Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.
Ionic liquids offer a unique suite of properties that make them important candidates for a number of energy related applications. Cation-anion combinations that exhibit low volatility coupled with high electrochemical and thermal stability, as well as ionic conductivity, create the possibility of designing ideal electrolytes for batteries, super-capacitors, actuators, dye sensitised solar cells and thermoelectrochemical cells. In the field of water splitting to produce hydrogen they have been used to synthesize some of the best performing water oxidation catalysts and some members of the protic ionic liquid family co-catalyse an unusual, very high energy efficiency water oxidation process. As fuel cell electrolytes, the high proton conductivity of some of the protic ionic liquid family offers the potential of fuel cells operating in the optimum temperature region above 100 C. Beyond electrochemical applications, the low vapour pressure of these liquids, along with their ability to offer tuneable functionality, also makes them ideal as CO 2 absorbents for post-combustion CO 2 capture. Similarly, the tuneable phase properties of the many members of this large family of salts are also allowing the creation of phase-change thermal energy storage materials having melting points tuned to the application. This perspective article provides an overview of these developing energy related applications of ionic liquids and offers some thoughts on the emerging challenges and opportunities.
A new family of molten salts is reported, based on the N-alkyl, N-alkyl pyrrolidinium cation and the bis-(trifluoromethane sulfonyl)imide anion. Some of the members of the family are molten at room temperature, while the smaller and more symmetrical members have melting points around 100°C. Of the room-temperature molten salt examples, the methyl butyl derivative exhibits the highest conductivity; at 2 × 10 -3 S/cm this is the highest molten salt conductivity observed to date at room temperature among the ammonium salts. This highly conductive behavior is rationalized in terms of the role of cation planarity. The salts also exhibit multiple crystalline phase behavior below their melting points and exhibit significant conductivity in at least their higher temperature crystal phase. For example, the methyl propyl derivative (mp ) 12°C) shows ion conductivity of 1 × 10 -6 S/cm at 0°C in its higher temperature crystalline phase.
Ammonia is a widely produced chemical that is the basis of most fertilisers. However, it is currently derived from fossil fuels and there is an urgent need to develop sustainable approaches to its production. Ammonia is also being considered as a renewable energy carrier, allowing efficient storage and transportation of renewables. For these reasons, the electrochemical nitrogen reduction reaction (NRR) is currently being intensely investigated as the basis for future mass production of ammonia from renewables. This Perspective critiques current steps and miss-steps towards this important goal in terms of experimental methodology and catalyst selection, proposing a protocol for rigorous experimentation. We discuss the issue of catalyst selectivity and the approaches to promoting the NRR over H 2 production. Finally, we translate these mechanistic discussions, and the key metrics being pursued in the field, into the bigger picture of ammonia production by other sustainable processes, discussing benchmarks by which NRR progress can be assessed.
Ionic liquids are liquids comprised totally of ions. However, not all of the ions present appear to be available to participate in conduction processes, to a degree that is dependent on the nature of the ionic liquid and its structure. There is much interest in quantifying and understanding this 'degree of ionicity' phenomenon. In this paper we present transport data for a range of ionic liquids and evaluate the data firstly in terms of the Walden plot as an approximate and readily accessible approach to estimating ionicity. An adjusted Walden plot that makes explicit allowance for differences in ion sizes is shown to be an improvement to this approach for the series of ionic liquids described. In some cases, where diffusion measurements are possible, it is feasible to directly quantify ionicity via the Nernst-Einstein equation, confirming the validity of the adjusted Walden plot approach. Some of the ionic liquids studied exhibit ionicity values very close to ideal; this is discussed in terms of a model of a highly associated liquid in which the ion correlations have similar impact on both the diffusive and conductive motions. Ionicity, as defined, is thus a useful measure of adherence to the Nernst-Einstein equation, but is not necessarily a measure of ion availability in the chemical sense.
pi-Conjugated polymers that are electrochemically cycled in ionic liquids have enhanced lifetimes without failure (up to 1 million cycles) and fast cycle switching speeds (100 ms). We report results for electrochemical mechanical actuators, electrochromic windows, and numeric displays made from three types of pi-conjugated polymers: polyaniline, polypyrrole, and polythiophene. Experiments were performed under ambient conditions, yet the polymers showed negligible loss in electroactivity. These performance advantages were obtained by using environmentally stable, room-temperature ionic liquids composed of 1-butyl-3-methyl imidazolium cations together with anions such as tetrafluoroborate or hexafluorophosphate.
Ammonia is increasingly recognized as an important, sustainable fuel for global use in the future. Applications of ammonia in heavy transport, power generation, and distributed energy storage are being actively developed. Produced at scale, ammonia could replace a substantial fraction of current-day liquid fuel consumption. This ammonia-based economy will emerge through multiple generations of technology development and scale-up. The pathways forward in regard to current-day technology (generation 1) and immediate future approaches (generation 2) that rely on Haber-Bosch process are discussed. Generation 3 technology breaks this nexus with the Haber-Bosch process and enables direct reduction of dinitrogen to ammonia electrochemically. However, the roadmap toward scale in this technology has become obscured by recent research missteps. Nevertheless, alternative generation 3 approaches are becoming viable. We conclude with perspectives on the broader scale sustainability of an ammonia economy and the need for further understanding of the planetary nitrogen cycles of which ammonia is an important part.
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