Ionic liquids as potential electrolytes for sodium-ion batteries: an overview.

In this study, we present an overview on the use of ionic liquids (ILs) as electrolytes in sodium-ion batteries (SIBs). The development of SIBs has gained traction over the last few years because Na is cheaper and more abundant than Li. In this case, although great efforts have been devoted to finding high-capacity and high cell potential materials for SIBs, electrolyte safety is an important factor in producing more competitive and reliable devices. Specifically, the intrinsic volatility of the organic solvent-based electrolytes commonly used in commercial systems is a safety risk during the operation of batteries, and thus replacing them with ILs is an alternative that should be considered. This family of electrolytes is more thermally stable than organic solvents, but they suffer from poor transport properties. Herein, we discuss these properties, considering neat ILs, effects of cations and anions, and effect of salt concentration. Moreover, the strategies to overcome the transport limitations are highlighted. Then, the recent applications of mixtures containing sodium salts and ILs as electrolytes for the negative and positive electrodes in SIBs are presented. Finally, the use of Na-IL mixtures in solid-state electrolytes is discussed.

Downplaying the role of water in the rheological changes of conducting polymers by using water-in-salt electrolytes.

Volumetric changes associated with solvent/electrolyte exchange in electronic conducting polymers (ECPs) play an important role in the mechanical stability of the polymers, as these changes are a critical factor in ECP-based energy storage devices. Thus, the present work explores the hindering of such volumetric deformations for polypyrrole films doped with dodecylbenzenesulphonate (PPy(DBS)) by employing highly concentrated aqueous electrolytes (or water-in-salt electrolytes, WiSEs), and their effects over the corresponding electrochemical capacitor cell energy retention. Electrochemical quartz crystal microbalance with dissipation monitoring measurements for thin PPy(DBS) films in the WiSEs revealed negligible dissipation changes (ΔDn ≈ 0), in contrast with those in dilute aqueous electrolyte (ΔDn ≠ 0), indicating inexpressive structural deformation of PPy(DBS) in the WiSE. This phenomenon is observed for thick freestanding PPy(DBS) films, which presented a maximum bending angle decay from ∼56° (diluted aqueous electrolyte) to 3.5° when working in the WiSE, thus proving the hindering of film bending. The observed trends are reflected in the PPy(DBS) cell energy retention, where the use of a WiSE decreased cell energy fading by 30% after 600 cycles, in comparison with cells based on diluted electrolytes.

An Overview on the Development of Electrochemical Capacitors and Batteries - part II.

In the second part of the review on electrochemical energy storage, the devolvement of batteries is explored. First, fundamental aspects of battery operation will be given, then, different materials and chemistry of rechargeable batteries will be explored, including each component of the cell. In negative electrodes, metallic, intercalation and transformation materials will be addressed. Examples are Li or Na metal batteries, graphite and other carbonaceous materials (such as graphene) for intercalation of metal-ions and transition metal oxides and silicon for transformation. In the positive electrode section, materials for intercalation and transformation will be reviewed. The state-of-the-art on intercalation as lithium cobalt oxide and nickel containing oxides will be approached for intercalation materials, whereas sulfur and metal-air will also be explored for transformation. Alongside, the role of electrolyte will be discussed concerning performance and safety, with examples for the next generation devices. Finally, a general future perspective will address both electrochemical capacitors and batteries.

An Overview on the Development of Electrochemical Capacitors and Batteries - Part I.

The Nobel Prize in Chemistry 2019 recognized the importance of Li-ion batteries and the revolution they allowed to happen during the past three decades. They are part of a broader class of electrochemical energy storage devices, which are employed where electrical energy is needed on demand and so, the electrochemical energy is converted into electrical energy as required by the application. This opens a variety of possibilities on the utilization of energy storage devices, beyond the well-known mobile applications, assisting on the decarbonization of energy production and distribution. In this series of reviews in two parts, two main types of energy storage devices will be explored: electrochemical capacitors (part I) and rechargeable batteries (part II). More specifically, we will discuss about the materials used in each type of device, their main role in the energy storage process, their advantages and drawbacks and, especially, strategies to improve their performance. In the present part, electrochemical capacitors will be addressed. Their fundamental difference to batteries is explained considering the process at the electrode/electrolyte surface and the impact in performance. Materials used in electrochemical capacitors, including double layer capacitors and pseudocapacitive materials will be reviewed, highlighting the importance of electrolytes. As an important part of these strategies, synthetic routes for the production of nanoparticles will also be approached (part I).

Improved Performance of Ionic Liquid Supercapacitors by using Tetracyanoborate Anions.

Supercapacitors are energy storage devices designed to operate at higher power densities than conventional batteries, but their energy density is still too low for many applications. Efforts are made to design new electrolytes with wider electrochemical windows than aqueous or conventional organic electrolytes in order to increase energy density. Ionic liquids (ILs) with wide electrochemical stability windows are excellent candidates to be employed as supercapacitor electrolytes. ILs containing tetracyanoborate anions [B(CN)4] offer wider electrochemical stability than conventional electrolytes and maintain a high ionic conductivity (6.9 mS cm-1). Herein, we report the use of ILs containing the [B(CN)4] anion for such an application. They presented a high maximum operating voltage of 3.7 V, and two-electrode devices demonstrate high specific capacitances even when operating at relatively high rates (ca. 20 F g-1 @ 15 A g-1). This supercapacitor stored more energy and operated at a higher power at all rates studied when compared with cells using a commonly studied ILs.

Ionic liquids containing tricyanomethanide anions: physicochemical characterisation and performance as electrochemical double-layer capacitor electrolytes.

We investigated the use of fluorine free ionic liquids (ILs) containing the tricyanomethanide anion ([C(CN)3]) as an electrolyte in electrochemical double-layer capacitors (EDLCs). Three cations were used; 1-butyl-3-methylimidazolium ([Im1,4]), N-butyl-N-methylpyrrolidinium ([Pyr1,4]) and N-butyl-N-methylpiperidinium ([Pip1,4]). Their physicochemical properties are discussed alongside with their performance as electrolytes. We found that the cyano-based ILs present higher ionic conductivity (9.4, 8.7 and 4.2 mS cm-1 at 25 °C for [Im1,4], [Pyr1,4] and [Pip1,4], respectively) than the widely studied IL containing the bis(trifluoromethylsulfonyl)imide anion, namely [Pyr1,4][Tf2N] (2.7 mS cm-1 at 25 °C). Of the three ILs investigated, [Pip1,4][C(CN)3] presents the widest electrochemical stability window, 3.0 V, while [Pyr1,4][C(CN)3] is stable up to 2.9 V and its [Tf2N] analogue can operate at 3.5 V. Despite operating at a lower voltage, [Pyr1,4][C(CN)3] EDLC is capable of delivering up to 4.5 W h kg-1 when operating at high specific power of 7.2 kW kg-1, while its [Pyr1,4][Tf2N] counterpart only delivered 3.0 W h kg-1 when operated at similar power.

Influence of Particle Size Distribution on the Performance of Ionic Liquid-based Electrochemical Double Layer Capacitors.

Electrochemical double layer capacitors (EDLCs) employing ionic liquid electrolytes are the subject of much research as they promise increased operating potentials, and hence energy densities, when compared with currently available devices. Herein we report on the influence of the particle size distribution of activated carbon material on the performance of ionic liquid based EDLCs. Mesoporous activated carbon was ball-milled for increasing durations and the resultant powders characterized physically (using laser diffraction, nitrogen sorption and SEM) and investigated electrochemically in the form of composite EDLC electrodes. A bi-modal particle size distribution was found for all materials demonstrating an increasing fraction of smaller particles with increased milling duration. In general, cell capacitance decreased with increased milling duration over a wide range of rates using CV and galvanostatic cycling. Reduced coulombic efficiency is observed at low rates (<25 mVs(-1)) and the efficiency decreases as the volume fraction of the smaller particles increases. Efficiency loss was attributed to side reactions, particularly electrolyte decomposition, arising from interactions with the smaller particles. The effect of reduced efficiency is confirmed by cycling for over 15,000 cycles, which has the important implication that diminished performance and reduced cycle life is caused by the presence of submicron-sized particles.

Two phosphonium ionic liquids with high Li(+) transport number.

This work presents the physicochemical characterization of two ionic liquids (ILs) with small phosphonium cations, triethylpenthylphosphonium bis(trifluoromethanesulfonyl)imide ([P2225][Tf2N]) and (2-methoxyethyl)trimethylphosphonium bis(trifluoromethanesulfonyl)imide ([P222(201)][Tf2N]), and their mixtures with Li(+). Properties such as the electrochemical window, density, viscosity and ionic conductivity are presented. The diffusion coefficient was obtained using two different techniques, PGSE-NMR and Li electrodeposition with microelectrodes. In addition, the Li(+) transport number was calculated using the PGSE-NMR technique and an electrochemical approach. The use of these three techniques showed that the PGSE-NMR technique underestimates the diffusion coefficient for charged species. The Li(+) transport number was found to be as high as 0.54. Raman spectroscopy and molecular dynamics simulations were used to evaluate the short-range structure of the liquids. These experiments suggested that the interaction between the Li(+) and the Tf2N(-) anion is similar to that seen with other ILs containing the same anion. However, the MD simulations also showed that the Li(+) ions interact differently with the cation containing an alkyl ether chain. The results found in this work suggest that these Li(+) mixtures have promising potential to be applied as electrolytes in batteries.

Physicochemical properties of three ionic liquids containing a tetracyanoborate anion and their lithium salt mixtures.

Given their relevant physicochemical properties, ionic liquids (ILs) are attracting great attention as electrolytes for use in different electrochemical devices, such as capacitors, sensors, and lithium ion batteries. In addition to the advantages of using ILs containing lithium cations as electrolytes in lithium ion batteries, the Li(+) transport in ILs containing the most common anion, bis(trifluoromethanesulfonyl) imide anion ([Tf2N]), is reportedly small; therefore, its contribution to the overall conductivity is also low. In this work, we describe the preparation and characterization of two new and one known IL containing the tetracyanoborate anion ([B(CN)4]) as the anionic species. These ILs have high thermal and chemical stabilities, with almost twice the ionic conductivity of the [Tf2N] ILs and, most importantly, provide a greater role for the Li(+) ion throughout the conductivity process. The experimental ionic conductivity and self-diffusion coefficient data show that the [B(CN)4]-based ILs and their Li(+) mixtures have a higher number of charge carriers. Molecular dynamics simulations showed a weaker interaction between Li(+) and [B(CN)4] than that with [Tf2N]. These results may stimulate new applications for ILs that have good Li(+) transport properties.

Influence of the water content on the structure and physicochemical properties of an ionic liquid and its Li+ mixture.

The effect of water on the hydrophobic ionic liquid (IL) 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonylimide) and its Li(+) mixture was evaluated. The electrochemical stability, density, viscosity, and ionic conductivity were measured for both systems in different concentrations of water. The presence of Li(+) causes a large increase in the water absorption ability of the IL. The experimental results suggest a break of the interactions between Li(+) and Tf2N(-) anions in the strong aggregates formed in dried Li(+) mixtures, modifying the size and physicochemical nature of these aggregates. It is also observed that the size of the ions aggregates with formal charge increases at high temperature and decreases the mobility of the charge carrier, explaining the break in the Walden rules at high temperature. Raman spectroscopy and molecular dynamic simulations show the structural change of these systems. In neat ILs, the water molecules interact mainly among each other, while in the Li(+) mixtures, water interacts preferentially with the metallic cation, causing an important change in the aggregates present in this system.

Ni(ii)-modified solid substrates as a platform to adsorb His-tag proteins.

This work investigated a simple and versatile modification to a solid substrate to develop electrochemical bio-recognition platforms based on bio-affinity interactions between histidine (His)-tagged proteins and Ni(ii) surface sites. Carboxylate (COO)-functionalized substrates were prepared in multiple steps, initiated with an amino-terminated self-assembled monolayer (SAM) on polycrystalline gold. Surface enhanced Raman spectroscopy (SERS), quartz crystal microbalance with dissipation monitoring (QCM-D) and contact angle measurements were used to follow the modification process. Upon completion of the modification process, the surface COO-Ni(ii) chelate complex and the coordination mode used to bind the His-tag proteins were characterized by X-ray absorption near-edge spectroscopy (XANES). Finally, the electrochemical stability and response of the modified substrates were evaluated. The versatility of the modification process was verified using silica as the substrate. QCM-D and SERS results indicated that two types of films were formed: a COO-terminated SAM, which resulted from the reduction of previously incorporated surface aldehyde groups, and a physically adsorbed polymeric glutaraldehyde film, which was produced in the alkaline medium. XANES spectral features indicated that COO-Ni(ii) formed a non-distorted octahedral complex on the substrate. The electrochemical stability and response towards a redox mediator of the COO-Ni(ii)-terminated SAM indicated that this platform could be easily coupled to an electrochemical method to detect bio-recognition events.