اشترك بالحزمة الذهبية واحصل على وصول غير محدود شمرا أكاديميا
تسجيل مستخدم جديدElectrochemistry of thin films with operando grazing incidence X-ray scattering: bypassing electrolyte scattering for high fidelity time resolved studies
284
0
0.0
(
0
)
اسأل ChatGPT حول البحث
ﻻ يوجد ملخص باللغة العربية
Electroactive polymer thin films undergo repeated reversible structural change during operation in electrochemical applications. While synchrotron X-ray scattering is powerful for the characterization of stand-alone and ex-situ organic thin films, in situ structural characterization has been underutilized--in large part due to complications arising from supporting electrolyte scattering. This has greatly hampered the development of application relevant structure property relationships. Therefore, we have developed a new methodology for in situ and operando X-ray characterization that separates the incident and scattered X-ray beam path from the electrolyte. As a proof of concept, we demonstrate the in situ structural changes of weakly-scattering, organic mixed ionic-electronic conductor thin films in an aqueous electrolyte environment, enabling access to previously unexplored changes in the pi-pi peak and diffuse scatter in situ, while capturing the solvent swollen thin film structure which was inaccessible in previous ex situ studies. These in situ measurements improve the sensitivity to structural changes, capturing minute changes not possible ex situ, and have multimodal potential such as combined Raman measurements that also serve to validate the true in situ/operando conditions of the cell. Finally, we examine new directions enabled by this operando cell design and compare state of the art measurements.
قيم البحث
اقرأ أيضاً
We present depth-resolved experimental results on the atomic and electronic structures of the Co-Cr interface on four IrMn/Cr/Co thin films with variable thickness of the Cr layer. Grazing incidence X-ray absorption near edge structure near the Cr K-
edge was used, and an Angstrom resolved depth-profile for this layer was obtained. An interdiffusion between chromium and cobalt layers was observed in all films, being more pronounced for samples with thinner Cr layers, where Cr behaves as an amorphous material. This causes a contraction in coordination distances in Cr near the interface with Co. In this region, a change in the electronic structure of chromiums 3d orbitals is also observed, and it appears that Cr and Co form a covalent bond resulting in a CrCo alloy. Ab initio numerical simulations support such an interpretation of the obtained experimental results.
We have developed an experimental system to simultaneously observe surface structure, morphology, composition, chemical state, and chemical activity for samples in gas phase environments. This is accomplished by simultaneously measuring X-ray photoel
ectron spectroscopy (XPS) and grazing incidence X-ray scattering (GIXS) in gas pressures as high as the multi-Torr regime, while also recording mass spectrometry. Scattering patterns reflect near-surface sample structures from the nano- to the meso-scale. The grazing incidence geometry provides tunable depth sensitivity while scattered X-rays are detected across a broad range of angles using a newly designed pivoting-UHV-manipulator for detector positioning. At the same time, XPS and mass spectrometry can be measured, all from the same sample spot and in ambient conditions. To demonstrate the capabilities of this system, we measured the chemical state, composition, and structure of Ag-behenate on a Si(001) wafer in vacuum and in O$_2$ atmosphere at various temperatures. These simultaneous structural, chemical, and gas phase product probes enable detailed insights into the interplay between structure and chemical state for samples in gas phase environments. The compact size of our pivoting-UHV-manipulator makes it possible to retrofit this technique into existing spectroscopic instruments installed at synchrotron beamlines. Because many synchrotron facilities are planning or undergoing upgrades to diffraction limited storage rings with transversely coherent beams, a newly emerging set of coherent X-ray scattering experiments can greatly benefit from the concepts we present here.
Non-destructive determination of lithium distribution in a working battery is key for addressing both efficiency and safety issues. Although various techniques have been developed to map the lithium distribution in electrodes, these methods are mostl
y applicable to test cells. Here we propose the use of high-energy x-ray Compton scattering spectroscopy to measure the local lithium concentration in closed electrochemical cells. A combination of experimental measurements and parallel first-principles computations is used to show that the shape parameter S of the Compton profile is linearly proportional to lithium concentration and thus provides a viable descriptor for this important quantity. The merits and applicability of our method are demonstrated with illustrative examples of LixMn2O4 cathodes and a working commercial lithium coin battery CR2032.
Grazing incidence x-ray surface scattering has been used to investigate liquid surfaces down to the molecular scale. The free surface of water is well described by the capillary wave model (<z(q)z(-q)> ~ q-2 spectrum) up to wavevectors > 10^8 m^-1. A
t larger wavevectors near-surface acoustic waves must be taken into account. When the interface is bounded by a surfactant monolayer, it exhibits a bending stiffness and the bending rigidity modulus can be measured. However, bending effects generally cannot be described using the Helfrich Hamiltonian and the characteristic exponent in the roughness power spectrum can smaller than 4. Finally, upon compression, tethered monolayers formed on a subphase containing divalent ions are shown to buckle in the third dimension with a characteristic wavelength on the order of 10^8 m^-1.
Observing ultrafast structural changes in nanoscale systems is essential for understanding the dynamics of intense light-matter interactions, which play a pivotal role in material processing, ultrafast phase transitions and diagnosis of matter under
extreme conditions. One of the most relevant applications of femtosecond laser plasma interactions is laser machining and surface structuring. For laser intensities on the order of $10^{14} , rm W/cm^2$, collisional plasmas are generated at the surface and subsequent transport processes such as electron-ion thermalization, melting and resolidification occur at picosecond and nanosecond time scales. Experimental techniques with nanometer spatial and femtosecond temporal resolution are required to test physical models and obtain quantitative measurements of the subsurface plasma dynamics. Here, we demonstrate grazing-incidence small-angle x-ray scattering (GISAXS) using x-ray free electron laser (XFEL) pulses allowing the in situ visualization of subsurface plasma dynamics with nanometer depth resolution. We measure the surface ablation and plasma density perturbation of multilayer samples following the femtosecond laser pulse interaction. This new methodology opens new possibilities for accurate characterization of subsurface dynamics in various applications of high-intensity laser-solid interactions including laser ablation, creation of warm dense matter, dynamic compression, and relativistic laser plasmas.
سجل دخول لتتمكن من نشر تعليقات
التعليقات
جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
