A Review on the Electroless Deposition of Functional Materials in Ionic Liquids for Batteries and Catalysis.

Developing functional materials via electroless deposition, without the need of external energy is a fascinating concept. Electroless deposition can be subcategorized into galvanic displacement reaction, disproportionation reaction, and deposition in presence of reducing agents. Galvanic displacement reaction is a spontaneous reduction process wherein the redox potentials of the metal/metal ion in the electrolyte govern the thermodynamic feasibility of the process. In aqueous solutions, the galvanic displacement reaction takes place according to the redox potentials of the standard electrochemical series. In comparison, in the case of ionic liquids, galvanic displacement reaction can be triggered by forming metal ion complexes with the anions of the ionic liquids. Therefore, the redox potentials in ILs can be different to those of metal complexes in aqueous solutions. In this review, we highlight the progress in the electroless deposition of metals and semiconductors nanostructures, from ionic liquids and their application toward lithium/sodium batteries, and in catalysis.

Electrochemically induced phase separation and in situ formation of mesoporous structures in ionic liquid mixtures.

Liquid-liquid phase separation is mainly dependent on temperature and composition. Electric fields have also been shown to influence demixing of binary liquid mixtures. However, a puzzling behavior that remains elusive is the electric field-induced phase separation in ion-containing solvents at low voltages, as predicted by Tsori and Leibler. Here, we report the first experimental study of such a phenomenon in ionic liquid-silane mixtures, which not only results in phase separation at the electrode-electrolyte interface (EEI) but also is accompanied by deposition of porous structures of micrometer size on the electrode. This multiscale phenomenon at the EEI was found to be triggered by an electrochemically induced process. Using several analytical methods, we reveal the involved mechanism in which the formation of new Si-N bonds becomes unstable and eventually decomposes into the formation of silane-rich and silane-poor phases. The deposition of porous structures on the electrode surface is therefore a realization of the silane-rich phase. The finding of an electrochemically induced phase separation not only brings a paradigm shift in understanding the EEI in ionic liquids but also provides alternative strategies toward designing porous surfaces.

Modification of the Electrolyte/Electrode Interface for the Template-free Electrochemical Synthesis of Metal Nanowires from Ionic Liquids.

In electrochemistry, the electrode/electrolyte interface (EEI) governs the charge/mass-transfer processes and controls the nucleation/growth phenomena. The EEI in ionic liquids (ILs) can be controlled by changing the cation/anion of the IL, salt concentration, electrode potential, and temperature. Here, we show that adding a dopant salt leads to the deposition of nanowires. To illustrate, zinc nanowires were electrodeposited from ZnCl2/1-butyl-1-methylpyrrolidinium trifluoromethylsulfonate in the presence of GaCl3 as a dopant salt. The choice of Zn salt and its ratio to GaCl3 were found to be crucial for Zn nanowires formation. AFM studies revealed that the solvation structure of Au(111)/IL changes significantly in the presence of GaCl3 and ZnCl2. Chronoamperometry showed changes in the nucleation/growth process, consequently leading to the formation of nanowires. A similar approach was adopted to synthesize Sn nanowires. Thus, modification of the EEI by adding a dopant to ILs can be a viable method to obtain nanowires.

Influence of a silver salt on the nanostructure of a Au(111)/ionic liquid interface: an atomic force microscopy study and theoretical concepts.

Ionic liquids (ILs) form a multilayered structure at the solid/electrolyte interface, and the addition of solutes can alter it. For this purpose, we have investigated the influence of the silver bis(trifluoromethylsulfonyl)amide (AgTFSA) concentration in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py1,4]TFSA) on the layering using in situ atomic force microscopy. AFM investigations revealed that the Au(111)/electrolyte interface indeed depends on the concentration of the salt where a typical " IL" multilayered structure is retained only at quite low concentrations of the silver salt (e.g. ≤200 µM). However, at 200 µM AgTFSA/[Py1,4]TFSA and above this "IL" multilayered structure is disturbed/varied. A simple double layer structure was observed at 500 µM AgTFSA in [Py1,4]TFSA. Furthermore, the widths of the innermost layers have been found to be dependent on the concentration and on the applied electrode potentials. Our AFM results show that the concentration of solutes strongly influences the structure of the electrode/electrolyte interface and can provide new insights into the electrical double layer structure of the electrode/ionic liquid interface. We also introduce a semi-continuum theory to discuss the double layer structure.

The Au(111)/IL interfacial nanostructure in the presence of precursors and its influence on the electrodeposition process.

Ionic liquids have attracted significant interest as electrolytes for the electrodeposition of metals and semiconductors, but the details of the deposition processes are not yet well understood. In this paper, we give an overview of how the addition of various precursors (TaF5, SiCl4, and GaCl3) affects the solid/IL interfacial structure. In situ Atomic Force Microscopy (AFM) and vibrational spectroscopy have been employed to study the changes of the Au(111)/IL interface and in the electrolytes, respectively. Ionic liquids with the 1-butyl-1-methylpyrrolidinium ([Py1,4]+) cation and bis(trifluoromethylsulfonyl)amide ([TFSA]-), trifluoromethylsulfonate ([TfO]-) and tris(pentafluoroethyl)trifluorophosphate ([FAP]-) as anions were chosen for this purpose. In situ AFM force-distance measurements reveal that both the anion of the IL and the solutes (TaF5 or GaCl3) influence the Electrical Double Layer (EDL) structure of the Au(111)/IL interface, which can affect the deposition process of Ta and the morphology of the Ga electrodeposits, respectively. Furthermore, the concentration of the precursor can significantly alter the Au(111)/[Py1,4][FAP]-SiCl4 interfacial structure wherein the presence of 0.25 M SiCl4 a double layer structure forms that facilitates Si deposition. This study may provide some critical insights into the structure of the electrode/IL interface for specific applications.

Anomalous electroless deposition of less noble metals on Cu in ionic liquids and its application towards battery electrodes.

Electroless deposition can be triggered by the difference in the redox potentials between two metals in an electrolyte. In aqueous electrochemistry, galvanic displacement takes place according to the electrochemical series wherein a more noble metal can displace a less noble metal. Herein we show anomalous behaviour in ionic liquids wherein less noble metals such as Fe and Sb were deposited on Cu at temperatures from 25 to 60 °C. Fe formed spherical structures whereas Cu2Sb/Sb formed nanoplates. A multistep process during the electroless deposition of Sb on Cu took place which was discerned from in situ XPS, and mass spectrometry. In situ AFM was also used to understand the nucleation and growth process of the galvanic displacement reaction. Subsequently, the Cu2Sb/Sb nanoplates were also tested as the anode for both Li-ion and Na-ion batteries. Thus, it is shown that the electrochemistry in ionic liquids significantly differs from aqueous electrolytes and opens up new routes for material synthesis.

How a Transition-Metal(II) Chloride Interacts with a Eutectic AlCl3 -Based Ionic Liquid: Insights into the Speciation of the Electrolyte and Electrodeposition of Magnetic Materials.

Electrostatic interactions are characteristic of ionic liquids (ILs) and play a pivotal role in determining the formation of species when solutes are dissolved in them. The formation of new species/complexes has been investigated for certain ILs. However, such investigations have not yet focused on eutectic liquids, which are a promising class of ILs. These liquids (or liquid coordination complexes, LCCs) are rather new and are composed of cationic and anionic chloro complexes of metals. To date, these liquids have been employed as electrolytes to deposit metals and as solvents for catalysis. The present study deals with a liquid that is prepared by mixing a 1.2:1 mol ratio of AlCl3 and 1-butylpyrrolidine. An attempt has been made to understand the interactions of FeCl2 with the organic molecule using spectroscopy. It was found that dissolved Fe(II) species interact mainly with the IL anion and such interactions can lead to changes in the cation of the electrolyte. Furthermore, the viability of depositing thick magnetic films of Fe and Fe-Al has been explored.

Electrodeposition of zinc nanoplates from an ionic liquid composed of 1-butylpyrrolidine and ZnCl2: electrochemical, in situ AFM and spectroscopic studies.

The mixtures of 1-butylpyrrolidine and ZnCl2 result in the formation of an ionic liquid, which can be used as an electrolyte for zinc electrodeposition. The feasibility of electrodepositing Zn from these electrolytes was investigated at RT and at 60 °C. The synthesized mixtures are rather viscous. Toluene was added to the mixtures to decrease the viscosity of the ILs. Vibrational spectroscopy was employed for the characterization of the liquids. The electrochemical behaviour of the liquids was evaluated by cyclic voltammetry. The electrode/electrolyte interface of this IL was probed by Atomic Force Microscopy (AFM). The suitable range for the electrodeposition of Zn was found to be ≥28.6 mol% of ZnCl2. Zn deposition occurs mainly from the cationic species of [ZnClxLy]+ (where x = 1, y = 1-2, and L = 1-butylpyrrolidine) in these electrolytes. This is in contrary to the well investigated chlorozincate ionic liquids where the deposition of Zn occurs mainly from anionic chlorozincates. Nanoplates of Zn were obtained from these mixtures of 1-butylpyrrolidine and ZnCl2.

Nanostructure of the H-terminated p-Si(111)/ionic liquid interface and the effect of added lithium salt.

Ionic liquids are potential electrolytes for safe lithium-ion batteries (LIB). Recent research has probed the use of silicon as an anode material for LIB with various electrolytes. However, the nanostructure of the ionic liquid/Si interface is unknown. The present communication probes the hydrogen terminated p-Si(111) interface using atomic force microscopy (AFM) in 1-ethyl-3-methylimidazolium bis(trifluoromethlysulfonyl)amide ([EMIm]TFSA) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethlysulfonyl)amide ([Py1,4]TFSA). AFM measurements reveal that the imidazolium cation adsorbs at the H-Si(111)/[EMIm]TFSA interface leading to an ordered clustered facet structure of ∼3.8 nm in size. In comparison, the Si(111)/[Py1,4]TFSA interface appeared the same as the native surface in argon. For both pure ILs, repulsive forces were measured as the tip approached the surface. On addition of LiTFSA attractive forces were measured, revealing marked changes in the interfacial structure.

A Prussian Blue/Zinc Secondary Battery with a Bio-Ionic Liquid-Water Mixture as Electrolyte.

The development of rechargeable zinc ion batteries with high capacity and high cycling stability is a great challenge in aqueous solution due to hydrogen evolution and dendritic growth of zinc. In this study, we present a zinc ion secondary battery, comprising a metallic zinc anode, a bio-ionic liquid-water electrolyte, and a nanostructured prussian blue analogue (PBA) cathode. Both the Zn anode and the PBA cathode exhibit good compatibility with the bio-ionic liquid-water electrolyte, which enables the electrochemical deposition/dissolution of zinc at the zinc anode, and reversible insertion/extraction of Zn(2+) ions at the PBA cathode. The cell exhibits a well-defined discharge voltage plateau of ∼1.1 V with a specific capacity of about 120 mAh g(-1) at a current of 10 mA g(-1) (∼0.1 C). The Zn anode shows great reversibility, and dendrite-free Zn deposits were obtained after 100 deposition/dissolution cycles. The integration of an environmentally friendly PBA cathode, a nontoxic and low-cost Zn anode, and a biodegradable ionic liquid-water electrolyte provides new perspective to develop rechargeable zinc ion batteries for various applications in electric energy storage.

Suppressing the dendritic growth of zinc in an ionic liquid containing cationic and anionic zinc complexes for battery applications.

Metallic zinc is a promising negative electrode for high energy rechargeable batteries due to its abundance, low-cost and non-toxic nature. However, the formation of dendritic zinc and low Columbic efficiency in aqueous alkaline solutions during charge/discharge processes remain a great challenge. Here we demonstrate that the dendritic growth of zinc can be effectively suppressed in an ionic liquid electrolyte containing highly concentrated cationic and anionic zinc complexes obtained by dissolving zinc oxide and zinc trifluoromethylsulfonate in a protic ionic liquid, 1-ethylimidazolium trifluoromethylsulfonate. The presence of both cationic and anionic zinc complexes alters the interfacial structure at the electrode/electrolyte interface and influences the nucleation and growth of zinc, leading to compact, homogeneous and dendrite-free zinc coatings. This study also provides insights into the development of highly concentrated metal salts in ionic liquids as electrolytes to deposit dendrite-free zinc as an anode material for energy storage applications.

Dendrite-Free Nanocrystalline Zinc Electrodeposition from an Ionic Liquid Containing Nickel Triflate for Rechargeable Zn-Based Batteries.

Metallic zinc is a promising anode material for rechargeable Zn-based batteries. However, the dendritic growth of zinc has prevented practical applications. Herein it is demonstrated that dendrite-free zinc deposits with a nanocrystalline structure can be obtained by using nickel triflate as an additive in a zinc triflate containing ionic liquid. The formation of a thin layer of Zn-Ni alloy (η- and γ-phases) on the surface and in the initial stages of deposition along with the formation of an interfacial layer on the electrode strongly affect the nucleation and growth of zinc. A well-defined and uniform nanocrystalline zinc deposit with particle sizes of about 25 nm was obtained in the presence of Ni(II) . Further, it is shown that the nanocrystalline Zn exhibits a high cycling stability even after 50 deposition/stripping cycles. This strategy of introducing an inorganic metal salt in ionic liquid electrolytes can be considered as an efficient way to obtain dendrite-free zinc.