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.

Phase evolution in calcium molybdate nanoparticles as a function of synthesis temperature and its electrochemical effect on energy storage.

The design of a suitable electrode is an essential and fundamental research challenge in the field of electrochemical energy storage because the electronic structures and morphologies determine the surface redox reactions. Calcium molybdate (CaMoO4) was synthesized by a combustion route at 300 °C and 500 °C. We describe new findings on the behaviour of CaMoO4 and evaluate the influence of crystallinity on energy storage performance. A wide range of characterization techniques was used to obtain detailed information about the physical and morphological characteristics of CaMoO4. The characterization results enable the phase evolution as a function of the electrode synthesis temperature to be understood. The crystallinity of the materials was found to increase with increasing temperature but with no second phases observed. Molecular dynamics simulation of electronic structures correlated well with the experimental findings. These results show that to enable faster energy storage and release for a given surface area, amorphous CaMoO4 is required, while larger energy storage can be obtained by using crystalline CaMoO4. CaMoO4 has been evaluated as a cathode material in classical lithium-ion batteries recently. However, determining the surface properties in a sodium-ion system experimentally, combined with computational modelling to understand the results has not been reported. The superior electrochemical properties of crystalline CaMoO4 are attributed to its morphology providing enhanced Na+ ion diffusivity and electron transport. However, the presence of carbon in amorphous CaMoO4 resulted in excellent rate capability, suitable for supercapacitor applications.

Modification of Carbon Fibre Surfaces by Sulfur-Fluoride Exchange Click Chemistry.

Technologies that enable surface modification are in high demand and are critical for the implementation of new functional materials and devices. Here, we describe the first modification of a carbon surface (in this case carbon fiber) using the sulfur-fluoride exchange (SuFEx) reaction. The parent sulfur (VI) fluoride moiety can be installed directly to the surface via electrochemical deposition of the fluorosulfate phenyldiazonium tetrafluoroborate salt, or by 'SuFExing' a phenol on the carbon surface followed by treatment of the material with SO2 F2 ; similar to a 'graft to' or 'graft from' functionalization approach. We demonstrate that these SuFEx-able surfaces readily undergo exchange with aryl silyl ethers, and that the subsequent sulfate linkages are themselves stable under electrochemical redox conditions. Finally, we showcase the utility of the SuFEx chemistry by installing a pendant amino group to the fiber surface resulting in interfacial shear strength improvements of up to 130 % in epoxy resin.

New insights into the electrochemistry of magnesium molybdate hierarchical architectures for high performance sodium devices.

Magnesium molybdate (MgMoO4), which possesses synergistic features combining both hierarchical plate-like nanomaterials and porous architectures, has been successfully synthesized through a facile combustion synthesis at a low temperature. The hierarchical architecture is characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), scanning transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analyses. The as-obtained MgMoO4 nanoplates showed a porous structure with a pore-size distribution ranging from 50 to 70 nm. This porosity provides an electron transport pathway and enhanced surface reaction kinetics. The binding energies measured for Mg 2p, Mo 3d, 3p and O 1s are consistent with the literature, and with the metal ions being present as M(ii) and M(vi) states, respectively. This indicates that the oxidation states of the metal cations are as expected. The electrochemical behaviour of MgMoO4 was investigated using aqueous (NaOH) and non-aqueous solvents (NaClO4 in EC : DMC : FEC) for supercapacitor and battery applications. The sodium-ion capacitor involves ion absorption and insertion into the MgMoO4 electrodes resulting in superior power and energy densities. However, the cycling stability was found to be stable only for an aqueous system. The formation of a solid electrolyte surface layer restricted the reversible capacity of the MgMoO4 in the sodium-battery. Nevertheless, it does offer some promise as an anode material for storing energy with high rate performance and excellent capacity retention. Detailed comparative analyses of various electrolytes in storage devices such as hybrid sodium-ion capacitors and sodium-ion batteries are vital for the integration of hierarchical structured materials into practical applications. The reaction mechanisms are postulated.

Demonstration of chemistry at a point through restructuring and catalytic activation at anchored nanoparticles.

Metal nanoparticles prepared by exsolution at the surface of perovskite oxides have been recently shown to enable new dimensions in catalysis and energy conversion and storage technologies owing to their socketed, well-anchored structure. Here we show that contrary to general belief, exsolved particles do not necessarily re-dissolve back into the underlying perovskite upon oxidation. Instead, they may remain pinned to their initial locations, allowing one to subject them to further chemical transformations to alter their composition, structure and functionality dramatically, while preserving their initial spatial arrangement. We refer to this concept as chemistry at a point and illustrate it by tracking individual nanoparticles throughout various chemical transformations. We demonstrate its remarkable practical utility by preparing a nanostructured earth abundant metal catalyst which rivals platinum on a weight basis over hundreds of hours of operation. Our concept enables the design of compositionally diverse confined oxide particles with superior stability and catalytic reactivity.

Two-Dimensional Metal Oxide Nanoflower-Like Architectures: A General Growth Method and Their Applications in Energy Storage and as Model Materials for Nanofabrication.

Nanoflower-like architectures represent a unique type of nanomaterials in which thin 2D nanosheets are self-organised into interconnected structures. Lack of restacking between nanosheets and significant internal porosity are the particular advantages of such nanoscale architectures. A general method for the preparation of nanoflowers of a range of oxides (e.g., FeTiO3 , TiO2 , Mn2 O3 ) through a two-step procedure of ball milling and subsequent hydrothermal treatment is outlined. Importantly, the synthetic method is valid not only for a single oxide, but is extendable to a family of oxide materials. It is established that the formation of the nanoflowers from ball-milled powders follows a dissolution-precipitation mechanism; this is confirmed by inductively coupled plasma time of flight mass spectrometry measurements. Additional information on the X-ray photoelectron spectroscopy characterisation and intermediate stage of growth of the nanostructures is included. Furthermore, two applications of Mn2 O3 nanostructures are briefly investigated. Firstly, their properties for energy storage in the electrodes of electrochemical supercapacitors are presented. A capacitive response in the potential window of -0.1-0.9 V versus an Ag/AgCl reference electrode is observed, with an associated increase of the capacitance values over cycling. Secondly, the use of Mn2 O3 nanoflowers as model systems for the development of novel nanofabrication techniques (such as nanopatterning with a He+ beam) is investigated.

Electroless Nickel Deposition: An Alternative for Graphene Contacting.

We report the first investigation into the potential of electroless nickel deposition to form ohmic contacts on single layer graphene. To minimize the contact resistance on graphene, a statistical model was used to improve metal purity, surface roughness, and coverage of the deposited film by controlling the nickel bath parameters (pH and temperature). The metalized graphene layers were patterned using photolithography and contacts deposited at temperatures as low as 60 °C. The contact resistance was 215 ± 23 Ω over a contact area of 200 µm × 200 µm, which improved upon rapid annealing to 107 ± 9 Ω. This method shows promise toward low-cost and large-scale graphene integration into functional devices such as flexible sensors and printed electronics.

Removing Beam Current Artifacts in Helium Ion Microscopy: A Comparison of Image Processing Techniques.

The development of the helium ion microscope (HIM) enables the imaging of both hard, inorganic materials and soft, organic or biological materials. Advantages include outstanding topographical contrast, superior resolution down to <0.5 nm at high magnification, high depth of field, and no need for conductive coatings. The instrument relies on helium atom adsorption and ionization at a cryogenically cooled tip that is atomically sharp. Under ideal conditions this arrangement provides a beam of ions that is stable for days to weeks, with beam currents in the order of picoamperes. Over time, however, this stability is lost as gaseous contamination builds up in the source region, leading to adsorbed atoms of species other than helium, which ultimately results in beam current fluctuations. This manifests itself as horizontal stripe artifacts in HIM images. We investigate post-processing methods to remove these artifacts from HIM images, such as median filtering, Gaussian blurring, fast Fourier transforms, and principal component analysis. We arrive at a simple method for completely removing beam current fluctuation effects from HIM images while maintaining the full integrity of the information within the image.