggested to be key to the increased conductivity of the Li-doped system, due to the creation of more free volume in the plastic crystal matrix, which enhances the self-diffusion of unbound ions.…”

Section: Resultsmentioning

confidence: 99%

“…Previous work has amply demonstrated the efficiency of computational modeling in the exploration of new materials; this has been widely used for RTILs, contributing significantly to the understanding of these materials for battery applications. ,− However, related studies on OIPCs are relatively rare, partly due to the difficulties in determining accurate single crystal structures that are desirable as a first starting configuration for the simulation box and also for determining the potential functions to be used during the simulation. A small number of previous MD studies have investigated the structures and dynamics (rotation and diffusion) of ions in pure OIPC systems, − plus we have recently reported the first study of a Li-doped OIPC system . These investigations have helped to elucidate the complicated thermodynamics and phase behavior of these materials from a structural point of view.…”

Section: Introductionmentioning

confidence: 92%

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Insights into the Transport of Alkali Metal Ions Doped into a Plastic Crystal Electrolyte

2015

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The application of organic ionic plastic crystals (OIPCs) as a new class of solid electrolyte for energy storage devices such as lithium batteries and, more recently, sodium batteries is attracting increasing attention. Key to this is achieving sufficient target ion transport through the material. This requires fundamental understanding of the structure and dynamics of OIPCs that have been doped with the necessary lithium or sodium salts. Here we report, for the first time, the atomic level structure and transport of both lithium and sodium ions in the plastic crystalline phases of an OIPC diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate. These molecular dynamics simulations reveal two types of coordination geometries of the alkali metal ion first solvation shells, which cooperate closely with the metal ion hopping motion. The significantly different ion migration rates between two metal ion doped systems could also be related to the differences in solvation structures.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 92%

Insights into the Transport of Alkali Metal Ions Doped into a Plastic Crystal Electrolyte

2015

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“…The transport mechanism of the alkali metal ion dopants, including both Li + and Na + , and their impacts on ionic conductivity were also investigated through MD simulations in the [P 122i4 ][PF 6 ] and tetramethylammonium dicyanamide ([TMA][DCA]) OIPCs . In the [TMA][DCA] system, Li dopants were found to strongly coordinate with the DCA anions, resulting in the shift of the DCA anions from their lattice sites, which increases the free volume in the OIPC, thereby enhancing the diffusion of the remaining “free” DCA anions.…”

Section: Simulation‐assisted Design Of New Solid‐state Electrolytesmentioning

confidence: 99%

Toward High‐Energy‐Density Lithium Metal Batteries: Opportunities and Challenges for Solid Organic Electrolytes

et al. 2020

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.201905219.With increasing demands for safe, high capacity energy storage to support personal electronics, newer devices such as unmanned aerial vehicles, as well as the commercialization of electric vehicles, current energy storage technologies are facing increased challenges. Although alternative batteries have been intensively investigated, lithium (Li) batteries are still recognized as the preferred energy storage solution for the consumer electronics markets and next generation automobiles. However, the commercialized Li batteries still have disadvantages, such as low capacities, potential safety issues, and unfavorable cycling life. Therefore, the design and development of electromaterials toward high-energy-density, long-life-span Li batteries with improved safety is a focus for researchers in the field of energy materials. Herein, recent advances in the development of novel organic electrolytes are summarized toward solid-state Li batteries with higher energy density and improved safety. On the basis of new insights into ionic conduction and design principles of organic-based solid-state electrolytes, specific strategies toward developing these electrolytes for Li metal anodes, high-energy-density cathode materials (e.g., high voltage materials), as well as the optimization of cathode formulations are outlined. Finally, prospects for next generation solid-state electrolytes are also proposed.

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“…23,24 Recently, the existence of one or more than one solid-solid phase transition in ionic liquid plastic crystals has drawn attention due to the specific contribution of various solid phases to the electrolytic properties. [24][25][26][27][28][29][30][31] Protic ionic liquids (PILs) were favoured for their potential use in portable and long life cycle energy devices over acid electrolytes mainly due to a high energy density, a large electrochemical window and a wide range of thermal stabilities. In the search for proton conducting ILs, the applicability of ammoniumbased PILs has been well examined in the past decade.…”

Section: Introductionmentioning

confidence: 99%

Molecular dynamics simulations of ammonium/phosphonium-based protic ionic liquids: influence of alkyl to aryl group

Mondal

Sunda

2018

Phys. Chem. Chem. Phys.

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The variation of the center atom in the cation from an N to a P-atom leads to improved physiochemical properties of protic ionic liquids (PILs) which are suitable for electrolyte applications. We present an atomistic simulations study to compare the effect of an alkyl or aryl group on trioctylammonium triflate ([HN(Oct)3][TFO]) and triphenylammonium triflate ([HN(Ph)3][TFO]) with their phosphonium analogues. We have computed the binding energy from quantum chemical calculations and physical properties such as the viscosity and the electrical conductivity of PILs from molecular dynamics simulations. The influence of the aromatic character in PILs is found to be significant to the physical properties. Gas phase quantum chemical calculations on clusters of ion pairs have revealed the presence of C-H/π interactions in aromatic PILs along with hydrogen bonding. The variation in strength of the ion-pair affinities is examined using electric-current correlation and velocity autocorrelation functions. The qualitative differences observed are due to the aromatic rings and change in the central atom of the quaternary cation from an N to a P-atom, substantiated quantitatively by diffusion coefficients and electrical conductivities. The relatively weaker ion-pair interactions and low binding energy (-73.34 kcal mol-1) lead to the highest electrical conductivity in [HP(Ph)3][TFO].

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Molecular insights: structure and dynamics of a Li ion doped organic ionic plastic crystal

Cited by 11 publications

References 28 publications

Insights into the Transport of Alkali Metal Ions Doped into a Plastic Crystal Electrolyte

Insights into the Transport of Alkali Metal Ions Doped into a Plastic Crystal Electrolyte

Toward High‐Energy‐Density Lithium Metal Batteries: Opportunities and Challenges for Solid Organic Electrolytes

Molecular dynamics simulations of ammonium/phosphonium-based protic ionic liquids: influence of alkyl to aryl group

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