<p>Oil/water microemulsions (µEs) are promising electrolytes for redox flow batteries (RFBs) as they simultaneously improve charge capacity and ionic conductivity. Here, we report the successful formulation of bicontinuous µEs where the oil phase is a solution of trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid in toluene with redox-active ferrocene. We examined the effect of supporting electrolyte anion (NO<sub>3</sub><sup>–</sup>, Cl<sup>–</sup>, ClO<sub>4</sub><sup>–</sup>) on the structure, reactivity, transport, and electrolytic performance of redox-active µEs. Neutron scattering and nuclear magnetic resonance showed that the domain size increased as Cl<sup>–</sup> &gt; NO<sub>3</sub><sup>–</sup> &gt; ClO<sub>4</sub><sup>–</sup> while the ferrocene diffusion coefficient increased as NO<sub>3</sub><sup>–</sup> &gt; Cl<sup>–</sup> &gt; ClO<sub>4</sub><sup>–</sup>. Scanning electrochemical microscopy indicated anion-dependent current fluctuations during electrolysis, with ClO<sub>4</sub><sup>–</sup> exhibiting the least high-frequency oscillations, which correlate to the highest charge and discharge capacity and reversibility. All ionic liquid containing systems improved the performance of toluene-based µEs, highlighting new design principles for these electrolytes.</p> Graphic Abstract <p></p>

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Structuring, stochastic behavior, and charge storage capacity of redox-active microemulsions formulated with mixtures of toluene and ionic liquid as oil phase

  • Armando Santiago-Carboney,
  • Mrinalini K. Ayilliath Kolaprath,
  • Adam Imel,
  • Mark D. Dadmun,
  • Joaquín Rodríguez-López

摘要

Oil/water microemulsions (µEs) are promising electrolytes for redox flow batteries (RFBs) as they simultaneously improve charge capacity and ionic conductivity. Here, we report the successful formulation of bicontinuous µEs where the oil phase is a solution of trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid in toluene with redox-active ferrocene. We examined the effect of supporting electrolyte anion (NO3, Cl, ClO4) on the structure, reactivity, transport, and electrolytic performance of redox-active µEs. Neutron scattering and nuclear magnetic resonance showed that the domain size increased as Cl > NO3 > ClO4 while the ferrocene diffusion coefficient increased as NO3 > Cl > ClO4. Scanning electrochemical microscopy indicated anion-dependent current fluctuations during electrolysis, with ClO4 exhibiting the least high-frequency oscillations, which correlate to the highest charge and discharge capacity and reversibility. All ionic liquid containing systems improved the performance of toluene-based µEs, highlighting new design principles for these electrolytes.

Graphic Abstract