Formation Of Intermediate Phase Research Articles

Removal of Residual Additive Enabling Perfect Crystallization of Photovoltaic Perovskites.

Achieving high-efficiency perovskite solar cells (PSCs) hinges on the precise control of the perovskite film crystallization process, often improved by the inclusion of additives. While dimethyl sulfoxide (DMSO) is traditionally used to manage this process, its removal from the films is problematic. In this work, methyl phenyl sulfoxide (MPSO) was employed instead of DMSO to slow the crystallization rate, as MPSO is more easily removed from the perovskite structure. The electron delocalization associated with the benzene ring in MPSO decreases the electron density around the oxygen atom in the sulfoxide group, thus reducing its interaction with PbI2. This strategy not only sustains the formation of a crystallization-slowing intermediate phase but also simplifies the elimination of the additive. Consequently, the optimized PSCs achieved a leading power conversion efficiency (PCE) of 25.95 % along with exceptional stability. This strategy provides a novel method for fine-tuning perovskite crystallization to enhance the overall performance of photovoltaic devices.

Across‐Interface Effect of Alkylamine Salt on the Formation of Intermediate Phase and Defect Passivation in High‐Performance of Perovskite Solar Cells

AbstractHigh‐quality and low‐defect perovskite active layer (PVK) and electron transport layer (ETL) are essential for high‐performance perovskite solar cells (PSCs). Herein, an alkylamine salt, cyclohexylmethylammonium chloride (CMACl) is introduced into tin oxide (SnO2) ETL. CMACl, possessing protonated −NH3+ group and Cl− ions, not only effectively inhibits the aggregation of SnO2 colloids and enhances the quality of the ETLs, but also reduces and passivates the defects on ETLs. On the other hand, via the across‐interface effect of alkylamine salt by thermal diffusion, the CMACl‐PbI2 intermediate phase is formed and leads to the high quality of PVK, meanwhile, the defect on the buried interfaces and in the bulk of PVK are passivated by CMA+ and Cl− ions. Consequently, the CMACl‐modified PSC achieves a preeminent power conversion efficiency of 25.47% and excellent stability. This work demonstrates a facile and effective approach for synchronous optimization of ETL and PVK for high‐performance PSCs by across‐interface effect.

Methylammonium-Free Ink for Blade-Coating of Pure-Phase α-FAPbI3 Perovskite Films in Air.

The α-c (α-FAPbI3) has been extensively employed in the fabrication of high-efficiency perovskite solar cells, yet heavily relied on multiple additives in upscalable fabrication in air. In this work, a simple α-FAPbI3 ink is developed for the blade-coating fabrication of phase-pure α-FAPbI3 in ambient air free from any additives containing extrinsic ions. The introduction of 2-imidazolidinone (IMD) to the FAPbI3 precursor inks leads to the formation of intermediate phases that change the phase transition pathway from δ-FAPbI3 to α-FAPbI3 by tilting the PbI6 octahedrons with strong coordination to Pb2+. Furthermore, the IMD ligands in the intermediate phase gradually escape from the perovskite film during the annealing, leaving a phase-pure α-FAPbI3 film vertically grown with large grains. Consequently, the small-sized PSCs fabricated with blade-coated α-FAPbI3 film achieve an efficiency of up to 23.14%, and the corresponding mini-module yields an efficiency of 19.66%. The device performance is among the highest reported for phase-pure α-FAPbI3 PSCs fabricated in the air without non-native cations or chloride additives, offering a simple and robust fabrication approach of phase-pure α-FAPbI3 films for PV application.

Controlling Intermediate Phase Formation to Enhance Photovoltaic Performance of Inverted FA-Based Perovskite Solar Cells

Controlling Intermediate Phase Formation to Enhance Photovoltaic Performance of Inverted FA-Based Perovskite Solar Cells

Precursor Ink Engineering to Implement Vacuum Extraction Method for Scalable Production of Perovskite Solar Cells.

Engineering perovskite precursor ink to widen the processing window is crucial to obtaining uniform, compact, and pinhole-free perovskite films at scale using industrially relevant solution coating techniques. Here, we introduce a ternary solvent system and systematically investigate the impacts of coordinating solvents, N-methyl-2-pyrrolidone (NMP) and N,N'-dimethylpropyleneurea (DMPU), on the physical properties of the slot-die-coated perovskite films and on the corresponding device performance. Tailoring NMP and DMPU concentrations in the precursor ink allows us to control the perovskite intermediate phase formation and widen the processing window, enabling the reproducible production of perovskite films with high photoelectrical quality at scale. Using the optimized precursor ink, we demonstrate slot-die-coated perovskite minimodules with power conversion efficiencies of 19 and 16% on 56 and 100 cm2 substrates, respectively.

Formation of YOF on Y2O3 through surface modification with NH4F and its plasma-resistance behavior

Yttrium oxyfluoride (YOF) is known for exhibiting superior plasma-resistance properties compared to Y2O3, particularly in a fluorocarbon plasma environment. The formation of the YOF layer directly on the surface of Y2O3 via surface modification may be considered as a viable and cost-effective method. In this study, we employed ammonium fluoride (NH4F) salt for the surface modification of Y2O3. By using a 40 wt% NH4F aqueous salt solution, the YOF layer with a thickness of about 8.6 μm was efficaciously formed in-situ on the surface of Y2O3 based on the fluorination mechanism. The composition and microstructure of the modified Y2O3 surface was thoroughly characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD analysis revealed the formation of distinct intermediate ammonium yttrium fluoride phases depending upon the heat treatment temperature (150 − 500 °C) through the fluorination of Y2O3 with NH4F. A stable YOF phase was formed ultimately at 300 °C. Plasma etching tests were performed using a mixture of CF4/Ar/O2 gases for 1 h. The microstructures of specimens are observed by SEM before and after plasma treatments. Plasma exposure tests demonstrated that specimens heat-treated at 500 °C for 2 h exhibit excellent plasma-resistance behavior with minimal surface damage, which is attributed to the presence of stable and dense YOF phase.

Advanced smectite alteration and the role of accessory reactants at 180 °C: New experimental constraints on the stability of bentonite

Bentonite clay is commonly accepted as an appropriate material for backfilling the space between the radioactive canisters and the host rock of planned underground repository sites for waste disposal. Despite its favourable properties as a hydrodynamic seal, its long-term stability remains a concern. This experimental study of a Bavarian bentonite investigated advanced montmorillonite (smectite) illitisation at 180 °C in the presence of K-oxalate and/or the accessory minerals of pyrite and calcite. The formation of mixed-layered illite-smectite was quantified by X-ray diffraction Rietveld refinement and the crystal chemistry was determined by transmission electron microscopy. The results showed neocrystallisation of a celadonitic illite-smectite (up to 63% illite-layers) after treatment with KCl or K-oxalate with increased Al3+ in the tetrahedral sheets, reduced amounts in the octahedral locations and increased fixation of non-exchangeable K+ ions in response to the increased layer charges. K-oxalate complexation of Al3+ and enhanced dissolution of the smectite resulted in the formation of a possible intermediate amorphous phase and illite-smectite crystallites with additional vacant sites explaining the lower number of octahedral ions (<2 per formula unit). Adding 10% pyrite, 10% calcite, or 5% of each, did influence the degree of alteration to a recognisable degree in the presence of KCl, but the effects on the rate of illitisation were minimal when reacted with K-oxalate, which further increased illitisation by up to 6.4 times. Although batch reactor experiments do have limitations compared to complex repository conditions, our results do indicate that claystone host rocks low in organic matter should be favoured over organic-rich lithologies that are likely to contain oxalate ligands or similar catalysing compounds.

(Invited) Understanding Electrochemical Reaction Mechanisms of Sulfur in All-Solid-State Batteries through Operando and Theoretical Studies

All-solid-state lithium-sulfur batteries (ASLSBs) have been considered a promising next-generation energy storage technology due to their remarkable safety and high energy density. In ASLSBs, the electrochemical pathways are intrinsically different from conventional Li-S batteries using liquid electrolytes. However, the mechanism still lacks clear identification and deep understanding. Herein, for the first time, we investigated the chemistries and explored the electrochemical reaction mechanism in ASLSBs through coupling operando Raman spectroscopy and ex-situ X-ray absorption spectroscopy. We proved that no long-chain lithium polysulfides (Li2Sn, 4≤n≤8) were formed during the redox reactions, but a short-chain polysulfide (Li2S2) intermediate phase formation was identified in the conversion between active material S8 and reduction product Li2S. This evidence explains the electrochemical behavior differences of Li-S batteries when using liquid and solid electrolytes. Moreover, there are partial S8 and Li2S2 remaining at the cathode even at fully lithiation stage, suggesting the sluggish reaction kinetics in the ASLSBs. This study revealed the generation of Li2S2 intermediates in ASLSBs, inspiring future research to further improve the performance of ASLSBs through completing the conversions and promoting reaction kinetics in ASLSBs.

Multiscale investigation on the formation path of the apatite phase in bioactive glasses

Mesoporous bioactive glasses (MBGs) have been reported as promising biomaterials to stimulate and promote the growth of bones. When exposed to Simulated Body Fluid (SBF), MBGs develop an apatite phase called carbonate hydroxyapatite (H(C)A) on their surfaces that closely mimics the mineral phase of bones. In order to gain deeper insights into the key stages of the surface reactions of two different types of MBGs (58S and 70S30C) soaked in SBF, we have used high energy total X-ray scattering coupled to Pair Distribution Function (PDF) analysis, along with Raman spectroscopy and scanning electron microscopy. This type of coupled analytical approach can ultimately help to unravel the details of the reaction kinetics in the complex calcium phosphate environment around the BGs surfaces. The data obtained in our in-vitro study point to the formation of other intermediate phases like amorphous calcium phosphate (ACP) and calcite (CC), that transform after a specific time into H(C)A depending on the composition of the MBGs, their surface properties and their interaction times with SBF.

Reaction dynamics simulation of MoO2 cluster precursor with melting, deoxygenation and sulfuration for MoS2 growth by chemical vapor deposition

Chemical vapor deposition (CVD) is a promising strategy for achieving fascinating large-scale production of MoS2. During CVD, MoO2 exhibits high reactivity and can effectively inhibit intermediate phase formation. Although, the experiments qualitatively demonstrate the MoO2 sulfuration mechanism, the reaction dynamics process on the atomic level is not clear. Herein, according to our previous experimental results of pre-deposited MoO2 vapor–liquid-solid growth MoS2, we investigate microscopic reaction events, including melting, deoxygenation, and sulfuration by reactive molecular dynamics simulation as follow: Terminal oxygen in pre-melting zone on the cluster surface has high reactivity, leading to deoxygenation occurring during melting. The unsaturated coordination Mo atoms are more accessible to sulfuration. With a long simulation time, MoO2 is transformed into MoO0.27S1.95 in which MoS2-like clusters account for up to 92.45 % after annealing. We hope that our work will provide theoretical support for the controlled CVD synthesis of MoS2 and other transition metal dichalcogenides.

A Morphological Study and Effect of Intermediate Phase Formation on Hard and Wear Resistant SiC-Co Composite Coating on Low Carbon Steel via Arc Based Heat Source

A Morphological Study and Effect of Intermediate Phase Formation on Hard and Wear Resistant SiC-Co Composite Coating on Low Carbon Steel via Arc Based Heat Source

Nanosized Tungsten Powder Synthesized Using the Nitridation–Decomposition Method

A facile, one-step nitridation–decomposition method was developed for the synthesis of nanosized tungsten powder with a high surface area. This approach involved the nitridation of WO3 in NH3 to form mesoporous tungsten nitride (W2N), followed by in situ decomposition of W2N to directly yield single-phase W particles. The phase and morphology evolution during the synthesis were systematically investigated and compared with the carbothermal reduction of WO3. It was revealed that powdered tungsten product with single-phase particles was obtained after nitridation at 800 °C combined with in situ decomposition at 1000 °C, displaying an average particle size of 15 nm and a large specific surface area of 6.52 m2/g. Furthermore, the proposed method avoided the limitations associated with intermediate phase formation and coarsening observed in carbothermal reduction, which resulted in the growth of W particles up to ~4.4 μm in size. This work demonstrates the potential of the nitridation–decomposition approach for the scalable and efficient synthesis of high-quality, fine-grained tungsten powder.

Effect of cyclic mechanical treatment on the final properties of Nb + 2Si powder mixtures prepared for SHS

The mechanical pretreatment of a powder mixture of niobium and silicon was studied experimentally and theoretically using the new macrokinetic theory of mechanochemical synthesis. The method of organizing the operation mode of the ball mill affects the degree of grinding and activation of the powder composition, as well as the rate of formation of intermediate phases. The effect of cycling on the temperature inside the mill drum, particle size of the powder mixture, formation of mechanically synthesized niobium silicides, and structure of the initial components has been studied. Varying the cycling can lead to safe and emergency operation of the mill. The final mixtures' characteristics may vary significantly depending on the number of cycles of discontinuous mechanical treatment, even if the total operating time of the ball mill remains the same. The safe conditions for cyclic operation of the mill were determined. The effects of different mechanical treatment modes on the grinding, activation, and phase formation of a powder mixture were investigated. Various parameters were analyzed, including thermophysical, physico-chemical, and kinetic characteristics of the cyclic operation of the AGO-3 ball mill, the kinetics of grinding and activation of Nb and Si particles, and the rate of mechanochemical reaction in the mechanically activated mixture of Nb + 2Si.

Unraveling the influence of Sb dopant to reversible capacity and initial Coulombic efficiency of SnO2-graphene as anodes for sodium storage

Sodium storage materials based on conversion and alloying reactions often suffer from low initial Coulombic efficiency (ICE). Most of literature shows that the SnO2-based anode commonly reveals an ICE below 50 %, and the reasons could be attributed to the partial reversibility in conversion reaction by forming an intermediate phase. This work focuses on using an element doping strategy to suppress the formation of an inert intermediate phase and improves the ICE for SnO2-based anodes in sodium storage applications. Mechanisms of performance enhancement are also carefully investigated. The 3 % Sb doped sample is demonstrated with enhanced electrochemical performance. Specifically, it delivers an initial discharge capacity of 847 mAh g−1 at 50 mA g−1, combining an average enhanced ICE of 57.1 % (37.8 % for the undoped comparison), and it also presents a good rate performance of 206 mAh g−1 at a high current density of 1600 mA g−1. It is found that the Sb dopant reduces the specific capacity of active materials, but it enhances reaction reversibility; improves the overall conductivity of active materials, but does not directly enhance the Na+ diffusion coefficient; helps to restrain the formation of inert phase (the SnO phase) in sodium storage reactions to improve reversibility and initial Coulombic efficiency. Therefore, reversible capacities and initial Coulombic efficiencies can be effectively enhanced after introducing the Sb dopant at an optimized percentage. This work could provide valuable inspiration for designing conversion and alloying-type anodes for sodium storage applications via ion doping methods.

Tin dioxide coated rice husk silica as lead-acid battery positive additive for enhancing the performance under power-intensive applications

Lead-acid batteries rapidly response to instantaneous high-current, rendering them particularly effective for high-power applications, including power traction batteries, starter batteries, and start-stop systems. However, issues arise during intense working rate (6–10C), causing significant polarization that leads to severe oxygen evolution side reactions and softening and shedding of positive active material (PAM), limiting the battery's cycle life. This study introduces a tin dioxide (SnO2) coated rice husk silica (RH-SiO2) composite as an positive additive in lead-acid batteries. The composite (SnO2/RH-SiO2) has a hierarchical pore structure from RH-SiO2, provides a robust conductive framework. The lattice structure of the SnO2 is similar to that of PbO2, while induces the formation of a PbSnO3 intermediate phase during formation process. SnO2/RH-SiO2 can also accelerates lead dioxide deposition and improves the interphase conversion efficiency, while significantly enhances the transformation of α- and β-PbO2, leading to a 20.7% increase in discharge specific capacity. Compared to a standard battery, up to 3.7 times longer at 100% deep discharge cycle life and 4.7 times longer in start-stop-mode testing. In our finding the SnO2/RH-SiO2 composite serves as a highly effective additive for augmenting the performance and longevity of lead-acid batteries in high-power applications, presenting a significant advancement in battery technology.

Changing Template/Al2O3 Ratio in Reaction Gel-An Effective Way to Regulate Nature of Intermediate Phases and Properties of SAPO-11 Molecular Sieves during Crystallization.

A study has been conducted to investigate the formation of intermediate phases during the crystallization of SAPO-11 molecular sieves from reaction mixtures with a varying template (di-n-propylamine) DPA/Al2O3 ratio. It was found that changing the DPA/Al2O3 ratio from 1.0 to 1.8 in the initial reaction gels leads to the formation of different intermediate phases during crystallization into a SAPO-11 molecular sieve. It is shown that at the ratio template/Al2O3 = 1.0, an intermediate amorphous silicoaluminophosphate is formed; at 1.4, a mixture consisting of amorphous and layered phases forms; and at 1.8, a layered phase is present. A simple and innovative approach for controlling the morphology, size, and characteristics of primary crystals and the secondary porous structure in hierarchical SAPO-11 is proposed. The method is based on regulating the DPA/Al2O3 ratio in the reaction gel. The synthesized SAPO-11 molecular sieves with a hierarchical porous structure exhibited high selectivity in the hydroisomerization of n-hexadecane.

Impact of tannic acid on iron oxide nanoclusters synthesized by a polyol solvothermal method

Raspberry-shaped iron oxide nanostructures (RSNs) correspond to oriented aggregated and hollow clusters of nanograins exhibiting a high saturation magnetization and a superparamagnetic behaviour. These nanostructures are promising for a wide range of applications, such as magnetic separation, catalysis, pollution control, and nanomedicine. However, for most applications, particularly nanomedecine and depollution, high colloidal stability is required, and the isoelectric point of iron oxide is around 6–7. Therefore, these nanoclusters need to be coated with a surfactant to obtain colloidal suspensions in water. Here, we have developed a one-pot polyol solvothermal synthesis process to coat these promising nanoclusters with tannic acid (TA), a natural compound with antimicrobial properties, which has been little studied with these nanoclusters. Different parameters of the synthesis were adjusted, such as the molar ratio TA:Fe, the synthesis temperature and duration. We showed that TA interferes deeply in the RSNs synthesis mechanism with the observed reduction of iron(III) to iron(II), the complexation of TA with iron, the formation of intermediate phases, as well as the growth of a parasitic iron carbonate phase and the loss of the oriented aggregation and hollowness of the iron oxide RSNs. Considering all these parameters, the optimal synthesis conditions were thus established (TA:Fe ratio = 0.010, temperature of 200°C and duration of 10.5 h), leading to RSNs with small nanograins, a rather high surface area (82 m2/g), high saturation magnetization (74 emu/g) and good colloidal stability. By combining different characterization techniques, a new synthesis mechanism was proposed different from previously established for RSNs without TA, based on strong TA-iron oxide interfaces.

ИЗУЧЕНИЕ ВОЗМОЖНОСТИ ИСПОЛЬЗОВАНИЯ РАЗЛИЧНЫХ КАРБОНАТНЫХ ПОРОД ПРИ СИНТЕЗЕ КАЛЬЦИЕВО-АЛЮМОФЕРРИТОВОГО КЛИНКЕРА

The article considers the possibility of using carbonate rocks of limestone, marl and chalk in the synthesis of calcium-aluminoferrite clinker (CAFC). The analysis of the structure of carbonate rocks, as well as their influence on the physico-chemical processes occurring during the synthesis of calcium-aluminoferrite clinker, is given. Phase formation has been studied in the temperature ranges 900-1000 °C and 1100-1200 °C with an isothermal exposure of 20 minutes. The heat treatment mode has been selected to obtain the basic phase composition of calcium-aluminoferrite clinker. The dynamics of changes in the qualitative phase composition of firing products at various temperatures, ranging from 900 °C to the clinker sintering temperature of 1200 ° C, as well as quantitative characteristics of the intensity of formation of the main clinker phases are presented. It was found that during the firing of CAFC in the temperature range of 900-1000 °C, raw materials mixtures gradually undergo a number of physico–chemical transformations, the main of which are thermal dissociation of CaCO3, the formation of intermediate phases (CS, CF, Al2O3•4SiO2, Al2O3•SiO2), as a result of decomposition of accompanying minerals and solid-phase interactions, as well as the beginning of the formation of clinker compounds CA, C2AS and C2F. It is proposed to use for the limestone-bauxite composition a temperature of 1150 °C with an exposure of 40-60 minutes, marl-bauxite - 1100 °C with an exposure of 30-40 minutes and chalk-bauxite- 1100 °C with an exposure of 30-40 minutes.

Facile Hydrogen‐Bonding Assisted Crystallization Modulation for Large‐area High‐quality CsPbI2Br Films and Efficient Solar Cells

AbstractThe thermally stable inorganic cesium‐based perovskites promise efficient and stable photovoltaics. Unfortunately, the strong ionic bonds lead to uncontrollable rapid crystallization, making it difficult in fabricating large‐area black‐phase film for photovoltaics. Herein, we developed a facile hydrogen‐bonding assisted strategy for modulating the crystallization of CsPbI2Br to achieve uniform large‐area phase‐pure films with much‐reduced defects. The simple addition of methylamine acetate in precursors not only promotes the formation of intermediate phase via hydrogen bonding to circumvent the direct crystallization of CsPbI2Br from ionic precursors but also widens the film processing window, thus enabling to fabricate large‐area high‐quality phase‐pure CsPbI2Br film under benign conditions. Combining with stable dopant‐free poly(3‐hexylthiophene), the CsPbI2Br solar cells achieve the record‐high efficiencies of 18.14 % and 16.46 % for 0.1 cm2 and 1 cm2 active area, respectively. The obtained high efficiency of 38.24 % under 1000 lux illumination suggests its potential in indoor photovoltaics for powering the Internet of Things, etc.

Facile Hydrogen-Bonding Assisted Crystallization Modulation for Large-area High-quality CsPbI2 Br Films and Efficient Solar Cells.

The thermally stable inorganic cesium-based perovskites promise efficient and stable photovoltaics. Unfortunately, the strong ionic bonds lead to uncontrollable rapid crystallization, making it difficult in fabricating large-area black-phase film for photovoltaics. Herein, we developed a facile hydrogen-bonding assisted strategy for modulating the crystallization of CsPbI2 Br to achieve uniform large-area phase-pure films with much-reduced defects. The simple addition of methylamine acetate in precursors not only promotes the formation of intermediate phase via hydrogen bonding to circumvent the direct crystallization of CsPbI2 Br from ionic precursors but also widens the film processing window, thus enabling to fabricate large-area high-quality phase-pure CsPbI2 Br film under benign conditions. Combining with stable dopant-free poly(3-hexylthiophene), the CsPbI2 Br solar cells achieve the record-high efficiencies of 18.14 % and 16.46 % for 0.1 cm2 and 1 cm2 active area, respectively. The obtained high efficiency of 38.24 % under 1000 lux illumination suggests its potential in indoor photovoltaics for powering the Internet of Things, etc.