Charge/discharge cycling of Li1+x(Ni0.6Co0.2Mn0.2)1−xO2 primary particles performed in a liquid microcell for transmission electron microscopy studies

Robin Pierre Alain Girod, Jing Hou, Tzu-Hsien Shen, Vasiliki Tileli
2020
Article

Résumé

Ni-rich layered oxides are promising positive electrodes for fulfillment of government and industry targets for lithium-ion-battery-operated electric mobility purposes. Apart from ongoing research focusing on their design and material production, advanced characterization techniques can provide valuable insights on their stabilization by monitoring in situ the degradation mechanisms. Herein, we use liquid-phase transmission electron microscopy to examine the effects of electrochemical stimuli on Ni-rich oxide cathodes by introducing an optimized micro-scale battery configuration. Ball-milled Li1+x(Ni0.6Co0.2Mn0.2)1−xO2 (NCM622) particles were cycled against a delithiated LiFePO4 anode and the effects of different cycling methods were investigated. We show that commonly used cyclic voltammetry measurements at high scan rates cannot be used to simulate battery operation in situ due to geometry limitations of the cell that inhibits Li ion transport. However, using galvanostatic charge/discharge cycling and introducing a pause every 10 cycles for a total of 50 cycles results in degradation in the form of Mn and Co ion dissolution from the first 20 nm of the surface. Our results suggest that although performing battery cycling using liquid cell electron microscopy may differ from the case of coin cells, by tuning the electrochemical profiles used similar degradation mechanisms can be attained.

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https://infoscience.epfl.ch/record/279307?ln=fr

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Robin Pierre Alain Girod, Jing Hou, Tzu-Hsien Shen, Vasiliki Tileli
2020
Article

Résumé

Official source

https://infoscience.epfl.ch/record/279307?ln=fr

À propos de ce résultat

Concepts associés (13)

Concepts associés

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Publications associées (16)

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Etude par microscopie électronique de particules nanostructurées d'oxalate de cobalt précipitées en milieu aqueux

The understanding of material self-assembling and self-organization mechanisms, at mesoscale, is crucial for nanotechnologies development. Such structures, hierarchically organized in superlattices or colloïdal crystals, are observed in inorganic or organo-metallic precipitates. The classical characterization, using electron microscopy and X-ray diffraction, of a synthesized powder is inadequate to describe the hierarchically organized polycrystalline structure of the final particles. Here, we have highlighted the successive steps that lead to the spontaneous formation of a cobalt oxalate dihydrate (COD) colloïdal crystals that precipitate in aqueous media. The characterization of the final particles, made by X-ray and electronic diffraction, has allowed us to determine the controversial crystalline phase of the precipitated COD. The β and γ COD phases has been discriminated by comparing experimental results with simulations of X-ray diffractogram and electron diffraction patterns for these both structures. The precipitated COD corresponds to the γ phase indicating that it comes from solid dehydration of cobalt oxalate tetrahydrate. The final powder characterization, performed by X-ray diffraction (XRD), atomic force microscopy (AFM), low voltage high resolution scanning electron microscopy (LVHRSEM) and transmission electron microscopy (TEM), gives some diverging results about monocrystalline or polycrystalline nature of the precipitates. XRD and AFM analysis show a polycrystalline structure of particles whereas LVHRSEM, TEM and electron diffraction observations indicate a monocrystalline structure. This apparent contradiction has led us to elaborate a new characterization method allowing to follow the growth and the structural evolution of the precipitate as a function of time. The cryo- preparation techniques are well adapted as they allow freezing and direct observation of solid state suspension by electron microscopy. The freeze/drying method has been modified and used for both SEM and TEM, and has allowed us to study the morphological and structural evolution of the COD precipitate from nanoscale to mesoscale. In addition, TEM analysis of samples prepared by classical techniques has been performed to complement cryo-electron microscopy observations. The combination of these two methods show that COD precipitation is a complex multi-step process leading to the formation of a core/shell heterostructure. The anisotropic core is porous and partially crystalline. It is formed by agglomeration of isolated primary particles and agregated ones (15-20 nm sized secondary particles). The crystalline shell corresponds to the final particles faces and is made up by the layer by layer self-assembling and alignment of 5-7 nm sized crystalline primary particles. These nanoparticles are aligned and perfectly ordered in strings of nanograins in the layer structure. The self-assembling occurs in the last step of growth where we have a lower ionic strength and supersaturation inducing slower kinetics of growth and aggregation. Moreover, the crystalline order in the primary and secondary particles increase with the time of reaction consistent with a continuous process of primary particle nucleation and growth. Our results show that self-assembling occurs layer by layer with terraces, kinks and steps that are present on the faces. This reminds the layer by layer crystalline growth models but in this case, the buiding blocks are colloïdal instead of atomic or molecular. Based on these different results, we propose an original model describing the COD precipitate growth. In addition, we have studied the poly(methacrylic acid-sodium salt) effect on the COD precipitation. This additive (PMMA) appeared to be a very good growth inhibitor. The PMMA effect on the final particles morphology is dramatic. Its concentration variation in solution slows down the nanoparticles aggregation rates along a [101] preferential direction. The crystal habit can then be controlled and we have synthesized platelets, cubes and rods with tailored length. The use of cryogenic electron microscopy has been shown to be a powerful tool for the understanding of time dependent aspects of particle growth. The use of such techniques for the study of other systems, where the final precipitate appearance may hide particle substructures, will help to elucidate growth mechanisms and allow finer control of nanostructured materials for many applications. The complex self-assembling and self-organization processes could then be highlighted and studied on a nanometer to micrometer scale.

EPFL2004

Chargement

Electron microscopy offers a wide range of techniques to study materials. Environmental Scanning Electron Microscopy (ESEM), in particular, allows the characterisation of samples at high-temperature using a laser heating stage, and under various gaseous atmospheres leading to direct observation of the sample surface morphology dynamics in conditions that are close to those in real operating devices (i.e. at high temperature in various gases). Solid Oxide Fuel Cells (SOFC) operating around 800°C in both oxidising and reducing gases, with proven co-generation efficiencies of 90%, offer very promising solutions in the ongoing energy transition. However, production costs and materials degradation in those demanding operating conditions remain significant barriers to their large-scale deployment. Studying SOFC materials' degradation through a combination of ESEM with other advanced microscopy techniques fulfilled the double aim of demonstrating the power of an ESEM and improving the understanding of SOFC materials' degradation during operation. Two materials from the SOFC stack were selected for degradation case studies at around 800°C in oxidising/reducing gases: coated ferritic steel interconnect and Ni-YSZ anode. The objectives were to explore the parameters' influence (temperature, heating ramp, pressure, gas exposure...), set the boundaries and define the guidelines of the ESEM technique while demonstrating its capabilities. The two different materials sets were selected for their relevance both for the SOFC field and for their different specific characteristics allowing a wide range of experiments to be explored. A specific method for the study of the oxidation of coated steel was developed combining ESEM, Focused Ion Beam (FIB) and Scanning Transmission Electron Microscopy (STEM). Post-test segmentation of the in-situ observed images demonstrated the possibility to obtain quantitative data. FIB sample preparation from the exact site of ESEM observation allowed to correlate the underlying microstructure with the in-situ surface observation. Applying this method, oxidation mechanisms of several coatings were characterised and specific behaviours observed and explained such as the appearance of oxide ridges and the behaviour of a cerium barrier layer in case of cobalt-cerium coated steel. The heating ramp speed and the oxidation temperature were demonstrated to be crucial parameters to obtain the desired microstructure. The nitriding pretreatment of interconnect was investigated too and shows promising results for improving the steel oxidation resistance. Another combination of techniques was developed for the study of the Ni-YSZ anode by complementing the ESEM observation with continuous Mass Spectrometer (MS) acquisition. The first reduction of the NiO-YsZ anode was analysed under gas flows of hydrogen and hydrocarbons. Redox cycling effect on the anode microstructure was investigated and the resulting observations were in line with models from the literature for the reduction and re-oxidation kinetics. Finally, the demonstration of an active solid oxide cell in the microscope operating at more than 700°C under mixed gas paves the way to further possible studies approaching the device's observation in real operating conditions. Limitation of the ESEM techniques are discussed and recommendations for further improvements and perspectives given.

EPFL2020

Chargement

Synthesis and Characterization of Amphiphilic Gold Nanoparticles

Urszula Beata Cendrowska, Matteo Gasbarri, Zekiye Pelin Güven, Paulo Henrique Jacob Silva, Samuel Thomas Jones, Zhi Luo, Francesco Stellacci

Gold nanoparticles covered with a mixture of 1-octanethiol (OT) and 11-mercapto-1-undecane sulfonic acid (MUS) have been extensively studied because of their interactions with cell membranes, lipid bilayers, and viruses. The hydrophilic ligands make these particles colloidally stable in aqueous solutions and the combination with hydrophobic ligands creates an amphiphilic particle that can be loaded with hydrophobic drugs, fuse with the lipid membranes, and resist nonspecific protein adsorption. Many of these properties depend on nanoparticle size and the composition of the ligand shell. It is, therefore, crucial to have a reproducible synthetic method and reliable characterization techniques that allow the determination of nanoparticle properties and the ligand shell composition. Here, a one-phase chemical reduction, followed by a thorough purification to synthesize these nanoparticles with diameters below 5 nm, is presented. The ratio between the two ligands on the surface of the nanoparticle can be tuned through their stoichiometric ratio used during synthesis. We demonstrate how various routine techniques, such as transmission electron microscopy (TEM), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), and ultraviolet-visible (UV-Vis) spectrometry, are combined to comprehensively characterize the physicochemical parameters of the nanoparticles.

JOURNAL OF VISUALIZED EXPERIMENTS2019

Chargement

Etude par microscopie électronique de particules nanostructurées d'oxalate de cobalt précipitées en milieu aqueux

EPFL2004

EPFL2020