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Rubloff, Gary

Publications and source records attributed to Rubloff, Gary.

Simultaneous Solid Electrolyte Deposition and Cathode Lithiation for Thin Film Batteries and Lithium Iontronic Devices

Here we show that the deposition of the solid-state electrolyte LiPON onto films of V 2 O 5 leads to their uniform lithiation of up to 2.2 Li per V 2 O 5 , without affecting the Li concentration in the LiPON and its ionic conductivity. Our results indicate that Li incorporation occurs during LiPON deposition, in contrast to earlier mechanisms proposed to explain postdeposition Li transfer between LiPON and LiCoO 2 . We use our discovery to demonstrate symmetric thin film batteries with a capacity of >270 mAh/g, at a rate of 20C, and 1600 cycles with only 8.4% loss in capacity. We also show how autolithiation can simplify fabrication of Li iontronic transistors attractive for emerging neuromorphic computing applications. Our discovery that LiPON deposition results in autolithiation of the underlying insertion oxide has the potential to substantially simplify and enhance the fabrication process for thin film solid state Li ion batteries and emerging lithium iontronic neuromorphic computing devices.

25 ENERGY STORAGE↗

In Situ Raman Mapping of Si Island Electrodes and Stress Modeling as a Function of Lithiation and Size

Si is known for cracking and delamination during electrochemical cycling of a battery due to the large volume change associated with Li insertion and extraction. However, it has been found experimentally that patterned Si island electrodes that are 200 nm thick and less than 7 μm wide can deform in a purely elastic manner. Inspired by this, we performed in situ Raman stress characterization of model poly-crystalline Si island electrodes using an electrochemical cell coupled with an immersion objective lens and designed for a short working distance. A 5 μm wide Si island electrode showed a parabolic stress profile during lithiation, while for a 15 μm Si island electrode, a stress plateau in the center of the electrode was observed. A continuum model with coupled electro-chemo-mechanical (ECM) physics was established to understand the stress measurement. A qualitative agreement was reached between modeling and experimental data, and the critical size effect could be explained by the Li diffusive flux as governed by competition between the Li concentration and hydrostatic stress gradients. Below the critical size, the stress gradient drives Li toward the edges, where the electrode volume is free to expand, while above the critical size, the stress plateau inhibits Li diffusion to the edge and forces destructive stress relief by cracking. Furthermore, this work represents a promising methodology for in situ characterization of ECM coupling in battery electrodes, with suggestions provided for further improvement.

25 ENERGY STORAGE↗

On-Wafer Wide-Pore Anodic Aluminum Oxide

Anodized aluminum oxide (AAO) has been used as nanotemplates for nanomaterials and nanodevice fabrications. Microfabrication techniques are attracting attention for nanodevice synthesis. However, AAO requires a microfabrication-compatible substrate due to its brittleness. While there are studies that already show AAO on compatible substrates, the pore sizes may not be applicable for multicomponent nanodevices. In this study, wide pore AAOs with ohmic bottom contacts are fabricated on 76 mm Si wafers. Sputtering was used to deposit Al along with supporting layers to achieve this goal. A quiescent electropolishing technique was used to smooth the surface of Al. Standard photolithography was used to define the active area on the Al for anodization. Then 195 V two-step anodization was performed to fabricate wide pore AAOs with pore diameters ranging from 130 ± 32 nm to 400 ± 31 nm with interpore distance of 480 ± 47 nm. Furthermore, it also showed that the ordering of the pores depended on the current density over the more conventional anodization time.

25 ENERGY STORAGE↗

Lithium Spatial Distribution and Split-Off Electronic Bands at Nanoscale V 2 O 5 /LiPON Interfaces

A combination of depth-resolved cathodoluminescence spectroscopy (DRCLS) and X-ray photoemission depth profiling (XPS) measured the pronounced changes in both the electronic density of states and lithium composition near the nanoscale LixV2O5/LiPON interface. DRCLS studies of electrochemically lithiated bare V2O5 and the sputterdeposited V2O5 plus LiPON overlayer electrochemically lithiated in stages both showed that in the bulk the luminescence intensity of the “split-off” hybridized bonding density of states was anticorrelated with XPSmeasured Li content, decreasing as the Li content increased. However, the LiPON overlayer was found to modify the band structure of the underlying LixV2O5 (LVO) to a depth of at least 30 nm beneath the V2O5 interface. DRCLS spectra near the electrochemically lithiated LiPON/ LVO interface showed a significant intensity of the split-off band, implying a low Li content. However, XPS depth profiling revealed a pronounced negative gradient of Li extending from a maximum Li content at the intimate LiPON boundary to its lowest content of ∼30 nm into the V2O5 in the same region, indicating a strong interaction between band structure and Li electrochemical potential near this heterojunction. These results provide evidence for substantial effects on the local band structure near an electrolyte/cathode interface and insights into the electrochemical interface behavior of solid-state batteries in general.

25 ENERGY STORAGE↗

Al 2 O 3 Thin Films on Magnesium: Assessing the Impact of an Artificial Solid Electrolyte Interphase

Among the many emerging technologies under investigation as alternatives to the successful Lithium-ion battery, the magnesium battery is promising due to the wide availability of magnesium, its high volumetric capacity, and the possibility for safety improvements. One of the largest challenges facing rechargeable magnesium batteries is the formation of a passivation layer at the Mg metal anode interface when reactive species in the electrolyte are reduced at the electrode-electrolyte interface. To control the solid electrolyte interphase in Lithium batteries, protective layers called artificial solid electrolyte interphase (ASEI) layers have been successful in improving Li metal anode performance. The approach of protecting Mg metal anodes from electrolyte degradation has been demonstrated by fewer studies in the literature than Li systems. In this work, we discuss the properties of Al 2 O 3 thin films deposited using atomic layer deposition as an artificial solid electrolyte interphase at the Mg anode. Our results demonstrate that Al 2 O 3 does prevent electrolyte degradation due to the reductive nature of Mg. However, undesirable properties such as defects and layer breakdown lead to Mg growth that causes soft-shorting. The soft-shorting occurs with and without the protection layer, indicating the ALD layer does not prevent it and hinders Al 2 O 3 from being an ideal candidate for a protection layer. Crucial effects of this layer on Mg electrochemistry at the interface were observed, including growth of Mg deposits leading to soft-shorting of the cell whose morphology showed a dependence on the Al 2 O 3 layer. These results may provide guidelines for the future design and development of protective ASEI layers for Mg anodes.

25 ENERGY STORAGE↗

Nanostructures for Electrical Energy Storage (NEES) (2020 Final Technical Report)

Nanostructures for Electrical Energy Storage (NEES, www.efrc.umd.edu) was an Energy Frontier Research Center supported by the DOE Office of Science, Basic Energy Sciences, from 8/1/2009 to 7/31/2020. Led by the University of Maryland, NEES enjoyed extensive collaborations with its funded partners, including two DOE Laboratories and six universities. The NEES vision has been to reveal a set of scientific insights and design principles that can underpin a next-generation electrical energy storage approach, building on advances in nanoscale science and technology to achieve simultaneous high power and high energy over extended charge/discharge cycling. The vision is motivated by the recognition that scaling into the nano regime opens the door to new physical phenomena and that the tools enlisted in nanoscale research provide major new opportunities for the synthesis not only of materials at molecular scale but for structures at nano scale and above. NEES has translated this vision into its research program based on two observations. First, while the behavior of ions and electrons in electrolytes and in electrode materials is crucial to electrical energy storage (or more appropriately electrochemical energy storage), it is the transport of ion and electron charge between different structural components of a storage device that ultimately determine its performance. With it well recognized that the choice of electrode materials typically constrain ion transport kinetics as well as maximum ion concentration, the search for better electrode materials has been a primary driver of battery research. At the same time the synthesis of electrodes is typically based on aggregation of particles with varying size, shape, and orientation in the electrode. Together with the presence of additional materials to impart electrical conductivity and cohesion to the composite electrode, change in electrode materials is necessarily accompanied by structural changes at the nano/micro scale that are difficult to categorize and manage. From the beginning, NEES’ vision has been to create and study simpler, highly controlled spatial arrangements of known materials as battery components (electrodes, current collectors, and electrolyte) and to understand how design and structure above the molecular scale determines the energy storage performance available from known materials. Second, advances in nanoscience dramatically expanded the portfolio of synthesis methods, structural motifs, and new phenomena available for research. Some of these gave rapid access to new building blocks at the deep nanoscale (e.g., carbon nanotubes grown by self-assembly, nanoscale arrays formed by electrochemical self-alignment, monolayer films controlled by self-limiting reaction). Such advances served as the enabler for the NEES vision to be pursued experimentally through study of 3D structures created and controlled at the nano, micro, and meso scales. Here, we use meso as in the BES MESO Report, implying not only intermediate or varying length scales, but very much the way behavior is influenced by other factors including aggregation of nanocomponents at different densities and spatial configurations, statistical variations in the aggregates, hierarchical architectures in which they can be assembled, or local 3D configurations that result from the architectures. Over its life cycle, NEES has pursued two overarching goals: (1) to understand the scientific fundamentals of electrochemical storage from the nanoscale to the mesoscale; and (2) to create and learn from innovative, controlled, heterogeneous nanostructures, where such nanostructures can enable the first goal and serve as models for future paradigms in energy storage. Specific goals have included: Synthesize heterogeneous nanostructures comprised of multiple materials arranged in controlled fashion and characterize their behavior; Demonstrate and elucidate design principles for achieving simultaneous high power and high energy; Develop materials processes which enable precision control of thin layers and 3D structures; Investigate the impact of artificial interphases on electrode stability during ion insertion/deinsertion; Create dense arrays of nanostructures to understand how the architecture of these assemblies, along with nanostructure design, influences energy storage behavior at the mesoscale; Identify and understand the consequences of nanoconfinement and local inhomogeneities in 3D mesoscale arrays; Develop and apply computational models to stimulate, guide and interpret experiments.

25 ENERGY STORAGE↗

Mg 2+ ion-catalyzed polymerization of 1,3-dioxolane in battery electrolytes

Electrolyte salts with Mg 2+ and Al 3+ Lewis acidic cations demonstrate polymerization of 1,3-dioxolane. The speed and extent of the reaction depends on coordination of the anion with the Mg 2+ cation catalyst. Weakly coordinating anions such as TFSI - aid faster polymerization while strongly coordinating anions such as ClO 4 - hinder the polymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗