The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developi...The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developing high oxide-ion conductivity in the electrolyte layer of SOFCs.In this context,for the first time,a dielectric material,CaCu_(3)Ti_(4)O_(12)(CCTO)is designed for LT-SOFCs electrolyte application in this study.Both individual CCTO and its heterostructure materials with a p-type Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2−δ)(NCAL)semiconductor are evaluated as alternative electrolytes in LT-SOFC at 450–550℃.The single cell with the individual CCTO electrolyte exhibits a power output of approximately 263 mW cm^(-2) and an open-circuit voltage(OCV)of 0.95 V at 550℃,while the cell with the CCTO–NCAL heterostructure electrolyte capably delivers an improved power output of approximately 605 mW cm^(-2) along with a higher OCV over 1.0 V,which indicates the introduction of high hole-conducting NCAL into the CCTO could enhance the cell performance rather than inducing any potential short-circuiting risk.It is found that these promising outcomes are due to the interplay of the dielectric material,its structure,and overall properties that led to improve electrochemical mechanism in CCTO–NCAL.Furthermore,density functional theory calculations provide the detailed information about the electronic and structural properties of the CCTO and NCAL and their heterostructure CCTO–NCAL.Our study thus provides a new approach for developing new advanced electrolytes for LT-SOFCs.展开更多
The effect of Cr2O3 on the nucleation and crystallization of Na2O-CaO-Al2O3-SiO2-F- glass has been investigated by means of ESR(Electron Spin Resonance), SEM(Scanning Electron Microscope), EDS(Energy Dispersive Specro...The effect of Cr2O3 on the nucleation and crystallization of Na2O-CaO-Al2O3-SiO2-F- glass has been investigated by means of ESR(Electron Spin Resonance), SEM(Scanning Electron Microscope), EDS(Energy Dispersive Specrometer) and so on. Computer pattern recognition is applied to optimize the heat-treatment schedules. The experimental results show that the base glass containing more than 1 .5 % (mass fraction) Cr2O3 can be nucleated internally and converted to spheroidal crystal glass materials. The spheroidal crystal consisted of fibrous wollastonite crystals radiating from a center. The residual glass phase filled in the interstices between the fibers and between the spherulites. During heat treatment process, the valence states ofchromium changed from Cr6- to Cr3-, and the Cr-spinel solidsolution [CaCr2O4] precipitated followed this valence change. At the primary stage of crystallization, the Cr-spinel could act as a nucleating center on which the principal or}stalline phase β-CaSiO3 grew epitaxially.展开更多
Pd/γ-Al2O3–TiO2catalysts containing various compositions of titania and alumina were prepared by sol–gel and wet-impregnation methods in attempt to study the particle size, nature of phases, morphology and structur...Pd/γ-Al2O3–TiO2catalysts containing various compositions of titania and alumina were prepared by sol–gel and wet-impregnation methods in attempt to study the particle size, nature of phases, morphology and structure of the composite samples. The ethanol oxidation experiments, N2adsorption–desorption,FTIR, XRD and XPS were conducted, and the effects of Al2O3content on the surface area, phase transformation and structural properties of TiO2were investigated. The optimal value of ethanol conversion appeared on Pd/Al(0.05)–Ti and Pd/Al(0.90)–Ti catalysts irrespective of the ethanol oxidation temperature, and we call this as a double peaks phenomenon of catalytic activity. The XRD results reveal that the phase composition and crystallite size of the mixed oxides depend on Al2O3/TiO2ratio and calcination temperature. Al2O3can effectively prevent the agglomeration of TiO2and this can be ascribed to the formation of Al–O–Ti chemical bonds in Al2O3–TiO2crystals. Binding energy and Pd surface concentration of the catalysts were modified apparently, which may also lead to catalyst activity changes.展开更多
A heat-resistant dispersion-strengthening nano-Al_2O_3/Cu composite with highstrength and high electric conductivity was fabricated in a multiplex medium. The internaloxidation product, microstructures and properties ...A heat-resistant dispersion-strengthening nano-Al_2O_3/Cu composite with highstrength and high electric conductivity was fabricated in a multiplex medium. The internaloxidation product, microstructures and properties of the composite, and the process flow weresystematically studied. It is confirmed that this new technique simplifies the process and improvesthe properties of the composite. X-ray analysis indicates that the alumina particles formed duringinternal oxidation consist of a large mount of gamma-Al_2O_3 and a certain amount of theta-Al_2O_3and alpha-Al_2O_3. TEM observation shows that the obtained gamma-Al_2O_3 nano-particles areuniformly distributed in the copper grains; their mean size and space between particles are 7 runand 30 nm, respectively. The main properties of the composite with 50 percent cold deformation areas follows: the electric conductivity is 51 MS/m (87 percent IACS), sigma_b = 628 MPa, and thehardness is HRB86. After annealing at 1273 K, all or most of the above properties remain, and themicrostructures are still dependent on elongated fiber-form grains.展开更多
The abrasive wear characteristics of Al_2O_3/PA1010 composite coatings on thesurface of quenched and low-temperature temper steel 45 were tested on the template abrasive weartesting machine and the same uncoated steel...The abrasive wear characteristics of Al_2O_3/PA1010 composite coatings on thesurface of quenched and low-temperature temper steel 45 were tested on the template abrasive weartesting machine and the same uncoated steel 45 was used as a reference material. Experimentalresults showed that the abrasive wear resistance of Al_2O_3/PA1010 composite coatings has a goodlinear relationship with the volume fraction of Al_2O_3 particles in Al_2O_3/PA1010 compositecoatings, and the linear correlative coefficient is 0.979. Under the experimental conditions, thesize of Al_2O_3 particles (40.5-161.0 μm) has little influence on the abrasive wear resistance ofAl_2O_3/PA1010 composite coatings. By treating the surface of Al_2O_3 particles with a suitablebonding agent, the distribution of Al_2O_3 particles in matrix PA1010 is more homogeneous and thebonding state between Al_2O_3 particles and matrix PA1010 is better. Therefore, the Al_2O_3particles in Al_2O_3/PA1010 composite coatings make the Al_2O_3/PA1010 composite coatings havebetter abrasive wear resistance than PA1010 coatings. The wear resistance of Al_2O_3/PA1010composite coatings is about 45% compared with that of steel 45.展开更多
MnO_x/Al_2O_3 and MnO_x/ZrO_2-Al_2O_3 catalysts were prepared by incipientwetness impregnation of Mn(CH_3COO)_2 on the corresponding supports, followed by thecharacterization using X-ray diffraction (XRD), temperature...MnO_x/Al_2O_3 and MnO_x/ZrO_2-Al_2O_3 catalysts were prepared by incipientwetness impregnation of Mn(CH_3COO)_2 on the corresponding supports, followed by thecharacterization using X-ray diffraction (XRD), temperature programmed reduction (TPR) and BETsurface area techniques. The result shows the BET surface area of ZrO_2-Al_2O_3 is lower than thatof Al_2O_3 due to the loading of ZrO_2. However the resulted MnO_x/ZrO_2-Al_2O_3 catalyst exhibitshigher activity for methane combustion than MnO_x/Al_2O_3, because the addition of ZrO_2 ontoAl_2O_3 is beneficial for the dispersion of Mn species and the improvement of the lattice oxygenactivity in MnO_x, subsequently the activation of methane during combustion. The optimum loading ofZr in MnO_x/ZrO_2-Al_2O_3 is in the range of 5%-10% correlated with the calcination temperatures ofcatalyst supports.展开更多
Li_(2)O-Al_(2)O_(3)-SiO_(2)(LAS)glass-ceramics were prepared by a melting method.Effects of different Al_(2)O_(3)content on the structure,crystallization,transmittance and fracture toughness of LAS glassceramics were ...Li_(2)O-Al_(2)O_(3)-SiO_(2)(LAS)glass-ceramics were prepared by a melting method.Effects of different Al_(2)O_(3)content on the structure,crystallization,transmittance and fracture toughness of LAS glassceramics were investigated by means of XRD,FESEM and other methods as well.The results showed that the glass transition temperature and crystallization temperature of samples increased as the content of Al_(2)O_(3)increased from 4.1 wt%to 13.1 wt%,which restrained the precipitation of lithium disilicate crystals.The main crystalline phase of glass-ceramics transformed from lithium disilicate and petalite to silicon dioxide,which reduced the fracture toughness of glass-ceramics.When the Al_(2)O_(3)content was 7.1 wt%,the specimen had outstanding transmittance and fracture toughness.The transmittance was 90.32%.The fracture toughness was 1.13 MPa•m^(1/2).Compared with high-alumina glass,the fracture toughness of the glass-ceramic was greatly improved,and it could be used as a new type of protective material for mobile devices.展开更多
The nano-Bi2O3 powders were prepared by a chemical precipitation method with Bi（NO3）3, HNO3 and NaOH as reactants. The structural characteristics and morphology of nano-Bi2O3 powders were investigated by X-ray diffr...The nano-Bi2O3 powders were prepared by a chemical precipitation method with Bi（NO3）3, HNO3 and NaOH as reactants. The structural characteristics and morphology of nano-Bi2O3 powders were investigated by X-ray diffraction and transmission electron microscopy, respectively. The results show that under the optimum condition that 300g/L Bi（NO3）3 reacts at 90℃ for 2h, the Bi2O3 powders with 60nm on the average and 99.5% in purity are obtained. The prepared nano-Bi2O3 powders contain a mixed crystal structure of monoclinic and triclinic instead of traditional structure of monoclinic α-Bi2O3. And the mixed crystal structure is stable in air. The reason for the appearance of the mixed crystal structure may be that the ionic radius ratio of Bi 3+ to O 2- changes easily during the formation of nano-Bi2O3 particles by a chemical precipitation method.展开更多
The preparation technique and properties of Ag-type inorganic antibiotic material carried by Al2O3 were studied. The results show that the material has good antibiotic and safety properties, the acute toxicity taken b...The preparation technique and properties of Ag-type inorganic antibiotic material carried by Al2O3 were studied. The results show that the material has good antibiotic and safety properties, the acute toxicity taken by stomata is LD 50 >8000mg/kg （little and big white rats）, and the normal quantity in subacute toxicity test is 80mg/（kg·d）. The better mass fraction of doping Ag2O in antibiotic material carried by Al2O3 is 4%CD*28%, and the optimal sintering temperature is from 1000℃ to 1100℃.展开更多
The adsorption of acetonitrile and its co-adsorption with CO on fresh Mo_2C/Al_2O_3 catalyst have been studied by insitu FT-IR spectroscopy.Linearly adsorbed CH_3CN and CH_3CH_2NH_2 were formed after CH_3CN adsorption...The adsorption of acetonitrile and its co-adsorption with CO on fresh Mo_2C/Al_2O_3 catalyst have been studied by insitu FT-IR spectroscopy.Linearly adsorbed CH_3CN and CH_3CH_2NH_2 were formed after CH_3CN adsorption on the Mo_2C/ Al_2O_3 catalyst.The appearance of a strong band at 1578 cm^(-1) indicates that CH_3CN was reactive with hydrogen on the Mo_2C/Al_2O_3 catalyst.展开更多
The synergistic influences of boron,oxygen,and titanium on growing large single-crystal diamonds are studied using different concentrations of B_(2)O_(3) in a solvent-carbon system under 5.5 GPa-5.7 GPa and 1300℃-150...The synergistic influences of boron,oxygen,and titanium on growing large single-crystal diamonds are studied using different concentrations of B_(2)O_(3) in a solvent-carbon system under 5.5 GPa-5.7 GPa and 1300℃-1500℃.It is found that the boron atoms are difficult to enter into the crystal when boron and oxygen impurities are doped using B_(2)O_(3) without the addition of Ti atoms.However,high boron content is achieved in the doped diamonds that were synthesized with the addition of Ti.Additionally,boron-oxygen complexes are found on the surface of the crystal,and oxygen-related impurities appear in the crystal interior when Ti atoms are added into the FeNi-C system.The results show that the introduction of Ti atoms into the synthesis cavity can effectively control the number of boron atoms and the number of oxygen atoms in the crystal.This has important scientific significance not only for understanding the synergistic influence of boron,oxygen,and titanium atoms on the growth of diamond in the earth,but also for preparing the high-concentration boron or oxygen containing semiconductor diamond technologies.展开更多
LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible cap...LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible capacity limits its replacement for LiCoO_(2) in high-end digital field.Herein,three-in-one modification,Na-doping and Al_(2)O_(3)@Li_(3)BO_(3) dual-coating simultaneously,is explored for single-crystalline LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(N-NCM@AB),which exhibits excellent high-voltage performance.N-NCM@AB displays a discharge-specific capacity of 201.8 mAh g^(−1) at 0.2 C with a high upper voltage of 4.6 V and maintains 158.9 mAh g^(−1) discharge capacity at 1 C over 200 cycles with the corresponding capacity retention of 87.8%.Remarkably,the N-NCM@AB||graphite pouch-type full cell retains 81.2% of its initial capacity with high working voltage of 4.4 V over 1600 cycles.More importantly,the fundamental understandings of three-in-one modification on surface morphology,crystal structure,and phase transformation of N-NCM@AB are clearly revealed.The Na+doped into the Li–O slab can enhance the bond energy,stabilize the crystal structure,and facilitate Li+transport.Additionally,the interior surface layer of Li^(+)-ions conductor Li_(3)BO_(3) relieves the charge transfer resistance with surface coating,whereas the outer surface Al_(2)O_(3) coating layer is beneficial for reducing the active materials loss and alleviating the electrode/electrolyte parasite reaction.This three-in-one strategy provides a reference for the further research on the performance attenuation mechanism of NCM,paving a new avenue to boost the high-voltage performance of NCM cathode in Li-ion batteries.展开更多
基金National Natural Science Foundation of China(NSFC)supported this work under Grant No.32250410309,11674086,51736006,and 51772080funding from Science and Technology Department of Jiangsu Province under Grant No.BE2022029Shenzhen University under Grant No.86902/000248 also supported part of this work.
文摘The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developing high oxide-ion conductivity in the electrolyte layer of SOFCs.In this context,for the first time,a dielectric material,CaCu_(3)Ti_(4)O_(12)(CCTO)is designed for LT-SOFCs electrolyte application in this study.Both individual CCTO and its heterostructure materials with a p-type Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2−δ)(NCAL)semiconductor are evaluated as alternative electrolytes in LT-SOFC at 450–550℃.The single cell with the individual CCTO electrolyte exhibits a power output of approximately 263 mW cm^(-2) and an open-circuit voltage(OCV)of 0.95 V at 550℃,while the cell with the CCTO–NCAL heterostructure electrolyte capably delivers an improved power output of approximately 605 mW cm^(-2) along with a higher OCV over 1.0 V,which indicates the introduction of high hole-conducting NCAL into the CCTO could enhance the cell performance rather than inducing any potential short-circuiting risk.It is found that these promising outcomes are due to the interplay of the dielectric material,its structure,and overall properties that led to improve electrochemical mechanism in CCTO–NCAL.Furthermore,density functional theory calculations provide the detailed information about the electronic and structural properties of the CCTO and NCAL and their heterostructure CCTO–NCAL.Our study thus provides a new approach for developing new advanced electrolytes for LT-SOFCs.
文摘The effect of Cr2O3 on the nucleation and crystallization of Na2O-CaO-Al2O3-SiO2-F- glass has been investigated by means of ESR(Electron Spin Resonance), SEM(Scanning Electron Microscope), EDS(Energy Dispersive Specrometer) and so on. Computer pattern recognition is applied to optimize the heat-treatment schedules. The experimental results show that the base glass containing more than 1 .5 % (mass fraction) Cr2O3 can be nucleated internally and converted to spheroidal crystal glass materials. The spheroidal crystal consisted of fibrous wollastonite crystals radiating from a center. The residual glass phase filled in the interstices between the fibers and between the spherulites. During heat treatment process, the valence states ofchromium changed from Cr6- to Cr3-, and the Cr-spinel solidsolution [CaCr2O4] precipitated followed this valence change. At the primary stage of crystallization, the Cr-spinel could act as a nucleating center on which the principal or}stalline phase β-CaSiO3 grew epitaxially.
基金supported by Shanxi Provincial Science and Technology Projects(No.20140313002-2)the National Natural Science Foundation of China(No.21073131)
文摘Pd/γ-Al2O3–TiO2catalysts containing various compositions of titania and alumina were prepared by sol–gel and wet-impregnation methods in attempt to study the particle size, nature of phases, morphology and structure of the composite samples. The ethanol oxidation experiments, N2adsorption–desorption,FTIR, XRD and XPS were conducted, and the effects of Al2O3content on the surface area, phase transformation and structural properties of TiO2were investigated. The optimal value of ethanol conversion appeared on Pd/Al(0.05)–Ti and Pd/Al(0.90)–Ti catalysts irrespective of the ethanol oxidation temperature, and we call this as a double peaks phenomenon of catalytic activity. The XRD results reveal that the phase composition and crystallite size of the mixed oxides depend on Al2O3/TiO2ratio and calcination temperature. Al2O3can effectively prevent the agglomeration of TiO2and this can be ascribed to the formation of Al–O–Ti chemical bonds in Al2O3–TiO2crystals. Binding energy and Pd surface concentration of the catalysts were modified apparently, which may also lead to catalyst activity changes.
文摘A heat-resistant dispersion-strengthening nano-Al_2O_3/Cu composite with highstrength and high electric conductivity was fabricated in a multiplex medium. The internaloxidation product, microstructures and properties of the composite, and the process flow weresystematically studied. It is confirmed that this new technique simplifies the process and improvesthe properties of the composite. X-ray analysis indicates that the alumina particles formed duringinternal oxidation consist of a large mount of gamma-Al_2O_3 and a certain amount of theta-Al_2O_3and alpha-Al_2O_3. TEM observation shows that the obtained gamma-Al_2O_3 nano-particles areuniformly distributed in the copper grains; their mean size and space between particles are 7 runand 30 nm, respectively. The main properties of the composite with 50 percent cold deformation areas follows: the electric conductivity is 51 MS/m (87 percent IACS), sigma_b = 628 MPa, and thehardness is HRB86. After annealing at 1273 K, all or most of the above properties remain, and themicrostructures are still dependent on elongated fiber-form grains.
文摘The abrasive wear characteristics of Al_2O_3/PA1010 composite coatings on thesurface of quenched and low-temperature temper steel 45 were tested on the template abrasive weartesting machine and the same uncoated steel 45 was used as a reference material. Experimentalresults showed that the abrasive wear resistance of Al_2O_3/PA1010 composite coatings has a goodlinear relationship with the volume fraction of Al_2O_3 particles in Al_2O_3/PA1010 compositecoatings, and the linear correlative coefficient is 0.979. Under the experimental conditions, thesize of Al_2O_3 particles (40.5-161.0 μm) has little influence on the abrasive wear resistance ofAl_2O_3/PA1010 composite coatings. By treating the surface of Al_2O_3 particles with a suitablebonding agent, the distribution of Al_2O_3 particles in matrix PA1010 is more homogeneous and thebonding state between Al_2O_3 particles and matrix PA1010 is better. Therefore, the Al_2O_3particles in Al_2O_3/PA1010 composite coatings make the Al_2O_3/PA1010 composite coatings havebetter abrasive wear resistance than PA1010 coatings. The wear resistance of Al_2O_3/PA1010composite coatings is about 45% compared with that of steel 45.
基金This work was financially supported by Shandong Provincial Department of Science and Technology(project number:981206403)and the State Key Laboratory of Coal Conversion at Institute of Coal Chemistry of CAS(2002-2003)
文摘MnO_x/Al_2O_3 and MnO_x/ZrO_2-Al_2O_3 catalysts were prepared by incipientwetness impregnation of Mn(CH_3COO)_2 on the corresponding supports, followed by thecharacterization using X-ray diffraction (XRD), temperature programmed reduction (TPR) and BETsurface area techniques. The result shows the BET surface area of ZrO_2-Al_2O_3 is lower than thatof Al_2O_3 due to the loading of ZrO_2. However the resulted MnO_x/ZrO_2-Al_2O_3 catalyst exhibitshigher activity for methane combustion than MnO_x/Al_2O_3, because the addition of ZrO_2 ontoAl_2O_3 is beneficial for the dispersion of Mn species and the improvement of the lattice oxygenactivity in MnO_x, subsequently the activation of methane during combustion. The optimum loading ofZr in MnO_x/ZrO_2-Al_2O_3 is in the range of 5%-10% correlated with the calcination temperatures ofcatalyst supports.
基金State Key Laboratory of Silicate Materials for Architectures(Wuhan University of Technology)(No.2011DA105356)。
文摘Li_(2)O-Al_(2)O_(3)-SiO_(2)(LAS)glass-ceramics were prepared by a melting method.Effects of different Al_(2)O_(3)content on the structure,crystallization,transmittance and fracture toughness of LAS glassceramics were investigated by means of XRD,FESEM and other methods as well.The results showed that the glass transition temperature and crystallization temperature of samples increased as the content of Al_(2)O_(3)increased from 4.1 wt%to 13.1 wt%,which restrained the precipitation of lithium disilicate crystals.The main crystalline phase of glass-ceramics transformed from lithium disilicate and petalite to silicon dioxide,which reduced the fracture toughness of glass-ceramics.When the Al_(2)O_(3)content was 7.1 wt%,the specimen had outstanding transmittance and fracture toughness.The transmittance was 90.32%.The fracture toughness was 1.13 MPa•m^(1/2).Compared with high-alumina glass,the fracture toughness of the glass-ceramic was greatly improved,and it could be used as a new type of protective material for mobile devices.
文摘The nano-Bi2O3 powders were prepared by a chemical precipitation method with Bi（NO3）3, HNO3 and NaOH as reactants. The structural characteristics and morphology of nano-Bi2O3 powders were investigated by X-ray diffraction and transmission electron microscopy, respectively. The results show that under the optimum condition that 300g/L Bi（NO3）3 reacts at 90℃ for 2h, the Bi2O3 powders with 60nm on the average and 99.5% in purity are obtained. The prepared nano-Bi2O3 powders contain a mixed crystal structure of monoclinic and triclinic instead of traditional structure of monoclinic α-Bi2O3. And the mixed crystal structure is stable in air. The reason for the appearance of the mixed crystal structure may be that the ionic radius ratio of Bi 3+ to O 2- changes easily during the formation of nano-Bi2O3 particles by a chemical precipitation method.
文摘The preparation technique and properties of Ag-type inorganic antibiotic material carried by Al2O3 were studied. The results show that the material has good antibiotic and safety properties, the acute toxicity taken by stomata is LD 50 >8000mg/kg （little and big white rats）, and the normal quantity in subacute toxicity test is 80mg/（kg·d）. The better mass fraction of doping Ag2O in antibiotic material carried by Al2O3 is 4%CD*28%, and the optimal sintering temperature is from 1000℃ to 1100℃.
文摘The adsorption of acetonitrile and its co-adsorption with CO on fresh Mo_2C/Al_2O_3 catalyst have been studied by insitu FT-IR spectroscopy.Linearly adsorbed CH_3CN and CH_3CH_2NH_2 were formed after CH_3CN adsorption on the Mo_2C/ Al_2O_3 catalyst.The appearance of a strong band at 1578 cm^(-1) indicates that CH_3CN was reactive with hydrogen on the Mo_2C/Al_2O_3 catalyst.
基金supported by the National Natural Science Foundation of China(Grant Nos.11804305,12004341,11704340,and 12004342)the Key Research Project of Higher Education Institution of Henan Province,China(Grant No.19A140006)+2 种基金the Scientific and Technological Project in Henan Province,China(Grant No.202102210198)the Natural Science Foundation of Chongqing,China(Grant No.cstc2019jcyjmsxmX0391)the Science and Technology Research Program of Chongqing Municipal Education Commission,China(Grant No.KJQN201901405)。
文摘The synergistic influences of boron,oxygen,and titanium on growing large single-crystal diamonds are studied using different concentrations of B_(2)O_(3) in a solvent-carbon system under 5.5 GPa-5.7 GPa and 1300℃-1500℃.It is found that the boron atoms are difficult to enter into the crystal when boron and oxygen impurities are doped using B_(2)O_(3) without the addition of Ti atoms.However,high boron content is achieved in the doped diamonds that were synthesized with the addition of Ti.Additionally,boron-oxygen complexes are found on the surface of the crystal,and oxygen-related impurities appear in the crystal interior when Ti atoms are added into the FeNi-C system.The results show that the introduction of Ti atoms into the synthesis cavity can effectively control the number of boron atoms and the number of oxygen atoms in the crystal.This has important scientific significance not only for understanding the synergistic influence of boron,oxygen,and titanium atoms on the growth of diamond in the earth,but also for preparing the high-concentration boron or oxygen containing semiconductor diamond technologies.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China(52070194,51902347,51908555,and 51822812)Natural Science Foundation of Hunan Province(2020JJ5741)the Graduate Innovation Project of Central South University(2020zzts093).
文摘LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) is extensively researched as one of the most widely used commercially materials for Li-ion batteries at present.However,the poor high-voltage performance(≥4.3 V)with low reversible capacity limits its replacement for LiCoO_(2) in high-end digital field.Herein,three-in-one modification,Na-doping and Al_(2)O_(3)@Li_(3)BO_(3) dual-coating simultaneously,is explored for single-crystalline LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(N-NCM@AB),which exhibits excellent high-voltage performance.N-NCM@AB displays a discharge-specific capacity of 201.8 mAh g^(−1) at 0.2 C with a high upper voltage of 4.6 V and maintains 158.9 mAh g^(−1) discharge capacity at 1 C over 200 cycles with the corresponding capacity retention of 87.8%.Remarkably,the N-NCM@AB||graphite pouch-type full cell retains 81.2% of its initial capacity with high working voltage of 4.4 V over 1600 cycles.More importantly,the fundamental understandings of three-in-one modification on surface morphology,crystal structure,and phase transformation of N-NCM@AB are clearly revealed.The Na+doped into the Li–O slab can enhance the bond energy,stabilize the crystal structure,and facilitate Li+transport.Additionally,the interior surface layer of Li^(+)-ions conductor Li_(3)BO_(3) relieves the charge transfer resistance with surface coating,whereas the outer surface Al_(2)O_(3) coating layer is beneficial for reducing the active materials loss and alleviating the electrode/electrolyte parasite reaction.This three-in-one strategy provides a reference for the further research on the performance attenuation mechanism of NCM,paving a new avenue to boost the high-voltage performance of NCM cathode in Li-ion batteries.
