This paper focuses on the preparation of rare earth oxide products from rare earth chloride solutions during the rare earth extraction and separation processes,as well as the recycling of magnesium chloride solutions....This paper focuses on the preparation of rare earth oxide products from rare earth chloride solutions during the rare earth extraction and separation processes,as well as the recycling of magnesium chloride solutions.It proposes the idea of introducing spray pyrolysis technology into the rare earth extraction and separation processes.This paper briefly describes the development history of chloride spray pyrolysis technology,focusing on the research status and application progress of rare earth chloride solution and magnesium chloride solution spray pyrolysis technology,as well as spray pyrolysis equipment.The paper also analyzes the challenges and technical intricacies associated with applying spray pyrolysis technology to chloride solutions in the rare earth extraction and separation processes.Additionally,it explores future trends and proposes strategies to facilitate the full recycling of acids and bases,streamline the process flow,and enhance the prospects for green and low-carbon rare earth metallurgy.展开更多
Nickel-rich cathode materials have received widespread attention due to their high energy density.However,the poor rate capability and inferior cycle stability seriously hinder their large-scale application.The tradit...Nickel-rich cathode materials have received widespread attention due to their high energy density.However,the poor rate capability and inferior cycle stability seriously hinder their large-scale application.The traditional co-precipitation method for preparing them has a long process and easily arises agglomeration leading to inhomogeneous element distribution.Here,a novel precursor containing Li element was prepared by ultrafast spray pyrolysis(SP)in 3–5 s.Then the precursor was used to synthesize pristine LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90)and 1%Mg modified LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90-Mg1).This method gets rid of mixing Li/Mg source and the precursor prepared by common co-precipitation,thus could achieve homogeneous lithiation and Mg2+doping.The cell parameter c is expanded,and the cation disorder is reduced after Mg2+doping.Furthermore,the harmful H2-H3 phase transition in NCM90-Mg1 is also well suppressed.As a result,the obtained NCM90-Mg1 shows better electrochemical performance than NCM90.Within 2.8–4.3 V(25℃),the specific discharge capacity of NCM90-Mg1 at 5 C is as high as 169.1m Ah/g,and an outstanding capacity retention of 70.0%(10.0%higher than NCM90)can be obtained after400 cycles at 0.5 C.At 45℃,a capacity retention of 81.9%after 100 cycles at 1 C is recorded for NCM90-Mg1.Moreover,the NCM90-Mg1 also exhibits superior cycle stability when cycled at high cut-off voltage(4.5 V,25℃),possessing the capacity retention of 79.2%after 200 cycles at 1 C.Therefore,SP can be proposed as a powerful method for the preparation of multi-element materials for next-generation high energy density LIBs.展开更多
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 ...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.展开更多
The lithium metal anode has emerged as a promising candidate for future high-energy-density batter-ies.However,its practical application is hindered by the uncontrollable growth of lithium dendrites.In this study,we d...The lithium metal anode has emerged as a promising candidate for future high-energy-density batter-ies.However,its practical application is hindered by the uncontrollable growth of lithium dendrites.In this study,we developed carbon nanotube(CNT)-decorated ZnO-C microspheres,containing multi-voids,as a lithiophilic host material for a stable lithium metal anode using a one-pot synthesis spray pyrolysis process.These microspheres offer ample space for accommodating lithium metal due to the presence of multi-voids.Additionally,the uniform distribution of ZnO nanocrystals and CNTs facilitates homogeneous lithium nucleation without dendrite formation.To understand the role of ZnO nanocrystals in achieving a stable lithium metal anode,density functional theory(DFT)calculations were employed,which demon-strated superior adsorption energies for lithium atoms as well as favorable electronic properties of the ZnO component.Consequently,the ZnO-C-CNT microspheres exhibit a stable lithium plating/stripping behavior,characterized by high Coulombic efficiency and the maintenance of stable voltage profiles in a symmetric cell configuration.When coupling this anode with the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)cathode,the assem-bled full cell demonstrates excellent cycling stability and high-rate capability,indicating its potential for practical applications.展开更多
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 transiti...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.展开更多
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 Sp...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.展开更多
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 con...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.展开更多
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 p...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.展开更多
A novel rapid and continuous process has developed for the synthesis of nitrogen-doped TiO2（N-TiO2）with flame spray pyrolysis（FSP） method. The nitrogen incorporation into TiO2 was achieved by a facile modification...A novel rapid and continuous process has developed for the synthesis of nitrogen-doped TiO2（N-TiO2）with flame spray pyrolysis（FSP） method. The nitrogen incorporation into TiO2 was achieved by a facile modification（addition of dilute nitric acid） in the precursor for the synthesis. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The doping of nitrogen into the TiO2 was confirmed by X-ray photoelectron spectroscopy（XPS） and energy dispersive X-ray（EDX） spectroscopy. The UV-vis spectra of the modified catalysts（with primary N source） exhibited band-gap narrowing for 4 N-TiO2 with band gap energy of 2.89 eV, which may be due to the presence of nitrogen in TiO2 structure. The introduction of secondary N-source（urea） into TiO2 crystal lattice results in additional reduction of the band gap energy to 2.68 eV and shows a significant improvement of visible light absorption. The N-TiO2 nanoparticles modified by using secondary N-source showed significant photocatalytic activity under visible light much higher than TiO2. The higher activity is attributed to the synergetic interaction of nitrogen with the TiO2 lattice. The lowering of the band-gap energy for the flame made N-doped TiO2 materials implies that the nitrogen doping in TiO2 by aerosol method is highly effective in extending the optical response of TiO2 in the visible region. The nitrogen atomic percentage has increased monotonically（0.09%-0.15%）with the increase in primary nitrogen source（nitric acid）, and significantly boosted to 0.97% when secondary nitrogen source（urea） was introduced. The highest rate of phenol degradation was obtained for catalysts with secondary N source due to increase in N content in the catalyst.展开更多
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...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.展开更多
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 ...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.展开更多
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...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.展开更多
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 su...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%）.展开更多
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....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.展开更多
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 ...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.展开更多
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 pe...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.展开更多
The commented paper [1] presents the results on structural, optical, and electrical properties of Zn-doped CdO thin films. Unfortunately, there are several mistakes and errors not found by any of referees. It is neces...The commented paper [1] presents the results on structural, optical, and electrical properties of Zn-doped CdO thin films. Unfortunately, there are several mistakes and errors not found by any of referees. It is necessary to show these mistakes or misleading statements to avoid their use in the future papers by authors and other peoples.展开更多
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 pyr...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.展开更多
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 ...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.展开更多
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 inv...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.展开更多
基金supported by the National Key Research and Development Program of China(2022YFB3504501)the National Natural Science Foundation of China(52274355)。
文摘This paper focuses on the preparation of rare earth oxide products from rare earth chloride solutions during the rare earth extraction and separation processes,as well as the recycling of magnesium chloride solutions.It proposes the idea of introducing spray pyrolysis technology into the rare earth extraction and separation processes.This paper briefly describes the development history of chloride spray pyrolysis technology,focusing on the research status and application progress of rare earth chloride solution and magnesium chloride solution spray pyrolysis technology,as well as spray pyrolysis equipment.The paper also analyzes the challenges and technical intricacies associated with applying spray pyrolysis technology to chloride solutions in the rare earth extraction and separation processes.Additionally,it explores future trends and proposes strategies to facilitate the full recycling of acids and bases,streamline the process flow,and enhance the prospects for green and low-carbon rare earth metallurgy.
基金supported by the National Natural Science Foundation of China(No.52122407)the Science and Technology Innovation Program of Hunan Province(No.2022RC3048)。
文摘Nickel-rich cathode materials have received widespread attention due to their high energy density.However,the poor rate capability and inferior cycle stability seriously hinder their large-scale application.The traditional co-precipitation method for preparing them has a long process and easily arises agglomeration leading to inhomogeneous element distribution.Here,a novel precursor containing Li element was prepared by ultrafast spray pyrolysis(SP)in 3–5 s.Then the precursor was used to synthesize pristine LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90)and 1%Mg modified LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90-Mg1).This method gets rid of mixing Li/Mg source and the precursor prepared by common co-precipitation,thus could achieve homogeneous lithiation and Mg2+doping.The cell parameter c is expanded,and the cation disorder is reduced after Mg2+doping.Furthermore,the harmful H2-H3 phase transition in NCM90-Mg1 is also well suppressed.As a result,the obtained NCM90-Mg1 shows better electrochemical performance than NCM90.Within 2.8–4.3 V(25℃),the specific discharge capacity of NCM90-Mg1 at 5 C is as high as 169.1m Ah/g,and an outstanding capacity retention of 70.0%(10.0%higher than NCM90)can be obtained after400 cycles at 0.5 C.At 45℃,a capacity retention of 81.9%after 100 cycles at 1 C is recorded for NCM90-Mg1.Moreover,the NCM90-Mg1 also exhibits superior cycle stability when cycled at high cut-off voltage(4.5 V,25℃),possessing the capacity retention of 79.2%after 200 cycles at 1 C.Therefore,SP can be proposed as a powerful method for the preparation of multi-element materials for next-generation high energy density LIBs.
基金Fund of University of South China (201RGC013 and 200XQD052)。
文摘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.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MEST)(No.NRF-2022R1F1A1070886)supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.RS-2023-00217581)+1 种基金supported by the Commercialization Promotion Agency for R&D Outcomes(COMPA)grant funded by the Korean Government(Ministry of Science and ICT)(No.RS-2023-00304768)supported by the Chungbuk National University BK21 program(2023).
文摘The lithium metal anode has emerged as a promising candidate for future high-energy-density batter-ies.However,its practical application is hindered by the uncontrollable growth of lithium dendrites.In this study,we developed carbon nanotube(CNT)-decorated ZnO-C microspheres,containing multi-voids,as a lithiophilic host material for a stable lithium metal anode using a one-pot synthesis spray pyrolysis process.These microspheres offer ample space for accommodating lithium metal due to the presence of multi-voids.Additionally,the uniform distribution of ZnO nanocrystals and CNTs facilitates homogeneous lithium nucleation without dendrite formation.To understand the role of ZnO nanocrystals in achieving a stable lithium metal anode,density functional theory(DFT)calculations were employed,which demon-strated superior adsorption energies for lithium atoms as well as favorable electronic properties of the ZnO component.Consequently,the ZnO-C-CNT microspheres exhibit a stable lithium plating/stripping behavior,characterized by high Coulombic efficiency and the maintenance of stable voltage profiles in a symmetric cell configuration.When coupling this anode with the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)cathode,the assem-bled full cell demonstrates excellent cycling stability and high-rate capability,indicating its potential for practical applications.
基金supported by the National Natural Science Foundation of China(No.52122407)the Science and Technology Innovation Program of Hunan Province,China(No.2022RC3048)the Key Research and Development Program of Yunnan Province,China(No.202103AA080019).
文摘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.
文摘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.
文摘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.
基金Project supported by National "The Tenth Five-Year"plan (2003BA316A01-03-05) and "The Tenth Five-Year"Plan(BE2004021) of Jiangsu provicce
文摘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.
基金the U.S. EPA/Pegasus contract (contract number EP-C-11-006) for financial support of this work through the scholarship to Siva Nagi Reddy Inturi
文摘A novel rapid and continuous process has developed for the synthesis of nitrogen-doped TiO2（N-TiO2）with flame spray pyrolysis（FSP） method. The nitrogen incorporation into TiO2 was achieved by a facile modification（addition of dilute nitric acid） in the precursor for the synthesis. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The doping of nitrogen into the TiO2 was confirmed by X-ray photoelectron spectroscopy（XPS） and energy dispersive X-ray（EDX） spectroscopy. The UV-vis spectra of the modified catalysts（with primary N source） exhibited band-gap narrowing for 4 N-TiO2 with band gap energy of 2.89 eV, which may be due to the presence of nitrogen in TiO2 structure. The introduction of secondary N-source（urea） into TiO2 crystal lattice results in additional reduction of the band gap energy to 2.68 eV and shows a significant improvement of visible light absorption. The N-TiO2 nanoparticles modified by using secondary N-source showed significant photocatalytic activity under visible light much higher than TiO2. The higher activity is attributed to the synergetic interaction of nitrogen with the TiO2 lattice. The lowering of the band-gap energy for the flame made N-doped TiO2 materials implies that the nitrogen doping in TiO2 by aerosol method is highly effective in extending the optical response of TiO2 in the visible region. The nitrogen atomic percentage has increased monotonically（0.09%-0.15%）with the increase in primary nitrogen source（nitric acid）, and significantly boosted to 0.97% when secondary nitrogen source（urea） was introduced. The highest rate of phenol degradation was obtained for catalysts with secondary N source due to increase in N content in the catalyst.
基金financially supported by the National Key R&D Program of China(No.2018YFB1502600)the National Natural Science Foundation of China(Nos.51922042 and 51872098)+1 种基金China Postdoctoral Science Foundation(No.2019M652888)the Sino-Singapore International Joint Research Institute(SSIJRI),China。
文摘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.
文摘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.
基金financially supported by the Scientific and Technological Research Council of Turkey (No. 107M505)
文摘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.
基金financial support of the National Basic Research Program of China (2014CB643406)the National Natural Science Foundation of China (51674296, 51704332)+1 种基金the National Postdoctoral Program for Innovative Talents (BX201700290)the Fundamental Research Funds for the Central Universities of Central South University (2017zzts125)
文摘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%）.
基金financially supported by the National Natural Science Foundation of China(NSFC,21805298,21905288,51904288)the Zhejiang Provincial Natural Science Foundation(Z21B030017)+2 种基金the K.C.Wong Education Foundation(GJTD-201913)the Ningbo major special projects of the Plan‘‘Science and Technology Innovation 2025”(2018B10056,2019B10046)the Ningbo 3315 Program。
文摘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.
文摘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.
基金Project(50604018) supported by the National Natural Science Foundation of China
文摘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.
文摘The commented paper [1] presents the results on structural, optical, and electrical properties of Zn-doped CdO thin films. Unfortunately, there are several mistakes and errors not found by any of referees. It is necessary to show these mistakes or misleading statements to avoid their use in the future papers by authors and other peoples.
基金Projects(U1202274,51004033,51204040)supported by the National Natural Science Foundation of ChinaProject(2012AA062303)supported by the National High Technology Research and Development Program of China+2 种基金Project(2012BAE01B02)supported by the National Science and Technology Support Program of ChinaProject(L2014096)supported by the Education Department of Liaoning Province,ChinaProject(N130702001)supported by the Fundamental Research Funds for the Central Universities,China
文摘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.
基金This work was partially supported by CONACyT under contract Number 166601.
文摘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.
文摘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.
