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McDowell, Matthew T.

Publications and source records attributed to McDowell, Matthew T..

12 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Fracture Dynamics in Silicon Anode Solid-State Batteries

Solid-state batteries (SSBs) with silicon anodes could enable improved safety and energy density compared to lithium-ion batteries. However, degradation arising from the massive volumetric changes of silicon anodes during cycling is not well understood in solid-state systems. Here, we use operando X-ray computed microtomography to reveal micro- to macro-scale chemo-mechanical degradation processes of silicon anodes in SSBs. Mud-type channel cracks driven by biaxial tensile stress form across the electrode during delithiation. We also find detrimental cracks at the silicon/ solid electrolyte interface that form due to local reaction competition between neighboring domains of different sizes. Continuum phase-field damage modeling quantifies stress-driven channel cracking and shows that the lithiated silicon stress state is critical for determining the extent of interfacial fracture. This work reveals the mechanisms that govern SSBs compared to conventional lithium-ion batteries and provides guidelines for engineering chemomechanically resilient electrodes for high-energy batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Epitaxial Metal Electrodeposition Controlled by Graphene Layer Thickness

Control over material structure and morphology during electrodeposition is necessary for material synthesis and energy applications. One approach to guide crystallite formation is to take advantage of epitaxy on a current collector to facilitate crystallographic control. Single-layer graphene on metal foils can promote “remote epitaxy” during Cu and Zn electrodeposition, resulting in growth of metal that is crystallographically aligned to the substrate beneath graphene. However, the substrate–graphene–deposit interactions that allow for epitaxial electrodeposition are not well understood. Here, we investigate how different graphene layer thicknesses (monolayer, bilayer, trilayer, and graphite) influence the electrodeposition of Zn and Cu. Scanning transmission electron microscopy and electron backscatter diffraction are leveraged to understand metal morphology and structure, demonstrating that remote epitaxy occurs on mono- and bilayer graphene but not trilayer or thicker. Density functional theory (DFT) simulations reveal the spatial electronic interactions through thin graphene that promote remote epitaxy. This work advances our understanding of electrochemical remote epitaxy and provides strategies for improving control over electrodeposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structural and electrochemical evolution of alloy interfacial layers in anode-free solid-state batteries

“Anode-free” solid-state batteries feature high energy density since there is no anode active material. Although the beneficial effects of interfacial layers at the anode-solid electrolyte interface have been demonstrated, the mechanisms through which they influence lithium plating/stripping are unclear. Here, in this study, we reveal the evolution of 100-nm silver and gold interfacial layers during lithium plating/stripping using electrochemical methods, electron microscopy, X-ray microcomputed tomography, and modeling. The alloy layers improve Coulombic efficiency and resistance to short circuiting, even though the alloys form solute regions or particulates that detach from the current collector during plating. In situ electrochemical impedance spectroscopy shows that the alloys return to the interface and mitigate contact loss at the end of stripping, avoiding a critical vulnerability of anode-free cells. Contact retention is driven by even Li thickness that promotes spatially uniform stripping, as well as local alloy delithiation in response to current concentrations that homogenizes current and diminishes voiding.

25 ENERGY STORAGE↗
DOE OSTI2023

Accelerated Short Circuiting in Anode-Free Solid-State Batteries Driven by Local Lithium Depletion

“Anode-free” solid-state batteries (SSBs), which have no anode active material, can exhibit extremely high energy density (≈1500 Wh L -1 ). However, there is a lack of understanding of the lithium plating/stripping mechanisms at initially lithium-free solid-state electrolyte (SSE) interfaces because excess lithium metal is often used. Here, it is demonstrated that commercially relevant quantities of lithium (>5 mAh cm -2 ) can be reliably plated at moderate current densities (1 mA cm -2 ) using the sulfide SSE Li 6 PS 5 Cl. Investigations of lithium plating/stripping mechanisms, in conjunction with cryo-ocused ion beam (FIB) imaging, synchrotron tomography, and phase-field modeling, reveal that the cycling stability of these cells is fundamentally limited by the nonuniform presence of lithium during stripping. Local lithium depletion causes isolated lithium regions toward the end of stripping, decreasing electrochemically active area and resulting in high local current densities and void formation. This accelerates subsequent filament growth and short circuiting compared to lithium-excess cells. Despite this degradation mode, here it is shown that anode-free cells exhibit comparable Coulombic efficiency to lithium-excess cells, and improved resistance to short circuiting is achieved by avoiding local lithium depletion through retention of thicker lithium at the interface. These new insights provide a foundation for engineering future high-energy anode-free SSBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Extending the low-temperature operation of sodium metal batteries combining linear and cyclic ether-based electrolyte solutions

Nonaqueous sodium-based batteries are ideal candidates for the next generation of electrochemical energy storage devices. However, despite the promising performance at ambient temperature, their low-temperature (e.g., < 0 °C) operation is detrimentally affected by the increase in the electrolyte resistance and solid electrolyte interphase (SEI) instability. Here, to circumvent these issues, we propose specific electrolyte formulations comprising linear and cyclic ether-based solvents and sodium trifluoromethanesulfonate salt that are thermally stable down to –150 °C and enable the formation of a stable SEI at low temperatures. When tested in the Na||Na coin cell configuration, the low-temperature electrolytes enable long-term cycling down to –80 °C. Via ex situ physicochemical (e.g., X-ray photoelectron spectroscopy, cryogenic transmission electron microscopy and atomic force microscopy) electrode measurements and density functional theory calculations, we investigate the mechanisms responsible for efficient low-temperature electrochemical performance. We also report the assembly and testing between –20 °C and –60 °C of full Na||Na 3 V 2 (PO 4 ) 3 coin cells. The cell tested at –40 °C shows an initial discharge capacity of 68 mAh g –1 with a capacity retention of approximately 94% after 100 cycles at 22 mA g –1 .

25 ENERGY STORAGE↗
DOE OSTI2021

Challenges for and Pathways toward Li-Metal-Based All-Solid-State Batteries

Solid-state batteries utilizing Li metal anodes have the potential to enable improved performance (specific energy >500 Wh/kg, energy density >1500 Wh/L), safety, recyclability, and potentially lower cost (<$100/kWh) compared to advanced Li-ion systems.1,2 These improvements are critical for the widespread adoption of electric vehicles (EVs) and trucks and could create a short-haul electric aviation industry.1-3 Expectations for solid-state batteries are high, but there are significant materials and processing challenges to overcome.

25 ENERGY STORAGE↗
DOE OSTI2021

Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography

Despite progress in solid-state battery engineering, our understanding of the chemo-mechanical phenomena that govern electrochemical behavior and stability at solid-solid interfaces remains limited compared to solid-liquid interfaces. Here, we use operando synchrotron X-ray computed microtomography to investigate the evolution of lithium/solid-state electrolyte interfaces during battery cycling, revealing how the complex interplay among void formation, interphase growth, and volumetric changes determines cell behavior. Void formation during lithium stripping is directly visualized in symmetric cells, and the loss of contact that drives current constriction at the interface between lithium and the solid-state electrolyte (Li10SnP2S12) is quantified and found to be the primary cause of cell failure. The interphase is found to be redox-active upon charge, and global volume changes occur due to partial molar volume mismatches at either electrode. Finally, these results provide new insight into how chemo-mechanical phenomena can impact cell performance, which is necessary to understand for the development of solid-state batteries.

42 ENGINEERING↗
DOE OSTI2020

Challenges for and Pathways Toward Solid-State Batteries

Solid-state batteries utilizing lithium metal anodes have the potential to enable batteries with a specific energy of >500 Wh/kg and an energy density of >1,500 Wh/L for thousands of cycles. When optimized they will improve the energy efficiency, operating temperature range, sustainability, and safety at a lower cost compared to projections for advanced Li-ion batteries. This improved performance is critical for the widespread adoption of electric vehicles and may enable future applications such as electric aviation. Expectations for solid-state batteries are high, there are significant materials and processing challenges that need to be overcome. Some of these challenges are well known; others are more subtle and are just becoming known. The challenges and their solutions must be clearly identified to realize high-energy solid-state Li metal batteries. In the United States, the U.S. Department of Energy (DOE) funds the majority of energy storage research and development, including solid state battery research. Web of Science publication analysis shows that worldwide DOE is second largest funder. Work on solid state batteries is distributed across different arms of DOE and is coordinated at headquarters to ensure a broad national portfolio for advanced batteries, including lithium batteries and solid-state battery devices. We note that university and national laboratory researchers in the US with a long-standing interest in solid state batteries is a small, integrated community with recognized impact for publications, patents and startup companies. The opportunity for this group to engage for research with international colleagues is growing, fostered by periodic bilateral meetings supported by DOE and by the recent joint US German research program for lithium battery interface studies. These are valuable opportunities to speed solid-state battery development. The ORNL led virtual workshop, overviewed here, confirms the community’s shared vision of the exciting advances, opportunities, and challenges. Further, we are seeing that this workshop has spawned several new informal collaborations and draft proposals. This encourages us to propose future discussion. On May 11, 2020, Oak Ridge National Laboratory (ORNL) hosted a 6-hour, on-line national workshop to discuss recent advances and most the prominent obstacles to realizing solid-state Li metal batteries. The workshop included more than 30+ experts from national laboratories, universities, and companies, all of whom have worked on solid-state batteries for multiple years. The participants shared recent advances, many not yet in print, illustrating that the community has gained significant new insights for solid-state Li battery materials over the last 5 years. In this report, the major outcomes of the workshop are organized to identify the gaps in our scientific knowledge for four core materials science areas: (1) Li metal anodes, (2) the solid electrolyte in contact with Li metal, (3) active cathode materials and solid-state composite cathodes, and (4) solid electrolytes. Illustrative examples and discussions are reported with the more comprehensive issues in the report. Discussion of additional challenges related to processing of solid-state battery materials and to the designs and architectures for mechanically robust, long-lived batteries received less attention due to time constraints. These are good themes for deeper discussion at a follow-on workshop, where a complete list of critical research topics can be identified.

25 ENERGY STORAGE↗
DOE OSTI2020

Spontaneous and reversible hollowing of alloy anode nanocrystals for stable battery cycling

High-capacity alloy anode materials for Li-ion batteries have long been held back by limited cyclability caused by the large volume changes during lithium insertion and removal. Hollow and yolk-shell nanostructures have been used to increase the cycling stability by providing an inner void space to accommodate volume changes and a mechanically and dimensionally stable outer surface. These materials, however, require complex synthesis procedures. Here, using in situ transmission electron microscopy, we show that sufficiently small antimony nanocrystals spontaneously form uniform voids on the removal of lithium, which are then reversibly filled and vacated during cycling. This behaviour is found to arise from a resilient native oxide layer that allows for an initial expansion during lithiation but mechanically prevents shrinkage as antimony forms voids during delithiation. In this work, we developed a chemomechanical model that explains these observations, and we demonstrate that this behaviour is size dependent. Thus, antimony naturally evolves to form optimal nanostructures for alloy anodes, as we show through electrochemical experiments in a half-cell configuration in which 15-nm antimony nanocrystals have a consistently higher Coulombic efficiency than larger nanoparticles.

25 ENERGY STORAGE↗
DOE OSTI2020

Challenges in Lithium Metal Anodes for Solid-State Batteries

In this Perspective, we highlight recent progress and challenges related to the integration of lithium metal anodes in solid-state batteries. While prior reports have suggested that solid electrolytes may be impermeable to lithium metal, this hypothesis has been disproven under a variety of electrolyte compositions and cycling conditions. Herein, we describe the mechanistic origins and importance of lithium filament growth and interphase formation in inorganic and organic solid electrolytes. Multimodal techniques that combine real and reciprocal space imaging and modeling will be necessary to fully understand nonequilibrium dynamics at these buried interfaces. Currently, most studies on lithium electrode kinetics at solid electrolyte interfaces are completed in symmetric Li–Li configurations. To fully understand the challenges and opportunities afforded by Li-metal anodes, full-cell experiments are necessary. Lastly, the impacts of operating conditions on solid-state batteries are largely unknown with respect to pressure, geometry, and break-in protocols. Given the rapid growth of this community and the diverse portfolio of solid electrolytes, we highlight the need for detailed reporting of experimental conditions and standardization of protocols across the community.

25 ENERGY STORAGE↗