Lithium-ion batteries have revolutionized portable electronics and will be a key to electrifying transport vehicles and delivering renewable electricity. Amorphous silicon (a-Si) is being intensively studied as a high-capacity anode material for next-generation lithium-ion batteries. Its lithiation has been widely thought to occur through a single-phase mechanism with gentle Li profiles, thus offering a significant potential for mitigating pulverization and capacity fade. Here, we discover a surprising two-phase process of electrochemical lithiation in a-Si by using in situ transmission electron microscopy. The lithiation occurs by the movement of a sharp phase boundary between the a-Si reactant and an amorphous Li(x)Si (a-Li(x)Si, x ~ 2.5) product. Such a striking amorphous-amorphous interface exists until the remaining a-Si is consumed. Then a second step of lithiation sets in without a visible interface, resulting in the final product of a-Li(x)Si (x ~ 3.75). We show that the two-phase lithiation can be the fundamental mechanism underpinning the anomalous morphological change of microfabricated a-Si electrodes, i.e., from a disk shape to a dome shape. Our results represent a significant step toward the understanding of the electrochemically driven reaction and degradation in amorphous materials, which is critical to the development of microstructurally stable electrodes for high-performance lithium-ion batteries.
Pump-probe transient thermoreflectance (TTR) techniques are powerful tools for measuring the thermophysical properties of thin films, such as thermal conductivity, Λ, or thermal boundary conductance, G. This paper examines the assumption of one-dimensional heating on, Λ and G, determination in nanostructures using a pump-probe transient thermoreflectance technique. The traditionally used one-dimensional and axially symmetric cylindrical conduction models for thermal transport are reviewed. To test the assumptions of the thermal models, experimental data from Al films on bulk substrates (Si and glass) are taken with the TTR technique. This analysis is extended to thin film multilayer structures. The results show that at 11 MHz modulation frequency, thermal transport is indeed one dimensional. Error among the various models arises due to pulse accumulation and not accounting for residual heating.
Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm(2) leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. The effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. We discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.
Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. Here, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge-discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed for the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Our results show that electrochemically induced solid-solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.
Lignin is a high-volume byproduct from the pulp and paper industry and is currently burned to generate electricity and process heat. The industry has been searching for high value-added uses of lignin to improve the process economics. In addition, battery manufacturers are seeking nonfossil sources of graphitic carbon for environmental sustainability. In this work, lignin (which is a cross-linked polymer of phenols, a component of biomass) is converted into graphitic porous carbon using a two-step conversion. Lignin is first carbonized in water at 300 °C and 1500 psi to produce biochar, which is then graphitized using a metal nitrate catalyst at 900–1100 °C in an inert gas at 15 psi. Graphitization effectiveness of three different catalystsiron, cobalt, and manganese nitratesis examined. The product is analyzed for morphology, thermal stability, surface properties, and electrical conductivity. Both temperature and catalyst type influenced the degree of graphitization. A good quality graphitic carbon was obtained using catalysis by Mn(NO3)2 at 900 °C and Co(NO3)2 at 1100 °C.
Terahertz (THz) photoconductive devices are used for generation, detection and modulation of THz waves, and they rely on the ability to switch electrical conductivity on a subpicosecond time scale using optical pulses. However, fast and efficient conductivity switching with high contrast has been a challenge, because the majority of photoexcited charge carriers in the switch do not contribute to the photocurrent due to fast recombination. Here, we improve efficiency of electrical conductivity switching using a network of electrically connected nano-scale GaAs resonators, which form a perfectly-absorbing photoconductive metasurface. We achieve perfect absorption without incorporating metallic elements, by breaking the symmetry of cubic Mie resonators. As a result, the metasurface can be switched between conductive and resistive states with extremely high contrast using an unprecedentedly low level of optical excitation. We integrate this metasurface with a THz antenna to produce an efficient photoconductive THz detector. The perfectly-absorbing photoconductive metasurface opens paths for developing a wide range of efficient optoelectronic devices, where required optical and electronic properties are achieved through nanostructuring the resonator network.
A hot wire probe has been developed for use inside a transmission electron microscope to measure the thermal resistance of individual nanowires, nanotubes, and their contacts. No microfabrication is involved. The probe is made from a platinum Wollaston wire and is pretensioned to minimize the effects of thermal expansion, intrinsic thermal vibrations, and Lorentz forces. An in situ nanomanipulator is used to select a particular nanowire or nanotube for measurement, and contacts are made with liquid metal droplets or by electron-beam induced deposition. Detailed thermal analysis shows that for best sensitivity, the thermal resistance of the hot-wire probe should be four times that of the sample, but a mismatch of more than two orders of magnitude may be acceptable. Data analysis using the ratio of two ac signals reduces the experimental uncertainty. The range of detectable sample thermal resistances spans from approximately 10(3) to 10(9) KW. The probe can also be adapted for measurements of the electrical conductance and Seebeck coefficient of the same sample. The probe was used to study a multiwalled carbon nanotube with liquid Ga contacts. The measured thermal resistance of 3.3 x 10(7) KW had a noise level of approximately +/-3% and was repeatable to within +/-10% upon breaking and re-making the contact.
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