Targeting the Right Metrics for an Efficient Solvent-Free Formulation of PEO:LiTFSI:Li6PS5Cl Hybrid Solid Electrolyte.

Hybrid solid electrolytes (HSEs) aim to combine the superior ionic conductivity of inorganic fillers with the scalable process of polymer electrolytes in a unique material for solid-state batteries. Pursuing the goal of optimizing the key metrics (σion ≥ 10-4 S·cm-1 at 25 °C and self-standing property), we successfully developed an HSE based on a modified poly(ethylene oxide):LiTFSI organic matrix, which binds together a high loading (75 wt %) of Li6PS5Cl particles, following a solvent-free route. A rational study of available formulation parameters has enabled us to understand the role of each component in conductivity, mixing, and mechanical cohesion. Especially, the type of activation mechanism (Arrhenius or Vogel-Fulcher-Tammann (VFT)) and its associated energy are proposed as a new metric to unravel the ionic pathway inside the HSE. We showed that a polymer-in-ceramic approach is mandatory to obtain enhanced conduction through the HSE ceramic network, as well as superior mechanical properties, revealed by the tensile test. Probing the compatibility of phases, using electrochemical impedance spectroscopy (EIS) alongside 7Li nuclear magnetic resonance (NMR), reveals the formation of an interphase, the quantity and resistivity of which grow with time and temperature. Finally, electrochemical performances are evaluated by assembling an HSE-based battery, which displays comparable stability as pure ceramic ones but still suffers from higher polarization and thus lower capacity. Altogether, we hope these findings provide valuable knowledge to develop a successful HSE, by placing the optimization of the right metrics at the core of the formulation.

Electrochemical Assessment of Indigo Carmine Dye in Lithium Metal Polymer Technology.

Lithium metal batteries are inspiring renewed interest in the battery community because the most advanced designs of Li-ion batteries could be on the verge of reaching their theoretical specific energy density values. Among the investigated alternative technologies for electrochemical storage, the all-solid-state Li battery concept based on the implementation of dry solid polymer electrolytes appears as a mature technology not only to power full electric vehicles but also to provide solutions for stationary storage applications. With an effective marketing started in 2011, BlueSolutions keeps developing further the so-called lithium metal polymer batteries based on this technology. The present study reports the electrochemical performance of such Li metal batteries involving indigo carmine, a cheap and renewable electroactive non-soluble organic salt, at the positive electrode. Our results demonstrate that this active material was able to reversibly insert two Li at an average potential of ≈2.4 V vs. Li+/Li with however, a relatively poor stability upon cycling. Post-mortem analyses revealed the poisoning of the Li electrode by Na upon ion exchange reaction between the Na countercations of indigo carmine and the conducting salt. The use of thinner positive electrodes led to much better capacity retention while enabling the identification of two successive one-electron plateaus.

Detection of defects in a 2D fluid-solid periodic cluster.

The present work deals with locating a defect buried in a medium composed of a fluid matrix and small solid inhomogeneities. Classical imaging methods are based on delay and sum principle and would implicitly assume that the undamaged medium is homogeneous. The topological imaging framework however allows to take into account the heterogeneous nature of the undamaged medium and potentially to take advantage of it. In this work, it is applied to a demanding test case with different assumptions on the knowledge of the medium properties using a specifically-designed fluid-solid compatible imaging function. It leads to the definition of three imaging processes whose results are compared using respectively synthetic and experimental data. The results show the relevance of using the inhomogeneities' locations information, but not necessarily at all steps of the imaging process, leading to the definition of so called hybrid topological imaging method.

Quantification of the Local Topological Variations of Stripped and Plated Lithium Metal by X-ray Tomography.

Lithium (Li) metal is the most promising negative electrode to be implemented in batteries for stationary and electric vehicle applications. For years, its use and subsequent industrialization were hampered because of the inhomogeneous Li+ ion reduction upon recharge onto Li metal leading to dendrite growth. The use of solid polymer electrolyte is a solution to mitigate dendrite growth. Li reduction leads typically to dense Li deposits, but the Li stripping and plating process remain nonuniform with local current heterogeneities. A precise characterization of the behavior of these heterogeneities during cycling is then essential to move toward an optimized negative electrode. In this work, we have developed a characterization method based on X-ray tomography applied to model Li symmetric cells to quantify and spatially probe the Li stripping/plating processes. Ante- and post-mortem cells are recut in smaller cells to allow a 1 µm voxel size resolution in a conventional laboratory scanner. The reconstructed cell volume is postprocessed to numerically reflatten the Li electrodes, allowing us a subsequent precise measurement of the electrode and electrolyte thicknesses and revealing local interface modifications. This in-depth analysis brings information about the location of heterogeneities and their impact on the electrode microstructure at both the electrode grains and grain boundaries. We show that the plating process (reduction) induces more pronounced heterogeneities compared to the stripping (oxidation) one. The existence of crosstalking between the electrodes is also highlighted. In addition, this simple methodology permits to finely retrieve and then surface map the local current density at both electrodes based on the local thickness change during the redox process.

Thermomechanical Polymer Binder Reactivity with Positive Active Materials for Li Metal Polymer and Li-Ion Batteries: An XPS and XPS Imaging Study.

The lithium and lithium-ion battery electrode chemical stability in the pristine state has rarely been considered as a function of the binder choice and the electrode processing. In this work, X-ray photoelectron spectroscopy (XPS) and XPS imaging analyses associated with complementary Mössbauer spectroscopy are used in order to study the chemical stability of two pristine positive electrodes: (i) an extruded LiFePO4-based electrode formulated with different polymer matrices [polyethylene oxide and a polyvinylidene difluoride (PVdF)] and processed at different temperatures (90 and 130 °C, respectively) and (ii) a Li[Ni0.5Mn0.3Co0.2]O2 (NMC)-based electrode processed by tape-casting, followed by a mild or heavy calendering treatment. These analyses have allowed the identification of reactivity mechanisms at the interface of the active material and the polymer in the case of PVdF-based electrodes.

Transient 3D elastodynamic field in an embedded multilayered anisotropic plate.

The aim of this paper is to study the ultrasonic response to a transient source that radiates ultrasonic waves in a 3D embedded multilayered anisotropic and dissipative plate. The source can be inside the plate or outside, in a fluid loading the plate for example. In the context of Non-Destructive Testing applied to composite materials, our goal is to create a robust algorithm to calculate ultrasonic field, irrespective of the source and receiver positions. The principle of the method described in this paper is well-established. This method is based on time analysis using the Laplace transform. In the present work, it has been customized for computing ultrasonic source interactions with multilayered dissipative anisotropic plates. The fields are transformed in the 2D Fourier wave-vector domain for the space variables related to the plate surface, and they are expressed in the partial-wave basis. Surprisingly, this method has been very little used in the ultrasonic community, while it is a useful tool which complements the much used technique based on generalized Lamb wave decomposition. By avoiding mode analysis - which can be problematic in some cases - exact numerical calculations (i.e., approximations by truncating infinite series that may be poorly convergent are not needed) can be made in a relatively short time for immersed plates and viscoelastic layers. Even for 3D cases, numerical costs are relatively low. Special attention is given to separate up- and down-going waves, which is a simple matter when using the Laplace transform. Numerical results show the effectiveness of this method. Three examples are presented here to investigate the quality of the model and the robustness of the algorithm: first, a comparison of experiment and simulation for a monolayer carbon-epoxy plate, where the diffracted field is due to a source located on the first free surface of the sample, for both dissipative and non-dissipative cases; second, the basic configuration of an aluminum plate immersed in water has been chosen to study wave propagation in ZGV (Zero Group Velocity) conditions; finally, a 2D plate consisting of 8 stacked carbon-epoxy layers immersed in water is treated, with a source located inside the plate, distributed in depth and extending over four layers.

Ultrasonic transient bounded-beam propagation in a solid cylinder waveguide embedded in a solid medium.

A semianalytical solution alternative and complementary to modal technique is presented to predict and interpret the ultrasonic pulsed-bounded-beam propagation in a solid cylinder embedded in a solid matrix. The spectral response to an inside axisymmetric velocity source of longitudinal and transversal cylindrical waves is derived from Debye series expansion of the embedded cylinder generalized cylindrical reflection/transmission coefficients. So, the transient guided wave response, synthesized by inverse double Fourier-Bessel transform, is expressed as a combination of the infinite medium contribution, longitudinal, transversal, and coupled longitudinal and transversal waveguide sidewall interactions. Simulated (f, 1/lambdaz) diagrams show the influence of the number of waveguide sidewall interactions to progressively recover dispersion curves. Besides, they show the embedding material filters specific signal portions by concentrating the propagating signal in regions where phase velocity is closer to phase velocity in steel. Then, simulated time waveforms using broadband high-frequency excitation show that signal leading portions exhibit a similar periodical pattern, for both free and embedded waveguides. Debye series-based interpretation shows that double longitudinal/transversal and transversal/longitudinal conversions govern the time waveform leading portion as well as the radiation attenuation in the surrounding cement grout. Finally, a methodology is deduced to minimize the radiation attenuation for the long-range inspection of embedded cylinders.