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Energy storage systems, particularly rechargeable batteries, play a crucial role in establishing a sustainable energy infrastructure. Today, researchers focus on improving battery energy density, cycling stability, and rate performance. This involves enhancing existing materials or creating new ones with advanced properties for cathodes and anodes to achieve peak battery performance. Graphene aerogels (GAs) possess extraordinary attributes, including a hierarchical porous and lightweight structure, high electrical conductivity, and robust mechanical stability. These qualities facilitate the uniform distribution of active sites within electrodes, mitigate volume changes during repeated cycling, and enhance overall conductivity. When integrated into batteries, GAs expedite electron/ion transport, offer exceptional structural stability, and deliver outstanding cycling performance. This review offers a comprehensive survey of the advancements in the preparation, functionalization, and modification of GAs in the context of battery research. It explores their application as electrodes and hosts for the dispersion of active material nanoparticles, resulting in the creation of hybrid electrodes for a wide range of rechargeable batteries including lithium-ion batteries (LIBs), Li-metal-air batteries, sodium-ion batteries (SIBs), zinc-ion batteries (AZIBs) and zinc-air batteries (ZABs), aluminum-ion batteries (AIBs) and aluminum-air batteries and other.
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Carbon nanowalls (CNWs) have attracted significant attention for gas sensing applications due to their exceptional material properties such as large specific surface area, electric conductivity, nano- and/or micro-porous structure, and high charge carrier mobility. In this work, CNW films were synthesized and used to fabricate gas sensors for carbon dioxide (CO2) gas sensing. The CNW films were synthesized using an inductively-coupled plasma (ICP) plasma-enhanced chemical vapor deposition (PECVD) method and their structural and morphological properties were characterized using Raman spectroscopy and electron microscopy. The obtained CNW films were used to fabricate gas sensors employing interdigitated gold (Au) microelectrodes. The gas sensors were fabricated using both direct synthesis of CNW films on interdigitated Au microelectrodes on quartz and also transferring presynthesized CNW films onto interdigitated Au microelectrodes on glass. The CO2gas-sensing properties of fabricated devices were investigated for different concentrations of CO2gas and temperature-ranges. The sensitivities of fabricated devices were found to have a linear dependence on the concentration of CO2gas and increase with temperature. It was revealed that devices, in which CNW films have a maze-like structure, perform better compared to the ones that have a petal-like structure. A sensitivity value of 1.18% was obtained at 500 ppm CO2concentration and 100 °C device temperature. The CNW-based gas sensors have the potential for the development of easy-to-manufacture and efficient gas sensors for toxic gas monitoring.
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Lithium-sulfur (Li-S) batteries are attracting tremendous attention owing to their critical advantages, such as high theoretical capacity of sulfur, cost-effectiveness, and environment-friendliness. Nevertheless, the vast commercialisation of Li-S batteries is severely hindered by sharp capacity decay upon operation and shortened cycle life because of the insulating nature of sulfur along with the solubility of intermediate redox products, lithium polysulfides (LiPSs), in electrolytes. This work proposes the use of multifunctional Ni/NiO-embedded carbon nanofibers (Ni/NiO@CNFs) synthesized by an electrospinning technique with the corresponding heat treatment as promising free-standing current collectors to enhance the kinetics of LiPS redox reactions and to provide prolonged cyclability by utilizing more efficient active materials. The electrochemical performance of the Li-S batteries with Ni/NiO@CNFs with â¼2.0 mg cm-2 sulfur loading at 0.5 and 1.0C current densities delivered initial specific capacities of 1335.1 mA h g-1 and 1190.4 mA h g-1, retrieving high-capacity retention of 77% and 70% after 100 and 200 cycles, respectively. The outcomes of this work disclose the beneficial auxiliary effect of metal and metal oxide nanoparticle embedment onto carbon nanofiber mats as being attractively suited up to achieve high-performance Li-S batteries.
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Chitosan (CS)-based anion exchange membranes (AEMs) have gained significant attention in fuel cell applications owing to their numerous benefits, such as environmental friendliness, flexibility for structural alteration, and improved mechanical, thermal and chemical durability. This study aims to enhance the cell performance of CS-based AEMs by addressing key factors including mechanical stability, ionic conductivity, water absorption and expansion rate. While previous reviews have predominantly focused on CS as a proton-conducting membrane, the present mini-review highlights the advancements of CS-based AEMs. Furthermore, the study investigates the stability of cationic head groups grafted to CS through simulations. Understanding the chemical properties of CS, including the behaviour of grafted head groups, provides valuable insights into the membrane's overall stability and performance. Additionally, the study mentions the potential of modern cellulose membranes for alkaline environments as promising biopolymers. While the primary focus is on CS-based AEMs, the inclusion of cellulose membranes underscores the broader exploration of biopolymer materials for fuel cell applications.
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With the expanding requirements of recent energy regulations and economic interest in high-performance batteries, the need to improve battery energy density and safety has gained prominence. High-energy-density lithium batteries, employed in next-generation energy storage devices, rely on nickel-rich cathode materials. Since they have extremely high charge/discharge capacity, high operating voltage, prolonged cycle life, and lower cost, nickel-rich cathode materials such as Ni-rich NCM (LiNix > 0.8CoyMnzO2) and Ni-rich NCA (LiNix > 0.8CoyAlzO2) are of particular interest to researchers. Several in situ characterization methodologies are currently used to understand lithium-ion battery electrode response and deterioration better. Nevertheless, in many contexts, these measurement methodologies must be combined with specially designed cells and electrode materials with distinct forms, which is sometimes inconvenient. As an alternative, thermo-voltammetric dynamic characterization may be utilized to describe the thermal internal characteristics of various electrode materials, such as the structural changes and electrode reactions that occur during charging and discharging. In this paper, a nondestructive entropy measurement method demonstrates that phase change occurs for NCM (LiNi0.83Co0.12Mn0.05O2) and NCA (LiNi0.88Co0.09Al0.03O2) at 40-30% of state of charge (SOC) and 90-80% of SOC, respectively. This is confirmed by ex situ X-ray diffraction (XRD) measurements for these highly popular cathodes.
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Free-standing tin phosphide/phosphate carbon composite nanofiber mats of unique nanostructure have been successfully synthesized by electrospinning and partially reducing the phosphate-containing precursors. An unusual effect of the Sn:P molar ratio in the precursor solution on the structure and physical-electrochemical properties of the material is observed. Physical characterizations, including X-Ray diffraction (XRD), Raman spectroscopy, X-Ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), confirm the formation of tin phosphide/phosphate nanoparticles of P-rich inner Snx P layer and Sn-rich outer layer uniformly distributed within carbon nanofiber matrix when the Sn:P=1:1. The prepared material is tested as an anode material for lithium-ion batteries and it retains 1141 mAh g-1 charge capacity after 300 cycles at a current density of 250 mA g-1 with almost 100% Coulombic efficiency at room temperature. Furthermore, it demonstrates six times higher capacity (846 mAh g-1 ) at 0 °C compared to a commercial graphite anode and stable cyclability at -20 °C and 50 mA g-1 . Post-mortem ex situ XRD and SEM analyses confirm the structural stability of the designed material and the formation of a uniform stable solid electrolyte interphase layer even after 100 cycles at 50 mA g- 1 .
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Rechargeable zinc aqueous batteries are key alternatives for replacing toxic, flammable, and expensive lithium-ion batteries in grid energy storage systems. However, these systems possess critical weaknesses, including the short electrochemical stability window of water and intrinsic fast zinc dendrite growth. Hydrogel electrolytes provide a possible solution, especially cross-linked zwitterionic polymers that possess strong water retention ability and high ionic conductivity. Herein, an in situ prepared fiberglass-incorporated dual-ion zwitterionic hydrogel electrolyte with an ionic conductivity of 24.32 mS cm-1 , electrochemical stability window up to 2.56 V, and high thermal stability is presented. By incorporating this hydrogel electrolyte of zinc and lithium triflate salts, a zinc//LiMn0.6 Fe0.4 PO4 pouch cell delivers a reversible capacity of 130 mAh g-1 in the range of 1.0-2.2 V at 0.1C, and the test at 2C provides an initial capacity of 82.4 mAh g-1 with 71.8% capacity retention after 1000 cycles with a coulombic efficiency of 97%. Additionally, the pouch cell is fire resistant and remains safe after cutting and piercing.
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Lithium iron phosphate (LiFePO4, LFP) is one of the most advanced commercial cathode materials for Li-ion batteries and is widely applied as battery cells for electric vehicles. In this work, a thin and uniform LFP cathode film on a conductive carbon-coated aluminum foil was besieged by the electrophoretic deposition (EPD) technique. Along with the LFP deposition conditions, the impact of two types of binders, poly(vinylidene fluoride) (PVdF) and poly(vinylpyrrolidone) (PVP), on the film quality and electrochemical results has been studied. The results revealed that the LFP_PVP composite cathode had a highly stable electrochemical performance compared with the LFP_PVdF counterpart due to the negligible influence of the PVP on the pore volume and size and retaining high surface area of LFP. The LFP_PVP composite cathode film unveiled a high discharge capacity of 145 mAh g-1 at 0.1C and performed over 100 cycles with capacity retention and Coulombic efficiency of 95 and 99%, respectively. The C-rate capability test also revealed a more stable performance of LFP_PVP compared to LFP_PVdF.
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Although lithium-sulfur batteries possess the highest theoretical capacity and lowest cost among all known rechargeable batteries, their commercialization is still hampered by the intrinsic disadvantages of low conductivity of sulfur and polysulfide shuttle effect, which is most critical. Considerable research efforts have been dedicated to solving these difficulties for every part of Li-S batteries. Separator modification with metal electrocatalysts is a promising approach to overcome the major part of these disadvantages. This work focuses on the development of Ni nanoparticles encapsulated in a few-layer nitrogen-doped graphene supported by nitrogen-doped graphitic carbon (Ni@NGC) with different metal loadings as separator modifications. The effect of metal loading on the Li-S electrochemical reaction kinetics and performance of Li-S batteries was investigated. Controlling the Ni loading allowed for the modulation of the surface area-to-metal content ratio, which influenced the reaction kinetics and cycling performance of Li-S cells. Among the separators with different Ni loadings, the one with 9 wt% Ni exhibited the most efficient acceleration of the polysulfide redox reaction and minimized the polysulfide shuttling effect. Batteries with this separator retained 77.2% capacity after 200 cycles at 0.5C, with a high sulfur loading of â¼4.0 mg cm-2, while a bare separator showed 51.3% capacity retention after 200 cycles under the same conditions. This work reveals that there is a vast utility space for carbon-encapsulated Ni nanoparticles in electrochemical energy storage devices with optimal selection and rational design.
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The three-dimensional (3D) structure of batteries nowadays obtains a lot of attention because it provides the electrodes a vast surface area to accommodate and employ more active material, resulting in a notable increase in areal capacity. However, the integration of polymer electrolytes to complicated three-dimensional structures without defects is appealing. This paper presents the creation of a flawless conformal coating for a distinctive 3D-structured NiO/Ni anode using a simple thermal oxidation technique and a polymer electrolyte consisting of three layers of PAN-(PAN-PVA)-PVA with the addition of Al2O3 nanoparticles as nanofillers. Such a composition with a unique combination of polymers demonstrated superior electrode performance. PAN in the polymer matrix provides mechanical stability and corrosion resistance, while PVA contributes to excellent ionic conductivity. As a result, NiO/Ni@PAN-(PAN-PVA)-PVA with 0.5 wt% Al2O3 NPs configuration demonstrated enhanced cycling stability and superior electrochemical performance, reaching 546 mAh g-1 at a 0.1 C rate.
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A two-phase anion-exchange membrane was prepared from quaternized chitosan (QCS) integrated with an electrospun polyacrylonitrile (PAN) scaffold by spin coating. To synthesize QCS, glycidyltrimethylammonium chloride in various amounts was introduced into the structure of CS. The characterization of the cast cross-linked QCS (CQCS) membranes by impedance spectroscopy revealed the ionic conductivity (IC) in the range of 2.8 × 10-4 to 8.2 × 10-4 S cm-1 and the degree of quaternization (DQ) of 26.4-51.0%, where the CQCS film with the DQ of 51.0% showed excellent performance. When CQCS was reinforced with a PAN fiber mat, the newly developed composite membrane demonstrated the highest IC of 34 × 10-4 S cm-1 at 80 °C, low swelling, and an almost eightfold increase in tensile strength at a fully hydrated state compared to pristine materials. Moreover, the CQCS/PAN membrane was chemically stable and revealed increasing hydroxide transport during 1 month immersion in alkaline media.
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A novel crosslinked electrospun nanofibrous membrane with maleated lignin (ML) and poly(acrylonitrile) (PAN) is presented as a separator for lithium-ion batteries (LIBs). Alkali lignin was treated with an esterification agent of maleic anhydride, resulting in a substantial hydroxyl group conversion to enhance the reactivity and mechanical properties of the final nanofiber membranes. The maleated lignin (ML) was subsequently mixed with UV-curable formulations (up to 30% wt) containing polyethylene glycol diacrylate (PEGDA), hydrolyzed 3-(Trimethoxysilyl)propyl methacrylate (HMEMO) as crosslinkers, and poly(acrylonitrile) (PAN) as a precursor polymer. UV-electrospinning was used to fabricate PAN/ML/HMEMO/PEGDA (PMHP) crosslinked membranes. PMHP membranes made of electrospun nanofibers feature a three-dimensional (3D) porous structure with interconnected voids between the fibers. The mechanical strength of PMHP membranes with a thickness of 25 µm was enhanced by the variation of the cross-linkable formulations. The cell assembled with PMHP2 membrane (20 wt% of ML) showed the maximum ionic conductivity value of 2.79*10-3 S cm-1, which is significantly higher than that of the same cell with the liquid electrolyte and commercial Celgard 2400 (6.5*10-4 S cm-1). The enhanced LIB efficiency with PMHP2 membrane can be attributed to its high porosity, which allows better electrolyte uptake and demonstrates higher ionic conductivity. As a result, the cell assembled with LiFePO4 cathode, Li metal anode, and PMHP2 membrane had a high initial discharge specific capacity of 147 mAh g-1 at 0.1 C and exhibited outstanding rate performance. Also, it effectively limits the formation of Li dendrites over 1000 h. PMHP separators have improved chemical and physical properties, including porosity, thermal, mechanical, and electrochemical characteristics, compared with the commercial ones.
Assuntos
Lignina , Lítio , Lítio/química , Fontes de Energia Elétrica , Íons/química , EletrólitosRESUMO
A pure-phase Ni3Sn2 intermetallic alloy encapsulated in a carbon nanofiber matrix (Ni3Sn2@CNF) was successfully prepared by electrospinning and applied as anode for lithium-ion batteries. The physical and electrochemical properties of the Ni3Sn2@CNF were compared to that of pure CNF. The resultant Ni3Sn2@CNF anode produced a high initial discharge capacity of â¼1300 mA h g-1, later stabilizing and retaining â¼350 mA h g-1 (vs. 133 mA h g-1 for CNF) after 100 cycles at 0.1C. Furthermore, even at a high current density of 1C, it delivered a high initial discharge capacity of â¼1000 mA h g-1, retaining â¼313 mA h g-1 (vs. 66 mA h g-1 for CNF) at the 200th cycle. The superior electrochemical properties of the Ni3Sn2@CNF over CNF were attributed to the presence of electrochemically active Sn and decreased charge-transfer resistance with the alloy encapsulation, as confirmed from cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) results. Finally, post-mortem field-emission scanning electron microscopy (FE-SEM) images proved the preservation of the carbon nanofibers and the alloy after cycling, confirming the successful accommodation of the volume changes during the alloying/dealloying reactions of Sn in the Ni3Sn2@CNF.
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All-solid-state Li-ion batteries (LIBs) with a solid electrolyte instead of a liquid one demonstrate significantly higher safety in contrast with the conventional liquid-based LIBs. An inorganic NASICON-type Li conductor Li1.3Al0.3Ti1.7(PO4)3 (LATP) is a promising solid electrolyte with an ionic conductivity of up to 10-3 S cm-1 at room temperature. However, LATP gradually degrades in contact with Li metal because of reduction of Ti4+ to Ti3+, resulting in a lower ionic conductivity at the electrolyte-electrode interface. Cation doping is a promising approach to stabilize the LATP structure and mitigate the Ti reduction. Here, we report our findings on the alternative polycationic doping strategy of the LiTi2(PO4)3 (LTP) structure, when a heterovalent cation is added along with Al. In particular, we studied the effect of tetravalent and divalent cation dopants (Zr, Hf, Ca, Mg, Sr) of LATP on the Li-ion conduction and Ti reduction during interaction with lithium metal. The samples were prepared by molten flux and solid-state reaction methods. The structure, morphology, and ion-transport properties of the samples were analyzed. The activation energy of Li-ion migration in all synthesized systems was calculated based on the electrochemical impedance spectroscopy (EIS) data retrieved for a temperature range of 25-100 °C. From the obtained results, the tetravalent doping (Zr4+ and Hf4+) appeared to be a more promissing route to improve the LATP electrolyte than the divalent doping (Mg2+, Ca2+, and Sr2+). The X-ray photoelectron spectroscopy analysis of the samples after their contact with lithium provided the data, which could shed light on the effect of the incorporated dopants onto the Ti reduction.
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Advanced all-solid-state batteries are considered as the most preferable power source for the next generation devices. Such batteries demand consumption of electrode materials with high energy and power density. One of the excellent solutions is the utilization of Li metal as anode which provides opportunity to fulfill such requirements. Yet, obstacles such as interfacial impedance and reactivity of Li metal with promising solid electrolytes prevent the consumption of the Li anode. Despite its outstanding stability under ambient conditions, high ionic conductivity and facile synthesis methods, NASICON-type Li1.3Al0.3Ti1.7(PO4)3 also suffers from the above mentioned problems. In this work, these critical issues were resolved by applying an artificial protective interlayer. Herein, the layer-by-layer polymer assembly approach of the ultra-thin interlayer of (PAA/PEO)30 on either side of solid electrolyte pellets simultaneously is presented. The introduction of the protective layer prevented a formation of mixed conduction interphase and effectively decreased the interfacial impedance. A symmetric cell with Li metal electrodes performed over 600 hours at 0.1 mA cm-2. Furthermore, an all-solid-state Li metal battery, assembled with the modified LATP solid electrolyte and LiFePO4 cathode, demonstrated an excellent electrochemical performance with an initial discharge capacity of 115 mA h g-1 and a capacity retention of 93% over 20 cycles with a coloumbic efficiency of almost 100%. The LATP with the (PAA/PEO)30 coating exhibited electrochemical stability up to 5 V.
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In this study, Ti-doped ZnO films with flower-rod-like nanostructures were synthesized by the successive ionic layer adsorption and reaction (SILAR) method for enhanced NO gas-sensing applications. The stoichiometric ratio of Ti in the host ZnO lattice was confirmed by atomic absorption and energy-dispersive X-ray spectroscopies. All of the synthesized films exhibited a pure wurtzite hexagonal structure that seemed to deteriorate at high Ti doping contents as was manifested by the measured X-ray diffraction patterns. Scanning electron microscopy images of ZnO revealed the coexistence of porous flower- and rod-like structures, which became finer, denser, and more compact with Ti doping. By UV-vis measurements, the transmittance of the synthesized pure ZnO thin film in the visible region (â¼75%) increased by about 10% with Ti doping, and the energy band gap seemed to decrease up to some limit of Ti content. Among the fabricated sensors (based on pure ZnO, 1% Ti-doped, 3% Ti-doped, and 5% Ti-doped ZnO films), the best sensing performance was observed for the 1% Ti-doped ZnO film. At first, this was associated with its high density of oxygen vacancies present on the surface of the film and ionized oxygen vacancies present in the ZnO lattice (confirmed, respectively, by X-ray photoelectron and photoluminescence spectroscopies). Nonetheless, this may also be due to its increased crystallinity (confirmed by X-ray diffraction and photoluminescence spectroscopy), high area-to-volume ratio (confirmed by scanning electron microscopy images), high specific surface area (confirmed by Brunauer-Emmett-Teller measurements) as well as high mobility and carrier concentration (confirmed by Hall measurements). The sensor was highly selective to NO gas and showed notable stability as well as very short response and recovery times, which makes it eligible for the early detection of any indoor or outdoor NO gas leakages.
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The microbatteries field is an important direction of energy storage systems, requiring the careful miniaturization of existing materials while maintaining their properties. Over recent decades, LiCoO2 has attracted considerable attention as cathode materials for lithium-ion batteries due to its promising electrochemical properties for high-performance batteries. In this work, the thin films of LiCoO2 were obtained by radio-frequency magnetron sputtering of the corresponding target. In order to obtain the desired crystal structure, the parameters such as annealing time, temperature, and heating rate were varied and found to influence the rhombohedral phase formation. The electrochemical performances of the prepared thin films were examined as a function of annealing time, temperature, and heating rate. The LiCoO2 thin film cathode annealed at 550 °C for 1 h 20 min demonstrated the best cycling performance with a discharge specific capacity of around 135 mAh g-1 and volumetric capacity of 50 µAh cm-2µm-1 with a 77% retention at 0.5 C rate.
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Zinc oxide (ZnO) is a well-known semiconductor material due to its excellent electrical, mechanical, and unique optical properties. ZnO nanoparticles are widely used for the industrial-scale manufacture of microelectronic and optoelectronic devices, including metal oxide semiconductor (MOS) gas sensors, light-emitting diodes, transistors, capacitors, and solar cells. This study proposes optimization of synthesis parameters of nanosized ZnO by the electrospinning technique. A Box-Behnken design (BB) has been applied using response surface methodology (RSM) to optimize the selected electrospinning and sintering conditions. The effects of the applied voltage, tip-to-collector distance, and annealing temperature on the size of ZnO particles were successfully investigated. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images confirm the formation of polyvinylpyrrolidone-zinc acetate (PVP-ZnAc) fibers and nanostructured ZnO after annealing. X-ray diffraction (XRD) patterns indicate a pure phase of the hexagonal structure of ZnO with high crystallinity. Minimal-sized ZnO nanoparticles were synthesized at a constant applied potential of 16 kV, with a distance between collector and nozzle of 12 cm, flow rate of 1 mL/h, and calcination temperature of 600 °C. The results suggest that nanosized ZnO with precise control of size and morphology can be fabricated by varying electrospinning conditions, precursor solution concentration, and sintering temperature.
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Zinc oxide (ZnO) is one of the most promising metal oxide semiconductor materials, particularly for optical and gas sensing applications. The influence of thickness and solvent on various features of ZnO thin films deposited at ambient temperature and barometric pressure by the sequential ionic layer adsorption and reaction method (SILAR) was carefully studied in this work. Ethanol and distilled water (DW) were alternatively used as a solvent for preparation of ZnO precursor solution. Superficial morphology, crystallite structure, optical and electrical characteristics of the thin films of various thickness are examined applying X-ray diffraction (XRD) system, scanning electron microscopy, the atomic force microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible spectroscopy, photoluminescence spectroscopy, Hall effect measurement analysis and UV response study. XRD analysis confirmed that thin films fabricated using ethanol or DW precursor solvents are hexagonal wurtzite ZnO with a preferred growth orientation (002). Furthermore, it was found that thin films made using ethanol are as highly crystalline as thin films made using DW. ZnO thin films prepared using aqueous solutions possess high optical band gaps. However, films prepared with ethanol solvent have low resistivity (10-2 Ω cm) and high electron mobility (750 cm2/Vs). The ethanol solvent-based SILAR method opens opportunities to synthase high quality ZnO thin films for various potential applications.
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Investigation of the physical properties of carbon nanowall (CNW) films is carried out in correlation with the growth time. The structural, electronic, optical and electrical properties of CNW films are investigated using electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, UV-Vis spectroscopy, Hall Effect measurement system, Four Point Probing system, and thermoelectric measurements. Shorter growth time results in thinner CNW films with a densely spaced labyrinth structure, while a longer growth time results in thicker CNW films with a petal structure. These changes in morphology further lead to changes in the structural, optical, and electrical properties of the CNW.