A comparison of the impact of cation chemistry in ionic liquid-based lithium battery electrolytes

Makhlooghiazad, Faezeh; Kang, Colin S. M.; Eftekharnia, Mojtaba; Howlett, Patrick C.; Hutt, Oliver; Forsyth, Maria; O’Dell, Luke A.; Pringle, Jennifer M.

doi:10.1039/d3ya00336a

Cited by 2 publications

(1 citation statement)

References 70 publications

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“…Self‐diffusion measurements for 1 H, 19 F, and 7 Li were performed at 50, 70, and 90 °C using a pulsed field gradient stimulated echo NMR pulse sequence with a Bruker Advance III 7.05 T spectrometer equipped with a 5 mm Bruker Diff50 probe with a maximum strength of 3000 G cm −1 . The gradient pulse length was 2 ms and the diffusion time was 20 ms. To extract the diffusion coefficients, the data were fitted in the Bruker Topspin software using the Stejskal–Tanner Equation (5): [ 60 ]

\begin{equation}I\ = {{I}_0}\ \rm .exp\left( { - D{{\gamma }^2}{{g}^2}{{\delta }^2}\left( {\Delta - \frac{\delta }{3}} \right)} \right)\end{equation}

…”

Section: Methodsmentioning

confidence: 99%

Enhanced Li⁺ and Mg²⁺ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors

Demarthe,

O'Dell,

Humbert

et al. 2024

Advanced Energy Materials

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With the widespread use of batteries, their increased performance is of growing in importance. One avenue for this is the enhancement of ion diffusion, particularly for solid‐state electrolytes, for different ions such as lithium (Li+) and magnesium (Mg2+). Unraveling the origin of better cation diffusion in confined ionic liquids (ILs) in a polymer matrix (ionogels) is compared to that of the IL itself. Ionic conductivity measured by electrochemical impedance spectroscopy for ionogels (7.0 mS cm−1 at 30 °C) is very close to the conductivity of the non‐confined IL (8.9 mS cm−1 at 30 °C), that is, 1‐ethyl‐3‐methyimidazolium bis(trifluorosulfonyl)imide (EMIM TFSI). An even better ionic conductivity is observed for confined EMIM TFSI with high concentrations (1 m) of lithium or magnesium salt added. The improved macroscopic transport properties can be explained by the higher self‐diffusion of each ion at the liquid‐to‐solid interface induced by the confinement in a poly‐vinylidenedifluoride (PVDF) polymer matrix. Upon confinement, the strong breaking down of ion aggregates enables a better diffusion, especially for TFSI anion and strongly polarizing cations (e.g., Li+, Mg2+.). The coordination number of these cations in the liquid phase confirmed that Li+ and Mg2+ interact with the polymer matrix. Moreover, it is a major result that the activation energy for diffusion is lowered.

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\begin{equation}I\ = {{I}_0}\ \rm .exp\left( { - D{{\gamma }^2}{{g}^2}{{\delta }^2}\left( {\Delta - \frac{\delta }{3}} \right)} \right)\end{equation}

…”

Section: Methodsmentioning

confidence: 99%

Enhanced Li⁺ and Mg²⁺ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors

Demarthe,

O'Dell,

Humbert

et al. 2024

Advanced Energy Materials

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A Novel High-Performing Ammonium Cation-Based Ionic Liquid Electrolyte for Advanced Lithium Metal Batteries

Pal,

Wu,

Periyapperuma

et al. 2024

J. Phys. Chem. C

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The continued development of ionic liquid electrolytes is a promising pathway toward enabling the safe operation of high-energy-density lithium metal batteries (LMBs), which incorporate a high-voltage cathode such as nickel manganese cobalt oxide (NMC). The physicochemical properties and LMB performance of an ionic liquid electrolyte using an ammonium-based organic ionic plastic crystal (OIPC), N-trimethyl-N-propylammonium bis(fluorosulfonyl)imide (N1113FSI), mixed with lithium bis(fluorosulfonyl)imide (LiFSI) salt are herein reported. Existing as an OIPC at room temperature, the melting temperature of N1113FSI is depressed by the addition of LiFSI. Interestingly, the resulting ionic liquid electrolyte possesses high ionic conductivity, relatively low viscosity, and faster lithium-ion diffusivity, as measured by pulsed-field gradient nuclear magnetic resonance spectroscopy, than other reported benchmark phosphonium and pyrrolidinium-based room-temperature ionic liquid electrolytes. The Li+ solvation structure was probed using molecular dynamics simulations, where the N1113FSI was found to occupy a higher fraction of the monodentate coordination environment than the pyrrolidinium-based IL, namely N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (C3mpyrFSI), which is the suggested basis for the higher conductivity and relative lithium-ion diffusivity. Similarly, the high salt concentration ionic liquid electrolyte formed upon the addition of 50 mol % LiFSI to the N1113FSI shows promising behavior toward LMB operation. Lithium metal cycling in symmetrical cell configuration was performed at 2 mA/cm2|2 mAh/cm2 at 50 °C and was shown to be stable for 100 cycles. Full cell cycling was performed in coin cells using an NMC811 cathode cycled up to 4.3 V (versus Li+|Li) at 50 °C at C/2 (1 mA/cm2), showing 100 cycles with high cathode active material (∼12 mg/cm2) utilization.

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A comparison of the impact of cation chemistry in ionic liquid-based lithium battery electrolytes

Abstract: There is an increasing interest in ionic liquid electrolytes for battery applications because they are potentially safer alternatives to conventional liquid electrolytes. As the properties of ionic liquid electrolytes strongly...

Cited by 2 publications

References 70 publications

Enhanced Li⁺ and Mg²⁺ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors

Enhanced Li⁺ and Mg²⁺ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors

A Novel High-Performing Ammonium Cation-Based Ionic Liquid Electrolyte for Advanced Lithium Metal Batteries

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A comparison of the impact of cation chemistry in ionic liquid-based lithium battery electrolytes

Abstract: There is an increasing interest in ionic liquid electrolytes for battery applications because they are potentially safer alternatives to conventional liquid electrolytes. As the properties of ionic liquid electrolytes strongly...

Cited by 2 publications

References 70 publications

Enhanced Li+ and Mg2+ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors

Enhanced Li+ and Mg2+ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors

A Novel High-Performing Ammonium Cation-Based Ionic Liquid Electrolyte for Advanced Lithium Metal Batteries

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Enhanced Li⁺ and Mg²⁺ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors

Enhanced Li⁺ and Mg²⁺ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors