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Decarbonisation of energy will rely heavily, at least initially, on the use of lithium ion batteries for automotive transportation. The projected volumes of batteries necessitate the development of fast and efficient recycling protocols. Current methods are based on either hydrometallurgical or pyrometallurgical methods. The development of efficient separation techniques of waste lithium ion batteries into processable waste streams is needed to reduce material loss during recycling. Here we show a rapid and simple method for removing the active material from composite electrodes using high powered ultrasound in a continuous flow process. Cavitation at the electrode interface enables rapid and selective breaking of the adhesive bond, enabling an electrode to be delaminated in a matter of seconds. This enables the amount of material that can be processed in a given time and volume to be increased by a factor of approximately 100. It also produces a material of higher purity and value that can potentially be directly recycled into new electrodes.

While ionic liquids and deep eutectic solvents, DESs, have been extensively used for natural product extraction relatively little is known about the factors affecting extraction efficiency. In this study, 7 simple solutes are extracted into 4 DESs at two temperatures and the thermodynamics of phase transfer are determined. It was found that solutes which are able to form hydrogen bond are more successfully extracted into the DES phase from cyclohexane. For less polar solutes, the extracting DES has a more pronounced effect on extraction efficiency with liquids of a lower surface tension being more effective. With polar solutes the effect of the DES is less pronounced. It is shown that the Gibbs energy of extraction is proportional to the pKa of the solute demonstrating the importance of hydrogen bonding in solute partition. The study was extended to 5 phenolic compounds commonly found in olive oil and again the extraction efficiency was shown to be related to the solute pKa. The green metrics for the extraction of a range of solutes were determined and shown in some cases to be superior to molecular solvents. The energy consumption of extraction was shown to be comparatively small even when mechanically assisted.

The integration of lithium-ion batteries (LIB) into transportation through the implementation of hybrid and electric vehicles is driving fundamental research into improving their performance and li...

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

The use of additives to modulate metal electrodeposition from deep eutectic solvents has, to date, apparently been of little interest given the dearth of such studies in the literature. Here, we have actively investigated the effects of nicotinic acid (NA) on the electrodeposition of copper in a choline chloride (ChCl)-ethylene glycol (EG)-based deep eutectic solvent (DES), (1ChCl:2EG), considered a “green solvent” due to its physiochemical properties. Bright copper deposits were formed when NA was added to the Cu electrolyte, while a dull Cu deposit was produced in its absence. New Cu species were found to have formed in the 1ChCl:2EG-based liquid when NA was added to the electrolyte. A number of analytical techniques, in this instance cyclic voltammetry, chronoamperometry, and chronocoulometery, have been employed to determine the various electrochemical properties, nucleation mechanisms, and kinetics of the Cu species reported herein. The diffusion coefficient for the Ethaline-Cu system was found to be affected by the concentration of NA. An electrochemical quartz crystal microbalance (EQCM) was used to monitor the current efficiency of the copper deposition in both systems. The morphologies, thicknesses, roughnesses, and crystal structures of the copper electrodeposited from the NA-modified electrolyte were characterised via scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD), which between them demonstrate that the NA introduced into this system acts as a highly effective brightener, producing highly uniform and smooth copper deposits.

Recycling is always seen as an end-of-pipe process returning as much material as possible into a circular economy. There is a growing school of thought that suggests product design should be an important step in the recycling process. While this review is aimed specifically at one technological product, it contains facets that are applicable to the recycling of any complex product. Decarbonisation of energy production necessitates a proliferation of efficient electrical storage and a significant proportion of this, particularly in automotive propulsion, will use lithium ion batteries. The scale of the projected electric vehicle market means that a circular economy model needs to be established while the scale of end-of-life product is still manageable to prevent a build-up of hazardous waste. This critical review investigates the issues of lithium ion battery recycling and discusses the aspects of pack, module and cell design that can simplify battery dismantling and recycling. It highlights not only Green aspects of elemental recovery, but also technoeconomic features which may govern the appropriate direction for recycling. It also shows that as cell design changes, the approach to recycling can become more efficient.

Rapid growth in the market for electric vehicles is imperative, to meet global targets for reducing greenhouse gas emissions, to improve air quality in urban centres and to meet the needs of consumers, with whom electric vehicles are increasingly popular. However, growing numbers of electric vehicles present a serious waste-management challenge for recyclers at end-of-life. Nevertheless, spent batteries may also present an opportunity as manufacturers require access to strategic elements and critical materials for key components in electric-vehicle manufacture: recycled lithium-ion batteries from electric vehicles could provide a valuable secondary source of materials. Here we outline and evaluate the current range of approaches to electric-vehicle lithium-ion battery recycling and re-use, and highlight areas for future progress. Processes for dismantling and recycling lithium-ion battery packs from scrap electric vehicles are outlined.

Most studies of metal electrodeposition in ionic liquids dry the electrolyte thoroughly, as water is thought to be detrimental. In some cases, water has a beneficial effect on deposit morph...

The effects of nicotinic acid (NA), boric acid (BA) and benzoquinone (BQ) on the electrodeposition of Zn have been studied in a choline chloride (ChCl) ethylene glycol (EG) based deep eutectic solvent (DES), (1ChCl:2 EG), and for the first time a bright zinc coating has been achieved when NA was used. In metal electroplating processes, small-molecule additives are often included in the plating bath to improve properties of coating such as brightness, roughness, thickness, hardness and resistance to corrosion. The effects of additives on the electrodeposition of Zn from aqueous solution have been extensively investigated. However, very few studies have considered the effects of additives on the electrodeposition of Zn from ionic liquids or deep eutectic solvents. The electrochemical properties of the plating liquid have been studied here using cyclic voltammetry, chronocoulometry, chronoamperometry and microgravimetry (EQCM). Redox peak currents decrease when additives were included in the Zn solution and total charge was also reduced in experiments where additives were present. The Zn deposition in the absence of additive is in good agreement with an instantaneous growth mechanism at short experimental time scales (being indeterminate over longer periods), however, this changes to one of a progressive growth mechanism when additives were included in the coating bath. The current efficiency of zinc deposition in the DES without additives was 95%, which was reduced when additives were included. The resultant surface morphologies, thickness, topography, roughness and crystal structure of the Zn coating were revealed by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD), demonstrating that those additives serve as effective brighteners that can produce highly uniform and smooth zinc deposits.

Aluminium (Al) batteries are a promising, next-generation technology and current research efforts are aimed at positioning this technology to compete with existing lithium-ion batteries (LIB). The development of non-aqueous electrolyte chemistries for Al battery systems has received renewed attention to address some of the shortcomings associated with LIB. Of particular importance in this development is the liquid electrolyte as its rheology governs the battery chemistry. The goals are to generate a liquid that is compatible with the other (solid) battery components, stable long-term with repeated use, and to optimise the rheology (i.e. target high conductivity and low viscosity). Chloroaluminate room temperature ionic liquid (RTIL) electrolytes made by mixing Lewis acidic aluminium chloride (AlCl3) salt with a (often chloride-containing) Lewis basic salt e.g. 1-ethyl-3-methylimidazolium chloride (EMIM-Cl) has been extensively studied. This tuneable electrolyte provides good thermal stability, good ionic conductivity, and a wide polarizable potential window. While these traits are advantageous these types of Lewis basic salt precursors are generally expensive, difficult to synthesize and in some instances can be toxic. Recently, ionic liquid analogues (ILA) that are made from abundant, inexpensive and often non-toxic materials have begun to be explored. To date the two most common Lewis basic salts examined have been urea and acetamide but their rheological and electrochemical properties need to be improved in order to complete with RTIL-based electrolytes. Our group have recently revealed that amidine-based chloroaluminate ILA electrolytes show promise over urea-, acetamide-, and pyrrolidinium-based electrolytes.[1] Specifically, guanidinium chloride (Guan-Cl) and acetamidinium chloride (Acet-Cl) based salts display reversible electrochemical plating/stripping of Al, good ionic conductivities (e.g. 10 mS cm-1), and moderate viscosities (e.g. 50 cP). Also, in this work we initially proposed a mathematical model to extract the conductivity from these electrolytes by fitting the voltammetric i-E curve (from Al deposition/dissolution) to a linear, modified Butler-Volmer formalism. The characteristic, anodic i-E trace shows a striking linearity often over very large potential ranges (e.g. >2 V), and this response is used to extract ionic conductivity. This represents a novel, electroanalytical method to obtain this important rheological metric. As such, in this contribution we will highlight our latest efforts to expand, benchmark (to common methods for measuring conductivity), and determine the limits of our i-E curve fitting method to measure ionic conductivity.[2] Specifically, we have examined the AlCl3:Acet-Cl electrolyte in depth by looking at the potential scanning rate, potential range probed, and the compositional (mole ratio Lewis acid : Lewis base) effect on the conductivity extracted from our fitting method. We have also studied a range of other common chloroaluminate electrolytes to compare with published literature. All of these values are then benchmarked to conductivity data measured both from a traditional impedance-based method and that from a commercial conductivity probe. Lastly, we also have examined temperature-dependent conductivities from all three of these methods. Overall, we find good agreement between values measured from our in situ i-E curve fitting method to those from more traditional conductivity measurement methods. This electroanalytical work serves to deepen our understanding of the conductivity of chloroaluminate ILAs for Al battery applications. References: [1] A.J. Lucio, I. Efimov, O.N. Efimov, C.J. Zaleski, S. Viles, B.B. Ignatiuk, A.P. Abbott, A.R. Hillman, K.S. Ryder. Chem. Commun., 2021, 57, 9834-9837. [2] A.J. Lucio, E. Bulmer, I. Sumarlan, A.R. Hillman, K.S. Ryder. 2022 in preparation. Figure 1

Deep eutectic solvents (DESs) were used as alternatives to the aqueous phase in solvent extraction of iron(iii), zinc(ii) and lead(ii). The selective extraction of iron(iii) and zinc(ii) was studied from a feed of ethaline (1 : 2 molar ratio of choline chloride : ethylene glycol) and lactiline (1 : 2 molar ratio of choline chloride : lactic acid), with the former DES being more selective. A commercial mixture of trialkylphosphine oxides (Cyanex 923, C923) diluted in an aliphatic diluent selectively extracted iron(iii) from a feed containing also zinc(ii) and lead(ii). The subsequent separation of zinc(ii) from lead(ii) was carried out using the basic extractant Aliquat 336 (A336). The equilibration time and the extractant concentration were optimized for both systems. Iron(iii) and zinc(ii) were stripped using 1.2 mol L-1 oxalic acid and 0.5 mol L-1 aqueous ammonia, respectively. An efficient solvometallurgical flowsheet is proposed for the separation and recovery of iron(iii), lead(ii) and zinc(ii) from ethaline using commercial extractants. Moreover, the process was upscaled in a countercurrent mixer-settler set-up resulting in successful separation and purification. ispartof: RSC ADVANCES vol:10 issue:55 pages:33161-33170 ispartof: location:England status: published

Electrodeposited conducting polymer films derived from aromatic monomers are known to possess properties that depend significantly on the deposition protocol, particularly the electrochemical control function employed. This study explores the underlying reasons for this common observation for the specific case of polypyrrole films deposited from aqueous media onto gold electrodes under potentiostatic, potentiodynamic and galvanostatic control. Although the control functions impose different conditions, the control parameters (potential, potential range and scan rate, and current) were selected so as generate films at comparable rates; this avoids inappropriate attribution of structural and compositional variations to different thickness regimes, irrespective of how they were generated. In each case, film deposition was periodically interrupted and the film characterised by specular neutron reflectivity measurements. By using d4-pyrrole monomer in H2O solvent, the isotopic selectivity of neutron reflectivity was used to extract polymer and solvent concentration profiles as a function of distance from the electrode/film interface. Spatial integration of these profiles was used to quantify total film solvent populations; these are expressed as solvent volume fractions. Films grown under the three different control regimes have measurably distinct solvent volume fraction profiles and there is evolution of these profiles with increasing thickness. Ultimately, for the conditions employed, the order of increasing porosity (i.e. solvent content) by control function was potentiostatic

Ionic liquids (ILs) and deep eutectic solvents have been used for the extraction of molecules, particularly natural products. An often studied system is that for thiophene removal from oil. In the current study, ILs have been used for the removal of thiophene (Th), benzothiophene (BT), and dibenzothiophene by liquid–liquid extraction. The equilibrium can be shifted by polymerizing the thiophenic compounds both electrochemically and chemically. A 1:1 mixture of 1-butyl-3-methylimidazolium chloride (Bmim)Cl and FeCl3 was used to extract Th and BT from alkane layers using electropolymerization to shift the position of the equilibrium. While the process could be carried out, the kinetics of polymer formation were too slow to make this a viable process. The final part of the study used a 1:2 (Bmim)Cl/FeCl3 mixture to chemically remove sulfur-containing compounds from alkane layer. It was shown that the chemical polymerization reaction of Th is around 1500 times faster than electrochemical polymerization. Issue...

The electrodeposition of metals in ionic liquids and deep eutectic solvents leads to deposits with significantly different morphologies to those seen with aqueous solutions. The classical m...

Electropolishing is a common method for decreasing surface roughness and removing surface irregularities. In this paper the electropolishing of nickel and cobalt are successfully demonstrated in a deep eutectic solvent, comprising a 2:1 molar mixture of ethylene glycol and choline chloride. Voltammetric and electrochemical impedance studies were used to characterise the polishing mechanism and show that film formation occurs prior to polishing. Scanning electron microscopy and atomic force microscopy were used to characterise the morphology before and after polishing and 3D optical microscopy was used in-situ to observe film formation during polishing. This study shows that the impact of film formation and subsequently mass transport are responsible for electropolishing of both metals in the choline chloride-based ionic liquid.

Here, we describe new developments in the study of electrodeposition processes with time-resolved dynamic neutron reflectivity (NR) methods to achieve insights into the differences between growth of metal films using a range of electrochemical control functions. We show that the temporal resolution has increased from 1 to 2 h per data set (in our previous studies) to approximately 8 min. We have studied the electrochemical deposition of copper and silver as thin-film metals onto a gold electrode substrate from a deep eutectic solvent using potentiodynamic (PD), potentiostatic (PS) and galvanostatic (GS) electrochemical control functions. In particular, we have utilised novel developments in neutron reflectivity methods to acquire real-time data for the growing metal films. Event mode capture of neutron scattering events, as a function of momentum transfer vector, Q, during electrochemical growth has enabled time-resolved measurement of the neutron reflectivity, R(Q), profiles of the growing metal films. Subsequent fitting and iterative optimisation of the R(Q,t) data reveals the thickness, roughness and relative density (spatially resolved solvent content) of the metal film during growth. These data show that the different electrochemical growth methodologies exhibit different trends in thickness, roughness and solvation. Silver films show an increasing roughness trend with time but these trends are largely independent of growth method. In contrast, the roughness of copper films, grown under similar conditions, shows a strong dependency on growth method with PS methods producing smoothest films. These conclusions are confirmed by ex-situ AFM measurements. The fitted NR data show that the Cu and Ag films contain between 5 and 10% volume fraction solvent. Furthermore, we have explored different NR data fitting methodologies in order to process the large numbers of data sets produced. Gratifyingly, the different methodologies and starting conditions yield a very consistent picture of metal film growth.

Despite the importance of ionic liquids in a variety of fields, little is understood about the behaviour of protons in these media. The main difficulty arises due to the unknown activity of protons in non-aqueous solvents. This study presents acid dissociation constants for nine organic acids in deep eutectic solvents (DESs) using standard pH indicator solutes. The pKIn value for bromophenol blue was found by titrating the DES with triflic acid. The experimental method was developed to understand the acid-base properties of deep eutectic solvents, and through this study it was found that the organic acids studied were slightly less dissociated in the DES than in water with pKa values between 0.2 and 0.5 higher. pKIn values were also determined for two ionic liquids, [Bmim][BF4] and [Emim][acetate]. The anion of the ionic liquid changes the pH of the solution by acting as a buffer. [Emim][acetate] was found to be more basic than water. It is also shown that water significantly affects the pH of ionic liquids. This is thought to arise because aqueous mixtures with ionic liquids form heterogeneous solutions and the proton partitions into the aqueous phase. This study also attempted to develop an electrochemical pH sensor. It was shown that a linear response of cell potential vs. ln aH+ could be obtained but the slope for the correlation was less than that obtained in aqueous solutions. Finally it was shown that the liquid junction potential between two reference electrodes immersed in different DESs was dependent upon the pH difference between the liquids.

Deep eutectic solvents (DESs) are mixtures of quaternary ammonium halides with hydrogen bond donors and are increasingly being used in applications where they are in contact with metals. This study investigates the corrosion of iron, nickel and aluminium in DESs. It shows that none of the metals show significant corrosion when glycerol is used as a hydrogen bond donor but when an acidic hydrogen bond donor such as oxalic acid is used, both iron and aluminium show catastrophic corrosion as may be expected. Surprisingly, however, nickel does not corrode in the acidic DES, Oxaline. The differences in corrosion observed for aluminium and iron are explained in terms of passivating films and the slowness of the oxygen reduction reaction despite the relatively high gas solubility. The high chloride ion content (roughly 4 mol dm−3) has a relatively small effect on the corrosion of the three metals. The formation of a passive layer as a result of hydrogen bond donor-metal ion complexes is shown to be more important. It is proposed that the low corrosion rates of some metals resulted from the slow rate of the cathodic reaction resulting from the high viscosity, low activity of water and low proton mobility.

Deep eutectic solvents (DESs) have been used for the purification of oils and the extraction of active ingredients from natural products but little is known about the mechanism of the extraction process. In this study a variety of molecular solutes are dissolved in alkanes and the thermodynamics of transfer into six DESs have been quantified. It is shown that the transfer of most solutes into the DES is endothermic and driven by entropy. The largest partition coefficients were demonstrated by the liquids with the lowest surface tensions and this is thought to arise because the enthalpy of hole formation controls the rate of solute transfer. Accordingly, it was shown that the size of the solute has an effect on the partition coefficient with smaller solutes partitioning preferably into the DES. As expected, solutes capable of strongly hydrogen bonding partitioned much better into the DES as the enthalpy of transfer was negative.

The amphiphilic nature of many pharmaceutical active ingredients often makes them difficult to solubilise and leads to significant wastage through non-optimal dosage. In this study it is shown that highly concentrated liquid formulations can be produced from pharmaceutical active ingredients which either contain a strong hydrogen bonding functionality e.g. -OH or -COOH or a quaternary ammonium moiety. These mixtures can overcome solubility issues in water as the eutectics prevent recrystallization of the active ingredient when dispersed in water. The depression of freezing point for these eutectic mixtures is modelled using the enthalpy of hydrogen bond formation which was calculated using calorimetric data. The study also demonstrates that complex drug molecules which exhibit polymorphism such as Adiphenine and Ranitidine can be formulated into a homogeneous liquid and the hydrogen bond donor can also be a pharmaceutical active ingredient e.g. aspirin.

It is reported in this study that the deep eutectic solvent (DES), (Ethylene glycol)2(Choline chloride), (2Eg:ChCl) is an effective medium in the electrolytic removal of the Fe-rich layer from Ni-based hot isostatic press (HIP) consolidation and that it is capable of sustaining etching at higher rates and at higher current efficiencies than a comparable aqueous electrolyte formulated from methane sulphonic acid/glycolic acid (MSA/GA). At high etch rates, the surface finish is not as good using 2Eg:ChCl, but high etch rates, current efficiency and excellent surface finish can be obtained from a 90%/10% hybrid mixture of 2Eg:ChCl MSA/GA electrolytes. This study has set out to compare the electropolishing and bulk electrolytic etching of HIP-formed bodies fabricated from RR1000 Ni-based superalloys in aqueous methane sulphonic acid/glycolic acid (MSA/GA) electrolyte and in DES-type ionic liquids. It is shown that the HIP alloy can be effectively removed under mild conditions using DES electrolytes that are o...

This chapter describes the development of several new processes relating to the fabrication, characterisation and recycling of printed circuit board (PCB) metal assemblies in alternative, sustainable solvent technologies based on an emergent class of liquids know as deep eutectic solvents (DES). It has been demonstrated that in many cases, the use of DES technologies can be disruptive to current process thinking and in principle can deliver benefits including increased efficiency, lower costs and better process control. These technologies offer the opportunity to incorporate new ideas into PCB fabrication and assembly that facilitate downstream, end-of-life recovery and separation consistent with a circular economy model. Current PCB manufacturing is carried out using many complex metal deposition processes involving aqueous solutions of toxic metal salts, strong inorganic acids, precious and expensive noble metals, and requires careful process control and monitoring. As a result, these processes are often costly to operate and inefficient. DES-based technologies can: (1) improve the economic and efficient use of essential metals; (2) reduce or eliminate use of precious and expensive metals; (3) reduce the use of complex and difficult to maintain process chemistry; (4) reduce reliance on toxic and noxious materials; and (5) improve recovery, recycling and reuse of PCB metals.

Polyaniline itself can be converted to its conductive form from its insulating form by applying an oxidising potential in which polyaniline is converted to its positive charge state. Anions in the target solution are driven into the positively charged polymer film by electrostatic force, and this process is reversed when a reduction potential is applied. Consequently, interfacial processes of polyaniline modified electrode make it viable to remove undesirable ions from the target solution. During this process, polyaniline operates as an ion-exchanger by directing specific ions at definite potentials, which is the principle of the electrochemically switched ion-exchange technique. Therefore, polyaniline can be employed as a convenient material to perform as a new ion-exchanger modified film in an acidic environment. On the other hand, an abrupt decrease in the electroactivity of polyaniline at elevated pH values restricts its use in such practical applications. To overcome this problem, copolymerization of aniline and o-toluidine is expedient as it will be able to enhance the electrochemical properties of polyaniline. Hence, several copolymers were synthesised in the presence of different aniline and o-toluidine feedstock ratios. It was found that the surface coverage value of a representative poly(aniline-co-o-toluidine) copolymer film was 139.7 nmol cm−2 compared with 76 nmol cm−2 for pure Pani under identical conditions. In addition, the redox cycling in monomer-free NaF solutions showed that the poly(aniline-co-o-toluidine) film exhibited excellent reversibility between redox reactions at pH 6.60. These outcomes clearly illustrate the contribution of o-toluidine to the electrochemical properties of polyaniline at raised pH medium.

Electroactive films based on conducting polymers have numerous potential applications, but practical devices frequently require a combination of properties not met by a single component. This has prompted an extension to composite materials, notably those in which particulates are immobilised within a polymer film. Irrespective of the polymer and the intended application, film wetting is important: by various means, it facilitates transport processes – of electronic charge, charge-balancing counter ions (“dopant”) and analyte/reactant molecules – and motion of polymer segments. While film solvent content and transfer have been widely studied for pristine polymer films exposed to molecular solvents, extension to non-conventional solvents (such as ionic liquids) or to composite films has been given much less attention. Here we consider such cases based on polyaniline films. We explore two factors, the nature of the electrolyte (solvent and film-permeating ions) and the effect of introducing particulate species into the film. In the first instance, we compare film behaviours when exposed to a conventional protic solvent (water) with an aprotic ionic liquid (Ethaline) and the intermediate case of a protic ionic liquid (Oxaline). Secondly, we explore the effect of inclusion of physically diverse particulates: multi-walled carbon nanotubes, graphite or molybdenum dioxide. We use electrochemistry to control and monitor the film redox state and change therein, and acoustic wave measurements to diagnose rheologicallyvs.gravimetrically determined response. The outcomes provide insights of relevance to future practical applications, including charge/discharge rates and cycle life for energy storage devices, “salt” transfer in water purification technologies, and the extent of film “memory” of previous environments when sequentially exposed to different media.

Organic and inorganic additives are often added to nickel electroplating solutions to improve surface finish, reduce roughness and promote uniform surface morphology of the coatings. Such additives are usually small molecules and often referred to as brighteners or levellers. However, there have been limited investigations into the effect of such additives on electrodeposition from ionic liquids (ILs) and deep eutectic solvents (DESs). Here we study the effect of four additives on electrolytic nickel plating from an ethyleneglycol based DES; these are nicotinic acid (NA), methylnicotinate (MN), 5,5-dimethylhydantoin (DMH) and boric acid (BA). The additives show limited influence on the bulk Ni(ii) speciation but have significant influence on the electrochemical behaviour of Ni deposition. Small concentrations (ca. 15 mM) of NA and MN show inhibition of Ni(ii) reduction whereas high concentrations of DMH and BA are required for a modest difference in behaviour from the additive free system. NA and MN also show that they significantly alter the nucleation and growth mechanism when compared to the additive free system and those with DMH and BA. Each of the additive systems had the effect of producing brighter and flatter bulk electrodeposits with increased coating hardness but XRD shows that NA and MN direct crystal growth to the [111] orientation whereas DMH and BA direct crystal growth to the [220] orientation.

Bismuth telluride (Bi2Te3) is the currently best performing thermoelectric (TE) material in commercial TE devices for refrigeration and waste heat recovery up to 200 °C. Up to 800 μm thick, compact, uniform and stoichiometric Bi2Te3 films were synthesized by pulsed electrodeposition from 2 M nitric acid baths containing bismuth and tellurium dioxide on 1 cm2 nickel (Ni) substrates at average film growth rates of ~50 μm/h. Pre-treatment of the Ni substrate was found to significantly enhance the adhesion of Bi2Te3 material onto Ni while pulsed electrodeposition was used to increase the compactness of the material. To maintain a homogeneous composition across the thickness of the films, a sacrificial Bi2Te3 anode was employed. All deposits produced were n-type with a Seebeck coefficient of up to −80 μV/K and an electrical conductivity of ~330 S/cm at room temperature. Keywords: Bismuth telluride, Electrodeposition, Thick films

While alloy deposition is a frequently studied topic analysis of the alloy phases formed is a complex and often destructive process. In the current study the complex copper–tin alloy system has been studied in deep eutectic solvents using a variety of electrochemical and surface analysis techniques to determine the mechanism of alloy deposition and composition of deposits. The use of electrochemical quartz crystal microbalance is shown to enable real-time monitoring of alloy composition and the latter is shown to be very dependent upon the concentration of ions in solution. For this system X-ray diffraction was also used to study the phase behaviour of the deposits as a function of solution composition and current density. Finally it was shown for the first time that brighteners used for copper deposition in aqueous solutions also work in ionic liquids.

Although the World Health Organization (WHO) recommends a limit of 1.5 mg l−1 fluoride ions in drinking water, this is not satisfied in many parts of the world. When this limit is exceeded, the electrochemically switched ion-exchange (ESIX) technique (mainly based on conductive polymers) has been identified as a promising method for removing the excess fluoride ions. The present study aimed to develop an efficient method based on the ESIX technique by using poly(aniline-co-o-aminophenol) copolymer to extract fluoride ions. Electrochemical quartz crystal microbalance (EQCM) and acoustic admittance data were utilized to assay the synthetic efficiency of copolymer deposition, and to evaluate the dependence of the defluoridation process on the proportions of the monomers in the copolymer matrix and on film thickness. The resulting films were characterised by Fourier transform infrared spectroscopy (FTIR) and scanning electrochemical microscopy (SEM) techniques. For optimized co-monomer ratio in the feedstock, poly(aniline-co-o-aminophenol) at an applied potential of 0.30 V showed excellent performance for fluoride removal from water at pH 6.6, to the extent of 20 (mg F−) (g polymer)−1. Comparison of the performance of ESIX using poly(aniline-co-o-aminophenol) with that of other techniques and materials reveal that it has significant potential for water defluoridation.

This article describes the electroplating of Zn Ni alloy from a modified deep eutectic solvent (DES), a mixture of choline chloride (ChCl) and ethylene glycol (EG) commonly known by its commercial name Ethaline. In this study the Ethaline was modified with propylene carbonate (PC) to decrease the solution viscosity. Boric acid was also used as an additive to improve surface finish and adhesion. The modifications were shown to increase the reduction rate of metal ions through improved mass transport and also to improve the quality of finish (morphology and interfacial adhesion) of the coating. We demonstrate that it is possible to produce dense, thick and adherent coatings of a γ-phase Zn Ni alloy with 81–85% Zn on mild steel substrates using either potentiostatic deposition or controlled current pulse-plating techniques. Mild steel is a typical substrate for a sacrificial anti-corrosion coating used in many applications where the alloy serves to protect the steel from corrosion in harsh environments.

The effects of additives on the electrodeposition of Zn Sn alloy from aqueous electrolyte have been the subject of considerable interest in the literature; however, to date there has been little consideration of their effects on alloy electrodeposition from Deep Eutectic Solvents (DESs). This work will show, for the first time, the effects of boric acid, ammonium chloride and nicotinic acid on the electrodeposition of Zn Sn alloys on copper from a DES consisting of a stoichiometric 1:2 mix of choline chloride and ethylene glycol (Ethaline 200). Cyclic voltammetry has been used to study the electrochemical properties of the Zn Sn electrolyte, and the resultant surface morphologies, composition and roughness of the Zn Sn coating were revealed via SEM/EDX and AFM, demonstrating that boric acid and nicotinic acid function as very effective brighteners, producing highly uniform and smooth Zn Sn deposits. It was found that these additives strongly affect the morphology, composition, and roughness of the Zn Sn coating. XRD was also used to examine the crystal structure of Zn Sn coatings, where it was found that the phase composition of the deposits depends on the additive(s) used. In addition, corrosion of the Zn Sn alloy in salty media was measured using the Tafel method.

The electropolymerisation of aniline is a well-studied and often used technology. While the mechanism has been investigated in a variety of media these have all concentrated on understanding the process on a molecular level. Anomalies in the electropolymerisation of aniline in four deep eutectic solvents, DESs, using urea, ethylene glycol, glycerol and oxalic acids as hydrogen bond donors with choline chloride led to an investigation of the aniline phase behaviour. It was only with oxalic acid that polymerisation was achieved and adjusting the pH of the other DESs using sulphuric acid did not enable polymer formation suggesting that pH was not the only factor enabling polymer growth. When 10 wt% water was added, polymers could be grown in all the DESs despite negligible change in solution pH. Dynamic light scattering showed that polymer only formed in systems where aniline formed an emulsion. Scanning electron microscopy, SEM and atomic force microscopy, AFM showed that the polyaniline films were formed of an agglomeration of small particles of the same dimensions as the dispersed monomer phase in solution. This suggests that the droplets of the monomer arrive at the electrode surface where they polymerise. This provides the first evidence that polyaniline grows by an emulsion polymerisation mechanism even in aqueous solutions.

Electroactive polymer films derived from aniline and substituted derivatives have attracted huge interest, as a consequence of their electronic, optical, chemical and charge storage properties. Surprisingly, there has been limited translation of these characteristics into practical devices. Two factors that have impeded progress here are an inability to deliver and optimise multiple characteristics in a single material and the absence of control of internal film structure. The latter is particularly difficult to maintain for soft matter, whose molecular geometry and spatial disposition at the mesoscopic scale necessarily changes in response to solvent influx/efflux during redox switching. These solvation phenomena have been variously described in terms of activity (thermodynamic) effects, volume constraints (polymer mechanical properties) and mobility (kinetic) effects. Quite generally, the dominant factor depends on the timescale, a feature of the experiments reported here. In this presentation, we explore strategies aimed at understanding and controlling internal film structure and solvation for polymer films based on aniline-type monomers. From a chemical perspective, we explore the effects of three factors: the nature of the solvent / electrolyte, extension from homopolymers to co-polymers, and the inclusion of geometrically distinct particulate species to generate hybrid organic/inorganic materials. In the first instance, we compare film deposition and subsequent redox chemistry when exposed to a conventional protic solvent (water) or to the aprotic ionic liquid Ethaline (a mixture of choline chloride and ethylene glycol). As an intermediate case, we consider film deposition and redox chemistry in the protic ionic liquid Oxaline (a mixture of choline chloride and oxalic acid). Quantitative nanogravimetric (QCM) measurements during deposition from ionic liquid reveal that the polymer film has substantially greater solvent content than if deposited from aqueous medium. A recognised phenomenon for electroactive polymer films is an anomalous response for the first redox cycle; this is generally attributed to solvation effects. This phenomenon is manifested quite differently for polyaniline films in water and Ethaline. In water, film evolution occurs over a number of cycles, while in Ethaline (in which the film is more highly solvated) the transition is complete with a single cycle. In the second instance, we consider copolymerization of aniline with o-toluidine or with o-aminophenol. Counter ion coordination by the hydrogen bond donors results in substantive differences in the effectively transferred entity. In the cases of Ethaline and Oxaline, the counter ion is no longer a small, mobile chloride ion, but rather a large hydrogen bond donor-coordinated species. In pursuit of possible environmental applications, we consider the extreme case of fluoride as a counter ion. Surprisingly, the relatively small changes in polymer composition effected by co-polymerisation with o-toluidine or o-aminophenol result in substantial changes in fluoride uptake. Finally, we explore the effect of inclusion of particulates, chosen so as to influence different aspects of film behaviour. Specifically, we chose multi-walled carbon nanotubes (MWCNT), graphite flakes and molybdenum oxide particles as examples of 1D, 2D and 3D entities, respectively. Electrochemical and imaging data will be presented to demonstrate their substantive effects on film structure and dynamics. The outcomes of these studies provide insights relevant to practical applications. A particular case is that of medium transfer experiments, in which a film is deposited from one medium (aqueous or ionic liquid), redox cycled in the second and then returned to the first. We discuss the responses in terms of a “nature vs nurture” competition, in which the “nature” of a film is dictated by the conditions (medium) of deposition, and “nurture” is represented by the conditions to which it is exposed. Nanogravimetric (EQCM) responses of films subjected to water / ionic liquid / water and ionic liquid / water / ionic liquid transfer experiments reveal that films do retain some memory of their deposition conditions, but that extended redox cycling results in slow evolution that reflects the immediate medium of exposure. We discuss this in terms of slow polymer structural relaxation.

I was delighted to attend the IMF AGM in November 2019 and to be inaugurated as the new President. It is both a privilege and an honour for me to serve the surface finishing community in this way and I very much look forward to making the most of my time in this role. Before looking forward, I would like to look to our immediate past and thank the outgoing President, Barry Gay, for his stewardship, time and dedication. I know that we will continue to benefit from Barry’s presence, experience and guidance in the running of the Institute. I am also delighted that we have been able to recruit David Neal as Vice-President. David is a fellow of the IMF and an international expert in organic coatings, based at Rolls-Royce. [Opening paragraph]

Exquisite control of the electrodeposition of metal films and coatings is critical to a number of high technology and manufacturing industries, delivering functionality as\ud diverse as anti-corrosion and anti-wear coatings, electronic device interconnects and energy storage. The frequent involvement of more than one metal motivates the\ud capability to control, maintain and monitor spatial disposition of the component metals, whether as multilayers, alloys or composites. Here we investigate the deposition, evolution and dissolution of single and two-component metal layers involving Ag, Cu, and Sn on Au substrates immersed in the deep eutectic solvent (DES) Ethaline. During galvanostatically controlled stripping of the metals from two-component systems the potential signature in simultaneous thickness electrochemical potential (STEP) measurements provides identification of the dissolving metal; coulometric assay of deposition efficiency is an additional outcome. When combined with quartz crystal microbalance (QCM) frequency responses, the mass change : charge ratio provides oxidation state data; this is significant for Cu in the high chloride environment provided by Ethaline. The spatial distribution (solvent penetration and external roughness) of multiple components in bilayer systems is provided by specular neutron reflectivity (NR). Significantly, the use of the recently established event mode capability shortens the\ud observational timescale of the NR measurements by an order of magnitude, permitting dynamic in situ observations on practically useful timescales. Ag,Cu bilayers of both\ud spatial configurations give identical STEP signatures indicating that, despite theextremely low layer porosity, thermodynamic constraints (rather than spatial accessibility) dictate reactivity; thus, surprisingly, Cu dissolves first in both instances. Sn penetrates the Au electrode on the timescale of deposition; this can be prevented by interposing a layer of either Ag or Cu.

The anodic dissolution of metals is an important topic for battery design, material finishing and metal digestion. Ionic liquids are being used in all of these areas but the research on the anodic dissolution is relatively few in these media. This study investigates the behaviour of 9 metals in an ionic liquid [C 4 mim][Cl] and a deep eutectic solvent, Ethaline, which is a 1:2 mol ratio mixture of choline chloride and ethylene glycol. It is shown that for the majority of metals studied a quasi-passivation of the metal surface occurs, primarily due to the formation of insoluble films on the electrode surface. The behaviour of most metals is different in [C 4 mim][Cl] to that in Ethaline due in part to the differences in viscosity. The formation of passivating salt films can be decreased with stirring or by increasing the electrolyte temperature, thereby increasing ligand transport to the electrode surface.

Metal electrodeposition using ionic liquid electrolytes and deep eutectic solvents is now well known but to our knowledge for electrolytic deposition of metals such as nickel no direct comparison has thus far been drawn between deposition using aqueous solutions and DES under otherwise identical conditions. In the current study it is shown that nickel deposition can be carried out with similar deposition rates in aqueous and ionic media despite the significant differences in viscosity and conductivity. It is, however, shown that in ionic media the morphology of the deposits is markedly different from that achieved using a Watts nickel bath and that one aspect of these differences manifests itself in significant increase in the coating hardness. It is proposed that the observed morphology differences occur due to the variations of nickel speciation in each electrolyte environment.

Alternating anodic and cathodic current pulses have been applied to a metal powder on an electrode surface to fuse the particles together. It is shown that homogeneous films can be electroformed with different morphologies depending on the size of the powder and the experimental conditions.

In this study we compare the electrochemical and structural properties of three gold salts AuCl, AuCN and KAu(CN)2 in a Deep Eutectic Solvent (DES) electrolyte (Ethaline 200) in order to elucidate factors affecting the galvanic deposition of gold coatings on nickel substrates. A chemically reversible diffusion limited response was observed for AuCl, whereas AuCN and KAu(CN)2 showed much more complicated, kinetically limited responses. Galvanic exchange reactions were performed on nickel substrates from DES solutions of the three gold salts; the AuCN gave a bright gold coating, the KAu(CN)2 solution give a visibly thin coating, whilst the coating from AuCl was dull, friable and poorly adhesive. This behaviour was rationalised by the differing speciation for each of these compounds, as evidenced by EXAFS methods. Analysis of EXAFS data shows that AuCl forms the chlorido-complex [AuCl2](-), AuCN forms a mixed [AuCl(CN)](-) species, whereas KAu(CN)2 maintains its [Au(CN)2](-) structure. The more labile Cl(-) enables easier reduction of Au when compared to the tightly bound cyanide species, hence leading to slower kinetics of deposition and differing electrochemical behaviour. We conclude that metal speciation in DESs is a function of the initial metal salt and that this has a strong influence on the mechanism and rate of growth, as well as on the morphology of the metal deposit obtained. In addition, these coatings are also extremely promising from a technological perspective as Electroless Nickel Immersion Gold (ENIG) finishes in the printed circuit board (PCB) industry, where the elimination of acid in gold plating formulation could potentially lead to more reliable coatings. Consequently, these results are both significant and timely.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

The electrochemical quartz crystal microbalance (EQCM) and probe beam deflection (PBD) have been widely used to study interfacial processes in molecular solvent-based electrolytes. However, there has been limited use of the EQCM and none of PBD in room temperature ionic liquids, including deep eutectic solvents (DES). Here we explore the use of the combined EQCM/PBD technique to the study of Ag and Sn electrodeposition from a DES comprising a 1:2 mixture of choline chloride and ethylene glycol. While overcoming the effect of viscous loss in the acoustic wave (EQCM) part of the experiment is understood, the optical (PBD) technique fails to provide a meaningful response in slow scan rate voltammetric experiments; this contrasts sharply with the straightforward behaviour seen in aqueous media. Solution transport considerations reveal this to be a consequence of long surface-to-beam transit times in the viscous DES. The problem can be overcome by operating at scan rates 1-2 orders of magnitude slower, permitting application of this powerful technique to novel media of technological interest. The PBD responses reveal unanticipated chemical effects: multiple complexes in the Ag system and solubility limitations in the Sn system, neither of which is evident from the electrochemical or QCM responses.

The speciation of metals in solution controls their reactivity, and this is extremely pertinent in the area of metal salts dissolved in ionic liquids. In the current study, the speciation of 25 metal salts is investigated in four deep eutectic solvents (DESs) and five imidazolium-based ionic liquids using extended X-ray absorption fine structure. It is shown that in diol-based DESs M(I) ions form [MCl2](-) and [MCl3](2-) complexes, while all M(II) ions form [MCl4](2-) complexes, with the exception of Ni(II), which exhibits a very unusual coordination by glycol molecules. This was also found in the X-ray crystal structure of the compound [Ni(phen)2(eg)]Cl2·2eg (eg = ethylene glycol). In a urea-based DES, either pure chloro or chloro-oxo coordination is observed. In [C6mim][Cl] pure chloro complexation is also observed, but coordination numbers are smaller (typically 3), which can be explained by the long alkyl chain of the cation. In [C2mim][SCN] metal ions are entirely coordinated by thiocyanate, either through the N or the S atom, depending on the hardness of the metal ion according to the hard-soft acid-base principle. With weaker coordinating anions, mixed coordination between solvent and solute anions is observed. The effect of hydrate or added water on speciation is insignificant for the diol-based DESs and small in other liquids with intermediate or strong ligands. One of the main findings of this study is that, with respect to metal speciation, there is no fundamental difference between deep eutectic solvents and classic ionic liquids.