Engineering topics

Mashayek, Farzad

Publications and source records attributed to Mashayek, Farzad.

6 records

DOE OSTI2020

Beyond Volume Variation: Anisotropic and Protrusive Lithiation in Bismuth Nanowire

Materials storing energy via an alloying reaction are promising anode candidates in rechargeable lithium-ion batteries (LIBs) due to their much higher energy density than the current graphite anode. Until now, the volumetric expansion of such electrode particles during lithiation has been considered as solely responsible for cycling-induced structural failure. Here, we report different structural failure mechanisms using single-crystalline bismuth nanowires as the alloying-based anode. The Li–Bi alloying process exhibits a two-step transition, that is, Bi–Li 1 Bi and Li 1 Bi–Li 3 Bi. Interestingly, the Bi–Li 1 Bi phase transition occurs not only in the bulk Bi nanowire but also on the particle surface showing its characteristic behavior. The bulk alloying kinetics favors a Bi-(012)-facilitated anisotropic lithiation, whose mechanism and energetics are further studied using the density functional theory calculations. More importantly, the protrusion of Li 1 Bi nanograins as a result of anisotropic Li–Bi alloying is found to dominate the surface morphology of Bi particles. The growth kinetics of Li 1 Bi protrusions is understood atomically with the identification of two different controlling mechanisms, that is, the dislocation-assisted strain relaxation at the Bi/Li 1 Bi interface and the short-range migration of Bi supporting the off-Bi growth of Li 1 Bi. As loosely rooted to the bulk substrate and easily peeled off and detached into the electrolyte, these nanoscale protrusions developed during battery cycling are believed to be an important factor responsible for the capacity decay of such alloying-based anodes at the electrode level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Highly-Cyclable Room-Temperature Phosphorene Polymer Electrolyte Composites for Li Metal Batteries

Despite significant interest toward solid-state electrolytes owing to their superior safety in comparison to liquid-based electrolytes, sluggish ion diffusion and high interfacial resistance limit their application in durable and high-power density batteries. Here, a novel quasi-solid Li + ion conductive nanocomposite polymer electrolyte containing black phosphorous (BP) nanosheets is reported. The developed electrolyte is successfully cycled against Li metal (over 550 h cycling) at 1 mA cm -2 at room temperature. The cycling overpotential is dropped by 75% in comparison to BP-free polymer composite electrolyte indicating lower interfacial resistance at the electrode/electrolyte interfaces. Molecular dynamics simulations reveal that the coordination number of Li + ions around (trifluoromethanesulfonyl)imide (TFSI - ) pairs and ethylene-oxide chains decreases at the Li metal/electrolyte interface, which facilitates the Li + transport through the polymer host. Here, density functional theory calculations confirm that the adsorption of the LiTFSI molecules at the BP surface leads to the weakening of N and Li atomic bonding and enhances the dissociation of Li + ions. This work offers a new potential mechanism to tune the bulk and interfacial ionic conductivity of solid-state electrolytes that may lead to a new generation of lithium polymer batteries with high ionic conduction kinetics and stable long-life cycling.

2D materials↗

DOE OSTI2019

Tuning Li 2 O 2 Formation Routes by Facet Engineering of MnO 2 Cathode Catalysts

In lithium-oxygen batteries, the solubility of LiO 2 intermediates in the electrolyte regulates the formation routes of the Li 2 O 2 discharge product. High-donor-number electrolytes with a high solubility of LiO 2 tend to promote the formation of Li 2 O 2 large particles following the solution route, which eventually benefits the cell capacity and cycle life. Here, we propose that facet engineering of cathode catalysts could be another direction in tuning the formation routes of Li 2 O 2 . In this work, fi-MnO 2 crystals with high occupancies of {111} or {100} facets were adopted as cathode catalysts in Li-O 2 batteries with a tetra(ethylene)glycol dimethyl ether electrolyte. The {111}-dominated beta-MnO 2 catalyzed the formation of the Li 2 O 2 discharge product into large toroids following the solution routes, while {100}-dominated beta-MnO 2 facilitated the formation of Li 2 O 2 thin films through the surface routes. Further computational studies indicate that the different formation routes of Li 2 O 2 could be related to different adsorption energies of LiO 2 on the two facets of beta-MnO 2 . Our results demonstrate that facet engineering of cathode catalysts could be a new way to tune the formation route of Li 2 O 2 in a low-donor-number electrolyte. Here, we anticipate that this new finding would offer more choices for the design of lithium-oxygen batteries with high capacities and ultimately a long cycle life.

25 ENERGY STORAGE↗

DOE OSTI2019

Plastic recovery and self-healing in longitudinally twinned SiGe nanowires

This paper reports on plastic recovery and self-healing behavior in longitudinally-twinned and [112] orientated SiGe nanowire (NW) beams when they are subjected to large bending strains. The NW alloys are comprised of lamellar nanotwin platelet(s) sandwiched between two semi-cylindrical twins. The loading curves, which are acquired from atomic force microscope (AFM) based three-point bending tests, reveal the onset of plastic deformation at a characteristic stress threshold, followed by further straining of the NWs. This ductility is attributed to dislocation activity within the semi-cylindrical crystal portions of the NW, which are hypothesized to undergo a combination of elastic and plastic straining. On the other hand, the lamellar nanoplatelets undergo purely elastic stretching. During the unloading process, the release of internal elastic stresses enables dislocation backflow and escape at the surface. As a result, the dislocations are predominantly annihilated and the NW samples evidenced self-healing via plastic recovery even at ultra-large strains, which are estimated using finite-element models at 16.3% in one of the tested devices. Finite element analysis also establishes the independence of the observed nanomechanical behavior on the relative orientation of the load with respect to the nanoplatelet. This first observation of reversible plasticity in the SiGe material system, which is aided by a concurrent evolution of segmented elastic and plastic deformation within its grains during the loading process, presents an important new pathway for mechanical stabilization of technologically important group-IV semiconductor nanomaterials.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Interpreting Electrochemical and Chemical Sodiation Mechanisms and Kinetics in Tin Antimony Battery Anodes Using in Situ Transmission Electron Microscopy and Computational Methods

Intermetallic compounds such as SnSb are promising anode materials for sodium ion batteries; however, their nanoscale sodiation mechanisms are not well understood. Here, we used a combination of in situ transmission electron microscopy (TEM), first-principles electronic structure calculations, computational thermodynamic modeling, and phase-field simulations to reveal the sodiation mechanisms and to quantify microstructural effects contributing to the underlying reaction kinetics in SnSb electrodes. During in situ sodiation experiments, the nanocrystalline SnSb thin films underwent a rapid amorphous phase transformation upon sodiation, as determined by in situ TEM and electron diffraction experiments. The Na + diffusion coefficients were measured with and without an external electrical bias, and the data showed that an applied potential increased Na + diffusion by an order of magnitude compared to solid-state diffusion. Furthermore, there was a distinct decrease in sodium diffusion upon the formation of the amorphous phase that resulted from a change in the local structure and grain boundaries. To further understand how the Na + transport mechanism correlated with the changes observed in the SnSb thin films, phase-field modeling was used, which considered sodium diffusion within the grain boundaries together with their evolution and stress–strain state. As a result, these findings enhance our understanding of sodiation mechanisms within intermetallic anode materials for sodium ion battery applications.

25 ENERGY STORAGE↗

DOE OSTI2018

Synergistic Effect of Graphene Oxide for Impeding the Dendritic Plating of Li

Dendritic growth of lithium (Li) has severely impeded the practical application of Li-metal batteries. Herein, a 3D conformal graphene oxide nanosheet (GOn) coating, confined into the woven structure of a glass fiber separator, is reported, which permits facile transport of Li-ions thought its structure, meanwhile regulating the Li deposition. Electrochemical measurements illustrate a remarkably enhanced cycle life and stability of the Li-metal anode, which is explained by various microscopy and modeling results. Utilizing scanning electron microscopy, focused ion beam, and optical imaging, the formation of an uniform Li film on the electrode surface in the case of GO-modified samples is revealed. Ab initio molecular dynamics (AIMD) simulations suggest that Li-ions initially get adsorbed to the lithiophilic GOn and then diffuse through defect sites. This delayed Li transfer eliminates the “tip effect” leading to a more homogeneous Li nucleation. Meanwhile, C-C bonds rupture observed in the GO during AIMD simulations creates more pathways for faster Li-ions transport. In addition, phase-field modeling demonstrates that mechanically rigid GOn coating with proper defect size (smaller than 25 nm) can physically block the anisotropic growth of Li. This new understanding is a significant step toward the employment of 2D materials for regulating the Li deposition

25 ENERGY STORAGE↗