Yunis R, Hollenkamp AF, Forsyth C, Doherty CM, Al-Masri D, and Pringle JM
Physical Chemistry Chemical Physics: PCCP [Phys Chem Chem Phys] 2019 Jun 21; Vol. 21 (23), pp. 12288-12300. Date of Electronic Publication: 2019 May 29.
The synthesis and characterisation of new solid-state electrolytes is a key step in advancing the development of safer and more reliable electrochemical energy storage technologies. Organic ionic plastic crystals (OIPCs) are an increasingly promising class of material for application in devices such as lithium or sodium metal batteries as they can support high ionic conductivity, with good electrochemical and thermal stability. However, the choice of OIPC-forming ions is still relatively limited. Furthermore, understanding of the influence of different cations and anions on the thermal, structural and transport properties of these materials is still in its infancy. Here we report the synthesis and in-depth characterisation of a range of new OIPCs utilising the hexamethylguanidinium cation ([HMG]) with five different anions. The thermal, structural, transport properties and free volume in the different salts have been investigated. The free volume within the salts has been investigated by positron annihilation lifetime spectroscopy, and the single crystal and powder X-ray diffraction analysis of [HMG] bis(trifluoromethanesulfonyl)imide ([TFSI]) in phase I and II, [HMG] hexafluorophosphate ([PF6]) and [HMG] tetrafluoroborate ([HMG][BF4]) are reported. The HMG cation can exhibit significant disorder, which is advantageous for plasticity and future use of these materials as high ionic conductivity matrices. The bis(fluorosulfonyl)imide salt, [HMG][FSI], is identified as particularly promising for use as an electrolyte, with good electrochemical stability and soft mechanical properties. The findings introduce a range of new materials to the solid-state electrolyte arena, while the insights into the physico-chemical relationships in these materials will be of importance for the future development and understanding of other ionic electrolytes.
Al-Masri D , Yunis R , Hollenkamp AF , and Pringle JM
Chemical Communications (Cambridge, England) [Chem Commun (Camb)] 2018 Apr 05; Vol. 54 (29), pp. 3660-3663.
Contrary to the accepted wisdom that avoids cation symmetry for the sake of optimum electrolyte properties, we reveal outstanding behaviour for the diethylpyrrolidinium cation ([C2epyr]), in combination with the bis(fluorosulfonyl)imide (FSI) anion and Li[FSI]. The equimolar [C2epyr][Li][FSI]2 is a liquid with high conductivity, high Li transference number and >90% lithium metal cycling efficiency. The high level of performance for these electrolytes invites consideration of a new class of electrolytes for lithium batteries.
Lazar MA, Al-Masri D, MacFarlane DR, and Pringle JM
Physical Chemistry Chemical Physics: PCCP [Phys Chem Chem Phys] 2016 Jan 21; Vol. 18 (3), pp. 1404-10. Date of Electronic Publication: 2015 Sep 08.
Thermoelectrochemical cells are increasingly promising devices for harvesting waste heat, offering an alternative to the traditional semiconductor-based design. Advancement of these devices relies on new redox couple/electrolyte systems and an understanding of the interplay between the different factors that dictate device performance. The Seebeck coefficient (Se) of the redox couple in the electrolyte gives the potential difference achievable for a given temperature gradient across the device. Prior work has shown that a cobalt bipyridyl redox couple in ionic liquids (ILs) displays high Seebeck coefficients, but the thermoelectrochemical cell performance was limited by mass transport. Here we present the Se and thermoelectrochemical power generation performance of the cobalt couple in novel mixed IL/molecular solvent electrolyte systems. The highest power density of 880 mW m(-2), at a ΔT of 70 °C, was achieved with a 3 : 1 (v/v) MPN-[C2mim][B(CN)4] electrolyte combination. The significant power enhancement compared to the single solvent or IL systems results from a combination of superior ionic conductivity and higher diffusion coefficients, shown by electrochemical analysis of the different electrolytes. This is the highest power output achieved to-date for a thermoelectrochemical cell utilising a high boiling point redox electrolyte.