Spray pyrolysis feasibility of tungsten substitution for cobalt in nickel-rich cathode materials

Cobalt(Co)serves as a stabilizer in the lattice structure of high-capacity nickel(Ni)-rich cathode materials.However,its high cost and toxicity still limit its development.In general,it is possible to perform transition metal substitution to reduce the Co content.However,the traditional coprecipitation method cannot satisfy the requirements of multielement coprecipitation and uniform distribution of elements due to the differences between element concentration and deposition rate.In this work,spray pyrolysis was used to prepare LiNi_(0.9)Co_(0.1-x)W_(x)O_(2)(LNCW).In this regard,the pyrolysis behavior of ammonium metatungstate was analyzed,together with the substitu-tion of W for Co.With the possibility of spray pyrolysis,the Ni-Co-W-containing oxide precursor presents a homogeneous distribution of metal elements,which is beneficial for the uniform substitution of W in the final materials.It was observed that with W substitution,the size of primary particles decreased from 338.06 to 71.76 nm,and cation disordering was as low as 3.34%.As a consequence,the pre-pared LNCW exhibited significantly improved electrochemical performance.Under optimal conditions,the lithium-ion battery assembled with LiNi_(0.9)Co_(0.0925)W_(0.0075)O_(2)(LNCW-0.75mol%)had an improved capacity retention of 82.7%after 200 cycles,which provides insight in-to the development of Ni-rich low-Co materials.This work presents that W can compensate for the loss caused by Co deficiency to a cer-tain extent.

Selective lithium recovery and regeneration of ternary cathode from spent lithium-ion batteries:Mixed HCl-H_(2)SO_(4) leaching-spray pyrolysis approach

The recycling of spent lithium-ion batteries(LIBs) is crucial for environmental protection and resource sustainability.However,the economic recovery of spent LIBs remains challenging due to low Li recovery efficiency and the need for multiple separation operations.Here,we propose a process involving mixed HCl-H_(2)SO_(4) leaching-spray pyrolysis for recycling spent ternary LIBs,achieving both selective Li recovery and the preparation of a ternary oxide precursor.Specifically,the process transforms spent ternary cathode(LiNi_(x)Co_yMn_(2)O_(2),NCM) powder into Li_(2)SO_(4) solution and ternary oxide,which can be directly used for synthesizing battery-grade Li_(2)CO_(3) and NCM cathode,respectively.Notably,SO_(4)^(2-) selectively precipitates with Li^(+) to form thermostable Li_(2)SO_(4) during the spray pyrolysis,which substantially improves the Li recovery efficiency by inhibiting Li evaporation and intercalation.Besides,SO_(2) emissions are avoided by controlling the molar ratio of Li^(+)/SO_(4)^(2-)(≥2:1),The mechanism of the preferential formation of Li_(2)SO_(4) is interpreted from its reverse solubility variation with temperature.During the recycling of spent NCM811,92% of Li is selectively recovered,and the regenerated NCM811 exhibits excellent cycling stability with a capacity retention of 81.7% after 300 cycles at 1 C.This work offers a simple and robust process for the recycling of spent NCM cathodes.

Synthesis and characterization of boron-doped NiO thin films pro-duced by spray pyrolysis

Boron-doped NiO thin films were prepared on glass substrates at 400℃ by airbrush spraying method using a solution of nickel nitrate hexahydrate. Their physical properties were investigated as a function of dopant concentration. From X-ray diffraction patterns, it is observed that the films have cubic structure with lattice parameters varying with boron concentration. The morphologies of the films were examined by using scanning electron microscopy, and the grain sizes were measured to be around 30-50 nm. Optical measurements show that the band gap energies of the films first decrease then increase with increasing boron concentration. The resistivities of the films were determined by four point probe method, and the changes in resistivity with boron concentration were investigated.

Spherical YAG∶Ce^(3+) Phosphor Particles Prepared by Spray Pyrolysis

Spherical YAG：Ce^3＋ phosphor particles with narrow size distribution were prepared by spray pyrolysis. The effects of the concentration of solution, the flow rate of cartier gas and the annexing temperature on the phosphor morphology were studied. The productivity of precursor particles shows a trend of drop after rising with the increase of concentration Raising the flow rate of nitrogen can improve the productivity of the precursor particles. Phosphor prepared by spray pyrolysis has obviously higher emission intensity than that synthesized by solid state reaction, spray pyrolysis makes Ce^3＋ ions well distributed in the crystal lattice as the luminescent centers, and phosphor particles have regular sphericity and narrow size distribution.

Production and characterization of ZnO nanoparticles and porous particles by ultrasonic spray pyrolysis using a zinc nitrate precursor

ZnO nanoparticles and porous particles were produced by an ultrasonic spray pyrolysis method using a zinc nitrate precursor at various temperatures under air atmosphere. The effects of reaction temperature on the size and morphology of ZnO particles were investi- gated. The samples were characterized by energy dispersive spectroscopy, X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. ZnO particles were obtained in a hexagonal crystal structure and the crystallite shapes changed from spherical to hex- agonal by elevating the reaction temperature. The crystallite size grew by increasing the temperature, in spite of reducing the residence time in the heated zone. ZnO nanoparticles were obtained at the lowest reaction temperature and ZnO porous particles, formed by aggregation of ZnO nanoparticles due to effective sintering, were prepared at higher temperatures. The results showed that the properties of ZnO particles can be controlled by changing the reaction temperature in the ultrasonic spray pyrolysis method.

Spray pyrolysis synthesis of nickel-rich layered cathodes LiNi_(1-2x)Co_xMn_xO_2(x = 0.075, 0.05, 0.025) for lithium-ion batteries

In this study we report a series of nickel-rich layered cathodes LiNi1-2xCoxMnxO2（x = 0.075, 0.05,0.025） prepared from chlorides solution via ultrasonic spray pyrolysis. SEM images illustrate that the samples are submicron-sized particles and the particle sizes increase with the increase of Ni content.LiNi0.85Co0.075Mn0.075O2 delivers a discharge capacity of 174.9 mAh g-1 with holding 93% reversible capacity at 1 C after 80 cycles, and can maintain a discharge capacity of 175.3 mAh g-1 at 5 C rate. With increasing Ni content, the initial specific capacity increases while the cycling and rate performance degrades in some extent. These satisfying results demonstrate that spray pyrolysis is a powerful and efficient synthesis technology for producing Ni-rich layered cathode（Ni content 〉 80%）.

Instant formation of excellent oxygen evolution catalyst film via controlled spray pyrolysis for electrocatalytic and photoelectrochemical water splitting

The retarded kinetics of oxygen evolution on electrodes is a bottleneck for electrochemical energy conversion and storage systems.NiFe-based electrocatalysts provide a cost-effective choice to confront this challenge.However,there is a lack of facile techniques for depositing compact catalytic films of high coverage and possessing a state-of-the-art performance,which is especially desired in photoelectrochemical(PEC)systems.Herein,we demonstrate a spray pyrolysis(SP)route to address this issue,featuring the kinetic selective preparation towards the desired catalytic-active material.Differing from reported SP protocols which only produce inactive oxides,this approach directly generates a unique composite film consisting of NiFe layered oxyhydroxides and amorphous oxides,exhibiting an overpotential as small as 255 mV(10 mA cm^(−2))and a turnover frequency of∼0.4 s^(−1)per metal atom.By using such a facile protocol,the surface rate-limiting issue of BiVO_(4)photoanodes can be effectively resolved,resulting in a charge injection efficiency of over 90%.Considering this deposition directly start from simple nitrates but only takes several seconds to complete,we believe it can be developed as a widely applicable and welcomed functionalization technique for diverse electrochemical devices.

Fabrication and Characterization of Nano Silver Powder Prepared by Spray Pyrolysis

Silver powder was fabricated by spray pyrolysis, using 2%-20% AgNO3 solution, 336-500 mL/h flux of AgNO3 solution, 0.28-0.32 MPa flux of carrier gas and in the 620-820 ℃ temperature range. The effects of furnace set temperature, concentration of AgNO3 aqueous solution, flux of AgNO3 aqueous solution as well as carrier gas on the morphology and particle size distribution of silver powder, were investigated. The experimental results showed that with the high concentration of AgNO3 aqueous solution, the average grain size of silver decreased with the increasing of furnace set temperature. But the gain size distribution was not homogenous, the discontinuous grain growth occurred. With the low concentration of AgNO3 aqueous solution, the higher furnace set temperature made the nano sliver grains sintered together to grow. Nano silver powder about 100 nm was fabricated by spray pyrolysis, using 2wt% AgNO3 solutions, 336 mL/h flux of AgNO3 aqueous solution, 0.32 MPa flux of carrier gas at 720 ℃ furnace set temperature.

Preparation of spherical and dense LiNi_(0.8)Co_(0.2)O_2 lithium-ion battery particles by spray pyrolysis

With citric acid as a polymeric agent layered LiNi0.8Co0.2O2 materials were synthesized by a spray pyrolysis method. The LiNi0.sCo0.2O2 particles were characterized by means of XRD, SEM and TEM. The electrochemical performances of LiNi0.8Co0.2O2 particles were studied in a voltage window of 3.00-4.35 V and at a current density of 30 mA/g. The results show that in the pilot-scale spray pyrolysis process, the morphology of particles is dependent upon the precursor concentration and flux of carrier gas. The initial discharge capacity of the LiNi0.8Co0.2O2particles at 720 ℃ for 12 h is 187.3 mA.h/g, and the capacity remains 96.8% with excellent cycleability after 30 cycles. The LiNi0.8Co0.2O2 samples synthesized under the optimized conditions by the spray pyrolysis method shows a good electrochemical performance.

Characteristics of SnO_(2):F Thin Films Deposited by Ultrasonic Spray Pyrolysis:Effect of Water Content in Solution and Substrate Temperature

Fluorine doped tin oxide, SnO2:F, thin films were deposited by ultrasonic chemical spray starting from tin chloride and hydrofluoric acid. The physical characteristics of the films as a function of both water content in the starting solution and substrate temperature were studied. The film structure was polycrystalline in all cases, showing that the intensity of (200) peak increased with the water content in the starting solution. The electrical resistivity decreased with the water content, reaching a minimum value, in the order of 8 × 10-4 Ωcm, for films deposited at 450℃ from a starting solution with a water content of 10 ml per 100 ml of solution;further increase in water content increased the corresponding resistivity. Optical transmittances of SnO2:F films were high, in the order of 75%, and the band gap values oscillated around 3.9 eV. SEM analysis showed uniform surface morphologies with different geometries depending on the deposition conditions. Composition analysis showed a stoichiometric compound with a [Sn/O] ratio around 1:2 in all samples. The presence of F into the SnO2 lattice was detected, within 2 at % respect to Sn.

Influences of Pr and Ta doping concentration on the characteristic features of FTO thin film deposited by spray pyrolysis

The Pr and Ta separately doped FTO（10 at.% F incorporated Sn O2） films are fabricated via spray pyrolysis. The microstructural, topographic, optical, and electrical features of fluorine-doped TO（FTO） films are investigated as functions of Pr and Ta dopant concentrations. The x-ray diffraction（XRD） measurements reveal that all deposited films show polycrystalline tin oxide crystal property. FTO film has（200） preferential orientation, but this orientation changes to（211） direction with Pr and Ta doping ratio increasing. Atomic force microscopy（AFM） and scanning electron microscopy（SEM） analyses show that all films have uniform and homogenous nanoparticle distributions. Furthermore, morphologies of the films depend on the ratio between Pr and Ta dopants. From ultraviolet-visible（UV-Vis） spectrophotometer measurements, it is shown that the transmittance value of FTO film decreases with Pr and Ta doping elements increasing. The band gap value of FTO film increases only at 1 at.% Ta doping level, it drops off with Pr and Ta doping ratio increasing at other doped FTO films. The electrical measurements indicate that the sheet resistance value of FTO film initially decreases with Pr and Ta doping ratio decreasing and then it increases with Pr and Ta doping ratio increasing. The highest value of figure of merit is obtained for 1 at.% Ta- and Pr-doped FTO film. These results suggest that Pr- and Ta-doped FTO films may be appealing candidates for TCO applications.

Double-layer indium doped zinc oxide for silicon thin-film solar cell prepared by ultrasonic spray pyrolysis

Indium doped zinc oxide （ZnO：In） thin films were prepared by ultrasonic spray pyrolysis on corning eagle 2000 glass substrate. 1 and 2 at.% indium doped single-layer ZnO：In thin films with different amounts of acetic acid added in the initial solution were fabricated. The 1 at.% indium doped single-layers have triangle grains. The 2 at.% indium doped single-layer with 0.18 acetic acid adding has the resistivity of 6.82 × 10^-3 Ω. cm and particle grains. The doublelayers structure is designed to fabricate the ZnO：In thin film with low resistivity （2.58 × 10^-3 Ω. cm） and good surface morphology. It is found that the surface morphology of the double-layer ZnO：In film strongly depends on the substratelayer, and the second-layer plays a large part in the resistivity of the doublewlayer ZnO：In thin film. Both total and direct transmittances of the double-layer ZnO：In film are above 80% in the visible light region. Single junction a-Si：H solar cell based on the double-layer ZnO：In as front electrode is also investigated.

Transparent conductive stannic oxide coatings employing an ultrasonic spray pyrolysis technique:The relevance of the molarity content in the aerosol solution for improvement the electrical properties

Highly transparent conductive stoichiometric nanocrystalline stannic oxide coatings were deposited onto Corning®EAGLE XG®slim glass substrates.Including each coating,it was deposited for various concentrations in the aerosol solution with the substrate temperature maintained at 623.15 K by an ultrasonic spray pyrolysis(USP)technique.Nitrogen was em-ployed both as the solution carrier in addition to aerosol directing gas,maintaining its flow rates at 3500.0 and 500.0 mL/min,respectively.The coatings were polycrystalline,with preferential growth along the stannic oxide(112)plane,irrespective of the molarity content in the spray solution.The coating prepared at 0.2 M,a concentration in the aerosol solution,showed an average transmission of 60%in the visible light region spectrum with a maximum conductivity of 24.86 S/cm.The coatings deposited exhibited in the general photoluminescence spectrum emission colors of green,greenish white,and bluish white calculated on the intensities of the excitonic and oxygen vacancy defect level emissions.

Influence of Cadmium Doping on Structural, Optical, electrical and Photocatalytic Properties of TiOz Thin Films Prepared by Spray Pyrolysis Technique

Undoped and doped cadmuim titanium oxide thin films at different percentage （1, 3, 4, and 5）% were fabricated by spray pyrolysis by using a solution of titanium tetrachloride and ethyl alcohol. The films have been deposited on heated quartz substrates at 623 K. After annealing for 120 min at 823 K, the initially amorphous films became polycrystalline with a predominant anatase structure and average crystallite sizes depending on dopant Cd concentration. Atomic force microscope （AIM） results show that the addition of the Cd to TiO2 thin films become smooth. Optical study shows the optical band gap, and transmission has been increasing with increasing doping concentration in TiO2 thin films. The electrical resistivity is decreases with increasing doping concentration Cd in TiO2 thin films could be attributed to the increasing charge concentration. Photocatalytic activity of the TiO2 films were studied by monitoring the degradation of aqueous methylene blue under UV light irradiation and was observed that increasing doping concentration had good photocatalytic activity which was explained as due to the structural and morphological properties of the films.

Synthesis and Characterization of ZnO Nanostructure by Chemical Spray Pyrolysis Method

Zinc Oxide （ZnO） nanostructure were synthesized by precipitating Zinc Chloride and analyzed structurally and optically. Samples were prepared at different thickness （62, 66, 74, 86, 92, and 110 nm）, and substrate temperature kept at 400 ℃ in all cases. Compressed Nitrogen was used as a cartier gas. The samples of the ZnO films were characterized by X-ray diffraction （XRD）, and atomic force microscopy （AFM）. The XRD results indicated that the synthesized ZnO thin films have a pure wurtzite （hexagonal phase） structure. It can be seen that the highest texture coefficient was in （002） plan for nanostructure films. AFM measurement showed the grain size ranging from 62-86 nm. The optical band gap energy （Ee,） of ZnO nanostructure have two values for the same sample and the Eg decrease with increasing thickness utilizing the optical data using UV-Vis spectrophotometer.

Direct spray pyrolysis of aluminum chloride solution for alumina preparation

The effects of pyrolysis mode and pyrolysis parameters on Cl content in alumina were investigated, and the alumina products were characterized by XRD, SEM and ASAP. The experimental results indicate that the spray pyrolysis efficiency is higher than that of static pyrolysis process, and the reaction and evaporation process lead to a multi-plot state of the alumina products by spray pyrolysis. Aluminum phase starts to transform into γ-Al2O3 at spray pyrolysis temperature of 600 °C, which is about 200 °C lower than that of static pyrolysis process. The primary particle size of γ-Al2O3 product is 27.62 nm, and Cl content in alumina products is 0.38% at 800 °C for 20 min.

Reply to Comments on "Structural,Optical,and Electrical Properties of Zn-Doped CdO Thin Films Fabricated by a Simplified Spray Pyrolysis Technique'' by K.Usharani and A.R.Balu published in Acta Metall.Sin.(Engl.Lett.) 28(1),64–71(2015)

Following are the comments for the queries raised by Prof. Pawel E. Tomaszewski on our published paper entitled ＂Structural, Optical, and Electrical Properties of Zn-Doped CdO Thin Films Fabricated by a Simplified Spray Pyrolysis Technique＂ by K. Usharani and A.R. Balu published in Acta Metall. Sin.

Gas template-assisted spray pyrolysis： A facile strategy to produce porous hollow Co3O4 with tunable porosity for high-performance lithium-ion battery anode materials

Porous hollow Co3O4 microspheres have been synthesized from a mixed cobalt nitrate and urea solution through spray pyrolysis followed by calcination at 600 ℃ in air. This porous hollow Co3O4 is assembled by nanoparticles and exhibits variable porosity depending on the amount of gas in the system. In pyrolysis process, urea continuously decomposes into gaseous components, which act as a template to control the porous structure. The amount of gas escaping from precursor droplets can directly influence the porosity of the microspheres and the size of the nanoparticles controlled by the ratio of urea to cobalt nitrate. Electrochemical measurements show that the performance of the porous hollow Co3O4 microspheres is related to the porosity and size of the nanopartides. The sample with optimal porosity delivers a high first charge capacity of 1,417.9 mAh·g^-1 at 0.2C （1C = 890 mA·g^-1）, and superior charge cycle performance of 1,012.7 mAh.g-1 after 100 cycles. In addition, the optimized material displays satisfactory rate performance of 1,012.4 mAh.g-1 at 1C after 50 cycles and 881.3 mAh·g^-1 at 2C after 300 cycles. Superior charge/discharge capacity, excellent rate performance and high yield achieved in this study is promising for the development of high-performance Co3O4 anode materials for lithium-ion batteries.

Characterization of CeO_(2)microspheres fabricated by an ultrasonic spray pyrolysis method

CeO_(2) is one of the main catalysts for solid oxide fuel cell(SOFC).It is critical to find a green and costeffective fabrication method for CeO_(2) at scale.In this study,the CeO_(2) microspheres were prepared by one-step ultrasonic spray pyrolysis of cerium chloride solution at700℃.Scanning electron microscopy(SEM)and transmission electron microscopy(TEM)study demonstrate that the prepared CeO_(2) microspheres exhibit a particle size of0.01-1.08μm with a mean particle size of 0.23μm,and more than 94%of the particles have a diameter less than0.5μm.But the presence of residual Cl in the fabricated CeO_(2) microspheres blocks the active sites and leads to the significant degradation of SOFC performance.The formation mechanism and distribution of residual Cl in the fabricated CeO_(2) microspheres were systemic ally studied.The water washing method was shown to effectively reduce the residual Cl in the CeO_(2) microspheres.Overall,this work provides a clean manufacturing process for the preparation of SOFC electrode/electrolyte materials.

Texture coefficient and band gap tailoring of Fe-doped SnO_(2) nanoparticles via thermal spray pyrolysis

An investigation of Fe-doping effect on SnO_(2) thin films was performed in this study using thermal spray pyrolysis(TSP) method.The surface morphology and structural,optical and electrical properties were studied by field energy scanning electron microscope(FESEM),X-ray diffraction(XRD),ultraviolet-visible(UV-Vis) spectroscopy and four-point probe method.FES EM images demonstrate that the surface morphology of the as-deposited films varies when Fe-doping content varies.XRD studies reveal that crystallite size and preferential growth orientations of the films are dependent on Fe-doping concentrations.The grain size is found to decrease with the increase in Fe content.These studies also specify that the films have tetragonal rutile-type structure with mixed secondary phases.The texture coefficient value of(110) plane increases with the concomitant in-plane(220) decrease in higher doping concentrations.The resistivity and the optical absorbance are found to increase with Fe concentration.The direct optical band gap decreases from 3.94 to3.52 eV with increasing Fe content.