SEI Formation on Sodium Metal Electrodes in Superconcentrated Ionic Liquid Electrolytes and the Effect of Additive Water.

We have previously reported that water addition (∼1000 ppm) to an N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (C3mpyrFSI) superconcentrated ionic liquid electrolyte (50 mol % NaFSI) promoted the formation of a favorable solid electrolyte interphase (SEI) and resulted in enhanced cycling stability. This study reports the characterization of Na-metal anode surfaces cycled with these electrolytes containing different water concentrations (up to 5000 ppm). Morphological and spectroscopic characterization showed that water addition greatly influences the formation of the SEI and that ∼1000 ppm of water promoted the formation of an active and more uniform deposit, with larger quantities of SEI species (S, O, F, and N) present. Water addition to the electrolyte system is also proposed to promote the formation of a new complex between the FSI anions, water molecules, and sodium cations as components of the SEI. For both dry and wet (∼1000 ppm) electrolytes, the SEIs were mainly composed of NaF, metal oxide (i.e., Na2O), and the complex, suggested to be Na2[SO3-N-SO2F]·nH2O (n = 0-2). Postcycling SEM analysis of the Na-metal electrodes after extensive cycling (500 cycles, 1.0 mA·cm-2, 1.0 mA·.cm-2) was used to estimate the minimal average cycling efficiency (ACE), which was enhanced by water addition: up to ∼99% for the 1000 ppm cell compared to ∼98% for the dry cell. Two distinct deposit morphologies, a microporous and a compact layer deposit, were evident after extended cycling in the wet and dry electrolytes. The presence of both the microporous and compact layer deposits on Na-metal surfaces cycled with the wet electrolyte, along with the distinct chemistry and morphology of the SEI, all contributed to a more stable symmetric cell voltage profile and lower cell polarization. In contrast, a higher fraction of microporous deposits and the absence of compact layer formation in the dry electrolyte were associated with higher cell polarization potentials and the occurrence of dendrites.

Tuning Sodium Interfacial Chemistry with Mixed-Anion Ionic Liquid Electrolytes.

The interphase layer that forms on either the anode or the cathode is considered to be one of the critical components of a high performing battery. This solid-electrolyte interphase (SEI) layer determines the stability of the electrode in the presence of a given electrolyte as well as the internal resistance of a battery, and hence the overpotential of a cell. In the case of lithium ion batteries where carbonate based electrolytes are used, additives including hexafluorophosphate (PF6), bis-trifluoromethylsulfonimide (TFSI), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI), and fluorosulfonimde (FSI) are used to obtain favorable SEI layers. Ionic liquids and salts based on anions containing nitrile groups, including dicyanamide (DCA), offer a less expensive alternative to a fluorinated anion and have also been shown to support stable electrochemistry in lithium and sodium systems. However, longer term cycling leads to the eventual passivation of the electrode, presumed to be due to the instability of the DCA anion. We herein consider the use of a fluorinated anion to control the interfacial electrochemistry and provide a more stable SEI in DCA ILs. We investigate the addition of NaDCA, NaFSI, NaTFSI, and NaFTFSI to the methylpropylpyrrolidinium dicyanamide ([C3mpyr]DCA) ionic liquid. NaFSI was found to generate a more stable SEI layer, as evidenced by extended symmetric cell cycling, while the TFSI and FTFSI salts both lead to thicker, highly passivating surfaces. We use molecular dynamics, infrared spectroscopy and X-ray photoelectron spectroscopy to interrogate and discuss the influence of the anion on the bulk electrolyte, the interfacial electrolyte structure, and the formation of the SEI layer, in order to rationalize the contrasting electrochemical observations.

Water as an Effective Additive for High-Energy-Density Na Metal Batteries? Studies in a Superconcentrated Ionic Liquid Electrolyte.

The effect of water on the properties of superconcentrated sodium salt solutions in ionic liquids (ILs) was investigated to design electrolytes for sodium battery applications with water as an additive. Water was added to a 50 mol % solution of NaFSI [FSI=bis(fluorosulfonyl)imide] in the ionic liquid N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (C3 mpyrFSI). Although the thermal properties (e.g., glass transition temperature) showed little dependence on the water content, the viscosity and, in particular, the ionic conductivity were strongly affected. The Na|Na symmetrical cell cycling performance was strongly dependent on the applied current density as well as on the water content. At higher current densities (1.0 mA cm-2 ) the polarization profiles showed a water dependence, suggesting that water was actively involved in the formation of an improved solid electrolyte interface layer (SEI) for high-water-content samples (1000-5000 ppm), resulting in improved long-term cycling stability. The initial impedance of cells cycled at 1.0 mA cm-2 (measured after 20 cycles) was elevated after water addition, and large polarizations occured for the "wet" samples. However, with further cycling the wet cells began to exhibit lower polarization and improved stability compared to the "dry" sample. The Na|NaFePO4 cell cycling performance was also demonstrated with minimal effect on the cell capacity, further highlighting the negligible activity of water in these electrolyte systems. In fact, reduced cell polarization and a more clearly defined charge profile were evident after water addition. The work shown here suggests that water may be used as a convenient and inexpensive additive for superconcentrated sodium IL electrolytes for improved device performance.

Water-Facilitated Electrodeposition of Neodymium in a Phosphonium-Based Ionic Liquid.

Rare-earth metals are considered critical metals due to their extensive use in energy-related applications such as wind turbines and nickel-metal hybrid batteries found in hybrid electrical vehicles. A key drawback of the current processing methods includes the generation of large amounts of toxic and radioactive waste. Thus the efficient recovery of these valuable metals as well as cleaner processing methods are becoming increasingly important. Here we report on a clean electrochemical route for neodymium (Nd) recovery from [P6,6,6,14][TFSI], trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide which is amplified three times by the presence of water, as evidenced by the cathodic current density and thicker deposits. The role of Nd salt concentrations and water content as an additive in the electrochemistry of Nd3+ in [P6,6,6,14][TFSI] has been studied. The presence of metallic neodymium in the deposits has been confirmed by X-ray photoelectron spectroscopy.

Spectroscopic Characterization of the SEI Layer Formed on Lithium Metal Electrodes in Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolytes.

The chemical composition of the solid electrolyte interphase (SEI) layer formed on the surface of lithium metal electrodes cycled in phosphonium bis(fluorosulfonyl)imide ionic liquid (IL) electrolytes are characterized by magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray photoelectron spectroscopy (XPS), fourier transformed infrared spectroscopy, and electrochemical impedance spectroscopy. A multiphase layered structure is revealed, which is shown to remain relatively unchanged during extended cycling (up to 250 cycles at 1.5 mA·cm-2, 3 mA h·cm-2, 50 °C). The main components detected by MAS NMR and XPS after several hundreds of cycles are LiF and breakdown products from the bis(fluorosulfonyl)imide anion including Li2S. Similarities in chemical composition are observed in the case of the dilute (0.5 mol·kg-1 of Li salt in IL) and the highly concentrated (3.8 mol·kg-1 of Li salt in IL) electrolyte during cycling. The concentrated system is found to promote the formation of a thicker and more uniform SEI with larger amounts of reduced species from the anion. These SEI features are thought to facilitate more stable and efficient Li cycling and a reduced tendency for dendrite formation.

Effect of mixed anions on the physicochemical properties of a sodium containing alkoxyammonium ionic liquid electrolyte.

The physicochemical properties of the ionic liquid N-ethyl-2-(2-methoxyethoxy)-N,N-bis(2-(2-methoxyethoxy)ethyl)ethan-1-ammonium bis(trifluoromethylsulfonyl)imide (N2(2O2O1)3TFSI) as well as its solutions with sodium bis(trifluoromethylsulfonyl)imide (NaTFSI) and sodium bis(fluorosulfonyl)imide (NaFSI) are compared in order to study the effects of the anion. The NaFSI solutions show weaker interactions as suggested by lower glass transition temperatures, lower densities, lower viscosities and higher conductivities as compared to their more strongly coordinating NaTFSI analogues. The transport properties follow Vogel-Tamman-Fulcher behaviour suggesting that the mixtures are fragile glass formers. The addition of a higher concentration of Na salts results in decoupling of the translational motion from the viscosity, as observed from Walden plots, and 23Na NMR data suggests that the sodium speciation is independent of the nature of the Na salt or the temperature but is affected by the salt concentration.

Electrochemical Behavior of PEDOT/Lignin in Ionic Liquid Electrolytes: Suitable Cathode/Electrolyte System for Sodium Batteries.

Biomass-derived polymers, such as lignin, contain quinone/ hydroquinone redox moieties that can be used to store charge. Composites based on the biopolymer lignin and several conjugated polymers have shown good charge-storage properties. However, their performance has been only studied in acidic aqueous media limiting their applications mainly to supercapacitors. Here, we show that PEDOT/lignin (PEDOT: poly(3,4-ethylenedioxythiophene)) biopolymers are electroactive in aprotic ionic liquids (ILs) and we move a step further by assembling sodium full cell batteries using PEDOT/lignin as electrode material and IL electrolytes. Thus, the electrochemical activity and cycling of PEDOT/lignin electrodes was investigated in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyrTFSI), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (BMPyrFSI), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI) and 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMImFSI) IL electrolytes. The effects of water and sodium salt addition to the ILs were investigated to obtain optimum electrolyte systems for sodium batteries. Finally, sodium batteries based on PEDOT/lignin cathode with imidazolium-based IL electrolyte showed higher capacity values than pyrrolidinium ones, reaching 70 mAhg-1 . Our results demonstrate that PEDOT/lignin composites can serve as low cost and sustainable cathode materials for sodium batteries.

In-Situ-Activated N-Doped Mesoporous Carbon from a Protic Salt and Its Performance in Supercapacitors.

Protic salts have been recently recognized to be an excellent carbon source to obtain highly ordered N-doped carbon without the need of tedious and time-consuming preparation steps that are usually involved in traditional polymer-based precursors. Herein, we report a direct co-pyrolysis of an easily synthesized protic salt (benzimidazolium triflate) with calcium and sodium citrate at 850 °C to obtain N-doped mesoporous carbons from a single calcination procedure. It was found that sodium citrate plays a role in the final carbon porosity and acts as an in situ activator. This results in a large surface area as high as 1738 m2/g with a homogeneous pore size distribution and a moderate nitrogen doping level of 3.1%. X-ray photoelectron spectroscopy (XPS) measurements revealed that graphitic and pyridinic groups are the main nitrogen species present in the material, and their content depends on the amount of sodium citrate used during pyrolysis. Transmission electron microscopy (TEM) investigation showed that sodium citrate assists the formation of graphitic domains and many carbon nanosheets were observed. When applied as supercapacitor electrodes, a specific capacitance of 111 F/g in organic electrolyte was obtained and an excellent capacitance retention of 85.9% was observed at a current density of 10 A/g. At an operating voltage of 3.0 V, the device provided a maximum energy density of 35 W h/kg and a maximum power density of 12 kW/kg.

Graphene/zinc nano-composites by electrochemical co-deposition.

We describe for the first time the electrochemical co-deposition of composites based on a reactive base metal and graphene directly from a one-pot aqueous mixture containing graphene oxide and Zn(2+). In order to overcome stability issues the Zn(2+) concentration was kept below a critical threshold concentration, ensuring stable graphene oxide suspensions in the presence of cationic base metal precursors. This approach ensures the compatibility between the cationic base metal precursor and graphene oxide, which is more challenging compared to previously reported anionic noble metal complexes. Spectroscopic evidence suggests that the reason for destabilisation is zinc complexation involving the carboxylate groups of graphene oxide. The composition of the electrodeposited co-composites can be tuned by adjusting the concentration of the precursors in the starting mixture. The nano-composites show zinc particles (<3 nm) being uniformly dispersed amongst the graphene sheets. It is also demonstrated that the composites are electrochemically active and suitable for energy storage and energy conversion applications. However, a factor limiting the discharge efficiency is the reactivity of the base metal (low reduction potential and small particle size) which undergoes rapid oxidation when exposed to aqueous electrolytes.

Direct electro-deposition of graphene from aqueous suspensions.

We describe the direct electro-chemical reduction of graphene oxide to graphene from aqueous suspension by applying reduction voltages exceeding -1.0 to -1.2 V. The conductivity of the deposition medium is of crucial importance and only values between 4-25 mS cm(-1) result in deposition. Above 25 mS cm(-1) the suspension de-stabilises while conductivities below 4 mS cm(-1) do not show a measurable deposition rate. Furthermore, we show that deposition can be carried out over a wide pH region ranging from 1.5 to 12.5. The electro-deposition process is characterised in terms of electro-chemical methods including cyclic voltammetry, quartz crystal microbalance, impedance spectroscopy, constant amperometry and potentiometric titrations, while the deposits are analysed via Raman spectroscopy, infra-red spectroscopy, X-ray photoelectron spectroscopy and X-ray diffractometry. The determined oxygen contents are similar to those of chemically reduced graphene oxide, and the conductivity of the deposits was found to be ∼20 S cm(-1).

The synthesis of a dichloroalane complex and its reaction with an alpha-diimine.

Reaction of an alpha-diimine, {MesN=CH}2 (Mes=2,4,6-trimethylphenyl), with the dichloroalane [AlCl2H(IMes)] (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) affords an N-heterocyclic carbene (NHC) transfer complex [AlCl2{MesNC(=IMes)C(H)NMes}] rather than the expected hydroalumination product.

The reactivity of N-heterocyclic carbenes and their precursors with [Ru(3)(CO)(12)].

The ambient temperature reaction of the N-heterocyclic carbenes (NHCs) 1,3-dimesitylimidazol-2-ylidene (IMes) and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IDipp) with the triruthenium cluster [Ru3(CO)12], in a 3:1 stoichiometric ratio, results in homolytic cleavage of the cluster to quantitatively afford the complexes [Ru(CO)4(NHC)] (1; NHC = IMes, 2; NHC = IDipp). Reaction of the 2-thione or hydrochloride precursors to IMes, i.e. SIMes and IMes.HCl, with the same triruthenium cluster affords the complexes [Ru4(mu4-S)2(CO)9(IMes)2] (3) and [Ru4(mu4-S)(CO)10(IMes)2] (4) (3:1 and 2:1 reaction), and [{Ru(mu-Cl)(CO)2(IMes)}2] (7) (3:1 reaction) respectively. By contrast, the complex [Ru3(mu3-S)2(CO)7(IMeMe)2] (6), where IMeMe is 1,3,4,5-tetramethylimidazol-2-ylidene, is the sole product of the 2:1 stoichiometric reaction of SIMeMe with [Ru3(CO)12]. Compounds 1-4, 6 and 7 have been structurally characterised by single crystal X-ray diffraction.