Project description:Compared with conventional liquid electrolytes, solid electrolytes can better improve the safety properties and achieve high-energy-density Li-ion batteries. Sulfide-based solid electrolytes have attracted significant attention owing to their high ionic conductivities, which are comparable to those of their liquid counterparts. Among them, Li thiophosphates, including Li-argyrodites, are widely studied. In this study, Li thiophosphate solid electrolytes containing BH4 - anions are prepared via a simple and fast milling method even without heat treatment. The synthesized materials exhibit a high ionic conductivity of up to 11 mS cm-1 at 25 °C, which is much higher than reported values. To elucidate the mechanism behind, the thiophosphate local structure, whose effect on the ionic conductivity remains unclear to date, is investigated. Raman and solid-state NMR spectroscopies are performed to identify the thiophosphate local structure in the sulfide samples. Based on the analysis results, the ratios of the different thiophosphate units in the prepared electrolyte samples are determined. It is found that the thiophosphate local structure can be varied by changing the amount of LiBH4 and the milling conditions, which significantly impact the ionic conductivity. The all-solid-state cell with the prepared solid electrolyte exhibits superior cycle and rate performances.
Project description:In graphene nanoribbons (GNRs), the lateral confinement of charge carriers opens a band gap, the key feature that enables novel graphene-based electronics. Despite great progress, reliable and reproducible fabrication of single-ribbon field-effect transistors (FETs) is still a challenge, impeding the understanding of the charge transport. Here, we present reproducible fabrication of armchair GNR-FETs based on networks of nanoribbons and analyze the charge transport mechanism using nine-atom wide and, in particular, five-atom-wide GNRs with large conductivity. We show formation of reliable Ohmic contacts and a yield of functional FETs close to unity by lamination of GNRs to electrodes. Modeling the charge transport in the networks reveals that transport is governed by inter-ribbon hopping mediated by nuclear tunneling, with a hopping length comparable to the physical GNR length. Overcoming the challenge of low-yield single-ribbon transistors by the networks and identifying the corresponding charge transport mechanism is a key step forward for functionalization of GNRs.
Project description:Solid-state Li batteries require solid electrolytes which have high Li+ conductivity and good chemical/mechanical compatibility with Li metal anodes and high energy cathodes. Structure/function correlations which relate local bonding to macroscopic properties are needed to guide development of new solid electrolyte materials. This study combines diffraction measurements with solid-state nuclear magnetic resonance spectroscopy (ssNMR) and neutron pair distribution function (nPDF) analysis to probe the short-range vs. long-range structure of glass-ceramic Li3PS4-based solid electrolytes. This work demonstrates how different synthesis conditions (e.g., solvent selection and thermal processing) affect the resulting polyanionic network. More specifically, structures with high P coordination numbers (e.g., PS43- and P2S74-) correlate with higher Li+ mobility compared to other polyanions (e.g., (PS3)nn- chains and P2S64-). Overall, this work demonstrates how ssNMR and nPDF can be used to draw key structure/function correlations for solid-state superionic conductors.
Project description:The semi-solid flow battery (SSFB) is a promising storage energy technology featured by employing semi-solid fluid electrodes containing conductive additive and active Li-ion battery materials. The state of art anode material for SSFB is Li4 Ti5 O12 (LTO). This work shows that LTO improves drastically the performance in fluid electrode via hydrogen annealing manifesting the importance of the electrical conductivity of the active material in SSFBs. On the other hand, the properties of fluid electrodes allow the contributions of ionic and electrical resistance to be separated in operando. The asymmetric overpotential observed in Li4 Ti5 O12 and TiO2 is proposed to originate from the so-called electron bottleneck mechanism based on the transformation from electrically insulator to conductor upon (de-)lithiation, or vice versa, which should be considered when modelling, evaluating or designing advanced materials based on Li4 Ti5 O12 , TiO2 or others with insulating-conducting behavior materials.
Project description:X-ray absorption spectroscopy (XAS) is a premier technique for materials characterization, providing key information about the local chemical environment of the absorber atom. In this work, we develop a database of sulfur K-edge XAS spectra of crystalline and amorphous lithium thiophosphate materials based on the atomic structures reported in Chem. Mater., 34, 6702 (2022). The XAS database is based on simulations using the excited electron and core-hole pseudopotential approach implemented in the Vienna Ab initio Simulation Package. Our database contains 2681 S K-edge XAS spectra for 66 crystalline and glassy structure models, making it the largest collection of first-principles computational XAS spectra for glass/ceramic lithium thiophosphates to date. This database can be used to correlate S spectral features with distinct S species based on their local coordination and short-range ordering in sulfide-based solid electrolytes. The data is openly distributed via the Materials Cloud, allowing researchers to access it for free and use it for further analysis, such as spectral fingerprinting, matching with experiments, and developing machine learning models.
Project description:All-solid-state Li-ion batteries are one of the most promising energy storage devices for future automotive applications as high energy density metallic Li anodes can be safely used. However, introducing solid-state electrolytes needs a better understanding of the forming electrified electrode/electrolyte interface to facilitate the charge and mass transport through it and design ever-high-performance batteries. This study investigates the interface between metallic lithium and solid-state electrolytes. Using spectroscopic ellipsometry, we detected the formation of the space charge depletion layers even in the presence of metallic Li. That is counterintuitive and has been a subject of intense debate in recent years. Using impedance measurements, we obtain key parameters characterizing these layers and, with the help of kinetic Monte Carlo simulations, construct a comprehensive model of the systems to gain insights into the mass transport and the underlying mechanisms of charge accumulation, which is crucial for developing high-performance solid-state batteries.
Project description:Nonstoichiometric silicon nitride SiNx is a promising material for developing a new generation of high-speed, reliable flash memory device based on the resistive effect. The advantage of silicon nitride over other dielectrics is its compatibility with the silicon technology. In the present work, a silicon nitride-based memristor deposited by the plasma-enhanced chemical vapor deposition method was studied. To develop a memristor based on silicon nitride, it is necessary to understand the charge transport mechanisms in all states. In the present work, it was established that the charge transport in high-resistance states is not described by the Frenkel effect model of Coulomb isolated trap ionization, Hill-Adachi model of overlapping Coulomb potentials, Makram-Ebeid and Lannoo model of multiphonon isolated trap ionization, Nasyrov-Gritsenko model of phonon-assisted tunneling between traps, Shklovskii-Efros percolation model, Schottky model and the thermally assisted tunneling mechanisms. It is established that, in the initial state, low-resistance state, intermediate-resistance state and high-resistance state, the charge transport in the forming-free SiNx-based memristor is described by the space charge limited current model. The trap parameters responsible for the charge transport in various memristor states are determined.
Project description:Lithium thiophosphates (LPSs) with the composition (Li2S) x (P2S5)1-x are among the most promising prospective electrolyte materials for solid-state batteries (SSBs), owing to their superionic conductivity at room temperature (>10-3 S cm-1), soft mechanical properties, and low grain boundary resistance. Several glass-ceramic (gc) LPSs with different compositions and good Li conductivity have been previously reported, but the relationship among composition, atomic structure, stability, and Li conductivity remains unclear due to the challenges in characterizing noncrystalline phases in experiments or simulations. Here, we mapped the LPS phase diagram by combining first-principles and artificial intelligence (AI) methods, integrating density functional theory, artificial neural network potentials, genetic-algorithm sampling, and ab initio molecular dynamics simulations. By means of an unsupervised structure-similarity analysis, the glassy/ceramic phases were correlated with the local structural motifs in the known LPS crystal structures, showing that the energetically most favorable Li environment varies with the composition. Based on the discovered trends in the LPS phase diagram, we propose a candidate solid-state electrolyte composition, (Li2S) x (P2S5)1-x (x ∼ 0.725), that exhibits high ionic conductivity (>10-2 S cm-1) in our simulations, thereby demonstrating a general design strategy for amorphous or glassy/ceramic solid electrolytes with enhanced conductivity and stability.
Project description:For lithium-sulfur (Li-S) batteries to become competitive, they require high stability and energy density. Organosulfur polymer-based cathodes have recently shown promising performance due to their ability to overcome common limitations of Li-S batteries, such as the insulating nature of sulfur. In this study, we use a multiscale modeling approach to explore the influence of the regiochemistry of a conjugated poly(4-(thiophene-3-yl)benzenethiol) (PTBT) polymer on its aggregation behavior and charge transport. Classical molecular dynamics simulations of the self-assembly of polymer chains with different regioregularity show that a head-to-tail/head-to-tail regularity can form a well-ordered crystalline phase of planar chains allowing for fast charge transport. Our X-ray diffraction measurements, in conjunction with our predicted crystal structure, confirm the presence of crystalline phases in the electropolymerized PTBT polymer. We quantitatively describe the charge transport in the crystalline phase in a band-like regime. Our results give detailed insights into the interplay between microstructural and electrical properties of conjugated polymer cathode materials, highlighting the effect of polymer chain regioregularity on its charge transport properties.
Project description:Spin crossover complexes are among the most studied classes of molecular switches and have attracted considerable attention for their potential technological use as active units in multifunctional devices. A fundamental step toward their practical implementation is the integration in macroscopic devices adopting hybrid vertical architectures. First, the physical properties of technological interest shown by these materials in the bulk phase have to be retained once they are deposited on a solid surface. Herein, we describe the study of a hybrid molecular inorganic junction embedding the spin crossover complex [Fe(qnal)2] (qnal = quinoline-naphthaldehyde) as an active switchable thin film sandwiched within energy-optimized metallic electrodes. In these junctions, developed and characterized with the support of state of the art techniques including synchrotron Mössbauer source (SMS) spectroscopy and focused-ion beam scanning transmission electron microscopy, we observed that the spin state conversion of the Fe(II)-based spin crossover film is associated with a transition from a space charge-limited current (SCLC) transport mechanism with shallow traps to a SCLC mechanism characterized by the presence of an exponential distribution of traps concomitant with the spin transition temperature.