Electroanalytical Applications of Semiintegral and Convolution Voltammetry in Room-Temperature Ionic Liquids

Bentley, Cameron Luke; Bond, Alan M.; Hollenkamp, Anthony F.; Mahon, Peter J.

doi:10.1007/978-3-319-13485-7_5

Cited by 4 publications

(11 citation statements)

References 74 publications

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“…14 These observations have given rise to doubts as to whether the iodide/triiodide (I À /I 3 À ) redox system is capable of sustaining reversible ORR/OER chemistry via LiOH formation and decomposition. [14][15][16][17] The electrochemical behavior of the iodide/triiodide redox system has been extensively reported in the literature, and it is by now well established that the (I À /I 3 À ) redox potential is solvent dependent 12,[18][19][20] : the oxidizing power of I 3 À can be readily tailored by means of adjusting the physicochemical parameters of the electrolyte (dielectric constant, ionic strength, Gutmann acceptor/donor numbers, etc.). Ionic liquids (ILs) have been shown to alter the solvation/coordination environments of this redox system, again substantially affecting the (I À /I 3…”

Section: Context and Scalementioning

confidence: 99%

“…) redox potential, 18 while still allowing high ionic conductivity and reducing solvent volatility. [21][22][23][24][25][26][27][28] However, the high viscosity of ILs, which reduces the O 2 diffusion coefficients, and the low O 2 solubility are disadvantageous for LAB performance.…”

Section: Context and Scalementioning

confidence: 99%

“…The (I À /I 3 À ) redox potential at standard (aqueous) conditions (E versus Li/Li + ) corresponds to 3.5761 V, 18,41 which is sufficiently large to drive oxygen evolution. However, the reversibility of iodide-mediated aprotic Li-O 2 batteries, cycling through LiOH, has been a much-discussed subject due to the difficulty of performing the OER process at low overpotentials (below 3.5 V).…”

Section: Articlementioning

confidence: 99%

“…This expression indicates that three key variables dictate the driving force for the OER: the redox equilibrium potential of the I À /I 3 À couple (EðI À =I À 3 Þ), the water activity (D sol GðH 2 OÞ), and the oxygen partial pressure ðP O 2 Þ. The redox potential of the iodide/triiodide redox system is solvent dependent, [18][19][20] the couple varying by over 0.5 V, 18 whereas variations in the solvent activity and gas partial pressure are of smaller magnitude (estimated to be $0.17 and $0.08 eV, respectively; Table S2). The variability in the values of the EðI À =I À…”

Section: Articlementioning

confidence: 99%

“…3 Þ is strongly influenced by stabilizing (donor-acceptor) interactions of I À species in solution, 18,20 since D r GðI À =I À 3 Þ is proportional to the difference in D sol G of I À and I 3 6)…”

Section: Articlementioning

confidence: 99%

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Li-air batteries have attracted significant attention due to their very high energy density, comparable to that of fossil fuels. For their development, a stable discharge product that can be reversibly decomposed during charge needs to be developed. LiOH is a promising candidate, but questions concerning the reversibility of the charge process have been raised. Here, we report for the first time Li-O 2 cells that can reversibly cycle via LiOH by using water and an ionic liquid as additives in the electrolyte.

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Section: Context and Scalementioning

confidence: 99%

Section: Context and Scalementioning

confidence: 99%

Section: Articlementioning

confidence: 99%

Section: Articlementioning

confidence: 99%

Section: Articlementioning

confidence: 99%

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Voltammetric Perspectives on the Acidity Scale and H⁺/H₂ Process in Ionic Liquid Media

Bentley

Bond

Zhang³

2018

Annual Rev. Anal. Chem.

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Nonhaloaluminate ionic liquids (ILs) have received considerable attention as alternatives to molecular solvents in diverse applications spanning the fields of physical, chemical, and biological science. One important and often overlooked aspect of the implementation of these designer solvents is how the properties of the IL formulation affect (electro)chemical reactivity. This aspect is emphasized herein, where recent (voltammetric) studies on the energetics of proton (H) transfer and electrode reaction mechanisms of the H/H process in IL media are highlighted and discussed. The energetics of proton transfer, quantified using the p K (minus logarithm of acidity equilibrium constant, K) formalism, is strongly governed by the constituent IL anion, and to a lesser extent, the IL cation. The H/H process, a model inner-sphere reaction, also displays electrochemical characteristics that are strongly IL-dependent. Overall, these studies highlight the need to carry out systematic investigations to resolve IL structure and function relationships in order to realize the potential of these diverse and versatile solvents.

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Organic Ionic Plastic Crystal/PVDF Composites Prepared by Solution Casting

Wang,

Rochefort

2024

Preprint

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Solid-state electrolytes have been considered as a promising candidate to address the safety issues for next-generation lithium batteries. Organic ionic plastic crystals (OIPCs) are attracting increasing interest as solid electrolyte materials due to their unique advantages. In this study, an OIPC-based composite electrolyte consisting of the OIPC 1-ethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr12TFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and the polymer polyvinylidene fluoride (PVDF) has been developed by a facile solution casting strategy. Free-standing and flexible OIPC/polymer composite membranes were fabricated by the solution casting method, which not only provides flexibility and better electrode/electrolyte contact, but also is more compatible with current battery processing methods. The thermal behavior and ionic conductivity of the OIPC-based composites with different molar proportions (10 mol% to 67 mol%) of LiTFSI in LiTFSI/Pyr12TFSI as well as different weight fractions (20 wt% to 50 wt%) of PVDF were studied to understand the effect on transport properties. Among all the compositions studied, the Li0.33Pyr0.67TFSI/30wt%PVDF composite exhibited high ionic conductivity (e.g. 1.2 × 10−4 S cm-1 at 30 °C). The Li0.33Pyr0.67TFSI/30wt%PVDF composite membrane was evaluated in Li/Li symmetric cell and was cycled stably over 900 h at a current density of 0.1 mA cm−2 at 50 °C, demonstrating that this OIPC/polymer composite electrolyte enabled the reversible and stable lithium plating and stripping behaviors. Further tests of the Li0.33Pyr0.67TFSI/30wt%PVDF composite membrane as solid electrolyte in LiFePO4/Li cell presented a high specific capacity of 149 mAh g−1 at 0.1 C and a long cycle life of over 440 cycles with capacity retention of 89% at 0.5 C at 50 °C, which showed improved rate capability and cycling stability in comparison with the composites with similar compositions but obtained by powder pressing method. This study demonstrated the potential of the OIPC/polymer composite solid electrolyte prepared by solution casting method and will promote the development of high-performance OIPC-based composite electrolytes for solid-state batteries.

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Electroanalytical Applications of Semiintegral and Convolution Voltammetry in Room-Temperature Ionic Liquids

Cited by 4 publications

References 74 publications

Toward Reversible and Moisture-Tolerant Aprotic Lithium-Air Batteries

Toward Reversible and Moisture-Tolerant Aprotic Lithium-Air Batteries

Voltammetric Perspectives on the Acidity Scale and H⁺/H₂ Process in Ionic Liquid Media

Organic Ionic Plastic Crystal/PVDF Composites Prepared by Solution Casting

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Electroanalytical Applications of Semiintegral and Convolution Voltammetry in Room-Temperature Ionic Liquids

Cited by 4 publications

References 74 publications

Toward Reversible and Moisture-Tolerant Aprotic Lithium-Air Batteries

Toward Reversible and Moisture-Tolerant Aprotic Lithium-Air Batteries

Voltammetric Perspectives on the Acidity Scale and H+/H2 Process in Ionic Liquid Media

Organic Ionic Plastic Crystal/PVDF Composites Prepared by Solution Casting

Contact Info

Product

Resources

About

Voltammetric Perspectives on the Acidity Scale and H⁺/H₂ Process in Ionic Liquid Media