Nucleation Growth Processes Research Articles

An Effective Precursor‐Solutioned Strategy for Developing Cu2ZnSn(S, Se)4 Thin Film Toward High Efficiency Solar Cell

AbstractEnhancing the efficiency of Cu2ZnSn (S, Se)4 (CZTSSe) thin‐film solar cells requires the development of well‐crystallized light‐absorbing layers. A deep understanding of the role of precursor solution chemistry in film nucleation and crystal growth processes is essential. Insights into these processes enable the development of innovative strategies to enhance absorber quality, minimize detrimental bulk defects, and ultimately improve device performance. This study elucidates the condensation reactions between thiourea and metal cations, as well as the alcoholysis of 2‐methoxyethanol (MOE), at different concentrations of precursor solutions. The primary focus of this study is implementing a simple and environmentally friendly innovative spin‐coating strategy, aimed at optimizing Cu2ZnSnS4 (CZTS) precursor films and adjusting the Se content within the film bulk to promote grain growth during selenization. This strategy effectively improves absorber morphology while suppressing the formation of deep‐level defects, thereby enhancing carrier transport in both interfacial and bulk regions of the absorber layer. Consequently, CZTSSe absorbers with enhanced crystallinity and reduced defects are synthesized, resulting in a solar cell with an impressive efficiency of 14.10%. These findings underscore the potential for creating highly efficient kesterite CZTSSe solar cells through the manipulation of precursor solution chemistry using environmentally friendly solvents.

Plasma-Structured Molybdenum Oxycarbides Enabling Ultrastable Acidic Hydrogen Evolution up to 10 a cm-2

Fabricating electrocatalysts capable of stable operation at high current densities is crucial for the industrial proton exchange membrane water electrolysis. However, current catalysts suffer from high overpotentials and rapid degradation when working in acid electrolytes at high current densities. Despite these advantages, critical challenges still exist in designing efficient catalysts for HER in acidic electrolytes at high current densities: 1) Poor long-term stability. The corrosive environment of strong acids, combined with the heat and mechanical stresses from hydrogen (H2) bubble generation at high current densities, severely challenges the stability of existing catalysts, including those noble metal-based ones. Catalysts with both excellent thermodynamic stability and robust physical adhesion to substrates are required to ensure long-term stability under these harsh conditions. 2) High overpotential at large current densities. At high current densities, high activation energy is required to drive HER because of the rapidly consumed H3O+ near the catalyst surface and the blocked active sites by the high-level H2 bubble coverage at catalyst surfaces, leading to increased overpotential and reduced energy efficiency.Existing transition metal-based catalysts generally exhibit optimal activities only at low current densities (1-100 mA cm−2) with limited stability, making their operation in acidic electrolytes at industrial-level current densities (> 3 A cm−2) quite challenging. Non-equilibrium plasmas, characterized by highly energetic reactive species in a far-from-equilibrium state and the capability to operate at low temperatures, offer distinct advantages in the development and fabrication of innovative materials. The existence of non-equilibrium plasmas can significantly influence nucleation and crystal growth processes in material synthesis, facilitating thermodynamically unfavorable reactions that are difficult or impossible to achieve using conventional equilibrium thermal methods.In this paper, we report the in-situ growth of vertically standing nanoedge-enriched molybdenum oxycarbide nanosheets (MoOxCy) through plasma-enhanced chemical vapor deposition (PECVD) based on earth-abundant salts (i.e., MoO3 and NaCl) as precursors to achieve ultrahigh-throughput acidic electrocatalytic hydrogen evolution at high current densities up to 10 A cm-2. The plasma-structured nanoedge-enriched MoOxCy catalysts offer the following benefits toward HER: 1) Significantly improved long-term stability of catalysts because of the non-equilibrium plasma-engineered structures, which are kinetically unfavorable to obtain through conventional equilibrium thermal methods; 2) Strong localized electric field near the ultrasharp edges of the catalysts, enabling fast diffusion of H3O+ from the electrolyte to catalyst surface; 3) Efficient hydrogen bubble detachment from the nanoedge-enriched structure with high roughness, maintaining continuous exposure of catalytic sites to the surrounding electrolyte. Benefiting from the unique plasma-induced morphology and chemical composition, the MoOxCy exhibits outstanding HER performance with a low overpotential (η) of 415 mV at an ultrahigh current density (j) of up to 10 A cm-2 for 1,000 h in 0.5 M H2SO4. This performance leads to an ultrahigh H2 throughput of 4,477.4 L cm-2, substantially outperforming the state-of-the-art transition metal- and even noble metal-based catalysts. This work paves new avenues for the development of high-efficiency catalysts for practical industrial applications in electrocatalytic hydrogen evolution.

Regulating Intermolecular Interactions and Film Formation Kinetics for Record Efficiency in Difluorobenzothiadizole‐Based Organic Solar Cells

AbstractThe difluorobenzothiadizole (ffBT) unit is one of the most classic electron‐accepting building blocks used to construct D‐A copolymers for applications in organic solar cells (OSCs). Historically, ffBT‐based polymers have achieved record power conversion efficiencies (PCEs) in fullerene‐based OSCs owing to their strong temperature‐dependent aggregation (TDA) characteristics. However, their excessive miscibility and rapid aggregation kinetics during film formation have hindered their performance with state‐of‐the‐art non‐fullerene acceptors (NFAs). Herein, we synthesized two ffBT‐based copolymers, PffBT‐2T and PffBT‐4T, incorporating different π‐bridges to modulate intermolecular interactions and aggregation tendencies. Experimental and theoretical studies revealed that PffBT‐4T exhibits reduced electrostatic potential differences and miscibility with L8‐BO compared to PffBT‐2T. This facilitates improved phase separation in the active layer, leading to enhanced molecular packing and optimized morphology. Moreover, PffBT‐4T demonstrated a prolonged nucleation and crystal growth process, leading to enhanced molecular packing and optimized morphology. Consequently, PffBT‐4T‐based devices achieved a remarkable PCE of 17.5 %, setting a new record for ffBT‐based photovoltaic polymers. Our findings underscore the importance of conjugate backbone modulation in controlling aggregation behavior and film formation kinetics, providing valuable insights for the design of high‐performance polymer donors in organic photovoltaics.

Regulating Intermolecular Interactions and Film Formation Kinetics for Record Efficiency in Difluorobenzothiadizole-Based Organic Solar Cells.

The difluorobenzothiadizole (ffBT) unit is one of the most classic electron-accepting building blocks used to construct D-A copolymers for applications in organic solar cells (OSCs). Historically, ffBT-based polymers have achieved record power conversion efficiencies (PCEs) in fullerene-based OSCs owing to their strong temperature-dependent aggregation (TDA) characteristics. However, their excessive miscibility and rapid aggregation kinetics during film formation have hindered their performance with state-of-the-art non-fullerene acceptors (NFAs). Herein, we synthesized two ffBT-based copolymers, PffBT-2T and PffBT-4T, incorporating different π-bridges to modulate intermolecular interactions and aggregation tendencies. Experimental and theoretical studies revealed that PffBT-4T exhibits reduced electrostatic potential differences and miscibility with L8-BO compared to PffBT-2T. This facilitates improved phase separation in the active layer, leading to enhanced molecular packing and optimized morphology. Moreover, PffBT-4T demonstrated a prolonged nucleation and crystal growth process, leading to enhanced molecular packing and optimized morphology. Consequently, PffBT-4T-based devices achieved a remarkable PCE of 17.5 %, setting a new record for ffBT-based photovoltaic polymers. Our findings underscore the importance of conjugate backbone modulation in controlling aggregation behavior and film formation kinetics, providing valuable insights for the design of high-performance polymer donors in organic photovoltaics.

Using a Flexible Fountain Pen to Directly Write Organic Semiconductor Patterns with Crystallization Regulated by the Precursor Film.

Organic semiconductor (OSC) films fabricated by meniscus-guided coating (MGC) methods are suitable for cost-effective and flexible electronics. However, achieving crystalline thin films by MGC methods is still challenging because the nucleation and crystal growth processes are influenced by the intertwined interactions among solvent evaporation, stochastic nucleation, and the fluid flow instabilities. Herein, a novel flexible fountain pen with active ink supply is designed and used to print OSCs. This direct-write method allows the flexible pen tip to contact the substrate, maintaining a robust meniscus by eliminating the gap found in conventional MGCs. An in situ optical microscopy observation system shows that the precursor film plays a critical role on the crystallization and the formation of coffee rings and dendrites. The computational fluid dynamics simulations demonstrate that the microstructure of the pen promotes extensional flows, facilitating mass transport and crystal alignment. Highly-aligned ribbon-shaped crystals of a small organic molecule (TIPS-pentacene), as well as a semiconducting polymer (N2200) with highly-ordered orientations, have been successfully printed by the flexible fountain pen. Organic field-effect transistors based on the flexible pen printed OSCs exhibit high performances and strong anisotropic mobility. In addition, the flexible fountain pen is expandable for printing multiple lines or large-area films.

Ultrafast recrystallization and grain refinement of 2A97 Al-Cu-Li alloy by electropulsing assisted annealing at lower temperature

In the current work, a pulsed current was applied on recrystallization annealing to promote the recrystallization of cold-rolled 2A97 Al-Cu-Li alloys. Besides, the effect of stored deformation energy on electropulsing assisted recrystallization was also investigated. The results indicated that, with the assistance of electropulsing, the complete recrystallization temperature of the 55 % cold-rolled alloys was decreased from 480 °C to 440 °C, and the holding time was significantly decreased from 30 min to 15 s. Moreover, the recrystallization promotion effect of electropulsing was enhanced with the increment of stored deformation energy. As the rolled reduction increased from 23 % to 55 %, the drop in complete recrystallization temperature induced by electropulsing rose from 20 °C to 40 °C. Additionally, the average grain size decreased from 46.8 μm to 22.6 μm, leading to an enhancement in the mechanical properties of the 2A97 alloy. The microstructure observation showed that the electropulsing assisted recrystallization was a process of nucleation and nuclei growth dominated by dislocation rearrangement, and the ultrafast recrystallization at lower temperature induced by electropulsing may be attributed to the reduction of the nucleation energy barrier and the promotion of dislocation rearrangement caused by the ‘local hot spot effect’ and ‘electromigration effect’.

On Morphology of Aluminum-Gallium Nitride Layers Grown by Halide Vapor Phase Epitaxy: The Role of Total Reactants' Pressure and Ammonia Flow Rate.

The focus of this study was the investigation of how the total pressure of reactants and ammonia flow rate influence the growth morphology of aluminum-gallium nitride layers crystallized by Halide Vapor Phase Epitaxy. It was established how these two critical parameters change the supersaturation levels of gallium and aluminum in the growth zone, and subsequently the morphology of the produced layers. A halide vapor phase epitaxy reactor built in-house was used, allowing for precise control over the growth conditions. Results demonstrate that both total pressure and ammonia flow rate significantly affect the nucleation and crystal growth processes which have an impact on the alloy composition, surface morphology and structural quality of aluminum-gallium nitride layers. Reducing the total pressure and adjusting the ammonia flow rate led to a notable enhancement in the homogeneity and crystallographic quality of the grown layers, along with increased aluminum incorporation. This research contributes to a deeper understanding of the growth mechanisms involved in the halide vapor phase epitaxy of aluminum-gallium nitride, and furthermore it suggests a trajectory for the optimization of growth parameters so as to obtain high-quality materials for advanced optoelectronic and electronic applications.

Gold Nanoclusters Whose Photoluminescent Properties are Dynamically Tunable by Modulating the Assembly Pathway Complexity.

Modulating the assembly pathway is an indispensable strategy for optimizing the performance of optical materials. However, implementing this strategy is nontrivial for metal nanocluster building blocks, due to the limited functional modification of nanoclusters and complexity of their emission mechanism. In this report, we demonstrate that a gold nanocluster modified by 4,6-diamino-2-pyrimidinethiol (DPT-AuNCs) self-assembles into two distinct aggregation structures in methanol (MeOH)/water mixed solvent, thus exhibiting pathway complexity. Kinetic studies show that DPT-AuNCs firstly assembles into non-luminescent nanofibers (kinetically controlled), which further transforms into strongly luminescent microflowers (thermodynamically controlled). In-depth analysis of the assembly mechanism reveals that the transformation of aggregation structures involves the disassembly of nanofibers and a subsequent nucleation-growth process. Temperature-dependent photoluminescence (PL) spectroscopy and infrared (IR) measurements reveal that inter-cluster hydrogen bonding bridged by solvent molecules and C-H⋅⋅⋅π interaction are the key factors for emission enhancement. The photoluminescent property of DPT-AuNCs can be controlled by varying the cosolvent in water, enabling DPT-AuNCs to distinguish different kind of alcohols, particularly the isomerism n-propanol (NPA) and isopropanol (IPA). Additionally, the addition of seeds effectively regulate the assembly kinetics of DPT-AuNCs. This study advances our understanding of assembly pathways and improves the luminescent performance of nanoclusters (NCs).

Improving spectral linewidth performance of InP quantum dots by promoting size-focused growth and decreasing exciton-phonon coupling.

InP-based quantum dots (QDs) are widely adopted as a superior alternative to CdSe-based QDs in various fields owing to their high quantum yield, environmental friendliness, and excellent stability. However, improving its color purity remains a challenging task. In this work, we employ a multistage heating strategy to optimize the nucleation and shell growth processes of amino-phosphine-based InP/ZnSe/ZnS QDs for reducing emission linewidths. The multistage heating strategy mitigates the undesired formation of small-size cores by decreasing monomer supersaturation during the nucleation process, thereby promoting size-focusing growth. During the shelling process, multistage heating effectively suppresses Zn2+ diffusion into the InP core while ensuring high-quality shell growth, thus reducing the homogeneous broadening caused by exciton-phonon coupling. Compared to classical synthesis, the multistage heating strategy can reduce the emission linewidth of nucleation and shelling by 13.2% and 30.9% respectively. The optimized InP/ZnSe/ZnS QDs exhibit a narrow full width at half maximum (FWHM) of 41.5 nm at 630 nm, representing significant progress in studying spectral linewidths of amino-phosphine InP QDs. This work provides potential insights for further improving the spectral linewidth performance of InP QDs or other nanocrystals with similar reaction-limited growth systems.

Continuous and Scalable Synthesis of Prussian Blue Analogues with Tunable Structure and Composition in Surfactant-Free Microreactor for Stable Zinc-Ion Storage.

We represent a segmented flow surfactant-free microfluidic strategy for continuous synthesis of Prussian blue analogues (PBAs) with high dispersity and high crystallization. Representative zinc hexacyanoferrate (ZnHCF) nanocubes were successfully synthesized in a microfluidic reactor within a few minutes via the cooperation method and possessed lower contents of crystal water and Fe(CN)6 3- vacancies than that of synthesis in bulk solution. The nucleation and particle growth process can be precisely controlled by the exploration of different flow rates and reaction temperatures during the formation of ZnHCF nanocubes in segmented flow microfluidic reactors. High crystallinity, low crystal water and vacancies in the ZnHCF structure were presented at relatively high temperatures for the crystal growth process. High-quality ZnHCF with a low content of crystal water showed excellent electrochemical activity and stability towards zinc-ion storage. The continuous and scalable synthesis approach can be extended to the fabrication of other PBAs such as NiHCF, CoHCF, MnHCF, and CuHCF with high dispersity without using any surfactants. The controllable construction of PBAs with tunable properties in microfluidic reactors provides a promising direction to minimize the gap between commercial reality and laboratory research.

Numerical and Analytical Simulation of the Growth of Amyloid-β Plaques.

Numerical and analytical solutions were employed to calculate the radius of an amyloid-β (Aβ) plaque over time. To the author's knowledge, this study presents the first model simulating the growth of Aβ plaques. Findings indicate that the plaque can attain a diameter of 50 μm after 20 years of growth, provided the Aβ monomer degradation machinery is malfunctioning. A mathematical model incorporates nucleation and autocatalytic growth processes using the Finke-Watzky model. The resulting system of ordinary differential equations was solved numerically, and for the simplified case of infinitely long Aβ monomer half-life, an analytical solution was found. Assuming that Aβ aggregates stick together and using the distance between the plaques as an input parameter of the model, it was possible to calculate the plaque radius from the concentration of Aβ aggregates. This led to the "cube root hypothesis," positing that Aβ plaque size increases proportionally to the cube root of time. This hypothesis helps explain why larger plaques grow more slowly. Furthermore, the obtained results suggest that the plaque size is independent of the kinetic constants governing Aβ plaque agglomeration, indicating that the kinetics of Aβ plaque agglomeration is not a limiting factor for plaque growth. Instead, the plaque growth rate is limited by the rates of Aβ monomer production and degradation.

Zeta Potential and Size Analysis of Zeolitic Imidazolate Framework-8 Nanocrystals Prepared by Surfactant-Assisted Synthesis.

The crystal nucleation and growth mechanism of monodispersed metal-organic framework nanoparticles were studied using time-resolved light dynamic, electrokinetic, and powder X-ray diffraction methods. We confirmed that zeolitic imidazolate framework-8 (ZIF-8) nanocrystals follow a nonclassical crystal growth pathway, where a fast nucleation occurs with dense liquid clusters or nanocrystals forming spontaneously when two precursors are mixed. We also explored the zeta potential and solvodynamic size changes of ZIF-8 prepared by a surfactant-assisted synthesis. Three modulators, including 1-methylimidazole (1-mIm), tris(hydroxymethyl)aminomethane (THAM), and (1-hexadecyl)trimethylammonium bromide (CTAB), were studied. We found that 1-mIm dramatically increases the rate of nucleation of ZIF-8. With an increasing amount of 1-mIm, which functions as a coordination modulator, the size increases, and the zeta potential of ZIF-8 decreases. Whereas THAM, as both a coordination and a deprotonation modulator, increases the size and zeta potential of ZIF-8 simultaneously, CTAB, as a long alkyl cationic surfactant, mainly adsorbs on the surface of ZIF-8, and the zeta potential of the formed ZIF-8 is controlled by the amount of CTAB in solution compared with its critical micelle concentration. Overall, we reveal that the modulator type and concentration can be used to control the size and zeta potential of the dispersed ZIF-8 nanocrystals in a colloid system. The experiments also enable identification of the nucleation and crystal growth processes of ZIF-8. The findings will be applicable to other nanocrystals in colloid systems, which are used for heterogeneous catalysis and guest molecular loadings.

In-situ preparation of Ni@ZrO2 nanocapsules powder by DC arc plasma for internal electrode of MLCC

Zirconium oxide-coated Ni nanocapsules (Ni@ZrO2 NCs) were in-situ fabricated by DC arc plasma in a nitrogen atmosphere. The co-evaporation of a target mixture consisting of coarse ZrO2 and Ni powders resulted in the formation of Ni@ZrO2 core-shell nanocomposites (NCs). The high energy states of excited ions (Ni3+, Zr4+, O2−, N2+, etc.) within the arc plasma region were recorded in real time by online optical emission spectroscopy (OES), which becomes visible evidences of the energy conditions for the fabrication of Ni@ZrO2 NCs. These nanocapsules underwent preferential formation of zirconium oxide species based on the oxygen potential rule, followed by the nucleation and subsequent growth processes. The Ni@ZrO2 NCs exhibited improved oxidation resistance, with an onset temperature for sintering approximately 40 °C higher than that of pristine Ni nanoparticles (NPs). Additionally, these NCs displayed an appropriate shrinkage rate, with a volume change of about 7.1% at 1200 °C. The symbiotic relationship between the ZrO2 shell and the Ni core within each nanoparticle suggests enhanced interfacial stability, rendering these NCs a promising material for the advancement of multi-layer ceramic capacitors (MLCCs).

Effect of adding W particles on the crystallization behaviour of Zr55Cu30Al10Ni5 amorphous alloy

The influence of W particles (Wp) addition on the crystallization behaviour was studied by comparing crystallization processes of Zr55Cu30Al10Ni5 amorphous alloy and Wp/Zr55Cu30Al10Ni5 amorphous composites by DSC, In-Situ XRD and SEM/EDS. Results showed that Wp addition increased Tg, decreased Tx, Tp, and ∆T, resulting in a decrease in the thermal stability of the amorphous alloy. Wp could play a role of non-spontaneous nucleation and promoted the crystallization process. At the same time, Wp increased the internal viscosity, hindered the growth process of grains and led to a higher crystallization-activation energy. The nucleation growth process was mainly controlled by diffusion, and the nucleation rate decreased with increasing time. The crystallization products are primarily comprised the Zr2Cu phase, accompanied by a small amount of the Zr6Ni8Al15 phase as well as some unknown phases.

Unveiling voltage evolution during Li plating-relaxation-Li stripping cycling of lithium-ion batteries

The unwanted Li plating on graphite anode surface in lithium-ion batteries causes poor cycling performance along with raised safety risk once Li dendrites penetrate separator. Voltage characteristics during relaxation and discharging have been recognized as the most direct and convenient indictor for Li plating detection, where unveiling voltage evolution during plating-relaxation-stripping cycling needs to be emphasized to facilitate Li plating detection. This study fabricates Li|graphite cells to implement Li plating-relaxation-stripping protocols through over-lithiation before internal short circuit, and the Li nucleation-growth process is linked to voltage evolution assisting with the post-mortem approaches. The Li plating voltage initially displays continuous decline indicated as Li nucleation, until the formation of Li plating plateau indicated as Li growth. The plating-relaxation-stripping voltage patterns show highly correlation that the occurrence of Li plating plateau exactly corresponds to the appearance of a mixed relaxation plateau attributed to the equilibrium of Li stripping and Li re-intercalation into graphite, while the disappearance of the mixed relaxation plateau just corresponds to the advent of Li stripping plateau. Three stages are finally divided associated with characteristic Li plating -relaxation-stripping voltage patterns, where Stage I indicates the occurrence of Li plating plateau behaving as predominant LixC6; Stage II is characterized as the occurrence of mixed relaxation plateau manifested as Li coexisting with LixC6; Stage III is distinguished by the appearance of Li stripping plateau indicated as predominant Li and dead Li. This work proposes underlying evolution mechanism of Li plating-relaxation-stripping cycling, which contributes to sufficient evidence for reliable Li plating detection.

Artificial neural networks in kinetic analysis of glass crystallization: The case of complex nucleation-growth mechanisms

The selected artificial neural networks were trained and tested to determine the kinetics of theoretically simulated signals for two overlapping independent nucleation-growth processes. Whereas the hybrid convolutional neural network did not perform well, the multilayer perceptron (MLP) showed great potential for the kinetic analysis of complex solid-state reactions and transformation mechanisms. In particular, the MLP architecture exhibited remarkable robustness with respect to the scatter in kinetic data as well as the ability to accurately deal with practically fully overlapping kinetic peaks. When trained on a full spectrum of double-process overlaps, the MLP architecture returned very precise estimates of the kinetic parameters during the testing phase despite the limited data sample used for some of the training. This level of accuracy was observed in the case of both overlapping processes being roughly similarly sized, and for the dominant process in the cases of the two processes being largely disproportionate in magnitude.

(Invited) To Prepare 2D Au Nanoplates and Its Controlled Molecular Self-Assembly (MS) Mechanism

It is very important to prepare 2D noble-metal nanomaterials, but very little is known about their chemical synthesis at molecular level. In this paper, we found the classic citric (CA) reduction method can prepare 2D Au nanoplates with a large range for 2D size (3-150nm). Furthermore, these 2D Au nanoplates exhibit thin thickness (8-20nm), along with two kinds of single crystal structure as 2D Au (110) –dominated and Au (111) –dominated nanoplates. To explore their preparation, we adjusted the CA reduction kinetic as CA additive→ acetone dicarboxylic acid (DCA) →acetone, revealing the intermediate species of DCA is crucial for nanoplate formation. Our DFT (Density-Functional-Theory) model further clarifies that the DCA has molecular interaction, preferentially transferring 2D clusters (Au3-Au7) towards Au(111) facets though accompanying with some Au (100) facets. These soft-hard interaction help us establish two kinds of controlled MS mechanisms towards (111) –dominated nanoplates and Au (110) –dominated nanoplates, revealing the cluster origination and its essential 2D growth process in nucleation-growth process. Consequently, our preparation for 2D Au nanoplates and controlled MS mechanisms open a gate towards nucleation-growth process, thus having great significance and broad impact for future studies.

Investigations on the Initial-Stages of Lithium Deposition/Dissolution Processes in Sulfolane Based Electrolytes

Li metal could be the ideal anode for rechargeable battery technologies, due to its negative redox potential (ca. -3 V vs. SHE), high specific capacity (3860 mAh g−1), and low density (0.534 g cm−3) [1-3]. Recent advances show a new design concept where there are no initial active materials in the anode (no carbon, Si, or Li metal) and the corresponding Li quantity is directly deposited on the current collector during charging. This approach will result in important practical advantages such as enhanced volumetric and gravimetric specific energies, ease of manufacturing and reduced complexity/safety concerns of the recycling process (ideally Li is completely removed in the discharged state). However, the applicability of the Li-metal batteries is constrained by the nonuniform lithium deposition, accompanied by dendrite growth and the formation of dead lithium during long-term cycling, which lead to low Coulombic efficiency and even cell failure [2]. The initial structure and morphology of the Li deposit has a vital influence on the later progression of the Li layer [4]. This underpins the importance of a fundamental understanding of the electrodeposition process. However, the presence of a solid-electrolyte interphase (SEI) makes such investigations difficult, since after the transport of the Li ions through the SEI, a subsequent charge transfer and nucleation growth process at the substrate-SEI interface, instead of substrate-liquid electrolyte interface occurs. This contribution will discuss lithium electrodeposition in a sulfolane based, localized high concentrated electrolyte system. Possible phase formation mechanisms as well as kinetic and thermodynamic aspects during the initial stages of the process are studied by classical electrochemical methods (Fig. 1, left). Furthermore, the mass-charge balance during deposition and stripping was monitored (Fig. 1, right) via in-situ microgravimetry (electrochemical quartz crystal microbalance). In the contribution we will discuss these transients in terms of lithium layer growth and SEI formation.

Crystallization behavior and Photoluminescence of cerium doped ZAS glasses and nano glass ceramics with different Li2O content and without added nucleating agents

In this research, ZnO-Al2O3-SiO2 glass-ceramics were prepared with various contents of Li2O (1–5 mol.%). No nucleating agent was used. The prepared glasses were converted into glass-ceramics through nucleation and crystal growth processes. The physical parameters and crystallization behavior of the samples were assessed through differential thermal analysis (DTA), dilatometry, x-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and Fourier transform infrared spectroscopy (FTIR). The incorporation of Li2O declined the Tg level from 820 °C to 768 °C. Gahnite and eucryptite were the dominant phases in the glass-ceramics. A rise in the Li2O content to 5 mol% led to an opaque glass-ceramic. Results showed that the addition of the lithium oxide led to the formation of a eucryptite phase alongside the primary gahnite phase. The dimension of the crystals was in the range of 20 nm through controlling the nucleation temperature and growth of the glass-ceramics. In order to induce photoluminescence (PL) property into the glasses, cerium oxide was added to all samples at 2 wt.%. The PL behavior was then investigated with the help of PL spectrum. TGC-Li3 sample exhibited up to 10 times higher PL intensities than the corresponding glass.

End-to-End Continuous Small-Scale Drug Substance Manufacturing: From a Continuous In Situ Nucleator to Free-Flowing Crystalline Particles

In the evolving landscape of pharmaceutical manufacturing, a comprehensive continuous production process is being crafted for the small-scale production of active pharmaceutical ingredients. This study focuses on continuous crystallization with separate nucleation and crystal growth units, as well as continuous downstream processing, encompassing filtration, washing, and drying until the formation of free-flowing particles. We introduce a novel continuous nucleator designed based on solubility data and produced via 3D printing, enabling the fast and precise small-scale manufacturing of a nucleator meeting the requirements for nucleation and further growth processes. The nucleator is evaluated with regard to its suitability for continuous long-term operation across various coupled crystallizers. As a practical application example, it is connected to a slug flow crystallizer to enable high-quality continuous crystallization. Additionally, the full integration of downstream processes using a continuous vacuum screw filter to achieve free-flowing product particles is realized. Even under non-optimized process conditions, with the help of the in situ generation of nuclei, free-flowing product particles are successfully obtained. This is particularly useful during drug development when no material is available for seed addition and to quickly obtain products for further characterization.