A solvent-free, SeCN-/(SeCN)3- based ionic liquid electrolyte for high-efficiency dye-sensitized nanocrystalline solar cells

A solvent-free ionic liquid electrolyte based on the SeCN-/(SeCN)3- redox couple has been employed for high-efficiency dye-sensitized nanocrystalline solar cells. For the first time an alternative redox couple has been identified to rival and even exceed the performance of the iodide/triiodide couple even at full sunlight. Unprecedented 7.5-8.3% power conversion efficiencies under AM 1.5 sunlight have been achieved for photovoltaic devices with solvent-free ionic liquid electrolytes.     

Effect of liquid paraffin on the stability of aqueous foam in the presence and absence of electrolytes

The foam stability of dodecyl diphenyl ether disulfonate solution with liquid paraffin droplets in the presence and absence of electrolytes was evaluated, and the stabilization mechanisms were deduced. The foam film is stabilized when the monovalent and divalent counterion concentration is lower than a critical value. However, the foam stability declined with the addition of trivalent counterions. There are two mechanisms we have speculated. Firstly, the counterions reduce the repulsive interaction between the polar groups of surfactants adsorbed at the air/water and oil/water interfaces in the pseudo-emulsion film. Secondly, comparing with the monovalent counterions, the multivalent counterions are not only able to interconnect head groups of adjacent ionic surfactant molecules which are adsorbed at the air/water or oil/water interface, but also to attract the couples of neighboring surfactant head groups adsorbed at the air/water and oil/water interfaces. The attractive interaction between both the interfaces promotes the emulsified droplets piercing the air/water interface.     

Ionophore‐Based Biphasic Chemical Sensing in Droplet Microfluidics

Droplet microfluidics is an enabling platform for high‐throughput screens, single‐cell studies, low‐volume chemical diagnostics, and microscale material syntheses. Analytical methods for real‐time and in situ detection of chemicals in the droplets will benefit these applications, but they remain limited. Reported herein is a novel heterogeneous chemical sensing strategy based on functionalization of the oil phase with rationally combined sensing reagents. Sub‐nanoliter oil segments containing pH‐sensitive fluorophores, ionophores, and ion‐exchangers enable highly selective and rapid fluorescence detection of physiologically important electrolytes (K⁺, Na⁺, and Cl^?) and polyions (protamine) in sub‐nanoliter aqueous droplets. Electrolyte analysis in whole blood is demonstrated without suffering from optical interference from the sample matrix. Moreover, an oil phase doped with an aza‐BODIPY dye allows indication of H₂O₂ in the aqueous droplets, exemplifying sensing of targets beyond ionic species.     

Redox-active electrolyte supercapacitors using electroactive ionic liquids

Here we present redox ionic liquid supercapacitors (RILSCs) which use electrolytes made from ionic liquids modified with an electroactive function to increase the energy density of activated carbon electrodes via faradaic reactions. More specifically, two different ionic liquids were made by modifying either the imidazolium cation or the bis(trifluoromethanesulfonyl)imide anion with ferrocene in order to determine the importance of the electroactive ion's polarity. The functionalization of an ionic liquid with ferrocene led to high concentrations of redox moieties in the electrolyte (2.4 M) and a large maximum operating voltage (2.5 V). An energy density of up to 13.2 Wh per kg (both electrodes) was obtained which represents an 83% increase vs. the unmodified ionic liquid. When the ionic liquid's anion is modified with ferrocene, the self-discharge at the positive electrode is fully suppressed due to the deposition of a film on the electrode. The results presented herein demonstrate that electroactive ionic liquids constitute a promising alternative to conventional solute in solvent electrolytes found in energy storage devices, and are particularly well-suited for redox-active electrolyte supercapacitors.     

Ion insertion into ionic liquid supported toluene generated by electrochemical redox reaction

Ion transfer across the toluene|water, toluene–ionic liquid mixture|water and ionic liquid|water boundary generated by electrochemical redox reaction of tert-butylferrocene (tBuFc) was studied with the glassy carbon (GC) electrode partially covered by the organic liquid deposit and immersed in the aqueous electrolyte solution. The electrooxidation of the redox probe in toluene deposit is followed by ejection of newly formed cation into the aqueous solution. The same reaction in the toluene–ionic liquid deposit promotes anion insertion. This pathway is also found at the electrode modified with ionic liquid.     

Electrokinetic motion of a micro oil droplet under a glass slide

Electrokinetic motion of a micro oil droplet beneath a glass slide was experimentally investigated in this paper. The micro oil droplets were released under the glass slide in an aqueous solution and the motion along the glass slide was measured by a microscope. The experimental results indicate that while the electrokinetic mobility increases with the applied electric field, it decreases with the oil droplet size and the ionic concentration of the aqueous solution, respectively. By changing the zeta potential of the glass‐liquid interface using polybrene coating from negative to positive, the direction of the electrokinetic mobility is reversed and the absolute value of the electrokinetic mobility increases significantly. Finally, pH effects were also investigated, and it was found that the electrokinetic mobility of the droplets reaches a maximum at pH = 6～8.     

Ion transfer processes at ionic liquid based redox active drop deposited on an electrode surface

Ion transfer across the boundary formed at an ionic liquid drop deposited on an electrode immersed in aqueous solution, generated by electrochemical redox reaction at the electrode-ionic liquid interface, is studied to obtain information about the ability of anions to be transferred into a room temperature ionic liquid.     

Particle self-assembly at ionic liquid-based interfaces

This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid–water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid–water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water–ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil or water is incorporated.     

Electroless deposition of metallic silver from a choline chloride-based ionic liquid: a study using acoustic impedance spectroscopy, SEM and atomic force microscopy

In this paper, we describe the first example of a sustained galvanic coating deposited on a surface from a non-aqueous liquid. We present the surface characterization of electroless silver deposits on copper substrates from a solution of Ag(+) ions in an ionic liquid based on a choline chloride (ChCl) eutectic. Through a study of these deposits and the mechanism of formation using acoustic impedance spectroscopy (QCM), probe microscopy (AFM) and electron microscopy (SEM/EDX), we demonstrate that sustained growth of the silver deposit is facilitated by the porous nature of the silver. This is in contrast to the dip-coating reaction of silver ions in aqueous media, where the reaction stops when surface coverage is reached. Electroless silver deposits of up to several microns have been obtained by dip coating in ionic liquids without the use of catalysts of strong inorganic acids.     

Describing the unsuspected advantage of redox ionic liquids applied to electrochemical energy storage

Ionic liquids are a class of solvents widely studied in the literature for various applications. As a subclass of ionic liquids, redox ionic liquids can endow charge exchange properties (electrons transfer) to these electrolytes for electrochemical energy storage. In this review article, we propose to study this family of ionic liquids and suggest a chronological classification. We introduce five generations of redox ionic liquids with different basic compounds such as polyethylene glycol, ferrocene, different linker lengths, TFSI anion, and biredox ionic liquids. The versatility of the redox ionic liquids synthesis will be discussed as well as the fundamental and applied aspects of their use as electrolytes, which have high charge densities. The impact of the redox ionic liquids on the electrochemical mechanisms will be described. We also present how the redox shuttle effect, detrimental to supercapacitors, can be prevented while it can be used to improve lithium-ion batteries.     

Remarkable Electrochemical Responses of Ferrocene/NaY Zeolite Composite modified Electrode Based on Hydrophobic Ionic Liquid

The ferrocene/NaY zeolite composites (Fc/NaY) are introduced on the surface of a glassy carbon electrode together with the hydrophobic ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆). The modified electrode thus constructed exhibits a pair of reversible redox peaks corresponding to ferrocene. Additionally the peak separation remains almost constant (58–75 mV) and the value of the ratio i_pa/i_pc is close to 1 for scan rates in the range from 10 to 1000 mV s^?1. The effects of the scan rate, aqueous supporting electrolytes, hydrophobic ionic liquid and the contents of ferrocene encapsulated by electrochemistry are investigated. The extrazeolite electron transfer process is discussed. Furthermore, the Fc/NaY/IL‐modified electrode shows good mediation towards oxidation of ascorbic acid, dopamine, hydroquinone, and catechol.     

Solubilization of thermotropic liquid crystal compounds in aqueous surfactant solutions

We study the micellar solubilization of three thermotropic liquid crystal compounds by immersing single drops in aqueous solutions of the ionic surfactant tetradecyltrimethylammonium bromide. For both nematic and isotropic drops, we observe a linear decrease of the drop size with time as well as convective flows and self-propelled motions. The solubilization is accompanied by the appearance of small aqueous droplets within the nematic or isotropic drop. At low temperatures, nematic drops expell small nematic droplets into the aqueous environment. Smectic drops show the spontaneous formation of filament-like structures which resemble the myelin figures observed in lyotropic lamellar systems. In all cases, the liquid crystal drops become completely solubilized, provided the weight fraction of the liquid crystal in the system is not larger than a few percent. The solubilization of the liquid crystal drops is compared with earlier studies of the solubilization of alkanes in ionic surfactant solutions.     

Systematic Study of Quaternary Ammonium Cations for Bromine Sequestering Application in High Energy Density Electrolytes for Hydrogen Bromine Redox Flow Batteries

Bromine complexing agents (BCAs) are used to reduce the vapor pressure of bromine in the aqueous electrolytes of bromine flow batteries. BCAs bind hazardous, volatile bromine by forming a second, heavy liquid fused salt. The properties of BCAs in a strongly acidic bromine electrolyte are largely unexplored. A total of 38 different quaternary ammonium halides are investigated ex situ regarding their properties and applicability in bromine electrolytes as BCAs. The focus is on the development of safe and performant HBr/Br₂/H₂O electrolytes with a theoretical capacity of 180 Ah L⁻¹ for hydrogen bromine redox flow batteries (H₂/Br₂-RFB). Stable liquid fused salts, moderate bromine complexation, large conductivities and large redox potentials in the aqueous phase of the electrolytes are investigated in order to determine the most applicable BCA for this kind of electrolyte. A detailed study on the properties of BCA cations in these parameters is provided for the first time, as well as for electrolyte mixtures at different states of charge of the electrolyte. 1-ethylpyridin-1-ium bromide [C2Py]Br is selected from 38 BCAs based on its properties as a BCA that should be focused on for application in electrolytes for H₂/Br₂-RFB in the future.     

The Electrochemistry of Tetraphenyl Porphyrin Iron(III) Within Immobilized Droplets Supported on Platinum Electrodes

For the first time, the voltammetry of an ensemble of immobilized benzonitrile microdroplets containing 5,10,15,20‐tetraphenyl‐21H,23H‐porphine iron (III) chloride, TPPFeCl immobilized at platinum electrodes immersed in various aqueous electrolytes has been explored. The reduction of TPPFeCl was observed with the voltammetric response seen to be highly dependent on the nature of ions in the surrounding aqueous phase. Unlike voltammetry in purely homogeneous solution the nature of the aqueous electrolyte can influence the voltammetry in the droplet phase. The electrochemical reduction of TPPFeCl contained within tetrabutylammonium chloride (TBACl) supported benzonitrile (PhCN) microdroplets immersed into an aqueous solution of TBACl was first studied. During TPPFeCl reduction the resulting [TPPFeCl]^? species is stabilized due to the excess of chloride anions inside the oil droplet. Voltammograms of homogeneous solutions of PhCN supported with TBACl show similar chemically reversible process which is also attributed to the stable [TPPFeCl]^? species. This anion stabilization was not observed when the oil droplets were supported with tetrabutylammonium perchlorate (TBAP) or when the PhCN solution bathing the microdroplet ensemble was supported with TBAP resulting in a chemically irreversible process. The voltammetry of unsupported droplets immobilized on a platinum electrode immersed in different aqueous electrolytes was also explored and the fate of the [TPPFeCl]^? species formed considered during the reduction sweep. Similarities and difference to voltammetry in purely homogeneous media are noted and the use of droplet voltammetry provides complimentary information.     

Electrochemical Studies of Vitamin K1 Microdroplets: Electrocatalytic Hydrogen Evolution

The voltammetry of a basal-plane pyrolytic graphite electrode modified with a random ensemble of unsupported microdroplets of vitamin K₁ is investigated when the electrode is immersed in aqueous electrolytes. It is shown that in dilute acidic solutions, electroreduction occurs in a single two-electron two-proton process to yield the corresponding hydroquinone at the electrode|vitamin K₁ microdroplet|aqueous-electrolyte three-phase boundary. On addition of ionic alkali-metal salts to the aqueous acidic phase, the electrochemical reduction of vitamin K₁ to the quinol is accompanied by catalytic hydrogen evolution within and alkali-metal-cation insertion into the organic microdroplets. In strongly alkaline solutions, electrochemical reduction of vitamin K₁ at the triple-phase junction is proposed as being a single two-electron process with concomitant uptake of alkali-metal cations in order to maintain electroneutrality within the oil phase. Surprisingly, the relative ease of cation insertion into the oil phase is demonstrated to be governed by the degree of ion-pair formation rather than by the Gibbs transfer energy of the cation across the liquid|liquid interface.     

Recent Progress in the Electrolytes of Aqueous Zinc-Ion Batteries

Rechargeable aqueous zinc-ion batteries (ZIBs) have garnered tremendous attention in the field of next energy storage devices due to their high safety, low cost, abundant resources, and eco-friendliness. As an important component of the zinc-ion battery, the electrolyte plays a vital role in the electrochemical properties, since it will provide a pathway for the migrations of the zinc ions between the cathode and anode, and determine the ionic conductivity, electrochemically stable potential window, and reaction mechanism. In this Minireview, a brief introduction of electrochemical principles of the aqueous ZIBs is discussed and the recent advances of various aqueous electrolytes for ZIBs, including liquid, gel, and multifunctional hydrogel electrolytes are also summarized. Furthermore, the remaining challenges and future directions of electrolytes in aqueous ZIBs are also discussed, which could provide clues for the following development.     

Solvate Ionic Liquids for Li,Na, K,and Mg Batteries

From the viewpoint of element strategy, non‐Li batteries with promising negative and positive electrodes have been widely studied to support a sustainable society. To develop non‐Li batteries having high energy density, research on electrolyte materials is pivotal. Solvate ionic liquids (SILs) are an emerging class of electrolytes possessing somewhat superior properties for battery applications compared to conventional ionic liquid electrolytes. In this account, we describe our recent efforts regarding SIL‐based electrolytes for Li, Na, K, and Mg batteries with respect to structural, physicochemical, and electrochemical characteristics. Systematic studies based on crystallography and Raman spectroscopy combined with thermal/electrochemical stability analysis showed that the balance of competitive cation?anion and cation?solvent interactions predominates the stability of the solvate cations. We also demonstrated battery applications of SILs as electrolytes for non‐Li batteries, particularly for Na batteries.     

Ab initio simulations of liquid electrolytes for energy conversion and storage

Understanding physicochemical properties of liquid electrolytes is essential for predicting and optimizing device performance for a wide variety of emerging energy technologies, including photoelectrochemical water splitting, supercapacitors, and batteries. In this work, we review recent progress and open challenges in predicting structural, dynamical, and electronic properties of the liquids using first-principles approaches. We briefly summarize the basic concepts of first-principles molecular dynamics (FPMD), and we discuss how FPMD methods have enriched our understanding of a number of liquids, including aqueous solutions, organic electrolytes and ionic liquids. We also discuss technical challenges in extending FPMD simulations to the study of liquid electrolytes in more complex environments, including the interface between electrolytes and electrodes, which is a key component in many energy storage and conversion systems.     

Conductive networked polymer gel electrolytes composed of poly(meth)acrylate,lithium salt,and ionic liquid

Self‐standing films of (meth)acrylate‐based polymer gel electrolytes with high ionic liquid content (80 wt %) were prepared by in situ thermally or photo induced radical copolymerization of mono‐functional and di‐functional (meth)acrylates in an ionic liquid in the presence/absence of a lithium salt. Their ionic conductivity, thermal property, mechanical property, and flammability were examined. 1‐Ethyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide (EMImTFSI) or 1‐ethyl‐3‐methylimidazolium bis(fluorosulfonyl)imide (EMImFSI) was used as the ionic liquid, and lithium bis(trifluoromethanesulfonyl)imide LiTFSI was used as the lithium salt. The obtained films were semitransparent and flexible with good to moderate thermal stability and mechanical strength with high ionic conductivity. The EMImFSI‐containing gel electrolytes showed higher ionic conductivity than the corresponding EMImTFSI‐containing gel electrolytes. The ionic conductivity in the acrylate‐based gel electrolytes was slightly increased by addition of lithium salt, while that in the corresponding methacrylate‐based electrolytes was decreased significantly. The flame test showed the ionic liquid containing networked polymer gel electrolytes to have low if any flammability and was therefore confirmed to be highly safe. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Reaction between l-cysteine and 10-methylphenothiazine cation radical released from droplet-modified electrodes

The electrochemical oxidation of 10-methylphenothiazine (PMe) dissolved in 1,2-trans-dibromocyclohexane oil droplets immobilised on a basal plane pyrolytic graphite (BPPG) electrode and bathed by an aqueous electrolyte is a one-electron quasi-reversible process which occurs with the expulsion of the electro-generated cation radical from the oil phase. In the presence of l-cysteine in the aqueous phase, the electro-released cation mediates the redox catalytic oxidation of the thiol. The peak catalytic current is observed to increase linearly with increasing cysteine concentration over the range analysed (10–100 mM).