Jennifer M. Pringle

Degradation observations of encapsulated planar CH3NH3PbI3 perovskite solar cells at high temperatures and humidity

The stability of encapsulated planar-structured CH3NH3PbI3 (MAPbI3) perovskite solar cells (PSCs) was investigated under various simulated environmental conditions. The tests were performed under approximately one sun (100 mW cm−2) illumination, varying temperature (up to 85 °C cell temperature) and humidity (up to 80%). The application of advanced sealing techniques improved the device stability, but all devices showed significant degradation after prolonged aging at high temperature and humidity. The degradation mechanism was studied by post-mortem analysis of the disassembled cells using SEM and XRD. This revealed that the degradation was mainly due to the decomposition of MAPbI3, as a result of reaction with H2O, and the subsequent reaction of hydroiodic acid, formed during MAPbI3 decomposition, with the silver back contact electrode layer.

Energy applications of ionic liquids

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 thermo-electrochemical 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 CO2 absorbents for post-combustion CO2 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.

Ionic Liquids—An Overview

Ionic liquids have become an increasingly popular class of solvent in the last decade as the potential applications of these materials become more diverse. Rather than being viewed simply as replacement for conventional organic solvent media, research into ionic liquids has progressed to the deliberate choice and design of these materials for reasons of improved rate, specificity, and yield. Design of ionic liquids centres on the development of novel cations and anions to impart the specific physical properties required for each application. Therefore, the materials being synthesized and studied are also becoming increasingly complex and diverse. Here we provide an overview of ionic liquids generally, and some of their current applications, as well as an introduction to some of the new cations and anions that have been developed for specific properties.

Extraction of lignin from lignocellulose at atmospheric pressure using alkylbenzenesulfonate ionic liquid

Lignocellulosic materials are a potentially valuable source of both aromatic compoundsvia the lignin component and sugars from the cellulose and hemicellulose components. However, efficient means of separating and depolymerising the components are required. An ionic liquid mixture containing the 1-ethyl-3-methylimidazolium cation and a mixture of alkylbenzenesulfonates with xylenesulfonate as the main anion was used to extract lignin from sugarcane plant waste at atmospheric pressure and elevated temperatures (170–190 °C). The lignin was recovered from the ionic liquid by precipitation, allowing the ionic liquid to be recycled. An extraction yield exceeding 93% was attained. The lignin produced had a molecular weight of 2220 g/mol after acetylation. The regenerated ionic liquid showed good retention of structure and properties. The other product of the extraction was a cellulose pulp, which can be used in further processing.

Thermal Degradation of Ionic Liquids at Elevated Temperatures

Ionic liquids based on the imidazolium cation are found to degrade, yielding volatile degradation products, at temperatures significantly lower than previously reported and thus a parameter Tz/x (the maximum operating temperature) is developed to provide a more appropriate estimate of thermal stability.

Organic ionic plastic crystals : recent advances

Investigations into the synthesis and utilisation of organic ionic plastic crystals have made significant progress in recent years, driven by a continued need for high conductivity solid state electrolytes for a range of electrochemical devices. There are a number of different aspects to research in this area; fundamental studies, utilising a wide range of analytical techniques, of both pure and doped plastic crystals, and the development of plastic crystal-based materials as electrolytes in, for example, lithium ion batteries. Progress in these areas is highlighted and the development of new organic ionic plastic crystals, including a new class of proton conductors, is discussed.

Lewis base ionic liquids.

Ionic liquids which are (weak) Lewis bases have a number of interesting and useful properties different to those of traditional ionic liquids, including volatility and the possibility of being distillable in some cases, a base catalysis effect in others and enhancement of the acidity of dissolved acids.

The effect of anion fluorination in ionic liquids : physical properties of a range of bis(methanesulfonyl)amide salts

The bis(trifluoromethanesulfonyl)amide, TFSA, anion is widely used in the genesis of room temperature ionic liquids as it is non-spherical, fluorinated and has a particularly diffuse charge. However, the extent to which each of these structural features is responsible for the low melting point, fluidity and excellent stability of the resultant ionic liquids has yet to be described. We present the synthesis and analysis of a range of analogous, non-fluorinated species containing the bis(methanesulfonyl)amide, NMes2−, ligand. Utilisation of this anion produces ionic liquids that are hydrophilic and extremely low melting, but with decreased thermal and electrical stability and significantly increased viscosity. The crystal structures of the dimethyl pyrrolidinium bis(methanesulfonyl)amide and TFSA species are compared, and the number of close contacts within each is assessed. Comparison of these structural and physical properties provides new insight into the effect of anion fluorination on these ionic liquids.

Physical trends and structural features in organic salts of the thiocyanate anion

A new series of ionic liquids based on the thiocyanate anion has been prepared. Incorporation of this anion with an imidazolium, tetraalkylammonium or pyrrolidinium cation produces ionic liquids with advantageously low melting points and good thermal stability. The low temperature phase behaviour of the salts has been investigated using differential scanning calorimetry and multiple solid phases have been observed. The electrochemical windows of representative imidazolium and pyrrolidinium species have been investigated by cyclic voltammetry and determined to be 2.4 and 3.5 V, respectively. In addition, the solid-state structure of N,N-dimethylpyrrolidinium thiocyanate has been determined by X-ray crystallography. This is the first reported structure of a pyrrolidinium thiocyanate species and shows a layered structure with linear thiocyanate groups having bond lengths comparable to those observed in similar SCN−-containing species.

Seebeck coefficients in ionic liquids -prospects for thermo-electrochemical cells

Measurement of Seebeck coefficients in a range of ionic liquids (ILs) suggests that these electrolytes could enable the development of thermoelectric devices to generate electrical energy from low-grade heat in the 100-150 °C range.