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Miller, Michael A.

Publications and source records attributed to Miller, Michael A..

Type I clathrates as novel silicon anodes: An electrochemical and structural investigation

In this study, silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. Here we present an electrochemical evaluation of type I silicon clathrates based on Ba 8 Al y Si 46-y for the anode material in lithium-ion batteries. Post-cycling characterization with NMR and XRD show no discernible structural or volume changes even after electrochemical insertion of 44 Li into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from larger volume changes. The lithiation/delithiation processes are proposed to occur in single phase reactions at approximately 0.2 and 0.4 V vs. Li/Li + , respectively, distinct from other diamond cubic or amorphous silicon anodes. Reversible capacities as high as 499 mAh g -1 at a 5 mA g -1 rate were observed for silicon clathrate with composition Ba 8 Al 8.54 S i37.46 , corresponding to Li:Si of 1.18:1. The results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.

36 MATERIALS SCIENCE↗

Standardized Testing Program for Solid-State Hydrogen Storage Technologies

In the US and abroad, major research and development initiatives toward establishing a hydrogen-based transportation infrastructure have been undertaken, encompassing key technological challenges in hydrogen production and delivery, fuel cells, and hydrogen storage. However, the principal obstacle to the implementation of a safe, low-pressure hydrogen fueling system for fuel-cell powered vehicles remains storage under conditions of near-ambient temperature and moderate pressure. The choices for viable hydrogen storage systems at the present time are limited to compressed gas storage tanks, cryogenic liquid hydrogen storage tanks, chemical hydrogen storage, and hydrogen absorbed or adsorbed in a solid-state material (a.k.a. solid-state storage). Solid-state hydrogen storage may offer overriding benefits in terms of storage capacity, kinetics and, most importantly, safety. The fervor among the research community to develop novel storage materials had, in many instances, the unfortunate consequence of making erroneous, if not wild, claims on the reported storage capacities achievable in such materials, to the extent that the potential viability of emerging materials was difficult to assess. This problem led to a widespread need to establish a capability to accurately and independently assess the storage behavior of a wide array of different classes of solid-state storage materials, employing qualified methods, thus allowing development efforts to focus on those materials that showed the most promise. However, standard guidelines, dedicated facilities, or certification programs specifically aimed at testing and assessing the performance, safety, and life cycle of these emergent materials had not been established. To address the stated need, the Testing Laboratory for Solid-State Hydrogen Storage Technologies was commissioned as a national-level focal point for evaluating new materials emerging from the designated Materials Centers of Excellence (MCoE) according to established and qualified standards. Working with industry, academia, and the U.S. government, SwRI set out to develop an accepted set of evaluation standards and analytical methodologies. Critical measurements of hydrogen sorption properties in the Laboratory have been based on three analytical capabilities: 1) a high-pressure Sievert-type volumetric analyzer, modified to improve low-temperature isothermal analyses of physisorption materials and permit in situ mass spectroscopic analysis of the sample’s gas space; 2) a static, high-pressure thermogravimetric analyzer employing an advanced magnetic suspension electro-balance, glove-box containment, and capillary interface for in situ mass spectroscopic analysis of the sample’s gas space; and 3) a Laser-induced Thermal Desorption Mass Spectrometer (LTDMS) system for high thermal-resolution desorption and mechanistic analyses. The Laboratory has played an important role in down-selecting materials and systems that have emerged from the MCoEs.

08 HYDROGEN↗