Rapidly Constructing Sodium Fluoride-Rich Interface by Pressure and Diglyme-Induced Defluorination Reaction for Stable Sodium Metal Anode.

Sodium (Na) metal is able to directly use as a battery anode but have a highly reductive ability of unavoidably occurring side reactions with organic electrolytes, resulting in interfacial instability as a primary factor in performance decay. Therefore, building stable Na metal anode is of utmost significance for both identifying the electrochemical performance of laboratory half-cells employed for quantifying samples and securing the success of room-temperature Na metal batteries. In this work, we propose an NaF-rich interface rapidly prepared by pressure and diglyme-induced defluorination reaction for stable Na metal anode. Once the electrolyte is dropped into the coin-type cells followed by a slight squeeze, the Na metal surface immediately forms a protective layer consisting of amorphous carbon and NaF, effectively inhibiting the dendrite growth and dead Na. The resultant Na metal anode exhibits a long-term cycling lifespan over 1800 h even under the area capacity of 3.0 mAh cm-2 . Furthermore, such a universal and facile method is readily applied in daily battery assembly regarding Na metal anode.

Insights into the Reaction Mechanisms of Nongraphitic High-Surface Porous Carbons for Application in Na- and Mg-Ion Batteries.

The fabrication of low-cost carbon materials and high-performance sodium- and magnesium-ion batteries comprising hierarchical porous electrodes and superior electrolytes is necessary for complementing Li-ion energy storage. In this work, nongraphitic high-surface porous carbons (NGHSPCs) exhibited an unprecedented formation of n-stages (stage-1 and stage-2) due to the co-intercalation of sodium (Na(dgm)2C20) with diglyme. X-ray diffraction patterns, Patterson diagram, Raman spectra, and IR spectra suggested the presence of n-stages. This phenomenon implies an increase of the initial capacity (∼200 mAh g-1) and good Na-ion diffusion (2.97 × 10-13 cm2 s-1), employing diglyme as compared to standard electrolytes containing propylene carbonate and fluoroethylene carbonate. Additionally, the current approach is scalable to full Na- and Mg-ion cells by using t-Na5V(PO4)2F2 and MgMnSiO4 cathodes, respectively, reaching 250 and 110 W h kg-1 based on the anode mass. The simultaneous Mg (de)insertion from/into MgMnSiO4 and the adsorption/desorption of bistriflimide ions on the NGHSPC surface is responsible for capacity enhancement.

Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na-O2 Batteries.

A series of hybrid electrolytes composed of diglyme and ionic liquids (ILs) have been investigated for Na-O2 batteries, as a strategy to control the growth and purity of the discharge products during battery operation. The dependence of chemical composition of the ILs on the size, purity, and distribution of the discharge products has been evaluated using a wide range of experimental and spectroscopic techniques. The morphology and composition of the discharge products found in the Na-O2 cells have a complex dependence on the physicochemical properties of the electrolyte as well as the speciation of the Na+ and superoxide radical anion. All of these factors control the nucleation and growth phenomena as well as electrolyte stability. Smaller discharge particle sizes and largely homogeneous (2.7 ± 0.5 µm) sodium superoxide (NaO2) crystals with only 9% of side products were found in the hybrid electrolyte containing the pyrrolidinium IL with a linear alkyl chain. The long-term cyclability of Na-O2 batteries with high Coulombic efficiency (>90%) was obtained for this electrolyte with fewer side products (20 cycles at 0.5 mA h cm-2). In contrast, rapid failure was observed with the use of the phosphonium-based electrolyte, which strongly stabilizes the superoxide anion. A high discharge capacity (4.46 mA h cm-2) was obtained for the hybrid electrolyte containing the pyrrolidinium-based IL bearing a linear alkyl chain with a slightly lower value (3.11 mA h cm-2) being obtained when the hybrid electrolyte contained similar pyrrolidinium-based IL bearing an alkoxy chain.

New Diglyme-based Gel Polymer Electrolytes for Na-based Energy Storage Devices.

This work presents for the first time a new diglyme-based gel polymer (DOBn-GPE) suitable for Na-based energy storage devices. The DOBn-GPE, which contains a methacrylate-based polymer, exhibited an excellent high ionic conductivity (2.3 mS cm-1 at 20 °C), broad electrochemical stability (>5.0 V), and high mechanical stability. DOBn-GPE could be successfully used for the realization of Na-ion capacitors, sodium-metal batteries, and sodium-ion batteries, displaying performance comparable with those of systems containing liquid electrolytes at room temperature and at 60 °C. The results of these investigation indicated that the development of diglyme-based gel polymer electrolytes represents a promising strategy for the realization of advanced Na-based energy storage devices.

A Concentrated AlCl3-Diglyme Electrolyte for Hard and Corrosion-Resistant Aluminum Electrodeposits.

A concentrated aluminum chloride (AlCl3)-diglyme (G2) electrolyte is used to prepare hard and corrosion-resistant aluminum (Al) electrodeposited films. The Al electrodeposits obtained from the electrolyte with an AlCl3/G2 molar ratio x = 0.4 showed a void-free microstructure composed of spherical particles, in stark contrast to flake-like morphologies with micro-voids for lower x. Neutral complexes rarely exist in the x = 0.4 electrolyte, resulting in a relatively high conductivity despite the high concentration and high viscosity. Nanoindentation measurements for the Al deposits with >99% purity revealed that the nanohardness was 2.86 GPa, three times higher than that for Al materials produced through electrodeposition from a well-known ionic liquid bath or through severe plastic deformation. Additionally, the void-free Al deposits had a <100> preferential crystal orientation, which accounted for better resistance to free corrosion and pitting corrosion. Discussions about the compact microstructure and <100> crystal orientation of deposits obtained only from the x = 0.4 concentrated electrolyte are also presented.

Adsorption and Thermal Decomposition of Electrolytes on Nanometer Magnesium Oxide: An in Situ 13C MAS NMR Study.

Mg batteries have been proposed as potential alternatives to lithium-ion batteries because of their lower cost, higher safety, and enhanced charge density. However, the Mg metal readily oxidizes when exposed to an oxidizer to form a thin MgO passivation surface layer that blocks the transport of Mg2+ across the solid electrode-electrolyte interface (SEI). In this work, the adsorption and thermal decomposition of diglyme (G2) and electrolytes containing Mg(TFSI)2 in G2 on 10 nm-sized MgO particles are evaluated by a combination of in situ 13C single-pulse, surface-sensitive 1H-13C cross-polarization (CP) magic-angle spinning (MAS) nuclear magnetic resonance, and quantum chemistry calculations. At 180 °C, neat G2 decomposes on MgO to form surface-adsorbed -OCH3 groups that are captured as a distinctive peak located at about 50 ppm in the CP/MAS spectrum. At low Mg(TFSI)2 salt concentration, the main solvation structure in this electrolyte is solvent-separated ion pairs without extensive Mg-TFSI contact ion pairs. G2, likely including a small amount of G2-solvated Mg2+, adsorbs onto the MgO surface. At high Mg(TFSI)2 salt concentrations, contact ion pairs between Mg and TFSI are formed extensively in the solution with the first solvation shell containing one pair of Mg-TFSI and two G2 molecules and the second solvation shell containing up to six G2 molecules, namely, MgTFSI(G2)2(G2)6+. In the presence of MgO, MgTFSI(G2)2(G2)6+ adsorbs onto the MgO surface. At 180 °C, the MgO surface stimulates a desolvation process converting MgTFSI(G2)2(G2)6+ to MgTFSI(G2)2+ and releasing G2 molecules from the second solvation shell of the MgTFSI(G2)2(G2)6+ cluster into the solution. MgTFSI(G2)2+ and MgTFSI(G2)2(G2)6+ tightly adsorb onto the MgO surface and are observed by 1H-13C CP/MAS experiments. The results contained herein show that electrolyte composition has a directing role in the species present on the electrode surface, which has implications on the structures and constituents of the solid-electrolyte interface on working electrodes and can be used to better understand its formation and the failure modes of batteries.

Stable and Unstable Diglyme-Based Electrolytes for Batteries with Sodium or Graphite as Electrode.

We study the stability of several diglyme-based electrolytes in sodium|sodium and sodium|graphite cells. The electrolyte behavior for different conductive salts [sodium trifluoromethanesulfonate (NaOTf), NaPF6, NaClO4, bis(fluorosulfonyl)imide (NaFSI), and sodium bis(trifluoromethanesulfonyl)imide (NaTFSI)] is compared and, in some cases, considerable differences are identified. Side reactions are studied with a variety of methods, including X-ray diffraction, scanning electron microscopy, transmission electron microscopy, online electrochemical mass spectrometry, and in situ electrochemical dilatometry. For Na|Na symmetric cells as well as for Na|graphite cells, we find that NaOTf and NaPF6 are the preferred salts followed by NaClO4 and NaFSI, as the latter two lead to more side reactions and increasing impedance. NaTFSI shows the worst performance leading to poor Coulombic efficiency and cycle life. In this case, excessive side reactions lead also to a strong increase in electrode thickness during cycling. In a qualitative order, the suitability of the conductive salts can be ranked as follows: NaOTf ≥ NaPF6 > NaClO4 > NaFSI ≫ NaTFSI. Our results also explain two recent, seemingly conflicting findings on the degree of solid electrolyte interphase formation on graphite electrodes in sodium-ion batteries [ Maibach , J. ; ACS Appl. Mater. Interfaces 2017 , 9 , 12373 - 12381 ; Goktas , M. ; Adv. Energy Mater. 2018 , 8 , 1702724 ]. The contradictory findings are due to the different conductive salts used in both studies.

NOx-smoke trade-off characteristics of minor vegetable oil blends synergy with oxygenate in a commercial CI engine.

The present study investigates the effect of blending oxygenate namely diethylene glycol dimethyl ether (diglyme) with minor vegetable oil namely rubber seed oil (RSO), babassu oil (BSO), and their blends in various proportions (R75B25, R50B50, and R25B75) on NOx-smoke trade-off and other engine characteristics. The tests were conducted on a commercial twin cylinder compression-ignition (CI) engine commonly used in tractors. The potential of the blends with diglyme is assessed based on performance, emission, and combustion characteristics of the engine at different load conditions. The tests were conducted at a constant speed of 1500 rpm maintaining the original injection timing and pressure. Compared to diesel, RSO, and BSO, and their blends exhibited inferior combustion due to poor physical properties like high viscosity and density. This resulted in a lower brake thermal efficiency with increase in HC, CO, and smoke emissions compared to diesel at all the load conditions. The augmented effect is observed with increase in BSO proportion for the blends and neat BSO. The poor combustion of minor vegetable oil and its blends lead to lower NOx emission as a result of lower in-cylinder temperature. To improve the performance and NOx-smoke trade-off, diglyme (DGM) was added with all the test fuels with the optimum share of 20% (by volume). Addition of DGM, increased brake thermal efficiency by 2-7% for all the test fuels due to improved combustion as a result of additional fuel bound oxygen in DGM and improved fuel blend properties. DGM addition reduced smoke, HC, and CO emission drastically with a slight increase in NOx emission compared to minor vegetable oil blends. The study shows that addition of DGM showed a promising note in NOx-smoke trade-off without affecting the other engine parameters.

Shedding Light on the Oxygen Reduction Reaction Mechanism in Ether-Based Electrolyte Solutions: A Study Using Operando UV-Vis Spectroscopy.

Using UV-vis spectroscopy in conjunction with various electrochemical techniques, we have developed a new effective operando methodology for investigating the oxygen reduction reactions (ORRs) and their mechanisms in nonaqueous solutions. We can follow the in situ formation and presence of superoxide moieties during ORR as a function of solvent, cations, anions, and additives in the solution. Thus, using operando UV-vis spectroscopy, we found evidence for the formation of superoxide radical anions during oxygen reduction in LiTFSI/diglyme electrolyte solutions. Nitro blue tetrazolium (NBT) was used to indicate the presence of superoxide moieties based on its unique spectral response. Indeed, the spectral response of NBT containing solutions undergoing ORR could provide a direct indication for the level of association of the Li cations with the electrolyte anions.

Dynamic Diglyme-Mediated Self-Assembly of Gold Nanoclusters.

We report the assembly of gold nanoclusters by the nonthiolate ligand diglyme into discrete and dynamic assemblies. To understand this surprising phenomenon, the assembly of Au20(SC2H4Ph)15-diglyme into Au20(SC2H4Ph)15-diglyme-Au20(SC2H4Ph)15 is explored in detail. The assembly is examined by high-angle annular dark field scanning transmission electron microscopy, size exclusion chromatography, mass spectrometry, IR spectroscopy, and calorimetry. We establish a dissociation constant for dimer to monomer conversion of 20.4 µM. Theoretical models validated by transient absorption spectroscopy predict a low-spin monomer and a high-spin dimer, with assembly enabled through weak diglyme oxygen-gold interactions. Close spatial coupling allows electron delocalization between the nanoparticle cores. The resulting assemblies thus possess optical and electronic properties that emerge as a result of assembly.