Comparative Study of Guanidine-, Acetamidine- and Urea-Based Chloroaluminate Electrolytes for an Aluminum Battery.

Aluminum-based batteries are a promising alternative to lithium-ion as they are considered to be low-cost and more friendly to the environment. In addition, aluminum is abundant and evenly distributed across the globe. Many studies and Al battery prototypes use imidazolium chloroaluminate electrolytes because of their good rheological and electrochemical performance. However, these electrolytes are very expensive, and so cost is a barrier to industrial scale-up. A urea-based electrolyte, AlCl3:Urea, has been proposed as an alternative, but its performance is relatively poor because of its high viscosity and low conductivity. This type of electrolyte has become known as an ionic liquid analogue (ILA). In this contribution, we proposed two Lewis base salt precursors, namely, guanidine hydrochloride and acetamidine hydrochloride, as alternatives to the urea-based ILA. We present the study of three ILAs, AlCl3:Guanidine, AlCl3:Acetamidine, and AlCl3:Urea, examining their rheology, electrochemistry, NMR spectra, and coin-cell performance. The room temperature viscosities of both AlCl3:Guanidine (52.9 cP) and AlCl3:Acetamidine (76.0 cP) were significantly lower than those of the urea-based liquid (240.9 cP), and their conductivities were correspondingly higher. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) showed that all three electrolytes exhibit reversible deposition/dissolution of Al, but LSV indicated that AlCl3:Guanidine and AlCl3:Acetamidine ILAs have superior anodic stability compared to the AlCl3:Urea electrolyte, as evidenced by anodic potential limits of +2.23 V for both AlCl3:Guanidine and AlCl3:Acetamidine and +2.12 V for AlCl3:Urea. Coin-cell tests showed that both AlCl3:Guanidine and AlCl3:Acetamidine ILA exhibit a higher Coulombic efficiency (98 and 97%, respectively) than the AlCl3:Urea electrolyte system, which has an efficiency of 88% after 100 cycles at 60 mA g-1. Overall, we show that AlCl3:Guanidine and AlCl3:Acetamidine have superior performance when compared to AlCl3:Urea, while maintaining low economic cost. We consider these to be valuable alternative materials for Al-based battery systems, especially for commercial production.

Measuring and Enhancing the Ionic Conductivity of Chloroaluminate Electrolytes for Al-Ion Batteries.

At the core of the aluminum (Al) ion battery is the liquid electrolyte, which governs the underlying chemistry. Optimizing the rheological properties of the electrolyte is critical to advance the state of the art. In the present work, the chloroaluminate electrolyte is made by reacting AlCl3 with a recently reported acetamidinium chloride (Acet-Cl) salt in an effort to make a more performant liquid electrolyte. Using AlCl3:Acet-Cl as a model electrolyte, we build on our previous work, which established a new method for extracting the ionic conductivity from fitting voltammetric data, and in this contribution, we validate the method across a range of measurement parameters in addition to highlighting the model electrolytes' conductivity relative to current chloroaluminate liquids. Specifically, our method allows the extraction of both the ionic conductivity and voltammetric data from a single, simple, and routine measurement. To bring these results in the context of current methods, we compare our results to two independent standard conductivity measurement techniques. Several different measurement parameters (potential scan rate, potential excursion, temperature, and composition) are examined. We find that our novel method can resolve similar trends in conductivity to conventional methods, but typically, the values are a factor of two higher. The values from our method, on the other hand, agree closely with literature values reported elsewhere. Importantly, having now established the approach for our new method, we discuss the conductivity of AlCl3:Acet-Cl-based formulations. These electrolytes provide a significant improvement (5-10× higher) over electrolytes made from similar Lewis base salts (e.g., urea or acetamide). The Lewis base salt precursors have a low economic cost compared to state-of-the-art imidazolium-based salts and are non-toxic, which is advantageous for scale-up. Overall, this is a noteworthy step at designing cost-effective and performant liquid electrolytes for Al-ion battery applications.

Iodine speciation in deep eutectic solvents.

Iodine has been shown to act as a good electrocatalyst for metal digestion in deep eutectic solvents (DESs) but little is known about its speciation or reactivity in these high chloride containing media. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements were made at the iodine K-edge in a range of DESs with different glycolic or acidic hydrogen bond donors (HBDs), along with examining the effect of iodine concentration between 0.01 and 0.5 mol dm-3. Three groups of speciation were detected: mixed I2Cl-/I3- (glycol and lactic acid systems), mixed I3-/I2 (oxalic acid and urea systems), and singular I3- (levulinic acid system). UV-vis spectroscopy was used to confirm the speciation. Electrochemistry showed that iodine redox behaviour was unaffected by the changing speciation. Leaching data showed that metal oxidation was related not only to changing iodine speciation, but also the reactivity and coordination ability of the HBD.

Amidine-based ionic liquid analogues with AlCl3: a credible new electrolyte for rechargeable Al batteries.

Here we demonstrate the generation of novel ionic liquid analogue (ILA) electrolytes for aluminium (Al) electrodeposition that are based on salts of amidine Lewis bases. The electrolytes exhibit reversible voltammetric plating/stripping of Al, good ionic conductivities (10-14 mS cm-1), and relatively low viscosities (50-80 cP). The rheological properties are an improvement on analogous amide-based ILAs and make these liquids credible alternatives to ILAs based on urea or acetamide, or conventional chloroaluminate ionic liquids (IL) for Al battery applications.

Combined Voltammetric Measurement of pH and Free Chlorine Speciation Using a Micro-Spot sp2 Bonded Carbon-Boron Doped Diamond Electrode.

This work demonstrates the use of an sp2-bonded carbon microspot boron doped diamond (BDD) electrode for voltammetric measurement of both pH and analyte concentration in a pH-dependent speciation process. In particular, the electrode was employed for the voltammetric detection of pH and hypochlorite (OCl-) in unbuffered, aerated solutions over the pH range 4-10. Knowledge of both pH and [OCl-] is essential for determination of free chlorine concentration. The whole surface of the microspot BDD electrode was found active toward the voltammetric oxidation of OCl-, with OCl- showing a characteristic response at +1.5 V vs SCE. In contrast, it was only the surface integrated quinones (Q) in sp2-bonded carbon regions of the BDD electrode that were responsible for the voltammetric pH signal. A Nernstian response for pH (gradient = 63 ± 1 mV pH-1) was determined from proton coupled electron transfer at the BDD-Q electrode, over the potential range -0.4-0.5 V vs SCE. By measuring both OCl- and pH voltammetrically, over the pH range 4-10, the OCl- oxidative current was found to correlate extremely well with the predicted pH-dependent [OCl-] speciation profile.

Investigation of sp2-Carbon Pattern Geometry in Boron-Doped Diamond Electrodes for the Electrochemical Quantification of Hypochlorite at High Concentrations.

An electrochemical sensor that contains patterned regions of sp2-carbon in a boron-doped diamond (BDD) matrix is presented for the quantitative detection of hypochlorite (OCl-) at high concentrations in the alkaline, chemically oxidizing environment associated with bleach. As BDD itself is unresponsive to OCl- reduction within the solvent window, by using a laser micromachining process, it is possible to write robust electrochemically active regions of sp2-carbon into the electrochemically inert sp3-BDD electrode. In this work, four different laser patterned BDD electrodes are examined, and their response compared across a range of OCl- concentrations (0.02-1.50 M). A single macrospot (0.37 mm diameter disk) electrode and a closely spaced microspot (46 µm diameter disk) hexagonal array electrode, containing the same surface area of sp2-carbon, are shown to provide the most linear response toward OCl- reduction. Finite element modeling (FEM) is employed to better understand the electrochemical system, due to the complexity of the electrode geometry, as well as the need to include contributions from migration and Ohmic drop at these high concentrations. FEM data suggest that only a small percentage (∼1 × 10-3%) of the total laser-machined sp2 area is active toward the OCl- reduction process and that this process is kinetically very sluggish (∼keff = 1 × 10-12 cm s-1). The sensitivity at the array electrode (-0.127 ± 0.004 mA M-1; R2 = 0.992) is higher than that at the single-spot electrode (-0.075 ± 0.002 mA M-1; R2 = 0.996) due to the enhanced effect of transport to the edges of the microspots, shown via simulation. The electrodes returned a relatively stable response over a greater than 3 month period of use in the OCl- solutions, demonstrating these hybrid sp2-BDD electrodes show promise for long-term monitoring applications in the harsh environments associated with bleaching applications.

Effects and controls of capacitive hysteresis in ionic liquid electrochemical measurements.

Capacitance vs. potential relationships help electrochemists better understand electrode-liquid interfacial behaviors. However, the current ionic liquid literature does not have a unified experimental approach, and hysteresis effects are of significant concern. Known experimental variables that can influence capacitance-potential data include electrode material and morphology, potential scan direction, equivalent circuit model applied during analysis, and, to some extent, the electrochemical technique employed. To our knowledge, the present work is the first systematic study of four major variables that are relevant to IL-based capacitance measurements, and of their effects on resulting capacitance curvature. We examine: (1) the potential range explored, (2) the potential scan direction applied, (3) the data acquisition protocol used to collect data, and (4) the electrochemical technique used to generate capacitance data. Specifically, we find that all four of these (some more than others) 'user-defined' experimental variables influence the resulting capacitance-potential curvature for a typical ionic liquid electrochemical system. In an effort to minimize bias and to permit better comparisons of data collected from different laboratories we provide guidelines to help critically assess IL capacitance-potential data.

Capacitive hysteresis at the 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate-polycrystalline gold interface.

We report potential-dependent capacitance curves over a 2-V potential range for the 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate (Emim FAP)-polycrystalline gold interface, and examine the effect of potential scan direction on results. We find very small levels of capacitive hysteresis in the Emim FAP-polycrystalline Au electrochemical system, where capacitance curves show minor dependence on the potential scan direction employed. This is a considerably different response than that reported for the Emim FAP-Au(111) interface where significant hysteresis is observed based on the potential scan direction (Drüschler et al. in J Phys Chem C 115 (14):6802-6808, 2011). Hysteresis effects have previously been suggested to be a general feature of an ionic liquid (IL) at electrified interfaces due to slow interfacial processes and has been demonstrated for numerous electrochemical systems. We provide new evidence that the experimental procedure used to acquire capacitance data and data workup could also have implications on capacitance-potential relationships in ILs. This work serves to progress our understanding of the nature of capacitive hysteresis at the IL-electrode interface. Graphical abstract Subtle changes in experimental methods can lead to significantly different capacitance measurements in ionic liquids. Which is the best approach?

Adventitious Water Sorption in a Hydrophilic and a Hydrophobic Ionic Liquid: Analysis and Implications.

The sorption of water in ionic liquids (ILs) is nearly impossible to prevent, and its presence is known to have a significant effect on the resulting mixtures' bulk and interfacial properties. The so-called "saturation" water concentrations have been reported, but water sorption rates and mixing behaviors in ILs are often overlooked as variables that can significantly change the resulting mixtures' physical properties over experimental time frames of several minutes to hours. The purpose of this work is to establish a range of these effects over similar time frames for two model ILs, protic ethylammonium nitrate (EAN) and aprotic butyltrimethylammonium bis(trifluoromethylsulfonyl)imide (N1114 TFSI), as they are exposed to controlled dry and humid environments. We report the water sorption rates for these liquids (270 ± 30 ppm/min for EAN and 30 ± 3 ppm/min for N1114 TFSI), examine the accuracy and precision associated with common methods for reporting water content, and discuss implications of changing water concentrations on experimental data and results.

Emulsions of crude glycerin from biodiesel processing with fuel oil for industrial heating.

There is considerable interest in using crude glycerin from biodiesel production as a heating fuel. In this work crude glycerin was emulsified into fuel oil to address difficulties with ignition and sustained combustion. Emulsions were prepared with several grades of glycerin and two grades of fuel oil using direct and phase inversion emulsification. Our findings reveal unique surfactant requirements for emulsifying glycerin into oil; these depend on the levels of several contaminants, including water, ash, and components in MONG (matter organic non-glycerin). A higher hydrophile-lipophile balance was required for a stable emulsion of crude glycerin in fuel oil compared to water in fuel oil. The high concentration of salts from biodiesel catalysts generally hindered emulsion stability. Geometric close-packing of micelles was carefully balanced to mechanically stabilize emulsions while also enabling low viscosity for pumping and fuel injection. Phase inversion emulsification produced more stable emulsions than direct emulsification. Emulsions were tested successfully as fuel for a waste oil burner.