Functional Nanomaterials: Functional Low-Dimensional (0D, 1D, 2D) Materials 2022: Functional Energy Nanomaterials: Electrochemistry & Sustainability/Lithium-based Energy Storage
Sponsored by: TMS Functional Materials Division, TMS: Nanomaterials Committee
Program Organizers: Michael Cai Wang, University of South Florida; Yong Lin Kong, University of Utah; Sarah Ying Zhong, University of South Florida; Surojit Gupta, University of North Dakota; Nasrin Hooshmand, Georgia Institute of Technology; Woochul Lee, University of Hawaii at Manoa; Min-Kyu Song, Washington State University; Simona Hunyadi Murph, Savannah River National Laboratory; Hagar Labouta, University of Manitoba; Max Anikovskiy, University of Calgary; Patrick Ward, Savannah River National Laboratory

Thursday 8:30 AM
March 3, 2022
Room: 260B
Location: Anaheim Convention Center

Session Chair: Sarah Ying Zhong, University of South Florida; Min-Kyu Song, Washington State University

8:30 AM  
The Influence of Magnetic Moment on Chemical Activity for Design of Hierarchical Electrochemical Systems: Chloe Groome1; Huong Ngo1; Jie Li1; Ruqian Wu1; Regina Ragan1; 1University of California Irvine
    We present results elucidating the role of magnetic moment on catalytic activation energy barriers of single transition metal atoms stabilized on graphene substrates with a first principles approach. While many structure-activity relationships have been uncovered, further insight is still needed to design new catalysts with performance comparable to platinum group metals. The effect of spin-dependent chemical pathways for transition metal single atom catalysts (SAC) supported on graphene defects has been examined only recently. We examine how the spin state of the SAC and reactants can affect catalytic energy barriers of V, Fe, Mo, and Ta atoms stabilized on two similar graphene defects with differing magnetic moments. We will present results suggesting that the magnetic moment of frontier orbitals could play a significant role in enhancing catalytic performance, as well as more traditionally understood mechanisms such as charge transfer and the proximity of frontier d-orbitals to the Fermi level.

8:50 AM  Invited
Real-time Observations of Chemo-mechanical Behaviors of Si-based Anodes for Advanced Lithium-ion Batteries: Jung-Hyun Kim1; 1The Ohio State University
     Wide-spread adoption of Si-based anodes have been obstructed by limited cycle life which stems from abnormal volumetric expansion behaviors. To address this issue, this presentation will introduce our recent efforts on characterization of Si-based anodes via distribution of relaxation times (DRT) analysis and in-situ/operando atomic force microscopy (AFM). First, systematic DRT analyses of Si and SiO anodes allowed to deconvolute the origins of individual polarization losses and their evolutions under different operating conditions. Second, we compared wetting behaviors of Na-alginate and poly(vinylidene fluoride) binders in contact with liquid electrolytes in terms of modulus and adhesion force. Finally, we performed real-time monitoring of Si particle pulverization – irreversible volume expansion – crack generation phenomena during early stage of anode cycling. The results provided a direct evidence for chemo-mechanical coupling effects of Si anodes and offered a strategy to mitigate their tensile stress during cycling.

9:15 AM  
Porous Assemblies of 2-D MnO2 Nanosheets and Their Conversion to 1-D Tunnel Structures: Peter Metz1; Alec Ladonis1; Peng Gao1; Madeleine Flint1; Scott Misture1; 1Alfred University
    In the case of exfoliated and re-assembled 2-D oxides, little work has been published concerning the thermal stability and phase transitions that occur upon heating these high surface area solids. The talk will show the high specific capacitance for ion intercalation into porous nanosheet assemblies and how the material responds to thermal annealing. We focus on measuring nucleation and growth of tunnel-structure phase fragments – to capture the mechanisms of structural phase transitions – using primarily in-situ Raman spectroscopy and X-ray total scattering. The result of heating MnO2 nanosheet clusters is to convert those regions of the material with 2 or more re-stacked nanosheets into the 1-D tunnel form of MnO2 at the local scale. In other words, a hierarchically porous solid results where the tunnel pores exist within the porous MnO2 nanosheet assembly. The electrochemical response dramatically changes throughout the conversion, supporting the structural evidence for the nanoscale transition.

9:35 AM  Invited
2D Materials for Lithium Batteries: Reza Shahbazian-Yassar1; 1University of Illinois at Chicago
    Two dimensional (2D) materials are emerging materials for innovative design of Lithium batteries that are safe and high energy density. This presentation encompasses recent progress in the PI's research team on addressing the Li battery challenges via 2D materials design and integration. I first showcase a Li-metal case where graphene oxide (GO) materials were used to control the deposition of Li-metal ions during charge and discharge reactions. We demonstrated high cycling performance of Li-metal cell modified with GO in comparison to typical Li-metal cells. In another work, we studied the electrochemical cycling of Li storage in phosphorene 2D materials and showed interesting structural ordering during Li insertion in these materials and remarkable fast ion diffusion across phosphorene. Moreover, we show that the encapsulation of cathode particles with 2D materials can be an innovative approach to suppress the oxygen release in the high voltage cathodes.

10:00 AM Break

10:20 AM  Invited
Electrochemical Imaging of Precisely Defined Redox and Reactive Nanomaterials: Venkateshkumar Prabhakaran1; 1Pacific Northwest National Laboratory
    The electrode-electrolyte interface (EEI) constitutes a critical frontier in the development of highly efficient energy conversion and storage systems. Electrochemical reactivity at the interface is influenced by heterogeneity resulting from the active site distribution, catalyst particle size and morphology. In this work, we demonstrated how single entity characterization and controlled electrode preparation techniques using ion soft landing can be used to isolate the influence of a specific chemical or physical entity, thereby unifying theory and experiment in both redox and reactive electrochemical systems. Ion soft landing enable deposition of charged ions directly onto conductive electrodes and it has been shown to be well suited for controlling the size and charge of the deposited ions. We establish that controlled electrode preparation with specific nanostructures and chemistry will be instrumental in filling the scientific gaps and provide us a unique platform to isolate and describe chemical and physical processes occurring at EEIs.

10:45 AM  Keynote
Electrochemical Behaviors of Two-dimensional Materials for Energy Applications: Jun Lou1; 1Rice University
    In this talk, several aspects of the electrochemical behaviors of two-dimensional (2D) materials for energy applications will be discussed. We developed a local probe electrochemical measurement method and successfully applied it to the electro-catalytic activity measurement of various kinds of transition metal dichalcogenides. The catalytic activity and turnover frequencies of the 2H-MoS2 basal plane versus edge as well as the 1T’-MoS2 basal plane are identified by this measurement. The basal plane activity and turnover frequencies of transition metal dichalcogenides from different element groups has also been systematically studied. VB-VIA dichalcogenides have been identified as the preferred selection for non noble metal hydrogen evolution reaction (HER) catalysts. Next, we have demonstrated dinitrogen conversion to ammonia via electrochemical reduction with over 10% Faradic efficiency using 2D catalyst. Sulfur vacancy on MoS2-x basal plane mimicking the natural Mo-nitrogenase active site is modified by Co doping and exhibits superior dinitrogen to ammonia conversion activity.

11:30 AM  Cancelled
Lithium Dendrite Growth and Stress Generation in Solid-state Batteries: Sulin Zhang1; 1Penn State
    The growth and penetration of nano-scale Li dendrites into the solid electrolytes and subsequent induced circuit shorting remain an unresolved issue in constructing safe and robust all-solid-state Li metal batteries. Here using in-situ transmission electron microscopy (TEM) in conjunction with multiphysical modeling we probe the growth conditions, morphologies, and materials properties of Li dendrites during electrochemical cycling. We show that the as-grown nanoscale Li dendrites are markedly stiffer than that of their bulk counterparts. The growing Li dendrites exhibit both displacive and diffusive deformations, presenting different stress-relaxation pathways. We further show that large growth induced pressure may develop during electrochemical cycling, and the Li dendrites act as an incompressible fluid that transmits the high pressure to the surrounding solid components, causing fracture. Our study sheds light on effective mitigation strategies for uncontrollable Li growth in solid electrolytes, and paves the way toward mechanically and electrochemically robust all-solid-state batteries.