Chemical Deposition Reactor Research Articles

In-situ micro-battery etching induced 3D Zn with amorphous interfacial coating for high-stable Zn metal batteries

Zn metal is one of the most prospective anodes for large-scale energy storage owing to its high volumetric capacity and safety. However, commercialization of the aqueous Zn metal batteries (AZMBs) is impeded by uneven Zn deposition and undesirable reaction issues. Herein, an in-situ micro-battery etching strategy is proposed to realize surface coating and 3D Zn construction simultaneously. It is worth noting that the amorphous Zn2+-intercalated ammonium vanadate (A-ZNVO) coating with abundant oxygen vacancy could not only inhibit the severe interface parasitic reactions but also facilitate the quick transmission of Zn2+. Beyond that, the 3D porous structure could reduce the local current density and induce uniform Zn deposition. As a result, such 3D Zn@A-ZNVO electrode ensures a remarkably long cycle lifespan of over 3700 h when a current density of 1 mA cm−2 is applied. By contrast, the bare Zn could only cycle for 110 h and encounter short-circuit subsequently. Meanwhile, the 3D Zn@A-ZNVO anode also exhibits superior rate capability and above-average Coulombic efficiency (99.55 %). Moreover, the full cell could retain 85.2 % of discharge capacity even after 900 cycles under 1 A g−1. This facile and multifunctional strategy offers a unique insight into the modification of metal-based electrodes.

Piperine and piperine-loaded albumin nanoparticles ameliorate adjuvant-induced arthritis and reduce IL-17 in rats

AimRheumatoid arthritis (RA) is one of the most common chronic, inflammatory, autoimmune diseases affecting mainly the joints. Piperine (PIP), an alkaloid found in black pepper, has anti-inflammatory properties and its use in drug delivery systems such as nanoparticles might be a treatment for RA. This study aims to evaluate the possible anti-inflammatory and anti-arthritic effects of PIP and its use in albumin nanoparticles as a possible approach for the treatment of Adjuvant-induced arthritis (AIA) rats. MethodsPIP-loaded Bovine Serum Albumin nanoparticles (PIP-BSA NPs) were prepared using a desolvation method. AIA rats were given intraperitoneal injections of either 40 mg PIP or 131 mg PIP-BSA NPs every two days until day 28 when animals were sacrificed. Clinical score, histopathology, X-ray radiography, and serum levels of pro-inflammatory cytokines such as IL-1β, IL-17, and TNF-α were evaluated. ResultsPIP and PIP-BSA NPs significantly reduced clinical scores, and alleviated inflammation within the joints. PIP was superior to PIP-BSA NPs for the alleviation of fibrin deposition and periosteal reactions while bone inflammation and erosion were less severe in the case of PIP-BSA NPs. Besides, both of the treatments suppressed serum levels of IL-17 in AIA rats (p = 0.003 and p = 0.02; respectively). ConclusionsPIP and PIP-BSA NPs effectively alleviate the severity of AIA and suppress inflammation. Due to the superiority of PIP in improving fibrin deposition and periosteal reactions and the efficacy of PIP-BSA NPs in suppressing bone inflammation and erosion, their simultaneous use might be investigated.

Constructing Dual Schottky Junctions for High‐Performance Zinc Anode

AbstractAqueous zinc ion batteries provide new solutions for achieving environmentally friendly and safe energy storage devices. Unfortunately, the further application is hampered by the growth of zinc dendrites caused by uneven zinc deposition, hydrogen evolution and other side interfacial reactions at the zinc anode. Herein, a multifunctional Bi‐Bi2O3 hybrid artificial interface layer is constructed on the surface of the zinc anode using an in situ conversion reaction. Among them, the Bi‐Bi2O3 Schottky structure not only significantly accelerates the migration of Zn2+ through its built‐in electric field, but also effectively improves the hydrogen evolution barrier (ΔGH*), thereby suppressing side reactions. Moreover, the Schottky contact formed between the interface layer and the metal zinc interface also regulates the electronic distribution state on the zinc surface and optimizes the deposition process of Zn2+, ensuring a more uniform and orderly zinc deposition process. Based on the synergistic effect of dual Schottky junctions, symmetric batteries achieve stable cycling for 2000 h under the conditions of 1.0 mA cm−2 and 1.0 mAh cm−2. The full cell assembled with α‐MnO2 as the cathode maintains capacity of 112.7 mAh g−1 after 1000 cycles at 1 A g−1 with a capacity retention rate of 84%.

A Facile In Situ Etching–coating of Artificial Solid‐Electrolyte Interphase on Zn Metal Anode for Aqueous Batteries

AbstractZn metal anode is desired for aqueous batteries due to its high capacity and low redox potential. However, uneven Zn deposition and hydrogen evolution reaction (HER) have hindered the electrochemical reversibility and stability. Herein, an artificial solid electrolyte interphase (SEI) composed of metal center incorporated siloxane coupling with fluoride is in situ generated on Zn surface by a facile “etching–coating” process. This SZ‐SEI provides interaction sites with Zn2+, which helps with its desolvation at the interface and enlarges the transference number. Uniform Zn deposition underneath the layer is thus realized. Meanwhile, the SZ‐component hinders the adsorption of hydrogen atom and effectively suppresses HER. Thanks to the above effects, the cycle life of symmtric cells with SZ‐Zn electrodes extends to 2200 and 1400 h at the current densities of 10 and 20 mA cm−2, respectively. The coulombic efficiency of Zn plating/stripping also reaches 99.8% for 3800 cycles. In addition, the SZ‐Zn anode enables better rate capability and cycling stability of full cells.

Emulating "Curvature-Enhanced Adsorbate Coverage" for Superconformal and Orientated Zn Electrodeposition in Zinc-ion-Batteries.

Uneven Zn deposition and unfavorable side reactions have prevented the reversibility of the Zn anode. Herein, we design a rearranged (002) textured Zn anode inspired by a traditional curvature-enhanced adsorbate coverage (CEAC) process to realize the highly reversible Zn anode. The rearranged (002) textured structure directs superconformal Zn deposition by controlling the spatial deposition rate of the rearranged crystal planes, thereby promoting bottom-up "superfilling" of the 3D Zn skeletons. Meanwhile, our designed anode also induces the epitaxial Zn deposition, alleviating the parasitic reactions owing to the lowest surface energy of the (002) plane. Attributed to these superiorities, uniform and oriented Zn deposition can be obtained, exhibiting an ultra-long lifespan over 479 hrs at an ultrahigh depth of discharge (DOD) of 82.12 %. The Zn|Na2V6O16 ⋅ 3H2O battery delivers an improved cycling performance, even at a high area capacity of 5.15 mAh/cm2 with a low negative/positive (N/P) capacity ratio of 1.63. The superconformal deposition approach for Zn anodes paves the way for the practical application of high-performance zinc-ion batteries.

Emulating “Curvature‐Enhanced Adsorbate Coverage” for Superconformal and Orientated Zn Electrodeposition in Zinc‐ion‐Batteries

AbstractUneven Zn deposition and unfavorable side reactions have prevented the reversibility of the Zn anode. Herein, we design a rearranged (002) textured Zn anode inspired by a traditional curvature‐enhanced adsorbate coverage (CEAC) process to realize the highly reversible Zn anode. The rearranged (002) textured structure directs superconformal Zn deposition by controlling the spatial deposition rate of the rearranged crystal planes, thereby promoting bottom‐up “superfilling” of the 3D Zn skeletons. Meanwhile, our designed anode also induces the epitaxial Zn deposition, alleviating the parasitic reactions owing to the lowest surface energy of the (002) plane. Attributed to these superiorities, uniform and oriented Zn deposition can be obtained, exhibiting an ultra‐long lifespan over 479 hrs at an ultrahigh depth of discharge (DOD) of 82.12 %. The Zn|Na2V6O16 ⋅ 3H2O battery delivers an improved cycling performance, even at a high area capacity of 5.15 mAh/cm2 with a low negative/positive (N/P) capacity ratio of 1.63. The superconformal deposition approach for Zn anodes paves the way for the practical application of high‐performance zinc‐ion batteries.

Controlling the Crystalline Quality and Yield of Single‐Walled Carbon Nanotubes via Floating Catalyst Chemical Vapor Deposition Synthesis

AbstractCarbon nanotubes (CNTs) were synthesized by floating catalyst chemical vapor deposition (FCCVD) reactions. The complicated processing parameters that included a precursor solution composition, reaction temperature, flow rate of the carrier gas, weak oxidants, and injection rate of the precursor solution were controlled to synthesize single‐walled carbon nanotubes (SWCNTs) during the reaction process. The effects of the processing parameters were analyzed with respect to the formation of SWCNTs, yield, and the crystallinity in the CNTs structure. The SWCNTs were characterized by the Raman spectroscopy, scanning electron microscope, high‐resolution transmission electron microscopy, and thermogravimetric analysis. A high reaction temperature, high H2 flow rate, low injection rate of solution precursor, and low concentrations of iron catalysts in the reaction were important factors to improve the crystalline quality of the SWCNTs. The purity of the initial product grown by the standard process was more than 90 wt %, with a yield of 0.5 g/h. The average G/D ratio of the initial product was 178, and it had a distinct RBM peak. HRTEM confirmed that the synthesized SWCNTs had high purity and crystallinity. The SWCNTs could be tunable to meet a particular application by varying the reaction conditions.

High-Energy Sodium Ion Batteries Enabled by Switching Sodiophobic Graphite into Sodiophilic and High-Capacity Anodes.

Owing to the crustal abundance of sodium element, sodium ion batteries (SIBs) are considered a promising complementary to lithium-ion battery for stationary energy storage applications. The cointercalation chemistry enables the use of cost-effective graphite as anodes, whereas the low capacity (<130 mAh g-1) and high redox potential (>0.6 V vs. Na/Na+) of graphite significantly limit the energy density of SIBs. Herein, we induce the high-capacity Na metal into sodiophilic ternary graphite intercalation compounds (t-GICs) via co-intercalation and deposition reactions, thereby achieving Na/t-GIC anodes with high capacities and low working voltage (0.18 V). The new anodes exhibit high coulombic efficiencies of above 99.7 % over 550 cycles and a high-rate capacity of 588.4 mAh g-1 at 6 C (10 min per charge). When it is paired with Na3V2(PO4)2F3 (NVPF) cathodes, the SIBs demonstrate a high energy density of 259 Wh kg-1 both electrodes surpassing that of commercial LiFePO4//graphite batteries. The outstanding anode performance is attributed to the tailored sodiophilicity of graphite through manipulating the ether solvents and the in situ generated space among t-GIC flakes to stably accommodate Na metal. Our findings for stable Na plating/striping on sodiophilic graphite materials provide an effective approach for developing advanced SIBs.

High‐Energy Sodium Ion Batteries Enabled by Switching Sodiophobic Graphite into Sodiophilic and High‐Capacity Anodes

AbstractOwing to the crustal abundance of sodium element, sodium ion batteries (SIBs) are considered a promising complementary to lithium‐ion battery for stationary energy storage applications. The cointercalation chemistry enables the use of cost‐effective graphite as anodes, whereas the low capacity (&lt;130 mAh g−1) and high redox potential (&gt;0.6 V vs. Na/Na+) of graphite significantly limit the energy density of SIBs. Herein, we induce the high‐capacity Na metal into sodiophilic ternary graphite intercalation compounds (t‐GICs) via co‐intercalation and deposition reactions, thereby achieving Na/t‐GIC anodes with high capacities and low working voltage (0.18 V). The new anodes exhibit high coulombic efficiencies of above 99.7 % over 550 cycles and a high‐rate capacity of 588.4 mAh g−1 at 6 C (10 min per charge). When it is paired with Na3V2(PO4)2F3 (NVPF) cathodes, the SIBs demonstrate a high energy density of 259 Wh kg−1both electrodes surpassing that of commercial LiFePO4//graphite batteries. The outstanding anode performance is attributed to the tailored sodiophilicity of graphite through manipulating the ether solvents and the in situ generated space among t‐GIC flakes to stably accommodate Na metal. Our findings for stable Na plating/striping on sodiophilic graphite materials provide an effective approach for developing advanced SIBs.

Ionic liquid-functionalized ZnO nanomaterial: Multifunctional additives enhancing tribological performance and corrosion resistance in ester oil

A multifunctional nanomaterial (ZnO-IL), comprising zinc oxide modified with corrosion-resistant ionic liquid groups, was designed and synthesized. It was used as an additive in bis(2-ethylhexyl) sebacate (DIOS) to evaluate its tribological and corrosion resistance properties, and compared with the commercial additive sulfurized isobutylene (SIB). ZnO-IL exhibited good solubility and thermal stability in DIOS. Lubricants containing ZnO-IL showed excellent anti-wear performance under various loads and temperatures. Its deposition on metal surfaces and the synergistic action of benzotriazole groups in the anions effectively prevented corrosion on the surfaces of metal friction pairs, thereby addressing the challenge of friction pair corrosion caused by the hydrolysis of ester-based oils. The ZnO-IL nanomaterial rapidly formed an organic-inorganic multilayer adsorption film on metal surfaces through electrostatic interactions. During friction, a boundary lubrication film composed of ZnO deposition and friction chemical reaction films was formed, thereby avoiding direct metal contact, reducing contact pressure, and exhibiting outstanding friction reduction and anti-wear properties.

A biomass-based protective layer with rigid structure and ion conductivity for high-performance lithium metal batteries

Lithium (Li) metal has been considered as an effective anode material because of its high theoretical capacity, but the uncontrolled dendrite growth and the unstable electrode/electrolyte interface limit its practical application. In this work, proanthocyanidin (PA), a natural extracted biomass, was designed and developed as a coating material to guide homogeneous deposition and restrain side reaction for lithium metal batteries. The rigid benzene ring structure of PA can increase the mechanical strength to restrain dendrite growth on Li surface. Moreover, the spontaneous formation of organolithium (PA-Li) structure from the reaction of phenolic hydroxyl group with Li metal increase the ion transportation ability of PA layer and induce the uniform deposition of Li+ ions to hinder the growth of Li dendrites, as well as prevent the direct contact of organic electrolyte with Li metal to suppress the interface side reaction. As a result, Li metal anode with PA-Li exhibits stable cycling properties for 2800 h at 2 mA cm-2 and 2 mAh cm-2, better that of bare Li (200 h). Li-sulfur full battery with PA-Li can still achieve a capacity of 570 mAh g-1 after 300 cycles. This work provides an effective strategy for the construction a natural functional layer on Li surface to enhance the electrochemical performance, as well as the implementation of high-value utilization for natural biomass.

Investigating the formation of soot in CH4 pyrolysis reactor: A numerical, experimental, and characterization study

Methane pyrolysis is a promising method for eco-friendly hydrogen production, but soot formation and carbon interaction pose challenges for scaling up. Therefore, understanding the dynamics of soot formation and carbon deposition is crucial. This study delves into the intricacies of soot formation in methane pyrolysis under industrially relevant conditions, namely operations at atmospheric pressure, employing a H2:CH4 ratio of 2 and exploring a range of hot zone temperatures (1473 K, 1573 K, 1673 K, and 1773 K) with a 5 s residence time. Utilizing a detailed gas-phase kinetic model with direct carbon deposition reactions, the research adopts the method of moments coupled with a one-dimensional plug flow reactor model to simulate soot formation. The model is validated by characterizing soot particles that were produced in a pyrolysis reactor by means of transmission electron microscopy, Dynamic light scattering (DLS), and Raman spectroscopy. Results show that lower temperatures lead to nucleation-dominated growth, whereas higher temperatures significantly restrain particle growth due to carbon deposition. DLS data indicate a complex balance between particle growth and deposition processes. These findings provide insights into operational parameters that can enhance reactor performance and sustainability in hydrogen production processes by mitigating soot and carbon deposition.

Accelerating sulfur redox kinetics by rare earth single-atom electrocatalysts toward efficient lithium–sulfur batteries

Toward practical lithium−sulfur (Li−S) batteries, there is a pressing need to improve the rate performance and longevity of cells. Herein, we report developing a cathode electrocatalyst Lu SA/NC, capable of accelerating sulfur redox kinetics with a high specific capacity of 1391.8 mAh g−1 at 0.1 C, and a low-capacity fading rate of 0.049 % per cycle over 1000 cycles even with a high sulfur loading (5.96 mg cm−2). The unparalleled cathodes are built upon the unique structure in which single-atoms of rare earth metals are doped in nitrogen-doped porous carbon (RM SAs/NC). The theoretical and experimental studies reveal that the rare earth Lu atom has an unrivaled adsorption capacity for polysulfides and can promote facile deposition and dissolution reactions in charge-discharge processes. The in-situ Raman experiments provide direct evidence for its promotion of polysulfide transformation to eliminate the shuttle effect. The theoretical calculations suggest that the presence of f-d-p hybridization enables accelerating sulfur reduction kinetics and enhancing lithium−sulfur battery performance. The strategic paradigm introduced in this study underscores significant practical potential in the exploration of rare earth single-atom catalysts for high performance Li−S batteries.

Structural, Morphological, and Optical Properties of TiO2/CdS Core-Shell System Prepared by Two Method for Photoelectrocatalytic Application

Abstract The present study utilized the hydrothermal technique to carry out the deposition of films of TiO2. The deposition of CdS on the TiO2 films was accomplished using the chemical bath deposition (CBD) and successive ionic layer adsorption and reaction (SILAR) methods. The morphological and structural characteristics of the TiO2/CdS thin films were investigated using a combination of XRD, SEM, EDX, and AFM techniques. Additionally, the optical properties of the nanostructures were examined using UV-Visible and PL spectroscopic techniques. The X-Ray Diffraction pattern of all TiO2 films revealed the formation of the anatase phase. The CdS present in the Ti/TiO2/CdS samples exhibited a hexagonal structure. The hydrothermal technique employed in the preparation of the TiO2 thin films resulted in the formation of nanofiber morphology, which was evident from the SEM images. The absorption edge data for the TiO2/CdS films demonstrated a shift towards the visible region, indicating a decrease in the bandgap as compared to the TiO2 nanostructure. Significantly improved photoelectrocatalytic performance was observed in the Ti/TiO2/CdS samples prepared using the CBD method, surpassing that of the Ti/TiO2/CdS samples prepared using the SILAR method.

Direct Synthesis of Ti-Al Compound Powders by Electrolysis in Molten LiCl-KCl

The deposition potential difference between Ti and Al is only 70 mV. The deposition reaction of Ti-Al compound happens at the potentials slightly higher than that of metallic Ti and Al. Through galvanostatic electrolysis of mixture solution of Al and Ti ions, all kinds of titanium aluminides can be directly synthesized. The composition of the product compound can be selected through adjusting the combination of Ti and Al ions in the electrolyte.

Sensitization of AgInS2 nanoparticles enhances photoelectrochemical water splitting performance of CeO2 nanosheet arrays photoanode

In this study, we present a promising CeO2/AgInS2 heterostructure photoanode for photoelectrochemical (PEC) water decomposition. Mott-Schottky analysis is employed to confirm the formation of a type-II heterostructure between AgInS2 nanoparticles and CeO2 nanosheet arrays (NSAs) fabricated through electrochemical deposition and successive ionic layer adsorption and reaction. Electrochemical impedance spectroscopy, photoluminescence analysis, and Bode diagram spectroscopy confirm the effective charge carrier separation and significantly prolonged the charge lifetime of the CeO2/AgInS2 heterojunction photoanode. Consequently, the maximum photocurrent density of the constructed CeO2/AgInS2 photoanode relative to Ag/AgCl under zero bias test conditions is 69.8 times higher than the pure CeO2 NSAs. Additionally, the charge transfer mechanism is further verified by the calculated work function and differential charge density of CeO2/AgInS2 heterojunction. This study provides a valuable reference for the synthesis and preparation of heterojunction photoanode for efficient PEC water decomposition.

Stepwise Reaction for Chemical Vapor Deposition of Stoichiometric SiC Films Using Methyltrichlorosilane and Hydrogen as Reactants

Stepwise Reaction for Chemical Vapor Deposition of Stoichiometric SiC Films Using Methyltrichlorosilane and Hydrogen as Reactants

Highly reversible Zn anode by guiding uniform Zn deposition through LiF protective layer

Deep-seated issues such as ineluctable dendrite deposition and parasitic reaction of Zn anode pose a major obstacle to the commercialization of aqueous zinc ion batteries (AZIBs). Herein, we proposed LiF as a solid-electrolyte interphase for highly reversible Zn anode. Combining experimental analyses and theoretical simulation calculations, the electronegative fluorine atoms could provide uniform zincophilic nucleation sites to regulate Zn deposition behavior. Additionally, a ZnF2 layer with outstanding Zn2+ conductive can be formed insitu thus further shielding bulk water molecules and expediting the Zn2+ transfer kinetics. Therefore, the LiF@Zn symmetric cells manifest long-cycling stability with 650 h at 1.0 mA/cm2 and 1.0 mAh/cm2 and 1000 h at 2.0 mA/cm2 and 1.0 mAh/cm2. Meanwhile, the rate performance of Zn//MnO2 and Zn//NH4V4O10 full cells are also enhanced by the LiF coating. This work provides a horizon for the design of artificial protective layer and promotes the large-scale practical development of AZIBs.

Silver-based bimetallic nanozyme fabrics with peroxidase-mimic activity for urinary glucose detection

The enhanced catalytic properties of bimetallic nanoparticles have been extensively investigated. In this study, bimetallic Ag-M (M = Au, Pt, or Pd) cotton fabrics were fabricated using a combination of electroless deposition and galvanic replacement reactions, and improvement in their peroxidase-mimicking catalytic activity compared to that of the parent Ag fabric was studied. The Ag-Pt bimetallic nanozyme fabric, which showed the highest catalytic activity and ability to simultaneously generate hydroxyl (•OH) and superoxide (O2•−) radicals, was assessed as a urine glucose sensor. This nanozyme fabric sensor could directly detect urinary glucose in the pathophysiologically relevant high millimolar range without requiring sample predilution. The sensor could achieve performance on par with that of the current clinical gold standard assay. These features of the Ag-Pt nanozyme sensor, particularly its ability to avoid interference effects from complex urinary matrices, position it as a viable candidate for point-of-care urinary glucose monitoring.Graphical

Printable and filament-drawable PDMS based adhesive assisted manufacturing of highly conductive copper micro-patterns

Manufacturing of copper micro-patterns is crucial in electronics for its utilization as high conductivity transparent conductive films (TCFs) and circuits. In the preparation process of current TCFs, a plethora of materials have emerged that can replace traditional indium tin oxide (ITO). However, even for the most promising metal-based nanowire materials, there are issues such as high cost, complex welding, and high contact resistance. To address these problems, this paper proposes a printable and filament-drawable polydimethylsiloxane (PDMS)-based adhesive, which, through a novel additive patterning technology, efficiently and economically manufactures self-welding copper micro-meshes and circuits. The adhesive can be processed into micro-patterns through printing and filament drawing, on which ionic Ag can be in situ reduced and anchored, thereby eliminating the need for tedious pre- and post-treatment steps. The fully exposed Ag particles dramatically minimize the usage of precious metal catalyst, thus efficiently catalyzing electroless copper deposition (ECD) reaction. Highly conductive (1.03 × 107 S m−1) copper circuits can be fabricated on the printed adhesive patterns, exhibiting versatile applicability to diverse substrates. Highly precise copper micro-meshes (∼50 μm) can be fabricated on the filament networks drawn by the adhesive. The copper meshes undergo complete self-welding at junctions during the ECD process, thus exhibiting ultra-low square resistance of 0.45 Ω sq−1 while maintaining a high transmittance of 82.2 %. This is far superior to most of TCFs in published literature.