Proton conducting plastic crystal electrolytes based on pivalic acid

Abu-Lebdeh, Yaser; Abouimrane, Ali; Alarco, Pierre‐Jean; Dividson, Isobel; Armand, Michel

doi:10.1016/j.jpowsour.2005.12.041

Cited by 18 publications

(19 citation statements)

References 25 publications

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“…The acid doping of succinonitrile to achieve good proton conductivity has been reported, 73,74 as has the addition of imidazole to pivalic acid. 75 However, the volatility and relatively low melting points of these molecular plastic crystals would be significant disadvantages for fuel cell applications. In contrast, the melting point of [choline][DHP] is 195 1C and the thermal stability of this OIPC doped with phosphoric acid is good, with minimal weight loss up to 200 1C.…”

Section: Perspective Pccpmentioning

confidence: 99%

Recent progress in the development and use of organic ionic plastic crystal electrolytes

Pringle

2013

Phys. Chem. Chem. Phys.

188

219

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Significant progress has been made recently in the development of Organic Ionic Plastic Crystals (OIPCs), a unique family of solid state electrolytes with applications in electrochemical devices such as lithium batteries and dye-sensitised solar cells. The negligible volatility of OIPCs renders them more suitable than molecular species for long-term device use, while the high thermal and electrochemical stability of many OIPCs fulfils an essential requirement for solid state electrolytes for many device applications. However, the complex mechanisms of conduction through these materials, both in their pure state and in the presence of a small amount of a second component (such as lithium salts to enable their use in lithium batteries) are still not fully understood. At the same time, the range of anions and cations utilised in the synthesis of plastic crystal phases continues to increase. This perspective concentrates on recent research into both fundamental and device-oriented aspects of these materials. Important fundamental understanding of the physical properties and transport mechanisms of different OIPCs has been achieved through use of techniques including variable temperature solid-state NMR and crystallographic analysis, as well as detailed molecular dynamics simulations. In parallel, the applicability of these materials as electrolytes for dye-sensitised solar cells and lithium batteries is being more widely demonstrated. The possibility of using OIPCs as solid state electrolytes for fuel cells is also discussed.

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Section: Perspective Pccpmentioning

confidence: 99%

Recent progress in the development and use of organic ionic plastic crystal electrolytes

Pringle

2013

Phys. Chem. Chem. Phys.

188

219

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“…An obvious step increase in ionic conductivity is sometimes observed in organic ionic plastic crystals at their solid-solid phase transitions, where the conductivity enhancement is attributed to an increased number of charge carriers with a higher mobility arising from the increase in rotational and/or translational motions. 34,[36][37][38] Fig. 4(a) shows that the conductivity increases significantly upon the addition of H 3 PO 4 with almost 3 orders of magnitude increase at room temperature (in the lower temperature phase III) and over an order of magnitude for the highest temperature phase I for the 18 mol% acid containing sample.…”

Section: Conductivity Analysismentioning

confidence: 99%

“…The solid phases of many ionic liquids have either rotator phases [27][28][29][30][31][32] or plastic crystal phases [33][34][35][36][37][38] in which one or more of the ions undergo rotation and/or translational motion, yielding quite high ionic conductivities in the solid state. Doping of small ions into these solid-state matrices has been shown to increase the ionic conductivity.…”

Section: Introductionmentioning

confidence: 99%

Proton transport in choline dihydrogen phosphate/H3PO4 mixtures

Rana

Bayley

Vijayaraghavan

et al. 2010

Phys. Chem. Chem. Phys.

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Mixtures of the plastic crystal material choline dihydrogen phosphate [Choline][DHP] and phosphoric acid, from 4.5 mol% to 18 mol% H(3)PO(4), were investigated and shown to have significantly higher proton conductivity compared to the pure [Choline][DHP]. This was particularly evident from the electrochemical hydrogen reduction reaction and the proton NMR diffusion measurements, in addition to ionic conductivity measured from the impedance spectroscopy. The ionic conductivity was observed to increase by more than an order of magnitude in phase I (i.e. the highest temperature solid phase in [Choline][DHP]) reaching up to 10(-2) S cm(-1). The multinuclear NMR spectroscopy data suggest that, at least on the timescale of the NMR measurement, the H(+) cations and [DHP] anions are equivalent in both phases. The pulsed field gradient NMR diffusion measurements of the 18 mol% acid sample indicate that all three ions are mobile, however the H(+) diffusion coefficient is an order of magnitude higher than for the [Choline] cation or the [DHP] anion, and therefore conduction in these materials is dominated by proton conductivity. The thermal stability, as measured by TGA, is unaffected with increasing acid additions and remains high; i.e. no significant mass loss below 200 °C.

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“…succinonitrile and choline triate). [26][27][28][29] Recently, a new class of proton-conducting OIPCs utilizing the dihydrogenphosphate anion, which can generate protons as a carrier and in fact correspond to Brønsted acidic ionic liquids, 4 has been reported. 30,31 25 Nevertheless, there are still very limited reports on protic OIPCs, 19,25,[32][33][34][35] which have intrinsic proton conductivity and are pure plastic crystals, obviating the need for the addition of a dopant that may be incompatible with the host matrix.…”

Section: Introductionmentioning

confidence: 99%

Imidazolium methanesulfonate as a high temperature proton conductor

2013

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Imidazolium methanesulfonate (1) has been studied as a model proton conductor for high temperature polymer electrolyte membrane fuel cells (PEMFCs). It is found that 1 undergoes transformation from crystalline to plastic crystalline and then molten states successively from ambient temperature to 200 C.The solid-solid phase transition of 1 at 174 C has been preliminarily verified by differential scanning calorimetry (DSC) and temperature-dependent X-ray diffraction (XRD). At the melting point of 188 C, 1 displays a low entropy of fusion of around 24 J mol À1 K À1 . In particular, a high ionic conductivity of 1.0 Â 10 À2 S cm À1 is reached at 185 C in the plastic phase. The activation energy for ionic conduction decreases as 1 is heated from the crystal phase to the melt phase. In the molten state, the contribution of protons to the ionic conductivity of 1 was corroborated electrochemically. In addition, 1 is electrochemically active for H 2 oxidation and O 2 reduction at a Pt electrode while it shows a high electrochemical window of 2.0 V. Furthermore, a NafionÒ membrane has been successfully doped with 1, as identified by infrared spectroscopy, powder XRD, grazing incidence XRD and thermogravimetric analysis. To the best of our knowledge, this may be the first report on a protic organic ionic plastic crystal (OIPC) consisting of protonated imidazole (C 3 H 5 N 2 + ) and an organic anion. The good thermal stability, high ionic conductivity, wide electrochemical window, favorable plastic crystal behavior and simple synthesis make 1 a highly interesting model proton conductor for high temperature PEMFCs.

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Proton conducting plastic crystal electrolytes based on pivalic acid

Cited by 18 publications

References 25 publications

Recent progress in the development and use of organic ionic plastic crystal electrolytes

Recent progress in the development and use of organic ionic plastic crystal electrolytes

Proton transport in choline dihydrogen phosphate/H3PO4 mixtures

Imidazolium methanesulfonate as a high temperature proton conductor

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