The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable struct...The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable structure and capacity.The LNMO,LiNi_(0.45)Al_(0.05)Mn_(1.5)O_(4)(LNAMO)and LiNi_(0.45)Co_(0.05)Mn_(1.5)O_(4)(LNCMO)were synthesized by calcination at 900℃ for 8 h,which was called as solid-phase method and applied universally in industry.XRD,FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures.Moreover,the incorporation of Al and Co increased the cation disordering of LNMO,thereby increasing the transfer rate of Li+.The SEM results showed that the doped samples performed more regular and ortho-octahedral.The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples.Moreover,the doped samples showed better electrochemical properties than undoped LNMO.The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^(-1)and 122.8 mA·h·g^(-1)at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature,respectively.The capacity fading phenomenon of the doped samples at 50℃ and 1 C rate was significantly improved.Further,cations doping also enhanced the rate performance,especially for the LNCMO,the discharge specific capacity of 117.9 mA·h·g^(-1)can be obtained at a rate of 5 C.展开更多
In order to analyze the influence of the addition of yttrium and manganese on the soot combustion performance and high temperature stability of CeO_(2) catalyst,a series of Y/Mn-modified CeO_(2) catalysts were prepare...In order to analyze the influence of the addition of yttrium and manganese on the soot combustion performance and high temperature stability of CeO_(2) catalyst,a series of Y/Mn-modified CeO_(2) catalysts were prepared.The effects of structural properties,textural properties,oxygen vacancies,Ce^(3+),surface adsorbed oxygen species,reduction properties and desorption properties of oxygen species on the activity were analyzed by various characterization methods.The results of the activity test show that the addition of manganese is beneficial to enhancement of the activity,while the addition of yttrium increases the amount of reactive oxygen species,but decreases the activity.After aging at 700℃,the activity of the CeMn catalyst decreases most sharply,while the catalytic activity of the CeY catalyst can be maintained to a certain extent.Interestingly,the addition of yttrium and manganese at the same time can stabilize the activity.The fundamental reason is that yttrium and manganese move to the surface of the solid solution after aging,which increases the reduction performance of the catalyst,thus contributing to the increase of activity.Although the activity of CeYMn catalyst decreases after aging at 800℃,it is still higher than that of other catalysts aged at 700℃.展开更多
Nuclear engineering materials are required to possess outstanding extreme environmental tolerance and irradiation resistance.A promising novel pyrochlore-type of(Sm_(0.2)Eu_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2))2 Hf_(2)O_(7)h...Nuclear engineering materials are required to possess outstanding extreme environmental tolerance and irradiation resistance.A promising novel pyrochlore-type of(Sm_(0.2)Eu_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2))2 Hf_(2)O_(7)high-entropy ceramic(HE-RE2 Hf_(2)O_(7))for control rod was prepared by solid-state reaction method.The ion irradiation of HE-RE_(2) Hf_(2)O_(7)with 400 keV Kr+at 400℃was investigated using a 400 kV ion implanter and compared with single-component pyrochlore Gd2 Hf_(2)O_(7)to evaluate the irradiation resistance.For HE-RE2 Hf_(2)O_(7),the phase transition from pyrochlore to defective fluorite is revealed after irradiation at 60 dpa.After irradiation at 120 dpa,it maintained crystalline,which is comparable to Gd2 Hf_(2)O_(7)but superior to the titanate pyrochlores previously studied.Moreover,the lattice expansion of HE-RE2 Hf_(2)O_(7)(_(0.2)2%)is much lower than that of Gd2 Hf_(2)O_(7)(0.62%),indicating excellent irradiation damage resistance.Nanoindentation tests displayed an irradiation-induced increase in hardness and a decrease in elastic modulus by about 2.6%.Irradiation-induced segregation of elements is observed on the surface of irradiated samples.In addition,HE-RE2 Hf_(2)O_(7)demonstrates a more sluggish grain growth rate than Gd2 Hf_(2)O_(7)at 1200℃,suggesting better high-temperature stability.The linear thermal expansion coefficient of HE-RE2 Hf_(2)O_(7)is 10.7×10-6 K-1 at 298–1273 K.In general,it provides a new strategy for the design of the next advanced nuclear engineering materials.展开更多
Electrocaloric effect(ECE)is promising in realizing solid-state cooling as an alternative to the conventional refrigeration with environmentally harmful coolant and low efficiency.High ECE in lead-free ferroelectric c...Electrocaloric effect(ECE)is promising in realizing solid-state cooling as an alternative to the conventional refrigeration with environmentally harmful coolant and low efficiency.High ECE in lead-free ferroelectric ceramics is highly desirable for the EC cooling.In this work,different from the researches that tune the ECE by conventional compositional design or external stress engineering,we fabricated the(1-x)BaTiO_(3)-xNaNbO_(3)(BTO-xNN)lead-free ceramics with a core-shell grain structure arising from the inhomogeneous stoichiometry of element distribution,leading to the internal compressing stress in the grains.It is interesting that the phase transition behavior,including the phase transition temperature and the diffusion property,is regulated by the core-shell grain structure induced internal stress,which can be capitalized on for the favorable ECE.Cooperated with 0.02 NN,a high ECE,e.g.adiabatic temperature change(ΔT)of 3.6 K and isothermal entropy change(ΔS)of 4.5 J kg^(-1) K^(-1),is attained in the BTO ceramic.As the internal stress further increases with more NN,the BTO-0.06NN exhibits an extremely stable ECE with a variety rate below ±4% in a wide temperature range from 300 K to 360 K.This work provides a novel approach to explore pronounced ECE in lead-free ferroelectrics for eco-friendly refrigeration.展开更多
基金supported by the National Natural Science Foundation of China(52022109 and 51834008)Beijing Municipal Natural Science Foundation(2202047)+1 种基金National Key Research and Development Program of China(2021YFC2901100)Science Foundation of China University of Petroleum,Beijing(2462021QNX2010,2462020YXZZ019,2462020YXZZ016,and 2462022QZDX008)。
文摘The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable structure and capacity.The LNMO,LiNi_(0.45)Al_(0.05)Mn_(1.5)O_(4)(LNAMO)and LiNi_(0.45)Co_(0.05)Mn_(1.5)O_(4)(LNCMO)were synthesized by calcination at 900℃ for 8 h,which was called as solid-phase method and applied universally in industry.XRD,FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures.Moreover,the incorporation of Al and Co increased the cation disordering of LNMO,thereby increasing the transfer rate of Li+.The SEM results showed that the doped samples performed more regular and ortho-octahedral.The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples.Moreover,the doped samples showed better electrochemical properties than undoped LNMO.The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^(-1)and 122.8 mA·h·g^(-1)at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature,respectively.The capacity fading phenomenon of the doped samples at 50℃ and 1 C rate was significantly improved.Further,cations doping also enhanced the rate performance,especially for the LNCMO,the discharge specific capacity of 117.9 mA·h·g^(-1)can be obtained at a rate of 5 C.
基金Project supported by the National Natural Science Foundation of China(21962021)the Yunnan Fundamental Research Projects(202001AU070121)+1 种基金the National Natural Science Foundation of China(51908091)the Special Basic Cooperative Research Programs of Yunnan Provincial Undergraduate Universities'Association(202101BA070001-084)。
文摘In order to analyze the influence of the addition of yttrium and manganese on the soot combustion performance and high temperature stability of CeO_(2) catalyst,a series of Y/Mn-modified CeO_(2) catalysts were prepared.The effects of structural properties,textural properties,oxygen vacancies,Ce^(3+),surface adsorbed oxygen species,reduction properties and desorption properties of oxygen species on the activity were analyzed by various characterization methods.The results of the activity test show that the addition of manganese is beneficial to enhancement of the activity,while the addition of yttrium increases the amount of reactive oxygen species,but decreases the activity.After aging at 700℃,the activity of the CeMn catalyst decreases most sharply,while the catalytic activity of the CeY catalyst can be maintained to a certain extent.Interestingly,the addition of yttrium and manganese at the same time can stabilize the activity.The fundamental reason is that yttrium and manganese move to the surface of the solid solution after aging,which increases the reduction performance of the catalyst,thus contributing to the increase of activity.Although the activity of CeYMn catalyst decreases after aging at 800℃,it is still higher than that of other catalysts aged at 700℃.
基金supported by the Lingchuang Research Project of China National Nuclear Corporation,the National Key Research and Development Program of China(No.2022YFB3504302)the key core technology research project in Beicang District,Ningbo(Grant No.2021BLG009)+4 种基金the key deployment project of the Chinese Academy of Sciences(Grant No.ZDRW-CN-2021-3)the Fujian Provincial Natural Fund Project(Grant No.2021J05101)the Young Elite Scientists Sponsorship Program by CAST(Grant No.2021QNRC001)the independent deployment project of Ganjiang Innovation Research Institute of Chinese Academy of Sciences(Grant No.E055A002)In addition,thanks for the assistance of Jinchi Huang from the School of Energy,Xiamen University for the ion irradiation experiment.
文摘Nuclear engineering materials are required to possess outstanding extreme environmental tolerance and irradiation resistance.A promising novel pyrochlore-type of(Sm_(0.2)Eu_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2))2 Hf_(2)O_(7)high-entropy ceramic(HE-RE2 Hf_(2)O_(7))for control rod was prepared by solid-state reaction method.The ion irradiation of HE-RE_(2) Hf_(2)O_(7)with 400 keV Kr+at 400℃was investigated using a 400 kV ion implanter and compared with single-component pyrochlore Gd2 Hf_(2)O_(7)to evaluate the irradiation resistance.For HE-RE2 Hf_(2)O_(7),the phase transition from pyrochlore to defective fluorite is revealed after irradiation at 60 dpa.After irradiation at 120 dpa,it maintained crystalline,which is comparable to Gd2 Hf_(2)O_(7)but superior to the titanate pyrochlores previously studied.Moreover,the lattice expansion of HE-RE2 Hf_(2)O_(7)(_(0.2)2%)is much lower than that of Gd2 Hf_(2)O_(7)(0.62%),indicating excellent irradiation damage resistance.Nanoindentation tests displayed an irradiation-induced increase in hardness and a decrease in elastic modulus by about 2.6%.Irradiation-induced segregation of elements is observed on the surface of irradiated samples.In addition,HE-RE2 Hf_(2)O_(7)demonstrates a more sluggish grain growth rate than Gd2 Hf_(2)O_(7)at 1200℃,suggesting better high-temperature stability.The linear thermal expansion coefficient of HE-RE2 Hf_(2)O_(7)is 10.7×10-6 K-1 at 298–1273 K.In general,it provides a new strategy for the design of the next advanced nuclear engineering materials.
基金supported by the National Science Foundation of China(Grant No.51972125,51772108,51972126 and 61675076)the Fund from Science,Technology and Innovation Commission of Shenzhen Municipality(JCYJ20180507182248925)+5 种基金the Innovation Fund of WNLO and the Fundamental Research Funds for the Central Universities(2019KFYRCPY126 and 2018KFYYXJJ052)the support from the Thousand Young Talent Program(Grant No.BE0200005)the support provided by the“Double First-Rate”Program(Grant No.WF220402017)the Prospective Research Program(Grant No.AF0200246)the Student Innovation Center at Shanghai Jiao Tong Universitysupported by the Key Research Program of Frontier Sciences,CAS(ZDBS-LY-JSC002).
文摘Electrocaloric effect(ECE)is promising in realizing solid-state cooling as an alternative to the conventional refrigeration with environmentally harmful coolant and low efficiency.High ECE in lead-free ferroelectric ceramics is highly desirable for the EC cooling.In this work,different from the researches that tune the ECE by conventional compositional design or external stress engineering,we fabricated the(1-x)BaTiO_(3)-xNaNbO_(3)(BTO-xNN)lead-free ceramics with a core-shell grain structure arising from the inhomogeneous stoichiometry of element distribution,leading to the internal compressing stress in the grains.It is interesting that the phase transition behavior,including the phase transition temperature and the diffusion property,is regulated by the core-shell grain structure induced internal stress,which can be capitalized on for the favorable ECE.Cooperated with 0.02 NN,a high ECE,e.g.adiabatic temperature change(ΔT)of 3.6 K and isothermal entropy change(ΔS)of 4.5 J kg^(-1) K^(-1),is attained in the BTO ceramic.As the internal stress further increases with more NN,the BTO-0.06NN exhibits an extremely stable ECE with a variety rate below ±4% in a wide temperature range from 300 K to 360 K.This work provides a novel approach to explore pronounced ECE in lead-free ferroelectrics for eco-friendly refrigeration.