Engineering topics

Müller, Alexander

Publications and source records attributed to Müller, Alexander.

5 records

DOE OSTI2021

The chain of chirality transfer in tellurium nanocrystals

Despite persistent and extensive observations of crystals with chiral shapes, the mechanisms underlying their formation are not well understood. Although past studies suggest that chiral shapes can form because of crystallization in the presence of chiral additives, or because of an intrinsic tendency that stems from the crystal structure, there are many cases in which these explanations are not suitable or have not been tested. Here, an investigation of model tellurium nanocrystals provides insights into the chain of chirality transfer between crystal structure and shape. We show that this transfer is mediated by screw dislocations, and shape chirality is not an outcome of the chiral crystal structure or ligands.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Limiting Current in Nanostructured Block Copolymer Electrolytes

The next-generation electrolytes for lithium batteries must be able to conduct ions at sufficiently high current densities; yet this regime is rarely studied directly. The limiting current density of an electrolyte quantifies the highest possible rate of ion transport under an applied dc potential. Herein, we report on the limiting current density in twelve nanostructured polystyrene-block-poly(ethylene oxide) (PS-b-PEO, or SEO) copolymer electrolytes. We find that the limiting current at a given salt concentration increases systematically with increasing volume fraction of the PEO block (φ EO ). In contrast, the effective-medium theory, commonly used to analyze conductivity in block copolymer electrolytes, predicts that limiting current is independent of φ EO . To resolve this conundrum, the ionic conductivity, the mutual diffusion coefficient of the salt, and the steady-state current fraction of the block copolymer electrolytes were measured. These measurements enable predictions of limiting current with no adjustable parameters using the concentrated solution theory. We found quantitative agreement between experimentally measured limiting current densities and predictions based on the concentrated solution theory. This work sheds light on how to reliably measure and predict limiting current density in composite electrolytes.

25 ENERGY STORAGE↗

DOE OSTI2021

Probing electronic structure in berkelium and californium via an electron microscopy nanosampling approach

Due to their rarity and radioactive nature, comparatively little is known about the actinides, particularly those with atomic numbers higher than that of plutonium, and their compounds. In this work, we describe how transmission electron microscopy can provide comprehensive, safe, and cost-effective characterization using only single nanogram amounts of highly-radioactive, solid compounds. Chlorides of the rare elements berkelium and californium are dropcast and then converted in situ to oxides using the electron beam. The f-band occupancies are probed using electron energy loss spectroscopy and an unexpectedly weak spin-orbit-coupling is identified for berkelium. In contrast, californium follows a jj coupling scheme. These results have important implications for the chemistries of these elements and solidify the status of californium as a transitional element in the actinide series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Multibeam Electron Diffraction

One of the primary uses for transmission electron microscopy (TEM) is to measure diffraction pattern images in order to determine a crystal structure and orientation. In nanobeam electron diffraction (NBED), we scan a moderately converged electron probe over the sample to acquire thousands or even millions of sequential diffraction images, a technique that is especially appropriate for polycrystalline samples. However, due to the large Ewald sphere of TEM, excitation of Bragg peaks can be extremely sensitive to sample tilt, varying strongly for even a few degrees of sample tilt for crystalline samples. In this paper, we present multibeam electron diffraction (MBED), where multiple probe-forming apertures are used to create multiple scanning transmission electron microscopy (STEM) probes, all of which interact with the sample simultaneously. We detail designs for MBED experiments, and a method for using a focused ion beam to produce MBED apertures. We show the efficacy of the MBED technique for crystalline orientation mapping using both simulations and proof-of-principle experiments. We also show how the angular information in MBED can be used to perform 3D tomographic reconstruction of samples without needing to tilt or scan the sample multiple times. Finally, we also discuss future opportunities for the MBED method.

47 OTHER INSTRUMENTATION↗

DOE OSTI2020

Effect of salt concentration profiles on protrusion growth in lithium-polymer-lithium cells

In this report, the formation of dendrites and other protrusions on lithium metal anodes is a subject of continued interest due to the potential to incorporate these anodes in next-generation rechargeable batteries with increased energy densities. Solid polymer electrolytes show improved stability against lithium metal compared to liquid carbonate electrolytes. We have studied the effect of salt concentration on the formation of protrusions formed on electrodeposited lithium through a rigid block copolymer electrolyte, polystyrene-block-poly(ethylene oxide) (PS-b-PEO or SEO), in a lithium-lithium symmetric cell. The cell lifetime decreases by a factor of 100 when salt concentration is increased by a factor of 5. Our main objective is to understand the reason for this observation. We show that this decrease is not due to a salt-induced change of the morphology of the block-copolymer electrolyte, nor is it due to a salt-induced change of mechanical properties. We use an approach based on Newman's concentrated solution theory to fully characterize ion transport in the block-copolymer electrolyte, and report the conductivity, salt diffusion coefficient, cation transference number, and thermodynamic factor. Neither cell lifetime nor protrusion density in failed cells correlate with any of these electrochemical parameters. However, the electrochemical parameters can be used to predict salt concentration profiles in our symmetric cells. We posit that an important parameter in protrusion growth is the magnitude of the salt concentration gradient, Δ. We observe a direct correlation between Δ and lithium protrusion growth.

25 ENERGY STORAGE↗