Vacancy Concentration Research Articles

Boost Electrocatalytic Activity of La0.6Sr0.4Co0.2Fe0.8O3-δ Air Electrode Prepared by High-Temperature Shock for Solid Oxide Electrochemical Cells.

High-temperature shock (HTS) is an emerging material synthesis technology with advantages, such as rapid processing, low energy consumption, and high controllability. This technology can prepare ultrafine nanoparticles with uniform particle size distribution and introduce additional oxygen vacancies, offering significant potential for the preparation of key materials for solid oxide electrochemical cells (SOCs). In this study, the La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) air electrode was successfully prepared using HTS technology. Compared to the conventional muffle furnace calcination, the HTS-prepared LSCF exhibits a larger specific surface area and a higher oxygen vacancy concentration, and it demonstrates significant improvements in performance. The oxygen ion conducting SOC (O-SOC) with the HTS-LSCF air electrode achieved a peak power density (PPD) of 960 mW cm-2 and a current density of 0.38 A cm-2 (at 1.3 V) at 700 °C. Meanwhile, the proton conducting SOC (P-SOC) with HTS-LSCF air electrode reached a PPD value of 1.34 W cm-2 and a current density of 3.43 A cm-2 (at 1.3 V) at 700 °C. Additionally, the P-SOC with HTS-LSCF air electrode showed no significant degradation during over 200 h of long-term testing, reflecting the excellent stability of HTS-LSCF. This work provides a fast, efficient, and economical approach for synthesizing high-performance, high-stability SOC air electrode materials.

Investigation on oxygen vacancy regulation mechanism of ZnO gas sensors under temperature modulation mode to distinguish alcohol homologue gases

Homologous gases are difficult to be detected due to their similar chemical properties, especially for metal oxide semiconductor gas sensors whose selectivity has always been a significant challenge. Dynamic temperature modulation method with periodically changing operating temperature was used to detect alcohol homologous gases. However, there are still problems with the deviceization of heating control circuits. In this paper, dynamic temperature modulated method which needs a simple heating circuit is used to distinguish alcohol homologous gases in combination with oxygen vacancy modulation of ZnO gas sensors. Ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol were measured by ZnO gas sensors with different oxygen vacancies content ratios under rectangular wave with a voltage range of 2–6 V. It was found that the greatest difference among the response curves when the material calcined at 600°C which has the largest oxygen vacancies content ratio. Finally, the recognition of the four homologue gases measured by ZnO-600 sensor was achieved by dynamic time warping and the recognition accuracy is 99.33 %.

Enhanced photocatalytic CO2 reduction to CH4 on oxygen vacancy-rich NiCo2O4 with surface pits: Synthesis, DFT calculations, and mechanistic insights

Unraveling the influence of surface microstructure in materials on their interaction with CO2 remains a critical challenge in achieving efficient and selective CO2 reduction. In this study, we report the engineering of pit structures on the NiCo2O4 surface for efficient photocatalytic reduction of CO2. Characterization results show that calcination temperature affects the distribution of surface pits and oxygen vacancy concentration. Oxygen vacancy sites accompanying surface pits facilitate the generation and movement of photogenerated electrons and holes, preventing their recombination and promoting the conversion of CO2. The CH4 yield from photocatalytic CO2 reduction reaches 52.4 μmol g−1 with the optimal pitted NiCo2O4 catalyst (PNCO2), significantly surpassing the 18.4 μmol g−1 yield of non-pitted NiCo2O4 (NPNCO). Additionally, PNCO2 improves selectivity from 81.8 % for NPNCO to 94.1 %. Density functional theory calculations show that CO2 adsorption on the PNCO2 surface is significantly enhanced as the d-band center shifts toward the Fermi level. The adsorbed CO2 combines with electrons enriched at the Ni sites at the edges of the surface pits, leading to further activation. The reduction of CO2 to intermediate products such as CHO* is analyzed based on in situ diffuse reflectance infrared Fourier transform spectroscopy, and a possible reaction pathway is proposed. This work offers fresh insights into engineering surface pit structures for the design and synthesis of catalysts for photocatalytic CO2 reduction.

Cause, Consequence, and Control of Ag Vacancies in BaAg2-xAs2.

The impact of transition metal (Ag) deficiencies on the structural and transport properties of ThCr2Si2-type arsenides are investigated. We experimentally confirm a partial occupancy of Ag in BaAg2-xAs2, which can be predictably controlled within 0.053(5) ≤ x ≤ 0.19(1) by varying the quenching temperature during the crystal growth. Density functional theory calculations reveal that substoichiometric concentrations of Ag lower the density of states at the Fermi level, providing an electronic cause for the tendency of Ag to form vacancies. This vacancy concentration is linked to a characteristic kink in electrical resistivity that can be substantially shifted from 22 to 125 K and is established as the metric of a low-temperature structural phase transition (SPT) in BaAg2-xAs2. Along with electrical resistivity, the Seebeck coefficient and heat capacity for selected BaAg2-xAs2 samples are presented, which also exhibit anomalies due to the SPT.

Hydrogen and vacancy concentrations in [formula omitted]-iron under high hydrogen gas pressure and external stress: A first-principles neural network simulation study

The metal-hydrogen-vacancy interaction in α-iron is crucial for understanding hydrogen embrittlement behavior and developing reliable materials for green gaseous hydrogen applications; however, it remains underexplored, particularly in contexts involving external stress and high hydrogen gas pressure. In this study, we performed quantitative analyses of metal-vacancy–hydrogen interactions in α-iron, measured by hydrogen solubility and the thermodynamics of vacancy–hydrogen complexes, under such challenging conditions using a reliable first-principles neural network potential. High hydrogen gas pressures reaching up to 2 GPa were investigated. As the atomic concentration surpasses approximately 0.01, hydrogen solubility is dominated by hydrogen-induced lattice distortion (primarily volumetric expansion) and the interactions between hydrogen atoms within the metal matrix, resulting in significant deviations from Sieverts’ law. Our results reveal a significant effect of shear stress on hydrogen solubility, deviating from previously used equations. Moreover, the influence of external stress on the thermodynamics of the vacancy–hydrogen complex, particularly vacancy formation free energy, is uniquely characterized by hydrogen solubility, regardless of the external stress magnitude. It thereby offers a rapid method to estimate the vacancy properties under external stress based on readily accessible external-stress-free data.

Recent Advances in Barium Cobaltite-Based Perovskite Oxides as Cathodes for Intermediate-Temperature Solid Oxide Fuel Cells.

Solid oxide fuel cells (SOFCs) are considered as advanced energy conversion technologies due to the high efficiency, fuel flexibility, and all-solid structure. Nevertheless, their widespread applications are strongly hindered by the high operational temperatures, limited material selection choices, inferior long-term stability, and relatively high costs. Therefore, reducing operational temperatures of SOFCs to intermediate-temperature (IT, 500-800°C) range can remarkably promote the practical applications by enabling the use of low-cost materials and enhancing the cell stability. Nevertheless, the conventional cathodes for high-temperature SOFCs display inferior electrocatalytic activity for oxygen reduction reaction (ORR) at reduced temperatures. Barium cobaltite (BaCoO3-δ)-based perovskite oxides are regarded as promising cathodes for IT-SOFCs because of the high free lattice volume and large oxygen vacancy content. However, BaCoO3-δ-based perovskite oxides suffer from poor structural stability, inferior thermal compatibility, and insufficient ionic conductivity. Herein, an in-time review about the recent advances in BaCoO3-δ-based cathodes for IT-SOFCs is presented by emphasizing the material design strategies including functional/selectively doping, deficiency control, and (nano)composite construction to enhance the ORR activity/durability and thermal compatibility. Finally, the currently existed challenges and future research trends are presented. This review will provide valuable insights for the development of BaCoO3-δ-based electrocatalysts for various energy conversion/storage technologies.

CaO composite improves the conversion efficiency of free radicals in the catalytic activation of permonsulfate by Cu-based oxides

The advanced oxidation technology based on persulfate has excellent performance in the efficient removal of refractory organic pollutants in water bodies, among which the heterogeneous catalytic activation system has been studied extensively due to its characteristics of convenient operation, low energy consumption, and no secondary pollution. Many studies have been focused on improving the overall oxidation efficiency of target substrates in heterogeneous catalytic oxidation systems. Herein, a series of bimetallic composite oxides (CaOMOx) (M = Cu, Fe, Ni, etc.) were prepared by combining inert metal oxides—CaO with various transition metal oxides, and were used for permonosulfate (PMS) activation. Among them, the introduction of CaO has the most obvious effect on the catalytic efficiency of CaOCuO/PMS system. Almost 100 % of benzothiazole (BTH) was degraded within 40 min at 0.3 g/L PMS and 0.15 g/L CaOCuO. The mechanism study showed that the introduction of CaO significantly increased the content of oxygen vacancies (OVs) on CaOCuO, and thus promoted the formation of surface hydroxyl groups to strengthen the adsorption capacity for PMS. In addition, the introduction of CaO enhanced the reducibility of Cu species and thus promoted the transformation of Cu2+ to Cu+, ensured the continuous and rapid generation of SO4•-, thereby promoting the improvement of oxidation efficiency. Our study provides a novel strategy for improving the conversion efficiency of free radical in heterogeneous persulfate catalytic oxidation systems.

The evolution of micro-photoluminescence spectra of PECVD diamond microcrystals along the vertical growth direction and their dependence on CH4 concentration

The changes in the shape of micro-photoluminescence spectra of PECVD diamond micro-crystal measured, depending on the position of the excitation laser spot along the crystallite height, were analyzed. It was ascertained that the processes of SiV defect formation non-monotonically depend on the distance from the Si substrate. At the distances of 2–20 μm the concentration of SiV defects increases, then at distances larger than 20 μm the number of SiV defects decreases. The concentration of NV− and NV0 defects monotonically increases with the distance from the Si substrate. The predomination of SiV defect formation at the beginning stages of the crystal growth is explained by the substantial concentration of carbon vacancies required for their formation. With the increase in the distance from the substrate, the crystalline perfection increases, the concentration of carbon vacancies decreases and the processes of NV− and NV0 defect formation dominate. The increase in CH4 fraction within 0.75–6 % leads to the increase in the volume fraction of graphite-like carbon, which is the good diffusion channel for Si atoms from the substrate into the plasma. Therefore, the concentration of SiV, NV−, and NV0 defects on the surface of the crystal depends on the volume fraction of graphite-like carbon defined by CH4 content.

Introducing oxygen vacancies into WO3 thin film for improving hydrogen sensing performance of Pd/WO3-x/AAO sensors

Introducing oxygen vacancy into semiconducting metal oxides (SMOs) is a strategic approach to promote their gas sensing performances. In this paper, the WO3-x thin films were meticulously deposited onto an anodic aluminum oxide (AAO) substrate, and the oxygen vacancies concentrations of WO3-x thin films were changed by adjusting the ratio of flux of Ar to O2 in magnetron sputtering process. Sequentially, a layer of palladium (Pd) was deposited on the WO3-x/AAO films, creating a nano-mesh structured hydrogen sensor with Pd as the catalytic element. The resulted amorphous WO3-x samples with varying concentration of oxygen vacancies were thoroughly analyzed using XPS and ESR, which confirmed that the oxygen vacancies concentration escalated with an increase in the ratio of flux of Ar to O2. The hydrogen sensitivity of prepared Pd/WO3-x/AAO sensors were examined. Our findings revealed an enhancement in hydrogen sensitivity for the sensors with an optimal concentration of oxygen vacancies. However, an excess of these vacancies was found to deteriorate their hydrogen sensing performance. Notably, the optimized Pd/WO3-x/AAO sensor exhibited a marked response even at a hydrogen concentration as low as 100 ppb, demonstrating its high sensitivity and selectivity towards hydrogen detection.

Effect of carbon vacancy on phase formation and mechanical properties of high-entropy (Ti,Nb,Ta,Hf,W)Cx

High-entropy (Ti0.2Nb0.2Ta0.2Hf0.2W0.2)Cx with different carbon vacancies were prepared from raw binary carbides in this study. The influences of stoichiometry, particle size of raw powder, and sintering temperature on phase formation, microstructure, and mechanical properties of (Ti0.2Nb0.2Ta0.2Hf0.2W0.2)Cx were systematically investigated. The results indicate that the introduction of carbon vacancies and using finer raw binary carbide powders can both significantly enhance the formation ability of single-phase composition with uniform elemental distributions. The formation of a high-entropy phase could enhance the Vicker’s hardness. The flexural strength is greatly influenced by the content of carbon vacancy, which is greatly detrimental to flexural strength. The fracture toughness is determined by both the content of carbon vacancies and the presence of secondary phases. By optimizing the content of carbon vacancies, particle size of raw powders, and sintering temperature, (Ti0.2Nb0.2Ta0.2Hf0.2W0.2)C shows super high flexural strength of 743 MPa and fracture toughness of 8.6 MPa m-1/2.

Molecular dynamics study of mechanical stability of Ti4C3 MXene subjected to chirality, temperature, strain rate, and point-vacancy for Lithium-ion batteries

Two-dimensional Ti4C3 MXene has recently emerged as a promising electrode for Lithium-ion batteries (LIBs) because of its outstanding ion-transport abilities and high Li-absorbability. This study employed molecular dynamics simulation to explore the mechanical stability of Ti4C3 MXene subjected to various temperatures, strain rates, and vacancy concentrations. A slightly superior tensile strength and elasticity modulus have been observed along zigzag directions, measuring 148.14 GPa and 29.17 GPa, respectively. On the other hand, armchair-oriented Ti4C3 MXene shows a considerably greater fracture strain of 0.259 due to its strain-hardening tendency at lower temperatures. Elevated temperature decreases both fracture strength and fracture strain, which is opposite to the effect of strain rate. Armchair loading has been revealed to be more sensitive to strain rate than its counter direction. Unlike temperature and strain rate, point vacancy significantly deteriorates the elastic modulus of Ti4C3 MXene. Carbon vacancies are more probable than titanium vacancies, which have less formation energy. The atomistic deformation profile supports the predicted values of fracture strain from stress-strain behavior. This in-depth study offers a detailed understanding of the mechanical behavior of Ti4C3 MXene under diverse circumstances, which will aid further experimental study and be beneficial for adopting Ti4C3 as anode materials in LIBs.

Characterization of A-site doped PrBaCo2O5+δ perovskites as cathode materials for IT-SOFCs

Creating highly efficient and durable cathodes persists as a formidable task in the realm of intermediate temperature solid oxide fuel cells (IT-SOFCs). Hence, we present a double perovskite oxide, Pr0.6Sr0.4BaCo2O5+δ (PS0.4BC), and its electrocatalytic activity is thoroughly investigated. The XRD test is carried out and a notable transformation in the phase structure is observed upon the introduction of Sr2+ ions into the PBC matrix. That is, the phase structure of the material changes from double perovskite structure to single perovskite structure. Through the TG and TEC test that the introduction of Sr2+ ions into the lattice can create additional sites for oxygen vacancy formation and reduce TEC values. Further verify that Sr doping can enhance the concentration of oxygen vacancies of the material. The PS0.4BC cathode material exhibits remarkably low polarization resistance, achieving an impressive value of 0.027 Ω cm2 at an operating temperature of 800 °C. Oxygen partial pressure test shows that as the oxygen partial pressure decreases, there is a notable increase in impedance, particularly evident in the low frequency region of the Nyquist plots. This indicates that the oxygen content has obvious effects on the low-frequency processes. When the oxygen partial pressure exceeds 0.05 atm, the oxygen adsorption-dissociation and diffusion process is the rate-limiting step in the ORR. However, when the oxygen partial pressure is less than 0.05 atm, the formation of lattice oxygen through the combination of oxygen ions and oxygen vacancies processes is the rate-limiting step. Compared PBC cathode material, the more pronounced changes in the high frequency arc of the PS0.4BC cathode at the same oxygen content. It shows that Sr doping significantly changes the high frequency process. After doping, the oxygen vacancy concentration increases, which facilitates the occurrence of the charge transfer process at high frequency.

Metal nitrides as electrocatalysts in green ammonia synthesis

Green ammonia is assumed to be an important part of the European hydrogen economy and one of the most important substrates of chemical industry. The future development of its manufacturing processes can be related to the electrocatalytic studies yielding in the development of the catalytic materials that would effectively break the nitrogen-nitrogen bond to successfully drive the N2RR—a process of molecular nitrogen electroreduction to ammonia. Molecular nitrogen is characterized with strong triple bond energies (942 kJ/mol) which leading into large dissociation energy of N2 (9,76 eV) and also large energy barrier of the first step of triple bond dissociation 410 kJ/mol (4,25 eV). Those large energies makes reduction to ammonia an extremely difficult task. Metal nitrides of d and f block became in interest due to their activity in ammonia production from molecular nitrogen and hydrogen. Practically all the transition elements occurs in one of the four types of crystalline structures: regular, regular face cantered, hexagonal and hexagonal close packed. The reactions of these metals with nitrogen (or ammonia) typically yields in nitride compounds of an identical type of crystalline structure as the initial metal. Dealing with single metal systems, their ternary counterparts and metal–metal nitride heterostructures, the presented review shows that nitrides are promising groups of electrocatalytic materials. Being property-prone to their internal structural features such as non-stoichiometry and correlated concentration of nitrogen vacancies, metal nitrides are a good candidate for joined investigations spanned between electrochemistry, inorganic chemistry and material engineering.

Perovskite/cobalt-based metal-organic framework hybrid promotes hydrogen production from oilfield wastewater electrolysis

Hydrogen has been recognized as a new green energy source. However, in regions where fresh water is scarce, research on the use of complex water systems, such as seawater and oilfield wastewater, to produce hydrogen by electrolysis instead of fresh water has become a pressing issue. In this paper, a low-cost and easy-to-synthesized hybrid catalyst composed of perovskite oxide SrCo0.7Fe0.3O3-δ (SCF) and cobalt-based metal-organic framework (Co-MOF) were synthesized using a simple and feasible in-situ coprecipitation method and exhibited excellent hydrogen evolution reaction (HER) activity in oilfield wastewater. The improvement of activity can be attributed to the synergistic effect between the two materials, which have more concentration of oxygen vacancies and more HER active sites due to Co ion migration. This work provides a practical approach to enhance HER activity in complex water systems by constructing spatial composite structures.

Ti- and Ba-rich phlogopitic micas in alkaline basic and upper mantle igneous rocks; stoichiometry, stability, and Fe valence estimation reassessed and rationalised

Ti- and Ba-rich tri-octahedral micas occur in fractionated basic igneous rocks, metasomatized mantle peridotites, metamorphosed pelites/carbonates, and hydrothermally altered mineral deposits. Electron microprobe analyses (EMP), with all iron reported as FeO, were widely used in the 1970/80s to interpret Ti and Ba substitution mechanisms, based on 22 O2– unit cell calculations, implying that cation vacancies occur in octahedral and/or intersheet sites. In 1996 EMP with chemical and physical analyses for ferric and total Fe, H2O, (OH), and element-specific Fe X-ray Absorption Spectroscopy (both K and L-edges) established valence states for Fe and Ti and cation site occupancies, that ∼50 % O replaces (OH) molecules, and that 24 anion cell formulae show the absence of cation vacancies. Cell formula calculation protocol for phlogopitic micas is refined here and results tested against the stoichiometric formula for vacancy-free phlogopite, XIIK2VIMg6IV[Si6Al2]O20(OH)4. Hypothetical sheet silicate compositions, calculated with fixed contents of vacancies linked to particular mixed-valence element substitutions, confirm that reliable unit cell formulae for natural mica solids require that each stoichiometric vacancy must be accounted for. If reliable estimates for ‘excess O’ (denoted WO2−) are assigned to EMP analyses, the proportion of the oxy-mica component in a mica solid solution can be defined. This approach is tested using published analyses for Ti- and Ba-rich biotites from fractionated basic and ultramafic volcanic igneous rocks (oxymica range 2.5–45 %; TiO2 up to 14 %; BaO up to 23 %), upper mantle peridotites (equivalent values 7–18 %; 6 %; 0.7 %), and metasomatised upper mantle (2–37 %; 9 %; 23 %). Enrichments of Ti and Ba in micas are clearly linked to the extra oxygen charge required to neutralise the more highly charged Ba2+ and Ti4+ replacing K+ and Mg2+.Substitution mechanisms involving Ba, Ti, and Fe3+ in ideal phlogopite involve coupled inter-site / inter-valence interactions so both site-ordering and valence-balance between the different cation sites must be accounted for. The cation exchange 2XIIK+ + 4VI(Mg2+ + Fe2+) + 4IVSi4+ ↔ XIIBa2+ + 3VITi4+ + 4(Altotal + Fe3+ + Crtotal)3+ is used here so that valence and site order can be considered together. Compositional variations show well-defined trends towards high-oxymica content and vacancy-free Ti and Ba mica end-members, rather than to oxy-free end-members with essential vacancies. Average compositions for different source rock micas are used to assess compositional trends; molecular WO2− values are refined by relating initial estimates directly to the wt.% TiO2 contents; and refined WO2− and stoichiometrically calculated Fe3+/Fetotal ratios ranging ∼0.1–0.5) are correlated with possible primary magmatic values.

Substitution of Ce4+ for ionic at both A/B sites greatly improves the microwave responses of (Sr0.9Ca0.1)1/2La1/2Al1/2Ti1/2O3 perovskite ceramics

In this paper, (Sr0.9Ca0.1)1/2La1/2Al1/2Ti1/2O3-x wt.% CeO2 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) ceramics were synthesized via solid state reaction. The effects of Ce4+ doping on microstructure and microwave dielectric properties were studied. All samples crystallized as perovskite single-phase. Ce4+ substitution for La3+ occurred at the A site for 0 < x ≤ 0.4, and for Ti4+ at the B site for 0.4 ≤ x ≤ 0.5. Oxygen vacancy concentration was linked to substitution sites, decreasing for x ≤ 0.3 and increasing for x ≥ 0.4, as shown by XPS analysis. The quality factor was influenced by oxygen vacancies, grain size, and packing fraction. Bonding valence and oxygen octahedral distortion affected the temperature coefficient of resonant frequency. At x = 0.4 and sintered at 1570 °C, the ceramics showed excellent properties: εr = 38.83, Q×f = 54058 GHz, τf = 2.137 ppm/°C, making it a promising low-loss dielectric ceramic for microwave communication applications.

Effect of diffusion barriers on steam oxidation properties and interface evolutions of Cr coating for zirconium alloy at 1200 °C

Currently, Cr-based coatings are considered the most promising protective coatings for zirconium alloy claddings under the ATF design concept. However, the primary factor affecting the oxidation resistance of Cr coatings is the interdiffusion of Cr and Zr. In this study, Cr coatings with three refractory metal interlayers of Nb, Mo, and Ta were deposited on zirconium alloy surfaces using closed-field unbalanced magnetron sputtering. The study investigated the effects of different interlayers on the microstructure, oxidation properties, and interface evolution process of Cr coatings under steam conditions at 1200 ℃, and compared them with Cr coatings without intermediate layers. The results indicate that the refractory metal interlayer influences the orientation and growth rate of Cr coating grains. The formation of a Laves phase mixed layer in the interlayer during oxidation effectively hinders the diffusion of O and Cr to the zirconium alloy matrix, enhancing its oxidation resistance. Furthermore, the diffusion rate and vacancy concentration of Mo and Ta elements to the Zr layer exceed that of diffusion to the Cr layer. During the cooling process, a precipitate phase forms in the Zr-4 matrix, while the Nb coating forms an infinite solid solution in the β-Zr.

Oxygen plasma-assisted magnetron sputtering deposition of non-stoichiometric Y2O3 films: Influence of oxygen vacancies on etching resistance

Yttrium oxide (Y2O3) films are widely used to protect equipment in plasma etching, a crucial technique in semiconductor processing, due to their exceptional resistance to plasma etching. Since oxygen vacancy affects the performance of Y2O3 and may impact physical etching resistance, the internal relationship necessitates further investigation. In this article, Y2O3 films with varying oxygen vacancy concentrations are prepared by reactive magnetron sputtering with the assistance of oxygen plasma. The formation and development of oxygen vacancies in cubic Y2O3 films and their impact on the physical etching resistance were investigated. The experiment results indicate that the accumulation of oxygen vacancies causes non-stoichiometry and the etching rate is significantly reduced. Combined with density-functional theory, it is revealed that oxygen vacancy distorts the lattice, which increases covalent YO bonding and the formation energy of atoms. Moreover, the vacancy line defects resulting from diffusion and aggregation of oxygen vacancies exert a similar influence on the adjacent yttrium and oxygen layers. The enhancement of physical etching resistance is attributed to the strengthened internal YO bonds led by increasing oxygen vacancy concentration in the cubic Y2O3 films without inducing phase transition. The discovery enriches the understanding of how plasma interacts with Y2O3, and the etching mechanism.

Self-acceleration effect of Mn/Ce-modified carbide slag in CO2 absorption for CaO/CaCO3 energy storage

Carbide slag, a solid waste from the chlor-alkali industry, can be used for CO2 capture and energy storage. Herein, the cyclic reaction activity of Mn/Ce-modified carbide slag under energy storage conditions was studied. The Mn/Ce-modified carbide slag shows energy storage density over 2100 kJ/kg and CO2 absorption capacity of 0.52 g CO2/g sorbent after 30 cycles. Notably, both carbonation and calcination rates are accelerated with the number of cycles. This self-acceleration effect is related to the evolution of oxygen vacancy concentration and texture structure of Mn/Ce-modified carbide slag during the cycles. In the cycles, CaMnO3 in the Mn/Ce-modified carbide slag reacts with the formed CaCO3 in the carbonation stage to produce more Ca2MnO4. The formation of Ca2MnO4 increases oxygen vacancies in the Mn/Ce-modified carbide slag, significantly enhancing its CO2 adsorption capacity. Thus, the release of the increased CO2 in the calcination stage generates more pores in the 10–100 nm diameter range in the modified carbide slag, facilitating rapid carbonation. Thus, the Mn/Ce-modified carbide slag exhibits good prospect for CaO/CaCO3 thermochemical energy storage.

Core-shell structure and high rate performance of Ce-doped Li4Ti5O12 for lithium-ion battery anode materials

Lithium titanate (LTO) can be a very promising anode material for lithium-ion batteries (LSBs) due to its inherent ability to inhibit the growth of lithium dendrites as well as its unique “zero-strain” properties. Unfortunately, the low electronic conductivity of LTO leads to serious shortcomings in higher electrochemical demands. In this work, the Ce3+-doped C@Li4Ti5-xCexO12 (x = 0, 0.1, 0.15 and 0.2) anode materials synthesized by the hydrothermal method using carbon spheres as templates showed more significant improvement in both structural and electrochemical properties. The results demonstrate that electronic conductivity, lithium-ion diffusion rate, discharge specific capacity, discharge rate capability, and significant improvement stability of C@Li4Ti5-xCexO12 (x = 0.1, 0.15 and 0.2) electrodes. Among them, C@Li4Ti4.85Ce0.15O12 electrode exhibits the highest initial discharge specific capacity (250.86 mAh/g) at 0.1C, which is 1.28-fold that of C@ Li4Ti5O12 (195.94 mAh/g), and initial discharge capacity from 205.96 mAh/g to 170.39 mAh/g after 500 cycles, corresponding to 82.7 % of the initial stable discharge capacity. The outstanding performance of C@Li4Ti4.85Ce0.15O12 can be attributed to the lower interfacial impedance, higher electronic conductivity, high oxygen vacancy concentration, and moderate amount of Ce3+ doping can enhance the electrochemical activity. In addition, carbon sphere surface defects shown to be effective in improving lithium-ion storage. This work demonstrates that Ce3+ doping is an effective method to improve the electrochemical performance of LTOs and provides a more effective guide for designing and optimizing anode electrode materials for lithium-ion batteries