Surface Reaction Products Research Articles

Role of the Coreactant on the Dual-Source Behavior of Lithium Hexamethyldisilazide for ALD Li-Containing Films.

Atomic layer deposition (ALD) of Li-containing thin films is deemed as highly relevant for the development of next-generation Li-ion batteries. Lithium hexamethyldisilazide (LiHMDS), as Li-containing precursor, is preferred over the widely used lithium tert-butoxide because of its lower melting point of 70 °C. However, the presence of silyl groups in the LiHMDS chemical structure can result in the undesired incorporation of Si in the film. Therefore, understanding the reaction mechanism of LiHMDS is required to control its dual-source behavior and grow Si-free Li-containing thin films. For this purpose LiHMDS was combined with O2 plasma or water as coreactant. In situ spectroscopic ellipsometry (SE) and X-ray photoelectron spectroscopy (XPS) revealed that using O2 plasma as coreactant results in linear growth and Si-containing films, whereas using H2O as coreactant leads to fast, nonsurface-reaction-limited growth and Si-free films. To shed light on the role of the coreactant on the reaction mechanism of LiHMDS, in situ studies by time-resolved quadrupole mass spectrometry (QMS) were performed on the O2 plasma and H2O-based ALD processes. Measurements taken during full ALD cycles and half-cycles were carefully compared to identify which half-cycle surface reaction products lead to silicon incorporation in the film. The QMS results of the LiHMDS + H2O process showed that LiHMDS both chemisorbs and physisorbs. Furthermore, it is concluded that Si incorporation occurs during the O2 plasma step, when the physisorbed ligands are combusted and Si-containing products are redeposited. This work also demonstrates that the incorporated Si can be abstracted from the film by means of a H2 plasma step following the O2 plasma step. These insights on the role of the coreactant in the synthesis of Li-containing films contribute to the development of LiHMDS-based ALD processes for Li-ion battery applications.

A study on microstructure evolution of MCrAlY coatings after thermal aging in Te environment

The effects of thermal exposure on tellurium (Te) diffusion behavior in MCrAlY coatings were investigated at 800 °C in Te vapor. The results showed that the diffusion depth of Te in MCrAlY coatings gradually increased with the exposure time, and the dense Cr3Te4 layer formed on the coating surface in the initial stage was no longer continuous, especially under aging conditions with higher Te concentration. The high Cr content of the coating promoted the solid phase transition of the surface reaction product from Cr3Te4 to Cr7Te8, and resulting in the formation of large α-Cr phase either within or beneath the reaction layer during long aging processes. As a result of this phase transition, excess Te atoms were released from Cr3Te4 and continued to diffuse into the coating. Te did not exhibit obvious intergranular diffusion characteristics within the coating. When it encountered Y, it was captured by Y and formed a YTe phase. After aging for 3000 h, Te was distributed throughout the coating, and numerous voids were formed at the interface between the coating and the substrate. These two factors deteriorated the plasticity and adhesion of the coating. Results from molten salt corrosion tests indicated that the high content of Cr and Al in the coating, as well as high densities of grain boundaries providing diffusion pathways, reduced the corrosion resistance of the coating to molten salt.

Understanding the Decomposition of Dimethyl Methyl Phosphonate on Metal-Modified TiO2(110) Surfaces Using Ensembles of Product Configurations.

The decomposition of dimethyl methyl phosphonate (DMMP), a simulant for the nerve agent sarin, was investigated on Cu4/TiO2(110) and K/Cu4/TiO2(110) surfaces using a combination of near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory calculations (DFT). Mass-selected Cu4 clusters and potassium (K) atoms were deposited onto TiO2(110) as a metal catalyst and alkali promoter to improve the reactivity and recyclability of the TiO2 surface after exposure to DMMP. Surface reaction products resulting from decomposition of DMMP were probed by NAP-XPS measurements of phosphorus (P) 2p and carbon 1s core-level spectra. The Cu4/TiO2(110) surface is found to be very active for DMMP decomposition with highly reduced P-species observed even at room temperature (RT). The codeposition of K atoms and Cu4 clusters further improves the reactivity with no intact DMMP detectable. Temperature-dependent measurements show that the presence of K atoms promotes the removal of residual P-species at temperatures > 600 K. Detailed DFT calculations were performed to determine the surface structures and energetically accessible pathways for DMMP decomposition on Cu4/TiO2(110) and K/Cu4/TiO2(110) surfaces. The calculations show that DMMP and P-containing reaction products preferentially bind to the TiO2 surface, while the molecular fragments, i.e., methoxy and methyl, bind to both the Cu4 clusters and TiO2. The Cu4 clusters make the P-O, O-C, and P-C bond cleavages of DMMP markedly more exothermic. The Cu4 clusters are highly fluxional with atomic structures that depend on the configuration of fragments bound to them. Finally, the manifold of P 2p chemical shifts calculated for a large number of energetically favorable configurations of decomposition products is in good agreement with the observed XPS spectra and provides an alternative way of interpreting incompletely resolved core-level spectra using an ensemble of observed structures.

Dynamical evolution of CO2 and H2O on garnet electrolyte elucidated by ambient pressure X-ray spectroscopies

Garnet-type Li6.5La3Zr1.5Ta0.5O12 (LLZO) is considered a promising solid electrolyte, but the surface degradation in air hinders its application for all-solid-state battery. Recent studies have mainly focused on the final products of the LLZO surface reactions due to lacking of powerful in situ characterization methods. Here, we use ambient pressure X-ray spectroscopies to in situ investigate the dynamical evolution of LLZO surface in different gas environments. The newly developed ambient pressure mapping of resonant Auger spectroscopy clearly distinguishes the lithium containing species, including LiOH, Li2O, Li2CO3 and lattice oxygen. The reaction of CO2 with LLZO to form Li2CO3 is found to be a thermodynamically favored self-limiting reaction. On the contrary, the reaction of H2O with LLZO lags behind that of CO2, but intensifies at high pressure. More interestingly, the results provide direct spectroscopic evidence for the existence of Li+/H+ exchange and reveal the importance of the initial layer formed on clean electrolyte surface in determining their air stability. This work demonstrates that the newly developed in situ technologies pave a new way to investigate the oxygen evolution and surface degradation mechanism in energy materials.

Configuration of ammonia on Cu{311}: Infrared spectroscopy and first-principles theory.

We describe Reflection Absorption Infrared Spectroscopy (RAIRS) and first-principles Density Functional Theory (DFT) studies of ammonia adsorption on the Cu{311} surface. Our experimental results indicate an upright chemisorbed species at low coverages, with at least one additional species accompanying this at higher coverages. Our high-coverage RAIRS data cannot be fully explained by DFT models containing only ammonia or its dissociation products, even allowing for molecular tilt and/or the formation of a bilayer. We therefore also consider urea and formamide as possible products of surface reaction with residual carbon monoxide, but these species are again not fully compatible with our observed spectra. The overlayer composition at high coverages remains mysterious.

IMPREGNATED ACTIVATED CARBON MATERIALS FOR RESPIRATORY PURPOSE. CHEMISORPTION OF SULFUR DIOXIDE

The review is devoted to the use of impregnated activated carbon materials as chemisorbents of sulfur (IV) oxide. General methods for obtaining ordinary activated carbon, preparation of raw materials, their chemical activation with alkalis and acids followed by heat treatment (carbonization) in an inert environment or in the presence of a gaseous oxidizer, the role of acid-base and redox catalysts in this process are considered. The influence of the chemical composition of the activated carbon surface, the presence of functional groups, and their acid-base properties, as well as the products of surface reactions on the peculiarities of sulfur (IV) oxide adsorption is analyzed from the point of view of SO2 removal efficiency and the possibility of SO2 regeneration. An important role in these processes is played by the pore size, the possibility of co-adsorption of water, and the presence of an oxidant. The nature of adsorbent-adsorbate interactions on the surface of activated carbon, their ener­gy, in particular, the contribution of so-called "physical" adsorption, van der Waals forces, hydrogen bonding, and the influence of surface functional groups are discussed. The activation of carbon raw materials with nitrogen-containing compounds leads to the N-doping of the surface, which increases the efficiency of SO2 adsorption, facilitating not only van der Waals and electrostatic interactions, but also S←N binding. The influence of oxygen and oxygen-containing functional groups on SO2 adsorption is also discussed. To obtain impregnated activated carbon for SO2 absorption, the original activated carbon of the required quality is impregnated with solutions of inorganic and organic compounds that remain on the inner surface of the activated carbon after drying. Impregnation blocks partly the porosity of activated carbon, but makes it more capable of chemical adsorption. Chemisorption, in which certain chemical bonds are formed between the surface of the activated carbon and the compound being adsorbed, is more selective than physical adsorption, where the size of molecules is critical for an effective capture process. It can be noted that unlike inorganic alkalis, which spoil the porous structure of activated carbon, treatment with a solution of ammonia or organic N-containing bases promotes SO2 absorption. A special place in gas purification is occupied by activated carbon impregnated with ionic liquids, non-aqueous solvents being used for impregnation. A separate issue of the chemisorption of sulfur (IV) oxide by samples of impregnated activated carbon based on d-metals will be discussed in detail below.

Modeling Equilibration Dynamics of Hyperthermal Products of Surface Reactions Using Scalable Neural Network Potential with First-Principles Accuracy.

Equilibration dynamics of hot oxygen atoms following the dissociation of O2 on Pd(100) and Pd(111) surfaces are investigated by molecular dynamics simulations based on a scalable neural network potential enabling first-principles description of the interaction of O2 and O interacting with variable Pd supercells. By analyzing hundreds of trajectories with appropriate initial sampling, the measured distance distribution of equilibrated atom pairs on Pd(111) is well reproduced. However, our results on Pd(100) suggest that the ballistic motion of hot atoms predicted previously is a rare event under ideal conditions, while initial molecular orientation and surface thermal fluctuation could significantly affect the overall postdissociation dynamics. On both surfaces, dissociated hyperthermal oxygen atoms primarily locate their nascent positions and experience a similar random walk motion nearby.

Investigation of Molecular Mechanism of Cobalt Porphyrin Catalyzed CO2 Electrochemical Reduction in Ionic Liquid by In-Situ SERS.

This study explores the electrochemical reduction in CO2 using room temperature ionic liquids as solvents or electrolytes, which can minimize the environmental impact of CO2 emissions. To design effective CO2 electrochemical systems, it is crucial to identify intermediate surface species and reaction products in situ. The study investigates the electrochemical reduction in CO2 using a cobalt porphyrin molecular immobilized electrode in 1-n-butyl-3-methyl imidazolium tetrafluoroborate (BMI.BF4) room temperature ionic liquids, through in-situ surface-enhanced Raman spectroscopy (SERS) and electrochemical technique. The results show that the highest faradaic efficiency of CO produced from the electrochemical reduction in CO2 can reach 98%. With the potential getting more negative, the faradaic efficiency of CO decreases while H2 is produced as a competitive product. Besides, water protonates porphyrin macrocycle, producing pholorin as the key intermediate for the hydrogen evolution reaction, leading to the out-of-plane mode of the porphyrin molecule. Absorption of CO2 by the ionic liquids leads to the formation of BMI·CO2 adduct in BMI·BF4 solution, causing vibration modes at 1100, 1457, and 1509 cm-1. However, the key intermediate of CO2-· radical is not observed. The υ(CO) stretching mode of absorbed CO is affected by the electrochemical Stark effect, typical of CO chemisorbed on a top site.

Correlation between Surface Reactions and Electrochemical Performance of Al2O3‐ and CeO2‐Coated NCM Thin Film Cathodes

AbstractDepositing ultrathin oxide coatings has been proven a successful approach to stabilize the surface of LiNixCoyMnzO2active cathode material in lithium‐ion batteries (LIB). The beneficial effect of Al2O3coatings arises at least partly from spontaneous reactions between coating and liquid electrolyte. However, it remains unclear if comparable surface reactions occur for other oxide coatings. One difficulty is the characterization of reaction products at the cathode–electrolyte interface due to the multi‐phase properties of composite cathodes. Here, thin films are utilized as model systems to correlate surface reactions with the performance of Al2O3‐ and CeO2‐coated nickel cobalt manganese oxides (NCM). Electrochemical characterization confirms that an Al2O3coating improves long‐term cycling stability, while CeO2‐coated thin films perform even worse than uncoated counterparts. The analysis of the surface reaction products using X‐ray photoelectron spectroscopy shows that both coatings are fluorinated upon contact with liquid electrolyte in agreement with thermodynamic considerations. The fluorinated Al2O3coating is stable during cycling, resulting in the improved cell performance. In contrast, the fluorinated CeO2coating changes chemical composition, facilitating corrosion of the NCM surface. The results demonstrate the importance of a detailed analysis of surface reactions to evaluate the suitability of ultrathin oxide layers as protective coatings for LIBs.

Adsorption and Oxidation of NO2 on Anatase TiO2: Concerted Nitrate Interaction and Photon-Stimulated Reaction

The catalytic and photon-induced oxidation of NO2 on anatase TiO2 has been studied and compared with the surface nitrate species obtained after adsorption of HNO3. Using a combination of in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), density functional theory (DFT), and temperature-programmed desorption (TPD), it is shown that identical products are obtained in all reaction systems but that their formation rates differ significantly. The surface reaction products are identified as combinations of surface–NO3– species, where NO2 bonds to the lattice oxygen, and freely adsorbed NO3– ions. These products can be obtained either by dissociative adsorption of HNO3 or by catalytic/photocatalytic oxidation of NO2, which is facilitated by UV light. A concerted reaction mechanism is unraveled that involves reorientation of bidentate nitrate that pushes out a neighboring protonated lattice oxygen to form a surface–NO3– species and a terminal OH group. The thermal stability of these surface species has been studied by means of TPD and simultaneous in situ DRIFTS measurements that reveal a main desorption peak (m/z = 46) at around 430 °C, which is attributed to concerted nitrate desorption through pentoxide (N2O5) formation. A weaker and broader TPD peak is found at about 185 °C and is attributed to desorption of nitrate species bonded in a compressed configuration. The experimental results can be explained by the changing stability of the identified nitrate products, which depends strongly on the surface chemical environment and the surface coverage. The DFT results show that the stabilization of intermediate NO2 adsorbates and the final nitrate reaction products occurs through a bifunctional charge exchange mechanism that is mediated by the TiO2 crystal. In particular, a stable surface–NO3– and NO3– ion pair configuration has been identified. This mechanism explains both the thermal and photoinduced oxidation of NO2 and their thermal stability and different formation rates, yielding high photoinduced oxidation reaction rates. Our results provide insights into the structure and chemical stability of nitrate surface products on TiO2 particles and their formation mechanism, which is important for understanding their catalyzed transformation into the harmful compounds HONO and N2O during continued UV light illumination.

Solid biofuel combustion or electrification for limestone calcination: Effects on quicklime surface microstructure

Net CO2 emissions from the production of quicklime can be reduced by introducing renewable solid fuels or sustainably produced electricity for heating of the process. This paper reports the results of a study examining the effects of new heat sources on quicklime surface reaction products and on quicklime microstructure. Limestone was heated to 1100 °C and 1350 °C in high CO2 atmosphere under three conditions: i) an ash mixture representing conventional coal and a solid biofuel (olive pomace); ii) olive pomace ash, and iii) no ash representing an electrically heated process. The ash-quicklime interfaces of the samples were analyzed for elemental composition and microstructure using SEM-EDX. Multi-component chemical equilibrium calculations were used to assess the stable chemical phases in the interface. Coal-olive pomace ash mixture resulted in coarsening of the quicklime microstructure; this effect was less severe compared to that of pure olive pomace ash. The calculations indicated that the potassium in olive pomace ash was bound to Si- and Al-rich coal ash phases. Exposure to potassium-rich olive pomace ash resulted in severe coarsening of the quicklime microstructure. The difference was most obvious at 1,350 °C, and was probably the result of intrusion of a potassium-rich salt melt. For limestone without ash, the quicklime showed enhanced sintering and reduced porosity at the higher temperature, in agreement with previous studies. Interface reactions and microstructure coarsening, here most apparent for the case with olive pomace, could be problematic in industrial quicklime production since they may contribute to decreased available CaO and reactivity.

Investigating the Mechanical Property and Enhanced Mechanism of Modified Pisha Sandstone Geopolymer via Ion Exchange Solidification

The Yellow River has the highest sediment concentration in the world, and the Yellow River coarse sediment mainly comes from a particular kind of argillaceous sandstone, Pisha sandstone. This paper reports an investigation of the possibility of development of low-cost engineering materials using Pisha sandstone via ion exchange modification. The effect of modifiers with different concentration on the inhibition of volume expansion and the strength enhancement of modified Pisha sandstone were studied via ion exchange solidification. The effects of the concentration of ten types of modifier solutions and curing age were considered. The hydration of the mineral components, particle surface potential and reaction products were studied, respectively, by XRD, zeta potential, TG/DTG and SEM. Expansion volume and shear strength tests were conducted to assess the volume stability and mechanical property of modified Pisha sandstone. It showed that the expansion of Pisha sandstone was controlled and that the volume stability and shear strength were improved via ion exchange modification. The results of XRD, TG/DTG and SEM showed that the spacing of the crystal layers of the Pisha sandstone clay mineral and the mass lost had decreased significantly. When the concentration of the modifier was 0.05 mol/L, the volume reduced by 54.55% maximum and the shear strength reached the peak of 138 kPa.

Ozone Initiates Human-Derived Emission of Nanocluster Aerosols.

Nanocluster aerosols (NCAs, particles <3 nm) are important players in driving climate feedbacks and processes that impact human health. This study reports, for the first time, NCA formation when gas-phase ozone reacts with human surfaces. In an occupied climate-controlled chamber, we detected NCA only when ozone was present. NCA emissions were dependent on clothing coverage, occupant age, air temperature, and humidity. Ozone-initiated chemistry with human skin lipids (particularly their primary surface reaction products) is the key mechanism driving NCA emissions, as evidenced by positive correlations with squalene in human skin wipe samples and known gaseous products from ozonolysis of skin lipids. Oxidation by OH radicals, autoxidation reactions, and human-emitted NH3 may also play a role in NCA formation. Such chemical processes are anticipated to generate aerosols of the smallest size (1.18-1.55 nm), whereas larger clusters result from subsequent growth of the smaller aerosols. This study shows that whenever we encounter ozone indoors, where we spend most of our lives, NCAs will be produced in the air around us.

Sources of Gas-Phase Species in an Art Museum from Comprehensive Real-Time Measurements

Indoor gases in an art museum were measured by two real-time chemical ionization mass spectrometers (CIMS; iodide (I-CIMS) and nitrate (NO3-CIMS) reagent ions) and a proton-transfer-reaction mass spectrometer (PTR-MS). A positive matrix factorization (PMF) analysis isolated nine different factors capturing the variability. Three factors were observed by all instruments, comprising over 30% of the organic carbon from each instrument. Of these three, one factor correlated with CO2, indicating a clear influence from human occupancy, and another was dominated by small carboxylic acids and was likely related to building materials. The third factor was dominated by HONO and ethylene glycol, with strong emission signatures after gallery painting. Additional factors correlated with ozone (O3) and nitrogen dioxide and are suggestive of indoor surface reaction products from outdoor-related oxidants. Outdoor-related factors contributed 20% of the measured organic carbon. Organic nitrogen compounds were measured and found to correlate with the estimated nitrate radical (NO3) concentration. The PTR-MS/I-CIMS/NO3-CIMS factors had higher, medium, and lower estimated volatility, respectively, while the carbon oxidation state followed the opposite trend. The majority of the VOC reactivity was due to indoor-related factors (52–77%) for all oxidants except O3 (44%). Human occupancy increased the reactivity of the human-related (×14), small acid (×1.5), terpene (×2), and acetone (×5) factors. The lifetime of oxidant reactivity (τOxR) against each oxidant for all factors was greater than the museum ventilation time scale, indicating that the reactivity from indoor sources is largely removed outdoors. The dominant VOC fates for all identified sources were ventilation and surface deposition.

Bulk defect-dependent initial steps of acetone oxidation on rutile TiO2(110)

Systematic model investigations revealed that defects, particularly bulk Ti3+ interstitials, play a crucial role in directing reactions of alcohols and aldehydes at rutile Titania (TiO2), a cheap, nontoxic and earth abundant catalyst. Coadsorption with oxygen may enhance the population of certain reaction paths. As systematic studies on the reactivity of ketones are rare, we studied the interaction of acetone with slightly (∼5%) and highly (∼20%) reduced rutile TiO2(110) surfaces by Temperature Programmed Desorption (TPD) and polarised Fourier-Transform Infrared Reflexion Absorption Spectroscopy (FT-IRRAS) to elucidate surface intermediates and reaction products. For low defect densities the only reaction observed occurs at high temperatures resulting in the formation of propane and propene of less than 1%. At high Ti3+ defect densities a stabilisation of acetone on the surface by the formation of a diolate was observed. In the presence of oxygen, the partial formation of a tilted acetone species is apparent in FT-IRRAS. A concomitant activation of the CH-bond can be attributed to the interaction with Oad atoms and can relate to thermally induced low temperature decomposition to water and carbon dioxide. However, in contrast to alcohols and aldehydes, both intermediates do not react to other more valuable products.

Model Studies on the Formation of the Solid Electrolyte Interphase: Reaction of Li with Ultrathin Adsorbed Ionic-Liquid Films and Co3 O4 (111) Thin Films.

In this work we aim towards the molecular understanding of the solid electrolyte interphase (SEI) formation at the electrode electrolyte interface (EEI). Herein, we investigated the interaction between the battery‐relevant ionic liquid (IL) 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP‐TFSI), Li and a Co3O4(111) thin film model anode grown on Ir(100) as a model study of the SEI formation in Li‐ion batteries (LIBs). We employed mostly X‐ray photoelectron spectroscopy (XPS) in combination with dispersion‐corrected density functional theory calculations (DFT‐D3). If the surface is pre‐covered by BMP‐TFSI species (model electrolyte), post‐deposition of Li (Li+ ion shuttle) reveals thermodynamically favorable TFSI decomposition products such as LiCN, Li2NSO2CF3, LiF, Li2S, Li2O2, Li2O, but also kinetic products like Li2NCH3C4H9 or LiNCH3C4H9 of BMP. Simultaneously, Li adsorption and/or lithiation of Co3O4(111) to LinCo3O4 takes place due to insertion via step edges or defects; a partial transformation to CoO cannot be excluded. Formation of Co0 could not be observed in the experiment indicating that surface reaction products and inserted/adsorbed Li at the step edges may inhibit or slow down further Li diffusion into the bulk. This study provides detailed insights of the SEI formation at the EEI, which might be crucial for the improvement of future batteries.

Chirality detection of surface desorption products using photoelectron circular dichroism.

Chirality detection of gas-phase molecules at low concentrations is challenging as the molecular number density is usually too low to perform conventional circular dichroism absorption experiments. In recent years, new spectroscopic methods have been developed to detect chirality in the gas phase. In particular, the angular distribution of photoelectrons after multiphoton laser ionization of chiral molecules using circularly polarized light is highly sensitive to the enantiomeric form of the ionized molecule [multiphoton photoelectron circular dichroism (MP-PECD)]. In this paper, we employ the MP-PECD as an analytic tool for chirality detection of the bicyclic monoterpene fenchone desorbing from a Ag(111) crystal. We record velocity-resolved kinetics of fenchone desorption on Ag(111) using pulsed molecular beams with ion imaging techniques. In addition, we measure temperature-programmed desorption spectra of the same system. Both experiments indicate weak physisorption of fenchone on Ag(111). We combine both experimental techniques with enantiomer-specific detection by recording MP-PECD of desorbing molecules using photoelectron imaging spectroscopy. We can clearly assign the enantiomeric form of the desorption product fenchone in sub-monolayer concentration. The experiment demonstrates the combination of MP-PECD with surface science experiments, paving the way for enantiomer-specific detection of surface reaction products on heterogeneous catalysts for asymmetric synthesis.

Unveiling the intrinsic reaction between silicon-graphite composite anode and ionic liquid electrolyte in lithium-ion battery

Due to the excellent theoretical capacity, silicon-based electrodes have been extensively studied to develop high energy-density lithium-ion batteries (LIBs). Nevertheless, the large volume expansion and unfavorable interface seriously hamper its application, and the underlying physics behind are still unclear. In this work, using in-situ environment scanning electron microscopy (ESEM), the morphological evolution of composite silicon-graphite electrodes with different ionic liquids as electrolytes are compared in the range of 20 °C–60 °C. Surprisingly, combining the microstructure and surface reaction products from transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS), it finds out that the fully reaction of lithium-silicon does not generate huge volume expansion, while the side reaction between graphite and electrolyte decomposition products causes dramatic volume expansion and hinders the further lithiation of silicon. On the other hand, the electrolyte which is capable of rapidly releasing F− to form LiF-rich solid electrolyte interphase (SEI) is favorable to maintain the structure integrity and cycling performance. This work casts new understanding from the perspective of intrinsic reaction between electrode and ionic liquid electrolyte, which suggests that the practical application of silicon-based electrodes with appropriate electrolyte is a promising route for high energy-density LIBs.

Kinetic modeling of oleic acid esterification with UiO-66: from intrinsic experimental data to kinetics via elementary reaction steps

This work reports the experimental conversion of oleic acid (OA) into methyl oleate via UiO-66 MOF catalyst. Strong focus is on the kinetic modeling: 67 models, based on elementary reaction steps for Eley-Rideal, Langmuir-Hinshelwood and Hattori kinetic mechanisms, are proposed. Via the application of initial reaction rate theory and nonisothermal kinetic modeling, one model adequately describes the experimental data. It is a variant on the Eley-Rideal type of model, such that the surface reaction includes the oleic acid adsorbate, methanol reacts from the liquid phase and one additional active site is considered to make the ester and water as surface reaction products, so that overall two active sites are used in the surface reaction. An activation energy of 54.9 ± 1.8 kJ mol−1 is reported and the desorption of the ester was found to be irreversible. In addition, NH3 TPD revealed at least two types of acid sites (#) on the UiO-66 MOF, from which turnover rates were calculated in the range of 2.54 ± 0.33 to 8.82 ± 0.87 mmolOA mol#−1 s−1. Since the catalyst is recyclable and no additional acids have to be used, this system can be considered as a green alternative for the well-known homogeneously catalyzed esterification reaction.

The Role of Diphenyl Carbonate Additive on the Interfacial Reactivity of Positive Electrodes in Li-ion Batteries

Understanding and controlling the (electro) chemical reactions between positive electrodes and electrolytes is essential to enhance the cycle life and safety of Li-ion batteries. Previous computational and experimental studies have shown that greater capacity loss of LiNixMnyCo1−x−yO2 (NMC) with increased Ni content can be attributed to the enhanced chemical oxidation of carbonate solvents by dehydrogenation and increased salt decomposition. In this study, we examine the role of a diphenyl carbonate (DPC) additive on the interfacial reactivity of LiNi1/3Mn1/3Co1/3O2, LiNi0.6Mn0.2Co0.2O2, LiNi0.8Mn0.1Co0.1O2 (NMC111, NMC622 and NMC811). Diffuse reflectance infrared Fourier Transform (DRIFT) spectroscopy on NMCs showed that adding DPC in the electrolyte suppressed signals associated with dehydrogenation of ethylene carbonate (EC) from LiNi1/3Mn1/3Ni1/3O2 to LiNi0.8Mn0.1Ni0.1O2 (NMC111 to NMC811). In addition, having DPC in the electrolyte was accompanied with less PF6− salt anion decomposition to form less-fluorine coordinated species such as lithium nickel oxyfluorides or PF3O-like species as revealed by combined infrared spectroscopy and X-ray Photoelectron Spectroscopy (XPS) for Ni-rich NMCs. Such observations are in agreement with previous work showing that DPC can increase the cycling performance of NMC811. The reduced reactivity between NMC such as NMC811 and electrolyte with DPC can be attributed to the formation of surface reaction products from the electrochemical oxidation of DPC occurring at lower voltages compared to the chemical oxidative dehydrogenation of carbonates. This hypothesis is supported by in situ infrared spectroscopy measurements, which revealed electrochemical oxidation of diphenyl carbonate upon charging at 3.9 VLi, accompanied by the detection of a feature around 1824 cm−1 attributed to organic oxidation products adsorbed on the oxide surface, and a stable electrode/electrolyte interface on NMC811 at higher voltages.