Advanced Materials for Energy Conversion and Storage 2022: On-Demand Oral Presentations
Sponsored by: TMS Functional Materials Division, TMS: Energy Conversion and Storage Committee
Program Organizers: Jung Choi, Pacific Northwest National Laboratory; Soumendra Basu, Boston University; Paul Ohodnicki, University of Pittsburgh; Partha Mukherjee, Purdue University; Surojit Gupta, University of North Dakota; Amit Pandey, Lockheed Martin Space; Kyle Brinkman, Clemson University

Monday 8:00 AM
March 14, 2022
Room: Energy & Environment (including REWAS 2022 Symposia)
Location: On-Demand Room

Materials and Manufacturing for High Temperature Concentrating Solar Power Applications: Kamala Raghavan1; Vijaykumar Rajgopal1; Nikkia McDonald1; Avi Shultz1; 1US Department of Energy
    Concentrating solar-thermal power (CSP) plants capture the sun’s energy from the heliostat field and convert it to thermal energy which can be stored and dispatched on-demand to generate electricity. DOE’s is targeting a cost of $0.05/kWhe for baseload CSP plants primarily focusing on high-efficiency sCO2 Brayton cycle, operating at temperatures higher than 700C and pressures of approximately 300 bar. These harsh conditions demand innovation in new material and fabrication technologies. To this end the Solar Energy Technologies Office (SETO) is supporting research in traditional high temperature alloys, MAX phase materials, cermets, and ceramics along with appropriate fabrication and material processing technologies. This presentation will discuss the ongoing material and fabrication research work supported by SETO and will present a longer term material and manufacturing strategy for high-temperature CSP components.

Feasibility Studies of Fully Inorganic Perovskite Cells through Experimental Degradation and Metrics Identification: Towards the Development of Hybrid Sensors for Biomedical Wearable Devices: Saquib Ahmed1; Sankha Banerjee2; Deidra Hodges3; 1State University of New York at Buffalo State; 2California State University, Fresno; 3Florida International University
    Over the past decade, perovskite-based halide structures have been demonstrated as promising energy conversion devices through their application in solar cells. Currently, lead-based perovskite halides exhibit the highest energy conversion efficiency, but they are toxic and unstable by nature. The goal of this research is to study the feasibility of lead-free alternative options for the development of stacked cell structures for application in biomedical devices. This work involves the simulation, fabrication, processing, and characterization of fully inorganic perovskite based photoactive cells on flexible substrates to study the feasibility of devices for use as photoactive sensors in biomedical wearables. The stacked cells have an FTO(transparent conductive oxide layer), electron transport layer made of Electroactive Material Systems (BaTiO3, or ZnO) (blocking layer) and TiO2(mesoporous layer), perovskite layer, P3HT(hole transport layer), and Palladium(back contact layer). The results were analyzed for feasibility, degradation, and metrics identification for application in biomedical wearable and diagnostic devices.

Machine Learning Enables Discovery of Ternary Alloy Catalysts for Oxygen Reduction: Youngtae Park1; Hyuck Mo Lee1; 1KAIST
    Pt is utilized as an electrocatalyst to accelerate the slow oxygen reduction reaction (ORR) rate in the cathode of proton exchange membrane fuel cells (PEMFCs). However, the high cost of Pt prevents PEMFCs from being commercially viable. Despite the fact that numerous studies attempt to lower the amount of Pt by alloying, most catalyst designs are confined to bimetallic alloys. Using a graph-based convolutional neural network (GCNN), we significantly extend the material design space from binary to ternary for ORR catalysts for PEMFCs. We have collected our own database of 9,267 surface binding energies composed of five key adsorbates (H, O, OH, OOH, and CO). With a mean absolute error of only 0.164 eV, the GCNN model has outstanding predictive performance. As a consequence, we discovered 10 promising ORR ternary alloy catalysts with lower costs and greater catalytic activity than Pt.

Interplay between Mechanics and Electrochemistry in FeS2 Electrode Performance: Scott Roberts1; Jeffrey Horner1; 1Sandia National Laboratories
    While traditionally used as a primary battery chemistry, there is current interest in using FeS2 as a high-energy density cathode material for specialized rechargeable battery applications. However, the combination of intercalation and conversion processes, large volume change upon reaction, and the formation of polysulfides complicate its cycling behavior and therefore wider adoption. We present computational models at both the mesoscale (particle-resolved) and macroscale (homogenized) that look at the coupled interplay between mechanical stress and strain and electrochemistry to determine the performance and degradation of FeS2 electrodes. These models are used to explore the role of particle size polydispersity and 3D electrode design to appropriately balance mechanics, transport, and kinetic limitations and optimize electrode performance. SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525.

X-ray Characterization of Battery Degradation: Johanna Nelson Weker1; 1SLAC National Accelerator Laboratory
    Synchrotron-based X-rays are a powerful characterization tool that can probe across many relevant length scales (from atomistic to millimeter) with different techniques that are sensitive to distinct features such as microstructure, chemistry, and morphology. Because of the high flux available and penetrating power of X-rays, batteries can be probed under realistic conditions, which enables us to understand and overcome failure mechanisms of the generation battery materials. I will discuss our multimodal approach combining information from high resolution transmission X-ray microscopy, X-ray diffraction, and X-ray absorption spectroscopy to study a range of different battery chemistries. Specifically, I will present recent work on using X-ray microscopy to study nanoporous architectures for alloying anode to accommodate their large volume changes. I will also show X-ray diffraction mapping to characterize Li metal plating on the graphite anode from fast charging and compare it to the local state of charge of the cathode.

Multi-layered Thin-films Metal Contacts for New Generation Solar Cells: Andriy Orlov1; Ivan Kruhlov1; Vitalii Yanchuk1; Sergey Prikhodko2; Svitlana Voloshko1; 1National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute”; 2University of California Los Angeles
    Solar cells’ (SCs) technologies are among the most capable alternative energy trends. One of the key components of any SC device is the metal contacts, which greatly determine their efficiency, stability, and cost. The utilization of Cu-based multi-layered thin-film contacts instead of commonly used Ag-based screen-printed electrodes is a promising alternative for the SCs’ cost and size reduction, while maintaining high electrical conductivity. The long-term stability of Cu-based contacts could be improved by the post-fabrication processing. Our recent studies on Ni/Cu/Cr/Si(001) films show their increased oxidation resistance and decreased O and C impurities content after the films’ low-energy (<2000 eV) Ar+ ion irradiation. Furthermore, ion pre-irradiation significantly promotes the wear resistance of thin-films subjected to annealing in vacuum. These findings are of relevance for the development of durable and low-cost contacts for the novel thin-film hetero-junction silicon SCs.

Magnetoelectrochemical Control of Interfacial Degradation during Fast Charging of LIB: Abhishek Sarkar1; Pranav Shrotriya2; Cajetan Nlebedim1; 1Ames Laboratory; 2Iowa State University
    Anodic degradations in graphitic materials under fast charging conditions cause severe performance loss and safety hazard in lithium batteries. We present a method of minimizing the growth of these ageing mechanisms by application of an external magnetic field. The magnetohydrodynamic forces on diffusing species in a magnetic field homogenizes ionic transport and minimizes interfacial overpotential hotspots, consequently reducing SEI growth, lithium plating, and interfacial fracture. Electrochemical measurements indicate a capacity gain in full LCO/C cells charged (1 – 5 C) under applied field (1.8 kG), with a maximum of 23% at 5C. FE-SEM/ EDS show charging under magnetic field have reduced lithium deposition at 3C and completely suppressed interfacial fracture at 5C. XPS indicates 24% reduction in the lithium deposition at 5C. Finally, a saturation behavior in capacity is observed at high fields (> 2 kG), thereby limiting the consequent energy requirements to obtain maximum capacity gain under extreme conditions.

Characterization of AlCl3-urea Electrolyte for Speciation, Conductivity, and Electrochemical Stability and Its Application in Al-ion Batteries: Monu Malik1; Kok Long Ng2; Gisele Azimi1; 1University of Toronto; 2University of Torornto
    In the present study, the physicochemical properties of AlCl3 and urea mixtures, a potential electrolyte for Al-ion batteries, are investigated by changing the molar ratio of AlCl3/urea in the range of 1.0–1.6. In recent years, Al-ion batteries are receiving growing attention due to the high abundance and low cost of Al, ease of handling in an ambient environment, and high theoretical capacities. A urea-based electrolyte is a cost-effective and environmentally friendly alternative to expensive 1-Ethyl-3-methylimidazolium chloride ([EMIM]Cl) based electrolyte for Al-ion batteries. Several characterization techniques such as nuclear magnetic resonance spectroscopy, electrochemical impedance spectroscopy, and linear sweep voltammetry are used to determine the speciation of ionic moieties, ionic conductivity, and electrochemical stability of this complex system. Based on the obtained results, the best composition was used as an electrolyte in an Al-ion battery, which delivered a specific capacity of 74 mAh g–1 at 100 mA g–1.

Ag@AgCl Core/shell Catalysts with Bumpy Surface to Enhance Oxygen Reduction Reaction : Suyeon Choi1; Changsoo Lee2; Jahyun Koo3; Hyuck Mo Lee1; 1Korea Advanced Institute of Science and Technology; 2Korea Institute of Energy Research; 3Korea University
    The commercialization of fuel cells is hindered by the high cost and poor stability of Pt catalysts. As an alternative material to Pt, Ag is attracting a lot of attention due to its low cost, long-term stability, and excellent electrical conductivity. Here, we additionally used Cl to enhance the oxygen reduction reaction (ORR) activity of Ag via ligand effect between Ag and Cl and designed Ag@AgCl core/shell nanowires (NWs) decorated with AgCl nanoparticles. Ag NWs core makes the high electrical conductivity of Ag maintained, and decorated AgCl particles increase the surface area, resolving the O2 mass transport issue in the high overpotential region. As a result, the ORR activity of AgCl-Ag@AgCl NWs is enhanced noticeably compared with Ag NWs, and the stability is confirmed through accelerated durability tests (ADTs) and morphology comparisons between before and after ADTs using scanning transmission electron microscopy and energy dispersive X-ray spectroscopy.

Photoabsorbers with Hybrid Organic-inorganic Structures for Optoelectronics and Solar Cells: Mohin Sharma1; Mritunjaya Parashar1; Anupama Kaul1; Ravindra Mehta1; 1University of North Texas
    Organic-inorganic hybrid lead halide perovskite solar cells (PSCs) have seen a huge surge in photovoltaic performance in recent years. There are still some hurdles such as its chemical instability, degradation in ambient, which are the critical bottlenecks from commercial perspectives. Two-dimensional (2D) perovskites have emerged as the possible solution to these hurdles. They have provided the PSCs with more stability but attaining high PCE with 2D perovskites is still a problem. This is due to the insulating nature of the hydrophobic spacer head groups which lie in-between the conducting inorganic slabs. We have fabricated PSCs with Ruddlesden Popper (RP) 2D perovskite as the photoabsorber using CH3(CH2)3NH3)2(CH3NH3)n-1PbnI3n+1 layers at multiple stoichiometric compositions to study the stability and impact on PCE for these various formulations. These results will shed insights toward the integration of solution-processed 2D perovskite films for solar cells to enhance stability and performance of the devices.

Simulating Microstructure Evolution in Ni-YSZ Electrodes of Solid Oxide Cells under Operating Conditions: Yinkai Lei1; William Epting1; Jerry Mason1; Tianle Cheng1; Harry Abernathy1; Gregory Hackett2; Youhai Wen2; 1US DOE National Energy Technology Laboratory, NETL support contractor; 2US DOE National Energy Technology Laboratory
    A model for simulating microstructure evolution in Ni-YSZ electrodes of solid oxide cells under fuel cell, electrolysis and reversible mode has been developed by coupling our recently developed phase field model, multiphysics model and microstructure analyzing tools. The mechanisms of Ni(OH)2 diffusion and Ni-YSZ wettability change have been considered. The model has been used to investigate the effect of temperature, current density, and gas compositions on the degradation of Ni-YSZ electrode. Both Ni coarsening and redistribution are found to be affected by gas composition and temperature, while current density only affects the Ni redistribution. The results are compared to available experiments. It shows both mechanisms cannot fully explain the Ni redistribution observed in the experiment.

Electric Field Process for Lithium Ion Batteries: Hiep Pham1; Yufang He1; Jie Li1; Susmita Sarkar1; Jonghyun Park1; 1Missouri University of Science and Technology
    In this work, an innovative method is proposed during electrode fabrication to improve lithium-ion battery (LIB) performance. Prior works have demonstrated that controlling the microstructure of a LIB electrode can improve its performance by enhancing the transport of lithium ions. It is known that particles tend to form “chains” under the influence of an electric field (EF) due to the dipolar interactions between particles. This paper investigates a unique method that applies an EF combined with conventional tape-casting to improve electrode performance via facile microstructure modification. From electrochemical tests, it is found that the specific capacity can be improved with higher electric field strength. From electrode microstructure analysis, it is revealed that the improved battery performance benefits from the increased porosity of electrodes under the influence of electric field. This work provides a clear framework in which an electric field treatment combined with conventional tape-casting can significantly improve battery performance.

Initiatory Plating and Stripping towards the Survival of Sodium Metal Electrodes: Susmita Sarkar1; Partha Mukherjee1; 1Purdue University
    Uncontrolled dendrite growth in sodium (Na) metal anode demands that the stabilized Na to be implemented judiciously at a low cost beyond Lithium-ion technologies, such as room-temperature Na-S batteries. The realization of this goal requires an in-depth understanding of the complex interfaces between Na metal and electrolytes and the mechanism of the Na deposition/dissolution process. This work comprehensively studies the importance of the initial plating/stripping process on the working electrode by observing the voltage variations during cycling using 2- and 3-electrode cells. Using the 3-electrode cells, the asymmetry in plating and stripping potential and limitation of plated or stripped electrodes in cell failure have been identified. The changes in the electrode's impedances, morphology, and surface products have also been probed along with electrochemical signatures in different electrolytes. This effort to understand the notable metal growth and dissolution process leads to the cognizance of energy-dense metal-based batteries with safe operation.

Mesoscale Analysis of Electrochemical-mechanical Interactions in Solid-state Batteries: Bairav Vishnugopi1; Partha Mukherjee1; 1Purdue University
    Development of solid electrolytes, along with the utilization of Li metal anodes can potentially enable rechargeable batteries with enhanced power density, energy density and safety. Achieving stable electrodeposition in solid-state batteries (SSBs) requires overcoming fundamental electro-chemo-mechanical, ion transport and interface stability challenges such as filament growth, mechanical failure and contact loss. In particular, microstructural arrangement of the solid electrolyte including grain boundaries and voids play a critical role in determining the morphological stability of the solid-solid interface. In this work, we present a mechanistic analysis of the ion transport response and electrochemical-mechanical interactions that dictate the propensity for metal penetration along grain boundaries in crystalline solid electrolytes. Based on the mesoscale analysis, key design strategies that can intrinsically modulate the stability of grain boundary-electrode junctions in SSB systems are discussed.

Impact of Low Operating Temperatures on the Performance of Li-ion Batteries: Amani Alhammadi1; Amarsingh Kanagaraj1; Prerna Chaturvedi1; Daniel Choi1; 1Khalifa University of Science and Technology
    At subzero temperatures, the performance of lithium (Li)-ion batteries declines rapidly, resulting in less capacity and shorter cycle life. This is attributed to the freezing of the non-solid electrolyte, which leads to unstable solid electrolyte interphase (SEI) film formation and weak permeation of electrolyte into the active material. Electrolyte freezing results in a significant decrease in the diffusivity of lithium ions and a substantial increase in the charge-transfer resistance. In this research, the behavior of Li-ion batteries at subzero temperatures is investigated by employing electrochemical characterization methods such as cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge. Material characterization methods such as X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) are also used to examine the change in the electrode and the electrolyte to determine the reasons behind the performance degradation. Optimization methods are proposed to solve the issues that hinder the use of Li-ion batteries in subzero-temperature environments.