69 Search Results

High-throughput MBE with cyclical growth and in situ etch increases experimental throughput by approximately 6× and substrate utilization by >40×.

Toward the development of high energy density and long lifetime batteries for behind-the-meter storage (BTMS) applications, Li- and Mn-rich layered oxide cathode (xLi ₂ MnO ₃ ·(1-x)LiMeO ₂ , Me = Ni, Mn, and etc., LMR-NM) and Li ₄ Ti ₅ O ₁₂ (LTO) anode system was examined. To mitigate the major degradation mechanisms at each electrode (i.e., loss of Li inventory (LLI) at the anode and transition metal dissolution and oxygen release at the cathode), two approaches were taken—prelithiating the LTO electrode and varying the electrolyte solvent compositions. The effect of prelithiation and electrolyte engineering on the long-term cyclemore » performance of LMR-NM/LTO cells were systematically evaluated via electrochemical analyses and post-mortem characterizations. By using a prelithiated LTO anode and supplying additional Li to the system, the capacity retention of LMR-NM/LTO system was improved. The degree of enhancement was dependent on the types of electrolytes used, as their decomposition products determined the level of LLI. With increased capacity retention, however, the cathode was utilized to a greater extent, resulting in more severe loss of the cathode active material. Thus, all degradation mechanisms should be considered comprehensively when designing high performance LMR-NM/LTO cells to account for their complex interplay.« less

The extent to which disorder influences the properties of topological semimetals is relevant to the understanding of topological states and their use in practical applications. Using molecular beam epitaxy, we achieve systematic control of point defect concentrations in the prototypical Dirac semimetal Cd₃As₂ to gain insight into the role of disorder on electron transport behavior. Using the guiding center diffusion model for linear magnetoresistance, we extract point defect densities as a function of deposition conditions. We find that reducing cadmium defect concentrations by an order of magnitude results in an 2x increase in the magnetoresistance from 450% to 900%. Thismore » finding yields important information in the quest to identify the origin of linear magnetoresistance in a wider range of materials.« less

Behind-the-meter storage (BTMS) systems - a viable method to minimize potential risk of blackout events and stabilize the grid - require a different type of cost-effective energy storage with excellent safety, ultra-long (>20 years) cycle life and reasonable energy density compared that of electric vehicles. To increase the energy density and reduce the cost of a long-term cyclable lithium-titanate-based cell, it is required to employ a critical-material-free high voltage cathode and an electrolyte with good electrochemical and transport properties. In this report the long-term electrochemical performance and behaviors of selected critical-material-free Li₄Ti₅O₁₂ (LTO)//LiNi_0.9Mn_0.1O₂ (LNMO) full cells for BTMS applications aremore » evaluated and analyzed in the optimized voltage range of 1.4-2.7 V at 45 degrees C with different fluorinated carbonate-based electrolytes. The fluoroethylene carbonate (FEC)-based electrolyte cell shows the highest capacity retention of 57.9% and Coulombic efficiency (CE) of 99.96% after 1000 cycles, potentially attributed to a dense, homogenous and less resistive LiF-rich solid-electrolyte interphase (SEI) layer formed on the surface of LTO that may mitigate electrolyte decomposition and maintain relatively low cell impedance during cycling. The 3,3,3-fluoroethylmethyl carbonate (F-EMC)-based electrolyte cell, however, presents the worst performance with lower capacity and a sharp decrease of CE, due to unstable and non-uniform SEI formation and continuous oxidative electrolyte decomposition. This mechanistic understanding of cell aging behaviors and failure mechanisms with detailed analysis of surface chemistry and electrode morphology can guide design of new electrode chemistries and electrolyte formulations for the development of BTMS batteries.« less

Composite silicon-graphite (Si-Gr) anodes can improve battery energy density, due to Si's high gravimetric capacity, while mitigating mechanical degradation of the anode and solid-electrolyte interphase (SEI) caused by Si volumetric expansion. Optimizing these anodes is challenging, in part due to difficulty characterizing the SEI structure and composition. In this work, we present multi-modal characterization of the SEI on composite Si-Gr anodes to relate SEI chemical composition and structure to functional properties. Discrepancies in elemental concentrations from X-ray photoelectron spectroscopy, Auger electron spectroscopy, and energy-dispersive X-ray spectroscopy (EDS) are attributed to varying information depth and lateral resolution of the individual probes.more » However, by combining quantitative composition information with spatially resolved element mapping from scanning transmission electron microscopy, EDS, and electron energy loss spectroscopy, a holistic picture of the SEI emerges. We observe the bilayer SEI structure and a direct correlation between elemental Li and F, suggesting that most Li in the SEI exists as lithium fluoride (LiF). Further, LiF concentration is directly proportional to the maximum SEI resistivity, as determined by scanning spreading resistance microscopy. Lastly, there is an inverse relationship between lithium carbonate and LiF concentration in the SEI, providing insight into the detailed chemistry of SEI formation and evolution.« less

The conversion of wet waste-derived volatile fatty acids into jet fuel-range hydrocarbons is a promising route for increasing the production of sustainable aviation fuel; however, the cost and moderate alkane selectivity of Pt-based hydrodeoxygenation catalysts present challenges for commercialization. Here, to address this, we used atomic layer deposition to apply TiO₂ overcoats to Pt/Al₂O₃ catalysts and create new interface sites that exhibited 8 times higher site time yield of the desirable n-alkane product than uncoated catalyst. Through TPR/TPD, XPS, CO DRIFTS, and DFT calculations, we found that the increased selectivity of the ALD-coated catalyst was due to the creation ofmore » O vacancies at the Pt-TiO₂ interface under reducing conditions, resulting in new Ti³⁺ acid sites near the active metal. Maximum conversion and alkane selectivity during HDO was achieved with an ALD-coated 0.5% wt Pt catalyst, indicating that TiO₂ ALD can be used to maximize the utility of precious-metal catalysts.« less

A 74 wt% silicon composite electrode delivers 1000 cycles with 74% capacity retention against NMC811 cathodes and a cell stack energy density of 212 W h kg ⁻¹ in a standard carbonate electrolyte with two simple chemical and process improvements.

Silicon oxides (SiO_x) have been considered as promising alternatives to pure Si in high energy anodes in lithium-ion batteries (LIBs) due to their improved cycling stability. However, their fundamental lithiation mechanism has not yet been systematically investigated, and potential collateral downsides remain unclear. In this work, we report on the role of oxygen in lithiation/delithiation and solid electrolyte interphase (SEI) formation processes in SiO_x thin film model electrodes with different oxygen contents. Here, we show that the SiO_x anodes with higher oxygen content experience smaller volume change and form a thinner and more stable SEI, both of which are beneficialmore » for cycling stability. However, these SiO_x anodes also show an irreversible lithiation at around 0.7 V attributed to the reduction of Si oxides, leading to lower first cycle coulombic efficiency that is undesirable for practical applications. Overall, these results offer a balanced perspective on the advantages and disadvantages that oxygen brings to Si-based anodes in LIBs.« less