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Johnson, David C.

Publications and source records attributed to Johnson, David C..

Evaluation of Lithium Metal Anode Volumetric Expansion through Laser Plasma Focused Ion Beam Cross-Sectional Imaging

Lithium metal is an ideal anode for high energy density batteries, however the implementation of lithium metal anodes remains challenging. Beyond the development of highly efficient electrolytes, degradation processes restrict cycle life and reduce practical energy density. Herein lithium volumetric expansion and degradation pathways are studied in half cells through coupling electrochemical analysis with cross-sectional imaging of the intact electrode stack using a cryogenic laser plasma focused ion beam and scanning electron microscope. Here, we find that the volumetric capacity is compromised as early as the first cycle, at best reaching values only half the theoretical capacity (1033 vs 2045 mAh cm -3 ). By the 101st electrodeposition, the practical volumetric capacity decreases to values ranging from 143 to 343 mAh cm -3 .

25 ENERGY STORAGE↗

Method to Determine the Distribution of Substituted or Intercalated Ions in Transition-Metal Dichalcogenides: Fe x VSe 2 and Fe 1– x V x Se 2

Multiple techniques are combined to determine the amount of intercalation and/or substitution in transition-metal dichalcogenides. Kiessig fringes in the X-ray reflectivity pattern are used to calculate thickness. Laue oscillations in the specular diffraction pattern of the crystallographically aligned samples determine the number of unit cells in the coherently diffracting domains. The amount of impurity phase(s) is estimated by the difference between the thickness of the films and the size of the domains. If the difference is small relative to the total film thickness, the composition of the crystalline phase can be determined from X-ray fluorescence measurements. The number of unit cells possible can be calculated from the amount of each element determined by X-ray fluorescence measurements using in-plane lattice parameters, and the amount of the anion should agree with the number of unit cells determined from the Laue oscillations. The total amount of the metal relative to that required for the number of unit cells from the Laue oscillations provides a direct determination of the relative amount of intercalation and/or substitution in the crystalline dichalcogenide. So the utility of this approach is illustrated in Fe x V 1–y Se 2 samples. The relative amount of intercalation versus substitution was determined independently using electron microscopy and Rietveld refinement of diffraction patterns and is consistent with this new approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Challenges in synthesis of heterostructures

Developing the ability to reproducibly prepare materials drives the advancement of human technology. Trends in historical advances and extrapolation of current technologies suggest that the next logical step is developing the ability to control structure and composition at near atomic scales in device manufacturing to take advantage of emergent properties discovered in 2D materials and heterostructures. This article reviews a subset of synthetic approaches used to prepare heterostructures, outlining key reaction steps, and how experimental parameters are used to control which product forms. The positive attributes of each synthesis approach are discussed along with some of their limitations. The elemental reactant (MER) approach is discussed in more depth.

36 MATERIALS SCIENCE↗

Growth of Crystallographically Aligned PbSe Films of Controlled Thickness on Amorphous Substrates

Lead selenide (PbSe) has extensively been investigated due to its thermoelectric and photoconductive properties. More recently, predictions of emergent properties have focused synthetic efforts on preparing ultra-smooth layers of crystallographically aligned PbSe layers with a thickness equal to an integer number of monolayers. While rough films are typically formed through Volmer-Weber growth on heated substrates, we report the data presented herein indicates that a crystallographically aligned, ultrathin layer with a defined number of PbSe layers forms on mostly amorphous Mo-Se and V-Se coated Si substrates during nominally room temperature deposition. Since the films are uniform in thickness, the number of PbSe bilayers formed depends on the amount of Pb (or Se) deposited. If the amount of Pb deposited is close to that required for an integral number of unit cells and there is sufficient Se, Laue oscillations are present in the as-deposited samples. The Laue oscillations reflect the quality and uniformity of the crystalline PbSe domains. This study demonstrates that the substrate does not need to be crystalline to form uniform, crystallographically aligned, integer monolayer thick PbSe films. These results suggest that tuning the strength of interactions be-tween substrate and growing film is necessary to form smooth, crystallographically aligned layers. The substrate does not need to be crystalline for these interactions to be strong enough to enable growth of crystallographically aligned films.

36 MATERIALS SCIENCE↗

Extracting information from X-ray diffraction patterns containing Laue oscillations

The presence of Laue oscillations in a film grown on a solid surface is broadly taken as indicating a high quality, crystallographically aligned film of the targeted compound. In this paper we briefly review the origins of both Laue oscillations and Kiessig fringes and show how they can be used together to determine if extra thickness exists above or below the coherently diffracting domains. The differences between experimental and “ideal” films are discussed and the effect of structural features (roughness, different thickness coherently diffracting domains and thickness in addition to the coherently diffracting domains) are illustrated with experimental and simulated data for metal and mixed-metal chalcogenide films of titanium, bismuth, vanadium/iron, and bismuth/molybdenum. Examples are given showing how quantitative information can be extracted from experimental diffraction patterns.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗