In-situ formed hierarchical transition metal oxide nanoarrays with rich antisite defects and oxygen vacancies for high-rate energy storage devices

Developing transition metal oxides(TMOs)with high energy,power,and long cycle lifetime for elec-tric energy storage devices remains a critical challenge to date.Herein,we demonstrate a facile method that enables in-situ transformation of nickel cobalt oxide nanowire arrays(NiCoO NWA)into hierarchical nanowire-nanosheet arrays(ac-NiCoO NWSA)for enhanced energy storage properties.More specifically,the method leads to formation of atomically thin nanosheets(only 2.0 nm)and creates abundant an-tisite defects and oxygen vacancies.Owing to these merits,the as-prepared ac-NiCoO NWSA electrode exhibits over five-fold higher specific capacity,superior rate capability(up to 100 A/g),and excellent cy-cling stability of 10,000 cycles at 50 A/g in alkaline electrolyte compared to pristine NiCoO NWA.Density functional theory(DFT)simulations elucidate the electrochemical activity enhancement mechanism of the TMOs.Moreover,our method triggers similar structural reconstruction phenomenon on other TMOs including ZnCo-,CoMn-and ZnNiCo-oxides,proving the universality of the method.Our findings provide a general method towards simultaneously manipulating the micro-morphologies and defects of TMOs for advanced energy storage devices.

Relationship between disorder,magnetism and band topology in Mn(Sb_(1-x)Bi_(x))_(2)Te_(4) single crystals

We investigate the evolution of magnetic properties as well as the content and distribution of Mn for Mn(Sb_(1-x)Bi_(x))_(2)Te_(4) single crystals grown by large-temperature-gradient chemical vapor transport method.It is found that the ferromagnetic MnSb_(2)Te_(4) changes to antiferromagnetism with Bi doping when x≥0.25.Further analysis implies that the occupations of Mn ions at Sb/Bi site Mn_(Sb/Bi) and Mn site Mn_(Mn) have a strong influence on the magnetic ground states of these systems.With the decrease of Mn_(Mn) increase of Mn_(Sb/Bi),the system will favor the ferromagnetic ground state.In addition,the rapid decrease of T_(C/N) with increasing Bi content when x ≤0.25 and the insensitivity of T_(N) to x when x> 0.25 suggest that the main magnetic interaction may change from the Ruderman-Kittel-Kasuya-Yosida type at low Bi doping region to the van-Vleck type in high Bi doped samples.

Understanding the failure mechanism towards developing high-voltage single-crystal Ni-rich Co-free cathodes

Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.

THEORETICAL CALCULATION OF POINT DEFECTS IN Ni_3Al

Equilibrium equation of point defects in Ll_2 type intermetallic compounds was established to calculate the relations of the concentration of antisite defects and vacancies and bulk composi- tion in Ni_3Al.The examination of temperature effects on the point defects cleared up the mis. understanding of the properties of the“constitutional point defects”in Ni_3Al.

Low temperature photoluminescence study of Ga As defect states

Low temperature(77 K)photoluminescence measurements have been performed on different GaAs substrates to evaluate the GaAs crystal quality.Several defect-related luminescence peaks have been observed,including 1.452 eV,1.476 eV,1.326 eV peaks deriving from 78 meV GaAs antisite defects,and 1.372 eV,1.289 eV peaks resulting from As vacancy related defects.Changes in photoluminescence emission intensity and emission energy as a function of temperature and excitation power lead to the identification of the defect states.The luminescence mechanisms of the defect states were studied by photoluminescence spectroscopy and the growth quality of GaAs crystal was evaluated.

Ce^(3+):Lu_(3)Al_(5)O_(12)–Al_(2)O_(3) optical nanoceramic scintillators elaborated via a low-temperature glass crystallization route

Transparent Ce:lutetium aluminum garnet(Ce:Lu_(3)A_(l5)O_(12),Ce:LuAG)ceramics have been regarded as potential scintillator materials due to their relatively high density and atomic number(Zeff).However,the current Ce:LuAG ceramics exhibit a light yield much lower than the expected theoretical value due to the inevitable presence of LuAl antisite defects at high sintering temperatures.This work demonstrates a low-temperature(1100℃)synthetic strategy for elaborating transparent LuAG–Al_(2)O_(3) nanoceramics through the crystallization of 72 mol%Al_(2)O_(3)–28 mol%Lu_(2)O_(3)(ALu28)bulk glass.The biphasic nanostructure composed of LuAG and Al_(2)O_(3) nanocrystals makes up the whole ceramic materials.Most of Al_(2)O_(3) is distributed among LuAG grains,and the rest is present inside the LuAG grains.Fully dense biphasic LuAG–Al_(2)O_(3) nanoceramics are highly transparent from the visible region to mid-infrared(MIR)region,and particularly the transmittance reaches 82%at 780 nm.Moreover,LuAl antisite defect-related centers are completely undetectable in X-ray excited luminescence(XEL)spectra of Ce:LuAG–Al_(2)O_(3) nanoceramics with 0.3–1.0 at%Ce.The light yield of 0.3 at%Ce:LuAG–Al_(2)O_(3) nanoceramics is estimated to be 20,000 ph/MeV with short 1μs shaping time,which is far superior to that of commercial Bi_(4)Ge_(3)O_(12)(BGO)single crystals.These results show that a low-temperature glass crystallization route provides an alternative approach for eliminating the antisite defects in LuAG-based ceramics,and is promising to produce garnet-based ceramic materials with excellent properties,thereby meeting the demands of advanced scintillation applications.

Electron-irradiation-facilitated production of chemically homogenized nanotwins in nanolaminated carbides

Twin boundaries have been exploited to stabilize ultrafine grains and improve mechanical properties of nanomaterials.The production of the twin boundaries and nanotwins is however prohibitively challenging in carbide ceramics.Using a scanning transmission electron microscope as a unique platform for atomic-scale structure engineering,we demonstrate that twin platelets could be produced in carbides by engineering antisite defects.The antisite defects at metal sites in various layered ternary carbides are collectively and controllably generated,and the metal elements are homogenized by electron irradiation,which transforms a twin-like lamellae into nanotwin platelets.Accompanying chemical homogenization,α-Ti_(3)AlC_(2) transforms to unconventionalβ-Ti_(3)AiC_(2).The chemical homogeneity and the width of the twin platelets can be tuned by dose and energy of bombarding electrons.Chemically homogenized nanotwins can boost hardness by~45%.Our results provide a new way to produce ultrathin(<5 nm)nanotwin platelets in scientifically and technologically important carbide materials and showcase feasibility of defect engineering by an angstrom-sized electron probe.

Thermal conductivity prediction of MgAl2O4:a non-equilibrium molecular dynamics calculation

Magnesium aluminate spinel(MgAl2O4)is widely used in steel metallurgy industry.Thermal conductivity at high temperature signifcantly infuences the cooling process of blast furnace and the heat preservation of steel converter.The efect of external(temperature)and internal(antisite defect and grain boundary)factors on the thermal conductivity of MgAl2O4 was studied with non-equilibrium molecular dynamics.The main factors afecting the thermal conductivity of MgAl2O4 were summarized.In the temperature range of 100-2000 K,the results showed that the thermal conductivity of MgAl2O4 changed from 11.54 to 4.95 W/(m K)with the increase in temperature and was relatively stable at the temperature above 1000 K.The thermal conductivity of MgAl2O4 declined frst and then rose with the increase in the antisite defects,and the minimum value was 6.95 W/(m K)at the inversion parameter i=0.35.In addition,grain boundaries reduced the thermal conductivity of MgAl2O4 by 20%-30%at temperature below 1000 K comparing with the non-grain boundary system.The grain boundary rotation angle at temperature above 1000 K had less efect on the thermal conductivity than that below 1000 K.Present simulation scheme for thermal conductivity of MgAl2O4 can also be applied to the study of other nonmetallic ceramics.

Atomic disorders in layer structured topological insulator SnBi2Te4 nanoplates

Identification of atomic disorders and their subsequent control has proven to be a key issue in predicting, understanding, and enhancing the properties of newly emerging topological insulator materials. Here, we demonstrate direct evidence of the cation antisites in single-crystal SnBi2Te4 nanoplates grown by chemical vapor deposition, through a combination of sub-angstr6m-resolution imaging, quantitative image simulations, and density functional theory calculations. The results of these combined techniques revealed a recognizable amount of cation antisites between Bi and Sn, and energetic calculations revealed that such cation antisites have a low formation energy. The impact of the cation antisites was also investigated by electronic structure calculations together with transport measurement. The topological surface properties of the nanoplates were further probed by angle-dependent magnetotransport, and from the results, we observed a two-dimensional weak antilocalization effect associated with surface carriers. Our approach provides a pathway to identify the antisite defects in ternary chalcogenides and the application potential of SnBi2Te4 nanostructures in next-generation electronic and spintronic devices.