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770 records · Page 43

Theory Aided Design of Active and Durable Nanoscale Cathode Catalysts (Final Report)

One of the greatest technological hurdles to deployment of fuel cells relates to the sluggish activity, low durability and the high cost of the catalysts that are currently employed. For automotive PEM fuel cells to become commercially viable, the Pt-specific power density would need to be reduced to less than 0.2gPt/kW (at cell voltages >0.65 V). This would require the Pt loadings to be less than 0.15 mg Pt /cm 2 MEA within the membrane electrode assembly. This could be achieved by enhancing the catalytic activity at the cathode, thus lowering its overpotential. Various different Pt-alloys have shown 2-4 times enhanced activities over Pt alone but still suffer some of the same durability issues as that of the pure Pt. There is a general loss of active Pt due to dissolution and sintering. While there have been a number of elegant fundamental experimental and theoretical studies on ideal single crystal Pt and Pt alloy surfaces which have helped to elucidate the factors that control the activity, there have been very few fundamental studies focused on the stability, reactivity and durability of well-defined Pt nanoparticles. We carried out ab initio density functional theory together with a novel double reference method that we developed to simulate constant potential electrochemical systems in order to model the electrocatalytic reduction of oxygen over model Pt alloy surfaces and nanoparticles. These simulations were used to probe the factors that control the electrocatalytic activity, guide the potential selection of new materials and test their stability under reaction conditions. Ab initio calculations were used to determine the reaction energies and activation barriers for a comprehensive array of different elementary adsorption, desorption, surface reaction and diffusion steps over Pt and Pt alloys involved in the electroreduction of oxygen as a function of surface coverage, the electrochemical potential and temperature. The calculations were used to simulate the potential dependent adsorption and surface reaction energies along with activation barriers in order to determine the kinetics for different surface structures and structural features (step edge and corner sites) to provide the necessary input for kinetic Monte Carlo simulations to follow the rates of reaction. More coarse-grained simulated annealing methods were used to help establish the lowest energy structures and morphologies for different Pt and Pt-alloy nanoparticles that form. The results from the DFT calculations were used to establish an ab initio-derived kinetic database that was used in both 2D and 3D kinetic Monte Carlo simulations that were used to follow the electrocatalytic performance over different particle sizes, shapes and compositions. The ab initio calculations together with the kinetic Monte Carlo simulations were used to complete the following objectives: 1) Determine the controlling elementary reaction pathways and intrinsic kinetics involved in ORR and their potential dependent behavior; 2) Establish the influence of the extrinsic reaction environment including surface structure, alloy composition and spatial arrangement and the humidity on ORR kinetics; 3) Elucidate the effects of particle size and morphology as well as the atomic structure and composition of nanoparticles of Pt, Pt 3 Co, Pt 3 Ni, Pt 3 Fe and other Pt-alloys on the electrocatalytic activity and reaction selectivity; 5) Construct surface Pourbaix phase diagrams for different Pt and Pt-alloys in order to map out the most stable surface phases for different material compositions and reaction conditions; 6) Elucidate the mechanisms that control dissolution and re-deposition of Pt.

08 HYDROGEN↗

Manual control in space research on perceptual-motor functions under zero gravity conditions (L-10)

Are human abilities to control vehicles and other machines the same in space as those on Earth? The L-10 Manual Control Experiment of the First Materials Processing Tests (FMPT) started from this question. Suppose a pilot has the task to align the head of a space vehicle toward a target. His actions are to look at the target, to determine the vehicle movement, and to operate the manipulator. If the activity of the nervous system were the same as on Earth, the movements, of the eye and hand would become excessive because the muscles do not have to oppose gravity. The timing and amount of movement must be arranged for appropriate actions. The sensation of motion would also be affected by the loss of gravity because the mechanism of the otolith, the major acceleration sensor, depends on gravity. The possible instability of the sensation of direction may cause mistakes in the direction of control of manipulator movement. Thus, the experimental data can be used for designing man-machine systems in space, as well as for investigation of physiological mechanisms. In this experiment, the direction of vehicle heading is expressed by a light spot on an array of light emitting diodes and the manipulator is of a finger stick type. As the light spot moves up and down, the Japanese Payload Specialist, and the subject, must move the manipulator forward and backward to keep the movement of the light spot within the neighborhood of the central point of the display. The position of the light spot is computed in such a manner that when the stick is kept at the neutral position, a motion whose acceleration is proportional to the angle of deflection is added to the movement of the light spot. The Operator Describing Function, which is an expression of human control characteristics, can be calculated from 2 minutes of raw data of the light spot position and stick deflection. The 2 minutes of operation is called a run, and 8 runs with resting periods composes a session. The on-orbit experiment will be conducted on the second, fourth, and seventh days. One session of experiment of each of these days is conducted following the L-4 experiment, which uses the same apparatus. The Payload Specialist, aided by a Mission Specialist, will take our apparatus from a rack container, set up the apparatus, attach electrodes for measurements of eye movement and muscle activity, conduct the L-4 Visual Stability Experiment, conduct one session of the manual control experiment, and then dissemble and stow the apparatus. In addition to the flight experiment, pre-flight and post-flight experiments will be conducted. The data of three sessions on orbit will reflect adaption of physiological systems to microgravity. The data of post-flight experiments, on the other hand, will reflect re-adaptation of physiological systems to the gravity condition on the ground. Control data collected with and without psychological tension will be scheduled just prior to and long before launch.

Tada, Akira↗

Structure and Electronic Properties of InSb Nanowires Grown in Flexible Polycarbonate Membranes

A dense array of vertically aligned indium antimonide (InSb) nanowires with high aspect ratio (diameter 150 nm, length 20 μ m) were grown in the pores of a track-etched polycarbonate membrane via a one-step electrochemical method. There are several reports on InSb nanowire growth in the pores of a mechanically rigid, nano-channel alumina template (NCA), where nanowire growth occurs in the pores of the NCA. This work on InSb nanowire growth in pores of track-etched polycarbonate (PC) membrane sheds light on the various factors that affect nucleation and nanowire growth. The average length and diameter of the as-grown nanowires was about 10 μ m and 150 nm, respectively. Two possible mechanisms accounting for two different morphologies of the as-grown nanowires are proposed. The polycrystallinity observed in some of the nanowires is explained using the 3D ‘nucleation-coalescence’ mechanism. On the other hand, single crystal nanowires with a high density of twin defects and stacking faults grow epitaxially by a two-dimensional (2D) nucleation/growth mechanism. To assess the electrical quality of the nanowires, two- and four-terminal devices were fabricated using a single InSb nanowire contacted by two Ni electrodes. It was found that, at low bias, the ohmic current is controlled by charge diffusion from the bulk contacts. On the other hand, at high bias, the effects of space charge limited current (SCLC) are evident in the current–voltage behavior, characteristic of transport through structures with reduced electrostatic screening. A cross-over from ohmic to SCLC occurs at about 0.14 V, yielding a free carrier concentration of the order of 10 14 cm -3 .

36 MATERIALS SCIENCE↗

Profiling Photoinduced Carrier Generation in Semiconductor Microwire Arrays via Photoelectrochemical Metal Deposition

Au was photoelectrochemically deposited onto cylindrical or tapered p-Si microwires on Si substrates to profile the photoinduced charge-carrier generation in individual wires in a photoactive semiconductor wire array. Similar experiments were repeated for otherwise identical Si microwires doped to be n-type. The metal plating profile was conformal for n-type wires, but for p-type wires was a function of distance from the substrate and was dependent on the illumination wavelength. Spatially resolved charge-carrier generation profiles were computed using full-wave electromagnetic simulations, and the localization of the deposition at the p-type wire surfaces observed experimentally correlated well with the regions of enhanced calculated carrier generation in the volumes of the microwires. Finally, this technique could potentially be extended to determine the spatially resolved carrier generation profiles in a variety of mesostructured, photoactive semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of purity, edge length, and growth area on field emission of multi-walled carbon nanotube emitter arrays

Present report aims to study the effect of purity, edge length, and growth area on field emission of patterned carbon nanotube (CNT) emitter arrays. For development of four CNT emitter arrays (CEAs), low resistively silicon substrates were coated with thin film of iron catalyst using photolithography, sputtering, and lift off process. Four CEAs were synthesized on these substrates using thermal chemical vapor deposition with minor changes in pretreatment duration. Out of these, two CEAs have 10 {mu}m Multiplication-Sign 10 {mu}m and 40 {mu}m Multiplication-Sign 40 {mu}m solid square dots of CNTs with constant 20 {mu}m inter-dot separation. Other two CEAs have ring square bundles of CNTs and these CEAs are envisioned as 10 {mu}m Multiplication-Sign 10 {mu}m square dots with 4 {mu}m Multiplication-Sign 4 {mu}m scooped out area and 15 {mu}m Multiplication-Sign 15 {mu}m square dots with 5 {mu}m Multiplication-Sign 5 {mu}m lift out area with constant 20 {mu}m inter-dot spacing. Solid square dot structures have exactly constant edge length per unit area with more than four-fold difference in CNT growth area however ring square dot patterns have minor difference in edge length per unit area with approximately two times difference in CNT growth area. Quality and morphology of synthesized CEAs were assessed by scanning electron microscope and Raman characterization which confirm major differences. Field emission of all CEAs was carried out under same vacuum condition and constant inter-electrode separation. Field emission of solid square dot CEAs show approximately identical current density-electric field curves and Fowler-Nordheim plots with little difference in emission current density at same electric field. Similar results were observed for ring square structure CEAs when compared separately. Maximum emission current density observed from these four CEAs reduces from 14.53, 12.23, 11.01, to 8.66 mA/cm{sup 2} at a constant electric field of 5 V/{mu}m, according to edge length of 1361.7, 1221.08, 872.20, to 872.16 mm rather than growth area and purity. Although, the 40 {mu}m Multiplication-Sign 40 {mu}m CEAs possessed highest CNT growth area of 8.7 mm{sup 2} and best purity defined in terms of lowest defect band to graphitic band ratio of 0.614, the current observed from this CEAs was least.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Wireless Chalcogenide Nanoionic-Based Radio-Frequency Switch

A new nonvolatile nanoionic switch is powered and controlled through wireless radio-frequency (RF) transmission. A thin layer of chalcogenide glass doped with a metal ion, such as silver, comprises the operational portion of the switch. For the switch to function, an oxidizable electrode is made positive (anode) with respect to an opposing electrode (cathode) when sufficient bias, typically on the order of a few tenths of a volt or more, is applied. This action causes the metal ions to flow toward the cathode through a coordinated hopping mechanism. At the cathode, a reduction reaction occurs to form a metal deposit. This metal deposit creates a conductive path that bridges the gap between electrodes to turn the switch on. Once this conductive path is formed, no further power is required to maintain it. To reverse this process, the metal deposit is made positive with respect to the original oxidizable electrode, causing the dissolution of the metal bridge thereby turning the switch off. Once the metal deposit has been completely dissolved, the process self-terminates. This switching process features the following attributes. It requires very little to change states (i.e., on and off). Furthermore, no power is required to maintain the states; hence, the state of the switch is nonvolatile. Because of these attributes the integration of a rectenna to provide the necessary power and control is unique to this embodiment. A rectenna, or rectifying antenna, generates DC power from an incident RF signal. The low voltages and power required for the nanoionic switch control are easily generated from this system and provide the switch with a novel capability to be operated and powered from an external wireless device. In one realization, an RF signal of a specific frequency can be used to set the switch into an off state, while another frequency can be used to set the switch to an on state. The wireless, miniaturized, and nomoving- part features of this switch make it suitable for applications such as integration into garments, RFID (radio-frequency identification) tags, and conformal structures (e.g., aircraft wings, sounding rockets contours, etc). In the case of RFID tags the innovation will provide countermeasures to attempts for identity theft and other uninvited attempts for retrieval of information. It could also be applicable to the automotive industry as well as the aerospace industry for collision avoidance and phased array radar systems, respectively

Nessel, James↗

Insights into ionic transport and structural changes in magnetite during multiple-electron transfer reactions

Metal oxides, such as Fe 3 O 4 , hold promise for future battery applications due to their abundance, low cost, and opportunity for high lithium storage capacity. In order to better understand the mechanisms of multiple-electron transfer reactions leading to high capacity in Fe 3 O 4 , a comprehensive investigation on local ionic transport and ordering is made by probing site occupancies of anions (O 2– ) and cations (Li + , Fe 3+ /Fe 2+ ) using multiple synchrotron X-ray and electron-beam techniques, in combination with ab-initio calculations. Results from this study provide the first experimental evidence that the cubic-close-packed (ccp) O-anion array in Fe 3 O 4 is sustained throughout the lithiation and delithiation processes, thereby enabling multiple lithium intercalation and conversion reactions. Cation displacement/reordering occurs within the ccp O-anion framework, which leads to a series of phase transformations, starting from the inverse spinel phase and turning into intermediate rock-salt-like phases (Li x Fe 3 O 4 ; 0 < x < 2), then into a cation-segregated phase (Li 2 O•FeO), and finally converting into metallic Fe and Li 2 O. Subsequent delithiation and lithiation processes involve interconversion between metallic Fe and FeO-like phases. Lastly, these results may offer new insights into the structure-determined ionic transport and electrochemical reactions in metal oxides, and those of other compounds sharing a ccp anion framework, reminiscent of magnetite.

25 ENERGY STORAGE↗

Plasma Guns for Magnetized Fuel Targets for PJMIF

In plasma jet driven magneto-inertial fusion (PJMIF) an array of discrete supersonic plasma jets is used to form a spherically imploding plasma liner, which then compresses a magnetized plasma target to fusion conditions. With funding from ARPA-E’s ALPHA program and from Strong Atomics LLC, HyperJet Fusion Corp and HyperV Technologies Corp. previously developed the plasma guns required for an experimental demonstration of the plasma liner formation part of the concept. A 36-gun demonstration of an imploding spherical plasma liner is currently underway on the PLX facility at Los Alamos National Laboratory. This present project addresses the next step required for a complete PJMIF concept, i.e. developing the magnetized plasma target. We proposed to form the target by stagnating a number of magnetized plasma jets in the center of the target chamber. This is accomplished by adding a bias field coil to the plasma liner gun to form a magnetized plasma jet. This experimental development took place at HyperJet in a geometry replicating the bias field environment that will be seen on a PLX port so the results are directly transferrable to the PLX experiment. The objective of this effort was the technical development and characterization of a new magnetized plasma jet using a high-performance, high momentum flux, contoured-gap coaxial plasma gun appropriate for use on the next stage of the PLX experiment. Electromagnetic modeling of the coil indicated the coil was best placed around the aluminum tubes of the gun transmission line, rather than around the chamber port as originally proposed. This maximized field strength in the breech and yielded much better flux linkage between gun electrodes. A 30-turn coil was ultimately implemented, allowing long pulses that could diffuse through the metal walls on the timescale of interest. \machtwo modeling predicted that less capacitance in the main PFN could potentially improve plasma jet velocities due to better matching of the current to the smaller plasma mass and the existing electrode contour designed to suppress blowby. This proved true, as testing showed markedly improved performance when the original 600uF bank was reduced to 400uF. A number of diagnostics were built and/or upgraded in order to characterize the plasma jets, inluding laser interferomtery for density, photodiodes for velocity, Bdot probes for magnetic field measurements, a Triple probe for temperature measurements, and spectroscopy for impurity content. A plasma gun with the 30-turn magnet coil installed, a 70% reduction in gas valve plenum volume, and a 33% reduction in main PFN capacitance produced a dense, high velocity, well magnetized plasma jet. We met or exceeded virtually all of the plasma jet parameter goals. Peak velocity of 135 km/s exceeded the 100 km/s goal by 35%, while the peak density of over 1.0x10 15 cm -3 was 3.3 times the goal of >3.0x10 14 cm -3 . Shot-to-shot repeatability is excellent, with a jitter of less than 300ns observed on the arrival fronts of the photodiode signals from one shot to the next. Average plasma jet lengths of 33cm (at 120km/s) were slightly longer than the 20cm goal, but jets as short as 11.8cm were observed at 135km/s. Mass is much higher than the targeted goal, averaging 106ug per shot compared to 20ug. The magnetic field is still a bit lower than desired, with a maximum to date of ~811G, compared to the goal of 1000G. Average values, though, were typically in the 300-450G range, when measured further downstream after some expected in flight decay. Temperature measurements are still a work in progress. Increasing the B field and completing temperature measurements will be continued on into the ongoing BETHE project.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Detection of Carbon Monoxide Using Polymer-Composite Films with a Porphyrin-Functionalized Polypyrrole

Post-fire air constituents that are of interest to NASA include CO and some acid gases (HCl and HCN). CO is an important analyte to be able to sense in human habitats since it is a marker for both prefire detection and post-fire cleanup. The need exists for a sensor that can be incorporated into an existing sensing array architecture. The CO sensor needs to be a low-power chemiresistor that operates at room temperature; the sensor fabrication techniques must be compatible with ceramic substrates. Early work on the JPL ElectronicNose indicated that some of the existing polymer-carbon black sensors might be suitable. In addition, the CO sensor based on polypyrrole functionalized with iron porphyrin was demonstrated to be a promising sensor that could meet the requirements. First, pyrrole was polymerized in a ferric chloride/iron porphyrin solution in methanol. The iron porphyrin is 5, 10, 15, 20-tetraphenyl-21H, 23Hporphine iron (III) chloride. This creates a polypyrrole that is functionalized with the porphyrin. After synthesis, the polymer is dried in an oven. Sensors were made from the functionalized polypyrrole by binding it with a small amount of polyethylene oxide (600 MW). This composite made films that were too resistive to be measured in the device. Subsequently, carbon black was added to the composite to bring the sensing film resistivity within a measurable range. A suspension was created in methanol using the functionalized polypyrrole (90% by weight), polyethylene oxide (600,000 MW, 5% by weight), and carbon black (5% by weight). The sensing films were then deposited, like the polymer-carbon black sensors. After deposition, the substrates were dried in a vacuum oven for four hours at 60 C. These sensors showed good response to CO at concentrations over 100 ppm. While the sensor is based on a functionalized pyrrole, the actual composite is more robust and flexible. A polymer binder was added to help keep the sensor material from delaminating from the electrodes, and carbon was added to improve the conductivity of the material.

Homer, Margie L.↗

A Multiphysics Study to Improve Specific Energy of Primary Batteries for Low Temperature Operation for Deep Space Missions

Several lander missions on the outer planets such as Europa, Enceladus, and Titan require electrical power to operate scientific and communication equipment. The traditional power generation methods, such as a photovoltaic array, are not feasible as their efficiency drops significantly at these vast distances. The novel radioisotope power systems are not practical today based on current lander designs and the effectiveness of these systems. To perform in situ science on distant planets, a high specific energy battery (>700 Wh/kg) needs to operate for about 480 hours under cold temperatures (-40C or 0C) [1]. While a primary battery such as Li-CFx can provide high specific energy at room temperature, its specific capacity decreases significantly at low temperatures. One of the causes for this drop is low ion and electrical conductivity, and slower reaction kinetics. Slower transport and facile kinetics lead to an increase in the battery’s resistance and higher voltage drops during the cell operation, thus reducing specific capacity. Both the transport and kinetics show a strong dependence on temperature. Thus, a small temperature rise can lead to an increase in the reaction rate and ion conductivity; since the temperature, cell resistance, and specific capacity are interdependent. A conventional battery model accounts for ohmic, thermodynamic, and, electrochemical, and chemical decomposition heating. The ohmic heating can be controlled by designing a resistive microstructure and varying the ratios of the active materials [2]. The kinetics can be improved by increasing the surface area, reducing the particle size, or adding a catalyst. These parameters are often optimized to achieve high specific energy at room temperatures. A similar optimization study is not available at low temperatures and for a primary (high specific energy) battery. For this presentation, we will explore the effect of geometrical, microstructural, and material properties on optimal specific capacity at low temperatures through multiphysics simulations. The ion transport resistance depends on the porosity and the tortuosity of an electrode and the separator.

M. Mehta↗

Resistive Switching Memory Performance of Two-Dimensional Polyimide Covalent Organic Framework Films

Two-dimensional polyimide covalent organic framework (2D PI-NT COF) films were constructed on indium tin oxide-coated glass substrates to fabricate two-terminal sandwiched resistive memory devices. The 2D PI-NT COF films condensated from the reaction between 4,4',4"-triaminotriphenylamine and naphthalene-1,4,5,8-tetracarboxylic dianhydride under solvothermal conditions demonstrated high crystallinity, good orientation preference, tunable thickness, and low surface roughness. The well-aligned electron-donor (triphenylamine unit) and -acceptor (naphthalene diimide unit) arrays rendered the 2D PI-NT COF films a promising candidate for electronic applications. The memory devices based on 2D PI-NT COF films exhibited a typical write-once-read-many-time resistive switching behavior under an operating voltage of +2.30 V on the positive scan and -2.64 V on the negative scan. A high ON/OFF current ratio (>10 6 for the positive scan and 10 4 -10 6 for the negative scan) and long-term retention time indicated the high fidelity, low error, and high stability of the resistive memory devices. The memory behavior was attributed to an electric field-induced intramolecular charge transfer in an ordered donor-acceptor system, which provided the effective charge-transfer channels for injected charge carriers. Furthermore, this work represents the first example that explores the resistive memory properties of 2D PI-COF films, shedding light on the potential application of 2D COFs as information storage media.

2D covalent organic framework film↗

Effect of shape in near-field thermal transfer for periodic structures

In this paper, the effect of the geometrical shape on the radiative thermal transfer between a periodic array of beams and a planar substrate is investigated. Specifically, we analyze the changes in the thermal transfer that occur when the cross-sectional shape of SiC beams is modified from rectangular to ellipsoidal and finally triangular. Numerical calculations are done based on the rigorous coupled wave analysis. These exact results from this analysis are compared to modified proximity and far-field approximations, which become valid for small and large spacings, respectively. Moreover, these results are also compared to effective medium theory, which becomes increasingly accurate in the limit of small periodicities. We show that a reduction in the periodicity will lead to a reduced thermal transfer for triangular and ellipsoidal shaped beams. Even though, in the limit of very small periodicity, thermal transfer for the case of rectangular shaped beams also decreases by decreasing the periodicity, this decrease is slower as compared to other cross-sectional shapes. Lastly, we show that even though changing periodicity will change the magnitude of thermal transfer, the scaling law for its variation with the beam to substrate spacing is primarily determined by the cross-sectional shape rather than the periodicity. We analytically prove this fact by investigating the large and small periodicity regimes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Near-field heat transfer between graphene/hBN multilayers

We study the radiative heat transfer between multilayer structures made by a periodic repetition of a graphene sheet and a hexagonal boron nitride (hBN) slab. Surface plasmons in a monolayer graphene can couple with a hyperbolic phonon polaritons in a single hBN lm to form hybrid polaritons that can assist photon tunneling. For periodic multilayer graphene/hBN structures, the stacked metallic/dielectric array can give rise to a further e ective hyperbolic behavior, in addition to the intrinsic natural hyperbolic behavior of hBN. The e ective hyperbolicity can enable more hyperbolic polaritons that enhance the photon tunneling and hence the near- eld heat transfer. However, the hybrid polaritons on the surface, i.e. surface plasmon-phonon polaritons, dominate the near- eld heat transfer between multilayer structures when the topmost layer is graphene. The e ective hyperbolic regions can be well predicted by the e ective medium theory (EMT), thought EMT fails to capture the hybrid surface polaritons and results in a heat transfer rate much lower compared to the exact calculation. The chemical potential of the graphene sheets can be tuned through electrical gating and results in an additional modulation of the heat transfer. We found that the near- eld heat transfer between multilayer structure does not increase monotonously with the number of layer in the stack, which provides a way to control the heat transfer rate by the number of graphene layers in the multilayer structure. The results may bene t the applications of near- eld energy harvesting and radiative cooling based on hybrid polaritons in two-dimensional materials.

36 MATERIALS SCIENCE↗

Tuning Solid Electrolyte Interphase Formation before Plating Onset in Anode-Free Sodium Batteries

Sodium (Na) batteries are of growing interest due to the higher earth abundance of sodium than lithium, as well as their promising theoretical energy density when metallic Na anodes are used. However, Na plating and stripping are heavily influenced by the physicochemical properties of the solid electrolyte interphase (SEI), which is directly influenced by the solvent and salt used for the electrolyte. While most studies focus on the SEI that forms on the surface of Na metal after plating, we expand this analysis by identifying a nanoscale “pre-plating” SEI that forms on the current collector (CC) prior to the onset of Na plating. Here, we systematically investigate an array of Na salt and glyme solvents in the electrolyte and determine the associated impacts on pre-plating SEI formation on aluminum CCs. By combining analytical electrochemistry approaches with a multimodal suite of spectroscopy techniques (X-ray, infrared, and Raman), supported by density functional theory calculations, we reveal a direct correlation between the Na + coordination environment and pre-plating SEI composition. We find that longer-chain glymes produce larger proportions of organic alkoxide products in the interphase, consistent with increased Na + −glyme interactions, while the fraction of salt-derived inorganic products (e.g., NaF) correlates with Na + −anion coordination. These insights highlight the critical influence of electrolyte composition particularly solvent identity and Na + coordination on the initial SEI formation in anode-free Na batteries.

anode-free batteries↗