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Recently, the formation of the ceramic-ionic liquid composite has attracted huge interest in the scientific community. In this work, we investigated the chemical reactions occurring between NASICON LAGP ceramic electrolyte and ionic liquid pyr13TFSI. This study allowed us to identify the cation exchange reaction pyr13-Li occurring on the LAGP surface, forming a LiTFSI salt that was detected by the nuclear magnetic resonance analysis. In addition, using 6Li foils, we succeeded in demonstrating that both LAGP and LiTFSI:pyr13TFSI participate in the diffusion of Li ions by the formation of an ionic bridge between two species.
Assuntos
Líquidos Iônicos , Cátions , Eletrólitos , LítioRESUMO
Li-10 wt % Mg alloy (Li-10 Mg) is used as an anode material for a solid-state battery with excellent electrochemical performance and no evidence of dendrite formation during cycling. Thermal treatment of Li metal during manufacturing improves the interfacial contact between a Li metal electrode and solid electrolyte to achieve an all solid-state battery with increased performance. To understand the properties of the alloy passivation layer, this paper presents the first direct observation of its evolution at elevated temperatures (up to 325°C) by in situ scanning electron microscopy. We found that the morphology of the surface passivation layer was unchanged above the alloy melting point, while the bulk of the material below the surface was melted at the expected melting point, as confirmed by in situ electron backscatter diffraction. In situ heat treatment of Li-based materials could be a key method to improve battery performance.
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A LiCoPO4-based high-voltage lithium-ion battery was fabricated in the format of a 1.2 Ah pouch cell that exhibited a highly stable cycle life at a cut-off voltage of 4.9 V. The high-voltage stability was achieved using a Fe-Cr-Si multi-ion-substituted LiCoPO4 cathode and lithium bis(fluorosulfonyl)imide in 1-methyl-1-propylpyrrolidinium bis(fluorosulfony)imide as the electrolyte. Due to the improved electrochemical stability at high voltage, the cell exhibited a stable capacity retention of 91% after 290 cycles without any gas evolution related to electrolyte decomposition at high voltage. In addition to improved cycling stability, the nominal 5 V LiCoPO4 pouch cell also exhibited excellent safety performance during a nail penetration safety test compared with a state-of-the-art lithium ion battery. Meanwhile, the thermal stabilities of the 1.2 Ah pouch cell as well as the delithiated LiCoPO4 were also studied by accelerating rate calorimetry (ARC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and in situ X-ray diffraction (XRD) analyses and reported.
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Dendrite formation, which could cause a battery short circuit, occurs in batteries that contain lithium metal anodes. In order to suppress dendrite growth, the use of electrolytes with a high shear modulus is suggested as an ionic conductive separator in batteries. One promising candidate for this application is Li7La3Zr2O12 (LLZO) because it has excellent mechanical properties and chemical stability. In this work, in situ scanning electron microscopy (SEM) technique was employed to monitor the interface behavior between lithium metal and LLZO electrolyte during cycling with pressure. Using the obtained SEM images, videos were created that show the inhomogeneous dissolution and deposition of lithium, which induce dendrite growth. The energy dispersive spectroscopy analyses of dendrites indicate the presence of Li, C, and O elements. Moreover, the cross-section mapping comparison of the LLZO shows the inhomogeneous distribution of La, Zr, and C after cycling that was caused by lithium loss near the Li electrode and possible side reactions. This work demonstrates the morphological and chemical evolution that occurs during cycling in a symmetrical Li-Li cell that contains LLZO. Although the superior mechanical properties of LLZO make it an excellent electrolyte candidate for batteries, the further improvement of the electrochemical stabilization of the garnet-lithium metal interface is suggested.
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Current quantitative X-ray microanalysis methods are only available for homogeneous materials. This paper presents a newly developed inverse modeling algorithm to determine both the structure and composition of two-dimensional (2D) heterogeneous materials from a series of X-ray intensity measurements under different beam energies and beam positions. It utilizes an iterative process of forward modeling to determine the optimal specimen to minimize the relative differences between the simulated and experimental characteristic X-ray intensities. The Monte Carlo method is used for the forward modeling to predict the X-ray radiation for a given specimen and experimental setup. Several examples of applications are presented for different types of samples with one-dimensional (1D) and 2D structures, in which the simulated X-ray intensities from phantom samples are used as input. Most of the results obtained from our algorithm agree well with the phantom samples. Some discrepancies are found for the voxels located at deeper depths of the 2D samples. And the discrepancies may be attributed to errors from the Monte Carlo simulations and from the variation of the X-ray range with beam energy. As a proof-of-concept work, this paper confirms the feasibility of our inverse modeling algorithm applied to 2D heterogeneous materials.
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In electron probe microanalysis or scanning electron microscopy, the Monte Carlo method is widely used for modeling electron transport within specimens and calculating X-ray spectra. For an accurate simulation, the calculation of secondary fluorescence (SF) is necessary, especially for samples with complex geometries. In this study, we developed a program, using a hybrid model that combines the Monte Carlo simulation with an analytical model, to perform SF correction for three-dimensional (3D) heterogeneous materials. The Monte Carlo simulation is performed using MC X-ray, a Monte Carlo program, to obtain the 3D primary X-ray distribution, which becomes the input of the analytical model. The voxel-based calculation of MC X-ray enables the model to be applicable to arbitrary samples. We demonstrate the derivation of the analytical model in detail and present the 3D X-ray distributions for both primary and secondary fluorescence to illustrate the capability of our program. Examples for non-diffusion couples and spherical inclusions inside matrices are shown. The results of our program are compared with experimental data from references and with results from other Monte Carlo codes. They are found to be in good agreement.
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Accurate elemental quantification of materials by X-ray detection techniques in electron microscopes or microprobes can only be carried out if the appropriate mass absorption coefficients (MACs) are known. With continuous advancements in experimental techniques, databases of MACs must be expanded in order to account for new detection limits. Soft X-ray emission spectroscopy (SXES) is a characterization technique that can detect emitted X-rays whose energies are in the range of 10 eV to 2 keV by using a varied-line-spaced grating. Transitions producing soft X-rays can be detected and accurate MACs are required for use in quantification. This work uses Monte Carlo modeling coupled with multivoltage SXES measurements in an electron probe micro-analyzer (EPMA) to compute MACs for the L2,3-M and Li Kα transitions in a variety of aluminum alloys. Electron depth distribution curves obtained by the software MC X-ray are used in a parametrized fitting equation. The MACs are calculated using a least-squares regression analysis. It is shown that X-ray distribution cross-sections at such low energies need to take into account additional contributions, such as CosterKronig transitions, Auger yields, and wave function effects in order to be accurate.
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We present the first results of in situ scanning electron microscopy (SEM) of an all-solid Li battery with a nickel-manganese-cobalt-oxide (NMC-622) cathode at 50 °C and an operating voltage of 2.7-4.3 V. Experiments were conducted under a constant current at several C rates (nC rate: cycling in 1/n h): C/12, C/6, and C/3. The microstructure evolution during cycling was monitored by continuous secondary electron imaging. We found that the chemical degradation of the solid polymer electrolyte (SPE) was the main mechanism for battery failure. This degradation was observed in the form of a gradual thinning of the SPE as a function of cycling time, resulting in gas generation from the cell. We also present various dynamic electrochemical and mechanical phenomena, as observed by SEM images, and compare the performance of this battery with that of an all-solid Li battery with a LiFePO4 cathode.
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A technique to characterize the native passivation layer (NPL) on pure lithium metal foils in a scanning electron microscope (SEM) is described in this paper. Lithium is a very reactive metal, and consequently, observing and quantifying its properties in a SEM is often compromised by rapid oxidation. In this work, a pure lithium energy-dispersive x-ray spectrum is obtained for the first time in a high vacuum SEM using a cold stage/cold trap with liquid nitrogen reservoir outside the SEM chamber. A nanomanipulator (OmniProbe 400) inside the microscope combined with x-ray microanalysis and windowless energy dispersive spectrometer is used to fully characterize the NPL of lithium metal and some of its alloys by a mechanical removal procedure. The results show that the native films of pure lithium and its alloys are composed of a thin (25 nm) outer layer that is carbon-rich and an inner layer containing a significant amount of oxygen. Differences in thickness between laminated and extruded samples are observed and vary depending on the alloy composition.
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Due to recent advances in modeling the production of characteristic X-rays, Monte Carlo simulation of electron-solid interactions can provide improved quantitative estimates of X-ray intensities for both homogeneous and heterogeneous interaction volumes. In the case of homogeneous materials, these modeled X-ray intensities can predict with excellent accuracy, matrix corrections for arbitrary compositions, arbitrary emission lines, and electron energies. By pre-calculating these Monte Carlo X-ray intensities for pure element standards and a range of compositions of binary systems, we can derive matrix corrections for complex compositions in real-time by parameterizing these k-ratios as the so-called alpha factors. This method allows one to perform Monte Carlo-based bulk matrix corrections in seconds for arbitrary and complex compositions (with two or more elements), by combining these binary alpha factors using the so-called beta expression. We are systematically calculating X-ray intensities for 11 compositions from 1 to 99 wt% for binary pairs of all emitters and absorbers in the periodic table, for the main emission lines (Kα, Kß, Lα, Lß, Mα, and Mß) at beam energies from 5 to 50 keV, using Monte Carlo calculations based on a modified PENELOPE electron-photon transport code, although any other Monte Carlo software could also be utilized. Comparison of k-ratios calculated with the proposed method and experimental k-ratios from the Pouchou and Pichoir database suggest improvements over typical φ(ρz) methods. Additional comparisons with k-ratio measurements from more complex compositions would be ideal, but our testing of the additivity of the beta equation suggests that arbitrary compositions can be handled as well, except in cases of extreme fluorescence or absorption.
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Secondary fluorescence effects are important sources of characteristic X-ray emissions, especially for materials with complicated geometries. Currently, three approaches are used to calculate fluorescence X-ray intensities. One is using Monte Carlo simulations, which are accurate but have drawbacks such as long computation times. The second one is to use analytical models, which are computationally efficient, but limited to specific geometries. The last approach is a hybrid model, which combines Monte Carlo simulations and analytical calculations. In this article, a program is developed by combining Monte Carlo simulations for X-ray depth distributions and an analytical model to calculate the secondary fluorescence. The X-ray depth distribution curves of both the characteristic and bremsstrahlung X-rays obtained from Monte Carlo program MC X-ray allow us to quickly calculate the total fluorescence X-ray intensities. The fluorescence correction program can be applied to both bulk and multilayer materials. Examples for both cases are shown. Simulated results of our program are compared with both experimental data from the literature and simulation data from PENEPMA and DTSA-II. The practical application of the hybrid model is presented by comparing with the complete Monte Carlo program.
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A nanolayer of reactive propyl acrylate silane groups was deposited on a lithium surface by using a simple dipping method. The polymerization of cross-linkable silane groups with a layer of ally-ether-ramified polyethylene oxide was induced by UV light. SEM analysis revealed a good dispersion of silane groups grafted on the lithium surface and a layer of polymer of about 4â µm was obtained after casting and reticulation. The electrochemical performance for the unmodified and modified lithium electrodes were compared in symmetrical Li/LLZO/Li cells. Stable plating/stripping and low interfacial resistance were obtained when the modified lithium was utilized, indicating that the combination of silane and polymer deposition is promising to increase Li-metal/garnet contact.
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The f-ratio quantitative X-ray microanalysis method has been recently developed for binary systems based on a scanning electron microscope/energy dispersive spectroscopy (SEM/EDS) system. This method incorporates traditional EDS experiments and Monte Carlo simulations, and calibration factors are calculated with standard samples to evaluate the differences between them. In this work, the f-ratio method was extended to Mg-Al-Zn multi-element systems using a cold field emission SEM and a tungsten emission SEM. Results show that the stability of the beam current does not influence the f-ratio quantification accuracy. Thus, the f-ratio method is suitable for quantitative X-ray mapping with a long-time acquisition or even an unstable beam current. Comparing with other quantitative techniques including the routine standardless analysis and the standard-based k-ratio method, the f-ratio method is a simple and accurate quantification method.
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A commercial electron energy-loss spectrometer (EELS) attached to a high-resolution cold-field emission scanning electron microscope in transmission mode (STEM) is evaluated and its potential for characterizing materials science thin specimens at low accelerating voltage is reviewed. Despite the increased beam radiation damage at SEM voltages on sensitive compounds, we describe some potential applications which benefit from lowering the primary electrons voltage on less-sensitive specimens. We report bandgap measurements on several dielectrics which were facilitated by the lack of Cherenkov radiation losses at 30â¯kV. The possibility of volume plasmon imaging to probe local composition changes in complex materials was demonstrated using energy-filtered STEM, either via spectrum imaging or elemental mapping using the "three-windows" method. As plasmonic materials are increasing used for energy, electronics or biomedical applications, the ability of reliably evaluate their properties at low accelerating voltage in a SEM is very appealing and is demonstrated. The energy resolution of the spectrometer, taken as the full width at half maximum of the zero-loss peak, was routinely measured at around 0.55â¯eV and it is demonstrated that t/λ ratios up to 1.5 allowed practical EEL spectroscopy at 30â¯kV.
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Li metal batteries suffer from dendrite formation which causes short circuit of the battery. Therefore, it is important to understand the chemical composition and growth mechanism of dendrites that limit battery efficiency and cycle life. In this study, in situ scanning electron microscopy was employed to monitor the cycling behavior of all-solid Li metal batteries with LiFePO4 cathodes. Chemical analyses of the dendrites were conducted using a windowless energy dispersive spectroscopy detector, which showed that the dendrites are not metallic lithium as universally recognized. Our results revealed the carbide nature of the dendrites with a hollow morphology and hardness greater than that of pure lithium. These carbide-based dendrites were able to perforate through the polymer, which was confirmed by milling the polymer using focused ion beam. It was also shown that applying pressure on the battery can suppress growth of the dendrites.
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A number of techniques for the characterization of rare earth minerals (REM) have been developed and are widely applied in the mining industry. However, most of them are limited to a global analysis due to their low spatial resolution. In this work, phase map analyses were performed on REM with an annular silicon drift detector (aSDD) attached to a field emission scanning electron microscope. The optimal conditions for the aSDD were explored, and the high-resolution phase maps generated at a low accelerating voltage identify phases at the micron scale. In comparisons between an annular and a conventional SDD, the aSDD performed at optimized conditions, making the phase map a practical solution for choosing an appropriate grinding size, judging the efficiency of different separation processes, and optimizing a REM beneficiation flowsheet.
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The spatial resolution of aberration-corrected annular dark field scanning transmission electron microscopy was studied as function of the vertical position z within a sample. The samples consisted of gold nanoparticles (AuNPs) positioned in different horizontal layers within aluminum matrices of 0.6 and 1.0 µm thickness. The highest resolution was achieved in the top layer, whereas the resolution was reduced by beam broadening for AuNPs deeper in the sample. To examine the influence of the beam broadening, the intensity profiles of line scans over nanoparticles at a certain vertical location were analyzed. The experimental data were compared with Monte Carlo simulations that accurately matched the data. The spatial resolution was also calculated using three different theoretical models of the beam blurring as function of the vertical position within the sample. One model considered beam blurring to occur as a single scattering event but was found to be inaccurate for larger depths of the AuNPs in the sample. Two models were adapted and evaluated that include estimates for multiple scattering, and these described the data with sufficient accuracy to be able to predict the resolution. The beam broadening depended on z 1.5 in all three models.
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Lithium is the key element for the development of battery and new technology and the development of an analytical technique to spatially and quantitatively resolve this element is of key importance. Detection of Li K in pure metallic lithium is now possible in the Scanning Electron Microscope (SEM) with newly designed Energy Dispersive Spectroscopy (EDS). However, this work is clearly showing, for the first time using EDS, the detection of Li K in several binary lithium compounds (LiH, Li3 N, Li2 S, LiF and LiCl). Experimental Li K X-rays intensity is compared with a specially modified Monte Carlo simulation program showing discrepancies between theoretical and experimental Li K measurements. The effect of chemical bounding on the X-rays emission using density functional theory with the all-electron linearized augmented plane wave is showing that the emission of Li K from the binary compounds studied should be, at least, 12 times lower than in metallic Li. SCANNING 38:571-578, 2016. © 2016 Wiley Periodicals, Inc.
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Dark-field (DF) images were acquired in the scanning electron microscope with an offline procedure based on electron backscatter diffraction (EBSD) patterns (EBSPs). These EBSD-DF images were generated by selecting a particular reflection on the electron backscatter diffraction pattern and by reporting the intensity of one or several pixels around this point at each pixel of the EBSD-DF image. Unlike previous studies, the diffraction information of the sample is the basis of the final image contrast with a pixel scale resolution at the EBSP providing DF imaging in the scanning electron microscope. The offline facility of this technique permits the selection of any diffraction condition available in the diffraction pattern and displaying the corresponding image. The high number of diffraction-based images available allows a better monitoring of deformation structures compared to electron channeling contrast imaging (ECCI) which is generally limited to a few images of the same area. This technique was applied to steel and iron specimens and showed its high capability in describing more rigorously the deformation structures around micro-hardness indents. Due to the offline relation between the reference EBSP and the EBSD-DF images, this new technique will undoubtedly greatly improve our knowledge of deformation mechanism and help to improve our understanding of the ECCI contrast mechanisms.