Stable Photoelectrochemical Reactions at Solid/Solid Interfaces toward Solar Energy Conversion and Storage.

Electrochemistry has extended from reactions at solid/liquid interfaces to those at solid/solid interfaces. However, photoelectrochemistry at solid/solid interfaces has been hardly reported. In this study, we achieve a stable photoelectrochemical reaction at the semiconductor-electrode/solid-electrolyte interface in a Nb-doped anatase-TiO2 (a-TiO2:Nb)/Li3PO4 (LPO)/Li all-solid-state cell. The oxidative currents of a-TiO2:Nb/LPO/Li increase upon light irradiation when a-TiO2:Nb is located at a potential that is more positive than its flat-band potential. This is because the photoexcited electrons migrate to the current collector due to the bending of the conduction band minimum toward the negative potential. The photoelectrochemical reaction at the semiconductor/solid-electrolyte interface is driven by the same principle as those at semiconductor/liquid-electrolyte interfaces. Moreover, oxidation under light irradiation exhibits reversibility with reduction in the dark. Thus, we extend photoelectrochemistry to all-solid-state systems composed of solid/solid interfaces. This extension would enable us to investigate photoelectrochemical phenomena uncleared at solid/liquid interfaces because of low stability and durability.

Tuning the interfacial friction force and thermal conductance by altering phonon properties at contact interface.

Controlling friction force and thermal conductance at solid/solid interface is of great importance but remains a significant challenge. In this work, we propose a method to control the matching degree of phonon spectra at the interface through modifying the atomic mass of contact materials, thereby regulating the interfacial friction force and thermal conductance. Results of Debye theory and molecular dynamics simulations show that the cutoff frequency of phonon spectrum decreases with increasing atomic mass. Thus, two contact surfaces with equal atomic mass have same vibrational characteristics, so that more phonons could pass through the interface. In these regards, the coupling strength of phonon modes on contact surfaces makes it possible to gain insight into the nonmonotonic variation of interfacial friction force and thermal conductance. Our investigations suggest that the overlap of phonon modes increases energy scattering channels and therefore phonon transmission at the interface, and finally, an enhanced energy dissipation in friction and heat transfer ability at interface.

Electrodeposition Stability Landscape for Solid-Solid Interfaces.

As solid-state batteries (SSBs) with lithium (Li) metal anodes gain increasing traction as promising next-generation energy storage systems, a fundamental understanding of coupled electro-chemo-mechanical interactions is essential to design stable solid-solid interfaces. Notably, uneven electrodeposition at the Li metal/solid electrolyte (SE) interface arising from intrinsic electrochemical and mechanical heterogeneities remains a significant challenge. In this work, the thermodynamic origins of mechanics-coupled reaction kinetics at the Li/SE interface are investigated and its implications on electrodeposition stability are unveiled. It is established that the mechanics-driven energetic contribution to the free energy landscape of the Li deposition/dissolution redox reaction has a critical influence on the interface stability. The study presents the competing effects of mechanical and electrical overpotential on the reaction distribution, and demarcates the regimes under which stress interactions can be tailored to enable stable electrodeposition. It is revealed that different degrees of mechanics contribution to the forward (dissolution) and backward (deposition) reaction rates result in widely varying stability regimes, and the mechanics-coupled kinetics scenario exhibited by the Li/SE interface is shown to depend strongly on the thermodynamic and mechanical properties of the SE. This work highlights the importance of discerning the underpinning nature of electro-chemo-mechanical coupling toward achieving stable solid/solid interfaces in SSBs.

Characterization of the Lithium/Solid Electrolyte Interface in the Presence of Nanometer-thin TiOx Layers for All-Solid-State Batteries.

It is unclear, which role space charge layers (SCLs) play within an all-solid-state battery during operation with high current densities, and to which extent they form. Herein, we use a solid electrolyte with a known SCL formation and investigate it in a symmetric cell under non-blocking conditions with Li metal electrodes. Since the used LICGC™ electrolyte is known for its instability against lithium, it is protected from rapid degradation by nanometer-thin layers of TiOx deployed by atomic layer deposition. Close attention is given to the interfacial properties, as now additional Li+ can traverse through the interface depending on the applied bias potential. The interlayer's impedance response shows efficient lithium-ion conduction for low bias potentials and a diffusion-limiting effect towards high positive and negative potentials. SCLs grow up to a thickness of 5.1 µm. Additionally, estimating the apparent rate constant of the charge transfer across the interface indicates that the potentials where kinetics are hindered coincide with the widest SCLs. In conclusion, the investigation under higher steady-state currents was only possible because of the improved stability due to the interlayer. No chemo-physical failure could be observed after 800+ hours of cycling. However, SEM study shows a new phase at the interface.

Cellulose hydrolysis reactor incorporating stirring apparatus for use with carbon-based solid acid catalyst.

A highly efficient reactor with a stirring device was specially designed with the intent of performing the hydrolysis of pure crystalline cellulose using a carbon-based solid acid catalyst. This catalyst comprised an amorphous carbon-based material bearing -SO3H, -COOH and -OH groups. The stirring apparatus had seven blades coated with polytetrafluoroethylene and arranged axially at regular intervals with a 60° offset. This design proved highly effective, providing double the glucose yield compared with conventional stirring systems. The basic properties of this novel reactor were investigated and analyzed and are discussed herein.

Surface and Electrical Characterization of Bilayers Based on BiFeO3 and VO2.

Thin films of BiFeO3, VO2, and BiFeO3/VO2 were grown on SrTiO3(100) and Al2O3(0001) monocrystalline substrates using radio frequency and direct current sputtering techniques. To observe the effect of the coupling between these materials, the surface of the films was characterized by profilometry, atomic force microscopy, and X-ray photoelectron spectroscopy. The heterostructures, monolayers, and bilayers based on BiFeO3 and VO2 grew with good adhesion and without delamination or signs of incompatibility between the layers. A good granular arrangement and RMS roughness between 1 and 5 nm for the individual layers (VO2 and BiFeO3) and between 6 and 18 nm for the bilayers (BiFeO3/VO2) were observed. Their grain size is between 20 nm and 26 nm for the individual layers and between 63 nm and 67 nm for the bilayers. X-ray photoelectron spectroscopy measurements show a higher proportion of V4+, Bi3+, and Fe3+ in the films obtained. The homogeneous ordering, low roughness, and oxidation states on the obtained surface show a good coupling in these films. The I-V curves show ohmic behavior at room temperature and change with increasing temperature. The effect of coupling these materials in a thin film shows the appearance of hysteresis cycles, I-V and R-T, which is typical of materials with high potential in applications, such as resistive memories and solar cells.

Plastic Monolithic Mixed-Conducting Interlayer for Dendrite-Free Solid-State Batteries.

Solid-state electrolytes (SSEs) hold a critical role in enabling high-energy-density and safe rechargeable batteries with Li metal anode. Unfortunately, nonuniform lithium deposition and dendrite penetration due to poor interfacial solid-solid contact are hindering their practical applications. Here, solid-state lithium naphthalenide (Li-Naph(s)) is introduced as a plastic monolithic mixed-conducting interlayer (PMMCI) between the garnet electrolyte and the Li anode via a facile cold process. The thin PMMCI shows a well-ordered layered crystalline structure with excellent mixed-conducting capability for both Li+ (4.38 × 10-3  S cm-1 ) and delocalized electrons (1.01 × 10-3  S cm-1 ). In contrast to previous composite interlayers, this monolithic material enables an intrinsically homogenous electric field and Li+ transport at the Li/garnet interface, thus significantly reducing the interfacial resistance and achieving uniform and dendrite-free Li anode plating/stripping. As a result, Li symmetric cells with the PMMCI-modified garnet electrolyte show highly stable cycling for 1200 h at 0.2 mA cm-2 and 500 h at a high current density of 1 mA cm-2 . The findings provide a new interface design strategy for solid-state batteries using monolithic mixed-conducting interlayers.

Unveiling Interfacial Li-Ion Dynamics in Li7La3Zr2O12/PEO(LiTFSI) Composite Polymer-Ceramic Solid Electrolytes for All-Solid-State Lithium Batteries.

Unlocking the full potential of solid-state electrolytes (SSEs) is key to enabling safer and more-energy dense technologies than today's Li-ion batteries. In particular, composite materials comprising a conductive, flexible polymer matrix embedding ceramic filler particles are emerging as a good strategy to provide the combination of conductivity and mechanical and chemical stability demanded from SSEs. However, the electrochemical activity of these materials strongly depends on their polymer/ceramic interfacial Li-ion dynamics at the molecular scale, whose fundamental understanding remains elusive. While this interface has been explored for nonconductive ceramic fillers, atomistic modeling of interfaces involving a potentially more promising conductive ceramic filler is still lacking. We address this shortfall by employing molecular dynamics and enhanced Monte Carlo techniques to gain unprecedented insights into the interfacial Li-ion dynamics in a composite polymer-ceramic electrolyte, which integrates polyethylene oxide plus LiN(CF3SO2)2 lithium imide salt (LiTFSI), and Li-ion conductive cubic Li7La3Zr2O12 (LLZO) inclusions. Our simulations automatically produce the interfacial Li-ion distribution assumed in space-charge models and, for the first time, a long-range impact of the garnet surface on the Li-ion diffusivity is unveiled. Based on our calculations and experimental measurements of tensile strength and ionic conductivity, we are able to explain a previously reported drop in conductivity at a critical filler fraction well below the theoretical percolation threshold. Our results pave the way for the computational modeling of other conductive filler/polymer combinations and the rational design of composite SSEs.

Interface structure prediction via CALYPSO method.

The atomistic structures of solid-solid interfaces are of fundamental interests for understanding physical properties of interfacial materials. However, determination of interface structures faces a substantial challenge, both experimentally and theoretically. Here, we propose an efficient method for predicting interface structures via the generalization of our in-house developed CALYPSO method for structure prediction. We devised a lattice match toolkit that allows us to automatically search for the optimal lattice-matched superlattice for construction of the interface structures. In addition, bonding constraints (e.g., constraints on interatomic distances and coordination numbers of atoms) are imposed to generate better starting interface structures by taking advantages of the known bonding environment derived from the stable bulk phases. The interface structures evolve by following interfacially confined swarm intelligence algorithm, which is known to be efficient for exploration of potential energy surface. The method was validated by correctly predicting a number of known interface structures with only given information of two parent solids. The application of the developed method leads to prediction of two unknown grain boundary (GB) structures (r-GB and p-GB) of rutile TiO2 Σ5(2 1 0) under an O reducing atmosphere that contained Ti3+ as the result of O defects. Further calculations revealed that the intrinsic band gap of p-GB is reduced to 0.7 eV owing to substantial broadening of the Ti-3d interfacial levels from Ti3+ centers. Our results demonstrated that introduction of grain boundaries is an effective strategy to engineer the electronic properties and thus enhance the visible-light photoactivity of TiO2.

Visible-light-driven photo-Fenton reaction with α-Fe2O3/BiOI at near neutral pH: Boosted photogenerated charge separation, optimum operating parameters and mechanism insight.

The performance of the Photo-Fenton process is still limited by the low conversion rate of Fe3+/Fe2+ under near neutral conditions. We report a α-Fe2O3/BiOI catalyst that enhanced the efficiency of Fe2+ generation. The structure, morphology, chemical composition and chemical states of the catalyst were characterized. The α-Fe2O3/BiOI catalyst exhibited remarkable degradation performance for methyl orange (MO), phenol and tetracycline hydrochloride (TCH). The degradation efficiency of α-Fe2O3/BiOI with an optimum α-Fe2O3 loading was 3 and 10 times higher than those of pristine BiOI and α-Fe2O3, respectively. The excellent degradation performance arose from the synergistic effect of the efficient separation and transfer of photogenerated charge at the α-Fe2O3/BiOI solid-solid interface and the optimized Fenton reaction at the solid-liquid interface. The effects of operating parameters including the H2O2 concentration, solution pH, catalyst concentration and MO concentration on the degradation efficiency were investigated. Electron spin resonance results and reactive oxidation species scavenger experiments indicated that superoxide radicals could be transferred into hydroxide radicals via the activation of H2O2. A possible degradation pathway of TCH is proposed. This strategy provides a new perspective for improving the cyclic ability of Fe3+/Fe2+ over heterogeneous catalysts.

Spark Plasma Sintering of Lithium Aluminum Germanium Phosphate Solid Electrolyte and its Electrochemical Properties.

Sodium superionic conductor (NASICON)-type lithium aluminum germanium phosphate (LAGP) has attracted increasing attention as a solid electrolyte for all-solid-state lithium-ion batteries (ASSLIBs), due to the good ionic conductivity and highly stable interface with Li metal. However, it still remains challenging to achieve high density and good ionic conductivity in LAGP pellets by using conventional sintering methods, because they required high temperatures (>800 °C) and long sintering time (>6 h), which could cause the loss of lithium, the formation of impurity phases, and thus the reduction of ionic conductivity. Herein, we report the utilization of a spark plasma sintering (SPS) method to synthesize LAGP pellets with a density of 3.477 g cm-3, a relative high density up to 97.6%, and a good ionic conductivity of 3.29 × 10-4 S cm-1. In contrast to the dry-pressing process followed with high-temperature annealing, the optimized SPS process only required a low operating temperature of 650 °C and short sintering time of 10 min. Despite the least energy and short time consumption, the SPS approach could still achieve LAGP pellets with high density, little voids and cracks, intimate grain-grain boundary, and high ionic conductivity. These advantages suggest the great potential of SPS as a fabrication technique for preparing solid electrolytes and composite electrodes used in ASSLIBs.

Evaluating Phthalate Contaminant Migration Using Thermal Desorption⁻Gas Chromatography⁻Mass Spectrometry (TD⁻GC⁻MS).

This study describes a methodology for evaluating regulatory levels of phthalate contamination. By collecting experimental data on short-term phthalate migration using thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS), the migration of di(2-ethylhexyl) phthalate (DEHP) from polyvinyl chloride (PVC) to polyethylene (PE) was found to be expressed by the Fickian approximation model, which was originally proposed for solid (PVC)/liquid (solvent) migration of phthalates. Consequently, good data correlation was obtained using the Fickian approximation model with a diffusion coefficient of 4.2 × 10-12 cm²/s for solid (PVC)/ solid (PE) migration of DEHP at 25 °C. Results showed that temporary contact with plasticized polymers under a normal, foreseeable condition may not pose an immediate risk of being contaminated by phthalates at regulatory levels. However, as phthalates are small organic molecules designed to be dispersed in a variety of polymers as plasticizers at a high compounding ratio, the risk of migration-related contamination can be high in comparison with other additives, especially under high temperatures. With these considerations in mind, the methodology for examining regulatory levels of phthalate contamination using TD-GC-MS has been successfully demonstrated from the viewpoint of its applicability to solid (PVC)/solid (PE) migration of phthalates.