More Like this

1. (Digital Presentation) Accelerating the Conversion Process of Polysulfides in High Mass Loading Sulfur Cathode for the Longevity Li-S Battery

   https://doi.org/10.1149/MA2022-012383mtgabs  

   Zhang, Yuxuan ; Kivevele, Thomas ; Song, Han Wook ; Lee, Sunghwan ( July 2022 , ECS Meeting Abstracts)

   Conventional lithium-ion batteries are unable to meet the increasing demands for high-energy storage systems, because of their limited theoretical capacity. 1 In recent years, intensive attention has been paid to enhancing battery energy storage capability to satisfy the increasing energy demand in modern society and reduce the average energy capacity cost. Among the candidates for next generation high energy storage systems, the lithium sulfur battery is especially attractive because of its high theoretical specific energy (around 2600 W h kg-1) and potential cost reduction. In addition, sulfur is a cost effective and environmentally friendly material due to its abundance and low-toxicity. 2 Despite all of these advantages, the practical application of lithium sulfur batteries to date has been hindered by a series of obstacles, including low active material loading, poor cycle life, and sluggish sulfur conversion kinetics. 3 Achieving high mass loading cathode in the traditional 2D planar thick electrode has been challenged. The high distorsion of the traditional planar thick electrodes for ion/electron transfer leads to the limited utilization of active materials and high resistance, which eventually results in restricted energy density and accelerated electrode failure. 4 Furthermore, of the electrolyte to pores in the cathode and utilization ratio of active materials. Catalysts such as MnO 2 and Co dopants were employed to accelerate the sulfur conversion reaction during the charge and discharge process. 5 However, catalysts based on transition metals suffer from poor electronic conductivity. Other catalysts such as transition metal dopants are also limited due to the increased process complexities. . In addition, the severe shuttle effects in Li-S batteries may lead to fast failures of the battery. Constructing a protection layer on the separator for limiting the transmission of soluble polysulfides is considered an effective way to eliminate the shuttle phenomenon. However, the soluble sulfides still can largely dissolve around the cathode side causing the sluggish reaction condition for sulfur conversion. 5 To mitigate the issues above, herein we demonstrate a novel sulfur electrode design strategy enabled by additive manufacturing and oxidative vapor deposition (oCVD). Specifically, the electrode is strategically designed into a hierarchal hollow structure via stereolithography technique to increase sulfur usage. The active material concentration loaded to the battery cathode is controlled precisely during 3D printing by adjusting the number of printed layers. Owing to its freedom in geometry and structure, the suggested design is expected to improve the Li ions and electron transport rate considerably, and hence, the battery power density. The printed cathode is sintered at 700 °C at N 2 atmosphere to achieve carbonization of the cathode during which intrinsic carbon defects (e.g., pentagon carbon) as catalytic defect sites are in-situ generated on the cathode. The intrinsic carbon defects equipped with adequate electronic conductivity. The sintered 3D cathode is then transferred to the oCVD chamber for depositing a thin PEDOT layer as a protection layer to restrict dissolutions of sulfur compounds in the cathode. Density functional theory calculation reveals the electronic state variance between the structures with and without defects, the structure with defects demonstrates the higher kinetic condition for sulfur conversion. To further identify the favorable reaction dynamic process, the in-situ XRD is used to characterize the transformation between soluble and insoluble polysulfides, which is the main barrier in the charge and discharge process of Li-S batteries. The results show the oCVD coated 3D printed sulfur cathode exhibits a much higher kinetic process for sulfur conversion, which benefits from the highly tailored hierarchal hollow structure and the defects engineering on the cathode. Further, the oCVD coated 3D printed sulfur cathode also demonstrates higher stability during long cycling enabled by the oCVD PEDOT protection layer, which is verified by an absorption energy calculation of polysulfides at PEDOT. Such modeling and analysis help to elucidate the fundamental mechanisms that govern cathode performance and degradation in Li-S batteries. The current study also provides design strategies for the sulfur cathode as well as selection approaches to novel battery systems. References: Bhargav, A., (2020). Lithium-Sulfur Batteries: Attaining the Critical Metrics. Joule 4 , 285-291. Chung, S.-H., (2018). Progress on the Critical Parameters for Lithium–Sulfur Batteries to be Practically Viable. Advanced Functional Materials 28 , 1801188. Peng, H.-J.,(2017). Review on High-Loading and High-Energy Lithium–Sulfur Batteries. Advanced Energy Materials 7 , 1700260. Chu, T., (2021). 3D printing‐enabled advanced electrode architecture design. Carbon Energy 3 , 424-439. Shi, Z., (2021). Defect Engineering for Expediting Li–S Chemistry: Strategies, Mechanisms, and Perspectives. Advanced Energy Materials 11 . Figure 1 

   more » « less
2. Micromechanical Fields Associated with Irregular Deformation Twins in Magnesium

   https://doi.org/10.1007/s11665-022-07196-3  

   Leu, Brandon ; Kumar, M. Arul ; Rottmann, Paul F. ; Hemker, Kevin J. ; Beyerlein, Irene J. ( March 2023 , Journal of Materials Engineering and Performance)

   Abstract Understanding and controlling the development of deformation twins is paramount for engineering strong and stable hexagonal close-packed (HCP) Mg alloys. Actual twins are often irregular in boundary morphology and twin crystallography, deviating from the classical picture commonly used in theory and simulation. In this work, the elastic strains and stresses around irregular twins are examined both experimentally and computationally to gain insight into how twins develop and the microstructural features that influence their development. A nanoprecession electron diffraction (N-PED) technique is used to measure the elastic strains within and around a $$\left\{ {10\overline{1}2} \right\}$$ 10 1 ¯ 2 tensile twin in AZ31B Mg alloy with nm scale resolution. A full-field elasto-viscoplastic fast Fourier transform (EVP-FFT) crystal plasticity model of the same sub-grain and irregular twin structure is employed to understand and interpret the measured elastic strain fields. The calculations predict spatially resolved elastic strain fields in good agreement with the measurement, as well as all the stress components and the dislocation density fields generated by the twin, which are not easily obtainable from the experiment. The model calculations find that neighboring twins, several twin thicknesses apart, have little influence on the twin-tip micromechanical fields. Furthermore, this work reveals that irregularity in the twin-tip shape has a negligible effect on the development of the elastic strains around and inside the twin. Importantly, the major contributor to these micromechanical fields is the alignment of the twinning shear direction with the twin boundary. 

   more » « less
3. Towards Horizontal Heterojunctions for Tunnel Field Effect Transistors with Template Assisted Selective Epitaxy via MOCVD

   Brunelli, Simone ; Markman, B ; Wu, J ; Tseng, HY ; Goswami, A ; Rodwell, M ; Palmstrøm, P ; Klamkin, K ( June 2018 , International conference on MOVPE)

   Tunneling field effect transistors (TFETs) have gained much interest in the previous decade for use in low power CMOS electronics due to their sub-thermal switching [1]. To date, all TFETs are fabricated as vertical nanowires or fins with long, difficult processes resulting in long learning cycle and incompatibility with modern CMOS processing. Because most TFETs are heterojunction TFETs (HJ-TFETs), the geometry of the device is inherently vertically because dictated by the orientation of the tunneling HJ, achieved by typical epitaxy. Template assisted selective epitaxy was demonstrated for vertical nanowires [2] and horizontally arranged nanorods [3] for III-V on Si integration. In this work, we report results on the area selective and template assisted epitaxial growth of InP, utilizing SiO2 based confined structures on InP substrates, which enables horizontal HJs, that can find application in the next generation of TFET devices. The geometries of the confined structures used are so that only a small area of the InP substrate, dubbed seed, is visible to the growth atmosphere. Growth is initiated selectively only at the seed and then proceeds in the hollow channel towards the source hole. As a result, growth resembles epitaxial lateral overgrowth from a single nucleation point [4], reaping the benefits of defect confinement and, contrary to spontaneous nanowire growth, allows orientation in an arbitrary, template defined direction. Indium phosphide 2-inch (110) wafers are used as the starting substrate. The process flow (Fig.1) consists of two plasma enhanced chemical vapor deposition (PECVD) steps of SiO2, appropriately patterned with electron beam lithography (EBL), around a PECVD amorphous silicon sacrificial layer. The sacrificial layer is ultimately wet etched with XeF2 to form the final, channel like template. Not shown in the schematic in Fig.1 is an additional, ALD deposited, 3 nm thick, alumina layer which prevents plasma damage to the starting substrate and is removed via a final tetramethylammonium hydroxide (TMAH) based wet etch. As-processed wafers were then diced and loaded in a Thomas Swan Horizontal reactor. Successful growth conditions found were 600°C with 4E6 mol/min of group III precursor, a V/III ratio of 400 and 8 lpm of hydrogen as carrier gas. Trimethylindium (TMIn) and tertiarybutylphosphine (TBP) were used as In and P precursors respectively. Top view SEM (Fig.2) confirms growth in the template thanks to sufficient Z-contrast despite the top oxide layer, not removed before imaging. TEM imaging shows a cross section of the confined structure taken at the seed hole (Fig.3). The initial growth interface suggests growth was initiated at the seed hole and atomic order of the InP conforms to the SiO2 template both at the seed and at the growth front. A sharp vertical facet is an encouraging result for the future development of vertical HJ based III-V semiconductor devices. 

   more » « less
4. Variational Convolutional Autoencoders for Anomaly Detection in Scanning Transmission Electron Microscopy

   https://doi.org/10.1002/smll.202205977  

   Prifti, Enea ; Buban, James P. ; Thind, Arashdeep Singh ; Klie, Robert F. ( January 2023 , Small)

   Identifying point defects and other structural anomalies using scanning transmission electron microscopy (STEM) is important to understand a material's properties caused by the disruption of the regular pattern of crystal lattice. Due to improvements in instrumentation stability and electron optics, atomic‐resolution images with a field of view of several hundred nanometers can now be routinely acquired at 1–10 Hz frame rates and such data, which often contain thousands of atomic columns, need to be analyzed. To date, image analysis is performed largely manually, but recent developments in computer vision (CV) and machine learning (ML) now enable automated analysis of atomic structures and associated defects. Here, the authors report on how a Convolutional Variational Autoencoder (CVAE) can be utilized to detect structural anomalies in atomic‐resolution STEM images. Specifically, the training set is limited to perfect crystal images , and the performance of a CVAE in differentiating between single‐crystal bulk data or point defects is demonstrated. It is found that the CVAE can reproduce the perfect crystal data but not the defect input data. The disagreesments between the CVAE‐predicted data for defects allows for a clear and automatic distinction and differentiation of several point defect types.

    

   more » « less
5. Differential multi-probe thermal transport measurements of multi-walled carbon nanotubes grown by chemical vapor deposition

   https://doi.org/10.1016/j.ijheatmasstransfer.2023.124535  

   Jia, Qianru ; Zhou, Yuanyuan ; Li, Xun ; Lindsay, Lucas ; Shi, Li ( December 2023 , International Journal of Heat and Mass Transfer)

   Carbon nanotubes (CNTs) are quasi-one dimensional nanostructures that display both high thermal conductivity for potential thermal management applications and intriguing low-dimensional phonon transport phenomena. In comparison to the advances made in the theoretical calculation of the lattice thermal conductivity of CNTs, thermal transport measurements of CNTs have been limited by either the poor temperature sensitivity of Raman thermometry technique or the presence of contact thermal resistance errors in sensitive two-probe resistance thermometry measurements. Here we report advances in a multi-probe measurement of the intrinsic thermal conductivity of individual multi-walled CNT samples that are transferred from the growth substrate onto the measurement device. The sample-thermometer thermal interface resistance is directly measured by this multi-probe method and used to model the temperature distribution along the contacted sample segment. The detailed temperature profile helps to eliminate the contact thermal resistance error in the obtained thermal conductivity of the suspended sample segment. A differential electro-thermal bridge measurement method is established to enhance the signal-to-noise ratio and reduce the measurement uncertainty by over 40%. The obtained thermal resistances of multiple suspended segments of the same MWCNT samples increase nearly linearly with increasing length, revealing diffusive phonon transport as a result of phonon-defect scattering in these MWCNT samples. The measured thermal conductivity increases with temperature and reaches up to 390 ± 20 W m-1 K-1 at room temperature for a 9-walled MWCNT. Theoretical analysis of the measurement results suggests submicron phonon mean free paths due to extrinsic phonon scattering by extended defects such as grain boundaries. The obtained thermal conductivity is decreased by a factor of 3 upon electron beam damage and surface contamination of the CNT sample. 

   more » « less