Electroconvective Flow in Liquid Electrolytes Containing Oligomer Additives.

Metal electrodeposition in batteries is fundamentally unstable and affected by different instabilities depending on operating conditions and electrolyte chemistry. Particularly, at high charging rates, a hydrodynamic instability loosely termed electroconvection sets in, which complicates all electrochemical processes by creating a nonuniform ion flux and preferential deposition at the electrode. Here, we isolate and study electroconvection by experimentally investigating how oligomer additives in liquid electrolytes interact with the hydrodynamic instability at a cation selective interface. From electrochemical measurements and direct visualization experiments, we find that electroconvection is delayed and suppressed at all voltages in the presence of oligomers. The underlying mechanism is revealed to involve formation of an oligomer ad-layer at the interface, which in response to perturbation is believed to exert an opposing body force on the surrounding fluid to preserve the ad-layer structure and in so doing suppresses electroconvection. Our results therefore reveal that in battery electrolytes without obvious sources of bulk elasticity, surface forces produced by adsorbed polymers can be used to advantage for suppressing instability.

A study of the application of graphite MALDI to the analysis of lanthanides and deconvolution of the isobaric species observed.

Matrix-assisted laser desorption/ionisation mass spectrometry has always suffered from matrix interference at low-masses making it an unsuitable method for the analysis of low molecular weight analytes. In recent years, there has been considerable interest in the use of graphite as a matrix. In this study, we demonstrate the application of colloidal graphite for the analysis of lanthanides in the positive ion mode. Positive ion mode is of academic interest as spectra are dominated by lanthanide cations, oxides, hydroxides and carbides with the metal having been reduced to oxidation state I, II or III. The ratios of the different ions are considered in terms of redox potentials of the lanthanides and rates of reaction with oxygen. Positive ion mode is shown to be useful as a rapid technique for confirming which metal(s) are present in a sample which can have an application in environmental monitoring, for example. Demonstration of a least squares approach to deconvolution is applied for the complete separation and relative quantification of the different isobaric species observed due to the complex isotope distributions of some lanthanides.

Structure and Dynamics of Electric-Field-Driven Convective Flows at the Interface between Liquid Electrolytes and Ion-Selective Membranes.

At voltages above a certain critical value, Vc ≈ 20 kT/e, a space charge layer forms near ion-selective interfaces in liquid electrolytes. Interactions between the space charge and an imposed electric field drives a hydrodynamic instability known as electroconvection. Through particle tracking velocimetry we experimentally study the structure and dynamics of the resultant electroconvective flow. Consistent with previous numerical simulations, we report that, following imposition of a sufficiently large voltage, electroconvection develops gradually as pairs of counter-rotating vortices, which nucleate at the interface between an ion-selective substrate and a liquid electrolyte. Depending on the imposed voltage and cell geometry, the vorticies grow to length scales of hundreds of micrometers. Electroconvective flows are also reported to be structured and multiscale, with the size ratio of the largest to the smallest observable vortices inversely proportional to the Debye screening length.

Sample preparation methods for optimal HS-AFM analysis: Duplex stainless steel.

The contact mode high-speed atomic force microscope (AFM) operates orders of magnitude faster than conventional AFMs. It is capable of capturing multiple frames per second with nanometre-scale lateral resolution and subatomic height resolution. This advancement in imaging rate allows for microscale analysis across macroscale surfaces, making it suitable for applications across materials science. However, the quality of the surface analysis obtained by high-speed AFM is highly dependent upon the standard of sample preparation and the resultant final surface finish. In this study, different surface preparation techniques that are commonly implemented within metallurgical studies are compared for samples of SAF 2205 duplex stainless steel. It was found that, while acid etching and electrolytic etching were optimal for the low resolution of optical microscopy, these methods were less suited for analysis by high resolution high-speed AFM. Mechanical and colloidal silica polishing was found to be the optimal method explored, as it provided a gentle etch of the surface allowing for high quality topographic maps of the sample surface.

Designing electrolytes with polymerlike glass-forming properties and fast ion transport at low temperatures.

In the presence of Lewis acid salts, the cyclic ether, dioxolane (DOL), is known to undergo ring-opening polymerization inside electrochemical cells to form solid-state polymer batteries with good interfacial charge-transport properties. Here we report that LiNO3, which is unable to ring-open DOL, possesses a previously unknown ability to coordinate with and strain DOL molecules in bulk liquids, completely arresting their crystallization. The strained DOL electrolytes exhibit physical properties analogous to amorphous polymers, including a prominent glass transition, elevated moduli, and low activation entropy for ion transport, but manifest unusually high, liquidlike ionic conductivities (e.g., 1 mS/cm) at temperatures as low as -50 °C. Systematic electrochemical studies reveal that the electrolytes also promote reversible cycling of Li metal anodes with high Coulombic efficiency (CE) on both conventional planar substrates (1 mAh/cm2 over 1,000 cycles with 99.1% CE; 3 mAh/cm2 over 300 cycles with 99.2% CE) and unconventional, nonplanar/three-dimensional (3D) substrates (10 mAh/cm2 over 100 cycles with 99.3% CE). Our finding that LiNO3 promotes reversibility of Li metal electrodes in liquid DOL electrolytes by a physical mechanism provides a possible solution to a long-standing puzzle in the field about the versatility of LiNO3 salt additives for enhancing reversibility of Li metal electrodes in essentially any aprotic liquid electrolyte solvent. As a first step toward understanding practical benefits of these findings, we create functional Li||lithium iron phosphate (LFP) batteries in which LFP cathodes with high capacity (5 to 10 mAh/cm2) are paired with thin (50 µm) lithium metal anodes, and investigate their galvanostatic electrochemical cycling behaviors.

Flavone as a novel matrix for the matrix-assisted laser desorption/ionisation analysis of lanthanide and transition metal salts.

The mass spectral analysis of metal salts, especially lanthanide and transition metal salts, can be challenging. Although getting information on the metal present is usually straightforward, obtaining information on the correct oxidation state and anion composition is challenging. Many ionisation techniques have some redox component to the ionisation process, which commonly results in changing the oxidation state of the metal and the associated loss of ligand and anion information. We present here a simple method for negative ion matrix-assisted laser desorption/ionisation mass spectrometry using the non-acidic flavonoid flavone as a novel matrix. This results in reliable information on the oxidation state of the metal as spectra are dominated by anion adduct ions with very little (typically no) redox processes occurring.

Structure, Rheology, and Electrokinetics of Soft Colloidal Suspension Electrolytes.

When ion transport in a binary liquid electrolyte is driven at potentials above the thermal voltage, an extended space charge region forms at the electrolyte/electrode interface and triggers the hydrodynamic instability termed electroconvection. We experimentally show that this instability can be completely arrested in soft colloidal suspension electrolytes composed of low concentrations of polymer-grafted nanoparticles in a liquid host. The mechanism is revealed by means of X-ray scattering, Brownian dynamics calculations, and linear stability analysis to involve overlap of the soft particles at low particle fractions to create a jammed, nanoporous medium that resists convective flow by a Darcy-Brinkman like drag on the electrolyte solvent.

Spontaneous and field-induced crystallographic reorientation of metal electrodeposits at battery anodes.

The propensity of metal anodes of contemporary interest (e.g., Li, Al, Na, and Zn) to form non-planar, dendritic morphologies during battery charging is a fundamental barrier to achievement of full reversibility. We experimentally investigate the origins of dendritic electrodeposition of Zn, Cu, and Li in a three-electrode electrochemical cell bounded at one end by a rotating disc electrode. We find that the classical picture of ion depletion-induced growth of dendrites is valid in dilute electrolytes but is essentially irrelevant in the concentrated (≥1 M) electrolytes typically used in rechargeable batteries. Using Zn as an example, we find that ion depletion at the mass transport limit may be overcome by spontaneous reorientation of Zn crystallites from orientations parallel to the electrode surface to dominantly homeotropic orientations, which appear to facilitate contact with cations outside the depletion layer. This chemotaxis-like process causes obvious texturing and increases the porosity of metal electrodeposits.

Solid-state polymer electrolytes for high-performance lithium metal batteries.

Electrochemical cells based on alkali metal anodes are receiving intensive scientific interest as potentially transformative technology platforms for electrical energy storage. Chemical, morphological, mechanical and hydrodynamic instabilities at the metal anode produce uneven metal electrodeposition and poor anode reversibility, which, are among the many known challenges that limit progress. Here, we report that solid-state electrolytes based on crosslinked polymer networks can address all of these challenges in cells based on lithium metal anodes. By means of transport and electrochemical analyses, we show that manipulating thermodynamic interactions between polymer segments covalently anchored in the network and "free" segments belonging to an oligomeric electrolyte hosted in the network pores, one can facilely create hybrid electrolytes that simultaneously exhibit liquid-like barriers to ion transport and solid-like resistance to morphological and hydrodynamic instability.

Confining electrodeposition of metals in structured electrolytes.

Electrochemical cells based on alkali metal (Li, Na) anodes have attracted significant recent attention because of their promise for producing large increases in gravimetric energy density for energy storage in batteries. To facilitate stable, long-term operation of such cells a variety of structured electrolytes have been designed in different physical forms, ranging from soft polymer gels to hard ceramics, including nanoporous versions of these ceramics that host a liquid or molten polymer in their pores. In almost every case, the electrolytes are reported to be substantially more effective than anticipated by early theories in improving uniformity of deposition and lifetime of the metal anode. These observations have been speculated to reflect the effect of electrolyte structure in regulating ion transport to the metal electrolyte interface, thereby stabilizing metal electrodeposition processes at the anode. Here we create and study model structured electrolytes composed of covalently linked polymer grafted nanoparticles that host a liquid electrolyte in the pores. The electrolytes exist as freestanding membranes with effective pore size that can be systematically manipulated through straightforward control of the volume fraction of the nanoparticles. By means of physical analysis and direct visualization experiments we report that at current densities approaching the diffusion limit, there is a clear transition from unstable to stable electrodeposition at Li metal electrodes in membranes with average pore sizes below 500 nm. We show that this transition is consistent with expectations from a recent theoretical analysis that takes into account local coupling between stress and ion transport at metal-electrolyte interfaces.

Methodologies for the airbrush application of MALDI matrices.

There is still a need to develop reliable and robust matrix deposition methods for matrix-assisted laser desorption/ionisation mass spectrometry that are applicable to a range of matrices, solvents and analyte types. This paper presents a robust methodology for the airbrush application of matrices along with the implications of varying the set-up and airbrush parameters. A small number of organic analytes and metal salts are analysed in both positive and negative ion modes to exemplify this methodology. In the analyses with the airbrush deposited matrices, performance was enhanced when compared to standard pipette deposition with the need for a search for sweat spots greatly diminished due to the increase homogeneity of the matrix surface and resultant analyte spots. As expected, the graphite matrices were shown to specifically outperform the organic matrices in negative ion mode.

Investigation of colloidal graphite as a matrix for matrix-assisted laser desorption/ionisation mass spectrometry of low molecular weight analytes.

The analysis of low molecular weight compounds by matrix-assisted laser desorption/ionisation mass spectrometry is problematic due to the interference and suppression of analyte ionisation by the matrices typically employed - which are themselves low molecular weight compounds. The application of colloidal graphite is demonstrated here as an easy to use matrix that can promote the ionisation of a wide range of analytes including low molecular weight organic compounds, complex natural products and inorganic complexes. Analyte ionisation with colloidal graphite is compared with traditional organic matrices along with various other sources of graphite (e.g. graphite rods and charcoal pencils). Factors such as ease of application, spectra reproducibility, spot longevity, spot-to-spot reproducibility and spot homogeneity (through single spot imaging) are explored. For some analytes, considerable matrix suppression effects are observed resulting in spectra completely devoid of matrix ions. We also report the observation of radical molecular ions [M(-●) ] in the negative ion mode, particularly with some aromatic analytes. Copyright © 2016 John Wiley & Sons, Ltd.

Endoscopic horizon stabilization in natural orifice translumenal endoscopic surgery: a randomized controlled trial.

BACKGROUND: Spatial orientation in natural orifice translumenal endoscopic surgery (NOTES) has been identified as a potential barrier to clinical application. We aim to evaluate a triaxial inertial sensor and software that automatically corrects any movements on the roll axis of the flexible endoscope, allowing for stabilization of the image horizon during NOTES operations in a randomized controlled trial. METHODS: A total of 18 participants (11 surgeons/7 gastroenterologists) performed a transgastric task in the ELITE simulator, which included navigation to the appendix and gallbladder, diathermy of the appendix base and gallbladder fossa, and clipping of the cystic duct using a single-channel gastroscope. Each participant performed the task twice with randomization to horizon stabilization occurring at the second attempt. The primary end point was change in overall performance (time taken and errors made) between the first and second attempt, and secondary end points were absolute performances in the second attempt and subjective evaluation. RESULTS: Without horizon stabilization, there was a median improvement of 42.4% in time taken and 38% in number of errors made from the first to the second attempt; however, with the software turned on, there was a statistically significant deterioration of 4.9% (P = .038) in time taken and an increase in errors made of 183% (P = ns). CONCLUSIONS: Although the software corrects the view to that preferred during surgery, the endoscopic control mechanism as well as the exit point of the instrument are altered in this process, leading to a deterioration of overall performance. Potential solutions include deploying intermittent horizon stabilization or using a robotic interface to achieve fully aligned perceptual-motor control.

Horizon stabilized--dynamic view expansion for robotic assisted surgery (HS-DVE).

PURPOSE: New surgical approaches based on natural orifice transluminal surgery (NOTES) have the potential to further decrease morbidity and hospital stay. However, a number of key challenges have been identified preventing its clinical adoption, including inadequate instrument design and spatial disorientation. Furthermore, retroflexion, missing fixed anatomical references, and limited field-of-view are key factors contributing to disorientation in NOTES. METHODS: A hybrid approach of integrated orientation sensing and real-time vision processing is proposed to restore orientation cues for improved surgical navigation. The distal tip of an articulated robotic endoscope is equipped with an inertial measurement unit (IMU) enabling video images to be reoriented and stabilized with respect to the horizon. This is performed by measuring the direction of gravity in relation to the cameras. Dynamic view expansion is used to increase the field-of-view of the endoscope. The method registers past video images to the current image and creates an enlarged visualization of the anatomy through simultaneous localization and mapping (SLAM). RESULTS: The clinical potential of the system is demonstrated on a NOTES appendectomy procedure performed on the NOSsE phantom. This involves an articulated robotic endoscope navigating to visualize the appendix while retroflexed. The horizon stabilization is additionally evaluated quantitatively against known ground truth. CONCLUSIONS: The combination of horizon stabilization and dynamic view expansion presents a realistic approach for reintroducing orientation and navigation cues during NOTES. The platform allows real-time implementation, which is an important prerequisite for further clinical evaluation.

Alchemy and mining: metallogenesis and prospecting in early mining books.

Historians have assumed that alchemy had a close association with mining, but exactly how and why miners were interested in alchemy remains unclear. This paper argues that alchemical theory began to be synthesised with classical and Christian theories of the earth in mining books after 1500, and served an important practical function. The theory of metals that mining officials addressed spoke of mineral vapours (Witterungen) that left visible markings on the earth's surface. The prospector searched for mineral ore in part by studying these indications. Mineral vapours also explained the functioning of the dowsing rod, which prospectors applied to the discovery of ore. Historians of early chemistry and mining have claimed that mining had a modernising influence by stripping alchemy of its theoretical component, but this paper shows something quite to the contrary: mining officials may have been sceptical of the possibility of artificial transmutation, but they were interested in a theory of the earth that could translate into prospecting knowledge.