Phase engineering of Ni-Mn binary layered oxide cathodes for sodiumion batteries

Nickel-manganese binary layered oxides with high working potential and low cost are potential candidates for sodium-ion batteries,but their electrochemical properties are highly related to compositional diversity.Diverse composite materials with various phase structures of P3,P2/P3,P2,P2/O3,and P2/P3/O3 were synthesized by manipulating the sodium content and calcination conditions,leading to the construction of a synthetic phase diagram for Na_(x)Ni_(0.25)Mn_(0.75)O_(2)(0.45≤x≤1.1).Then,we compared the electrochemical characteristics and structural evolution during the desodiation/sodiation process of P2,P2/P3,P2/03,and P2/P3/O3-Na_(x)Ni_(0.25)Mn_(0.75)O_(2).Among them,P2/P3-Na0.75Ni0.25Mn0.75O2exhibits the best rate capability of 90.9 mA h g^(-1)at 5 C,with an initial discharge capacity of 142.62 mA h g^(-1)at 0.1 C and a capacity retention rate of 78.25%after 100 cycles at 1 C in the voltage range of 2-4.3 V.The observed superior sodium storage performance of P2/P3 hybrids compared to other composite phases can be attributed to the enhanced Na^(+)transfer dynamic,reduction of the Jahn-teller effect,and improved reaction reversibility induced by the synergistic effect of P2 and P3 phases.The systematic research and exploration of phases in Na_(x)Ni_(0.25)Mn_(0.75)O_(2)provide new sights into high-performance nickel-manganese binary layered oxide for sodium-ion batteries.

Using a Modified Soil-Plant-Atmosphere Scheme(MSPAS)to Simulate the Interaction between Land Surface Processes and Atmospheric Boundary Layer in Semi-Arid Regions

This paper uses a Modified Soil-Plant-Atmosphere Scheme (MSPAS) to study the interaction between land surface and atmospheric boundary layer processes. The scheme is composed of two main parts: atmospheric boundary layer processes and land surface processes. Compared with SiB and BATS, which are famous for their detailed parameterizations of physical variables, this simplified model is more convenient and saves much more computation time. Though simple, the feasibility of the model is well proved in this paper. The numerical simulation results from MSPAS show good agreement with reality. The scheme is used to obtain reasonable simulations for diurnal variations of heat balance, potential temperature of boundary layer, and wind field, and spatial distributions of temperature, specific humidity, vertical velocity, turbulence kinetic energy, and turbulence exchange coefficient over desert and oasis. In addition, MSPAS is used to simulate the interaction between desert and oasis at night, and again it obtains reasonable results. This indicates that MSPAS can be used to study the interaction between land surface processes and the atmospheric boundary layer over various underlying surfaces and can be extended for regional climate and numerical weather prediction study.

Effect of Layered Double Hydroxides on Ultraviolet Aging Resistance of SBS Modified Bitumen Membrane

Layered double hydroxides （LDHs）/styrene-butadiene-styrene （SBS） eopolymer modified bitumen was prepared by melt blending. The effect of LDHs on the ultraviolet （UV） aging behavior of SBS modified bitumen was investigated. The changes of chemical structures of modified bitumen before and after UV aging were characterized by Fourier transform infrared spectroscopy （FTIR）. The results show that LDHs obviously reduce the variation of softening point and low temperature flexibility of SBS modified bitumen under different UV radiation intensities, which indicates that the UV aging resistance performance of SBS modified bitumen is improved effectively by LDHs. Compared with SBS modified bitumen, the changes of carbonyl, sulfoxide and butadienyl of LDHs/SBS modified bitumen decrease significantly after UV aging according to FTIR analysis, demonstrating that the oxidation and degradation reactions of SBS modified bitumen were restrained effectively by adding LDHs.

MODIFIED LAYER REMOVAL METHOD FOR MEASUREMENT OF RESIDUAL STRESS DISTRIBUTION IN THICK PRE-STRETCHED ALUMINUM PLATE

The integrated structure parts are widely used in aircraft. The distortion caused by residual stresses in thick pre-stretched aluminum plates during machining integrated parts is a common and serious problem. To predict and control the machining distortion, the residual stress distribution in the thick plate must be measured firstly. The modified removal method for measuring residual stress in thick pre-stretched aluminum plates is proposed and the stress-strain relation matrix is deduced by elasticity theory. The residual stress distribution in specimen of 7050T7451 plate is measured by using the method, and measurement results are analyzed and compared with data obtained by other methods. The method is effective to measure the residual stress.

The Effect of Varied Dietary Crude Protein Levels with Balanced Amino Acids on Performance and Egg Quality Characteristics of Layers at First Laying Phase

Four diets were formulated to study the influence of varying crude protein levels on the performance, egg quality, serum and haematological characteristics at the first phase of laying cycle of sixty Bovan Nera laying birds that were randomly allotted to dietary treatments. The four experimental diets had five replicates each and three birds per repli-cate. Diet 1 contained 14% crude protein (CP), while diet 2 contained 15% CP, diets 3 and 4 contained 16% and 17% CP respectively. The experimental birds were fed for 10 weeks and the data collected were statistically analysed. Apparent variations recorded for all the performance characteristics such as Egg number, Hen-day production, Feed Conversion Ratio (FCR) and weight gain were significantly different (p < 0.05). The best FCR value were recorded by birds fed 17% CP (3.45), while the highest weight gain mean value were also recorded by birds fed 17% CP value. Findings indicated a direct relationship between dietary crude protein values and performance.

Unexpected Li displacement and suppressed phase transition enabling highly stabilized oxygen redox in P3-type Na layered oxide cathode

Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics.Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na_(0.7)[Li_(0.1)Cu_(0.2)Mn_(0.7)]O_(2) cathode delivers a large specific capacity of ~212 mA h g^(-1)at 15 mA g^(-1). The discharge capacity is maintained up to ~90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.

The effect of Laves phases and nano-precipitates on the electrochemical corrosion resistance of Mg-Al-Ca alloys under alkaline conditions

The electrochemical corrosion mechanisms of Mg alloys were extensively studied in previous investigations of different chemical com-positions,modified surface states and various electrolyte conditions.However,recent research focused on the active state of Mg dissolution,leading to unresolved effects of secondary phases adjacent to a stableα-solid solution passive layer.The present study investigates the fundamental electrochemical corrosion mechanisms of three different Laves phases with varying phase morphologies and phase fractions in the passive state of Mg-Al-Ca alloys.The microstructure was characterized by(transmission-)electron microscopy and synchrotron-based transmission X-ray microscopy.The electrochemical corrosion resistance was determined with a standard three-electrode setup and advanced in-situ flow cell measurements.A new electrochemical activity sequence(C15>C36>α-Mg>C14)was obtained,as a result of a stable passive layer formation on theα-solid solution.Furthermore,nm-scale Mg-rich precipitates were identified within the Laves phases,which tend to inhibit the corrosion kinetics.

Recent Progress and Regulation Strategies of Layered Materials as Cathode of Aqueous Zinc-Ion Batteries

Aqueous zinc-ion batteries(ZIBs)have shown great potential in the fields of wearable devices,consumer electronics,and electric vehicles due to their high level of safety,low cost,and multiple electron transfer.The layered cathode materials of ZIBs hold a stable structure during charge and discharge reactions owing to the ultrafast and straightforward(de)intercalation-type storage mechanism of Zn^(2+)ions in their tunable interlayer spacing and their abilities to accommodate other guest ions or molecules.Nevertheless,the challenges of inadequate energy density,dissolution of active materials,uncontrollable byproducts,increased internal pressure,and a large de-solvation penalty have been deemed an obstacle to the development of ZIBs.In this review,recent strategies on the structure regulation of layered materials for aqueous zinc-ion energy storage devices are systematically summarized.Finally,critical science challenges and future outlooks are proposed to guide and promote the development of advanced cathode materials for ZIBs.

Approaching Ultimate Synthesis Reaction Rate of Ni-Rich Layered Cathodes for Lithium-Ion Batteries

Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,sluggish reaction dynamics,high energy consumption,and long reaction time.To overcome these chal-lenges,we first employed a high-temperature shock(HTS)strategy for fast synthesis of the NCM,and the approaching ultimate reaction rate of solid phase transition is deeply investigated for the first time.In the HTS process,ultrafast average reaction rate of phase transition from Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_(2) to Li-containing oxides is 66.7(%s^(-1)),that is,taking only 1.5 s.An ultrahigh heating rate leads to fast reaction kinetics,which induces the rapid phase transition of NCM cathodes.The HTS-synthesized nickel-rich layered oxides perform good cycling performances(94%for NCM523,94%for NCM622,and 80%for NCM811 after 200 cycles at 4.3 V).These findings might also assist to pave the way for preparing effectively Ni-rich layered oxides for lithium-ion batteries.

Early-stage latent thermal failure of single-crystal Ni-rich layered cathode

High nickel content worsens the thermal stability of layered cathodes for lithium-ion batteries,raising safety concerns for their applications.Thoroughly understanding the thermal failure process can offer valuable guidance for material optimization on thermal stability and new opportunities in monitoring battery thermal runaway(TR).Herein,this work comprehensively investigates the thermal failure process of a single-crystal nickel-rich layered cathode and finds that the latent thermal failure starts at∼120℃far below the TR temperature(225℃).During this stage of heat accumulation,sequential structure transition is revealed by atomic resolution electron microscopy,which follows the layered→cation mixing layered→LiMn_(2)O_(4)-type spinel→disordered spinel→rock salt.This progression occurs as a result of the continuous migration and densification of transition metal cations.Phase transition generates gaseous oxygen,initially confined within the isolated closed pores,thereby not showing any thermal failure phenomena at the macro-level.Increasing temperature leads to pore growth and coalescence,and eventually to the formation of open pores,causing oxygen gas release and weight loss,which are the typical TR features.We highlight that latent thermal instability occurs before the macro-level TR,suggesting that suppressing phase transitions caused by early thermal instability is a crucial direction for material optimization.Our findings can also be used for early warning of battery thermal runaway.

Achieving structurally stable O3-type layered oxide cathodes through site-specific cation-anion co-substitution for sodium-ion batteries

O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.

Effect of Modified Vermiculite on the Interface of a Capric Acid-expanded Vermiculite Composite Phase Change Material with Phase Transition Kinetics

A new type of capric acid(CA)-acid expanded vermiculite(AEV) composite phase change material(PCM) with improved adsorption ability and interface adhesive strength was developed. Through the analysis of non-isothermal phase transition kinetics, modified vermiculite was observed to change and affect the phase transformation mechanism of the composite. AEV was treated with hydrochloric acid to improve the specific surface area and micro-pore structure. The surface area measured by BET increased from 81.94 m^2/g for expanded vermiculite(EV) to 544.13 m^2/g for AEV. CA-EV and CA-AEV composite PCMs were prepared by direct impregnation. The non-isothermal phase transition isotherms of CA-EV and CA-AEV were recorded by DSC at different heating rates(1, 5, 10, 15, and 20 ℃/min), which indicated that the phase transition rate increased with the heating rate and the phase transition process changed. Kinetics parameters were analyzed by a double extrapolation method. The activation energy(E) under the original state(E_(α→0)) of CA-AEV and CA-EV was 1 117 kJ/mol and 937 kJ/mol, respectively, and 1 205 kJ/mol and 1 016 kJ/mol under the thermal equilibrium state(E_(β→0)). The most probabilistic mechanism function of CA-AEV satisfied G(α)=α^(2/3), which followed the Mample special rule, and the function of CA-EV satisfied G(α)=[(1+α)^(1/3)-1]~2, which followed the anti-Jander function.

Lowering Sodium-Storage Lattice Strains of Layered Oxide Cathodes by Pushing Charge Transfer on Anions

Due to a high energy density,layered transition-metal oxides have gained much attention as the promising sodium-ion batteries cathodes.However,they readily suffer from multiple phase transitions during the Na extraction process,resulting in large lattice strains which are the origin of cycledstructure degradations.Here,we demonstrate that the Na-storage lattice strains of layered oxides can be reduced by pushing charge transfer on anions(O^(2-)).Specifically,the designed O3-type Ru-based model compound,which shows an increased charge transfer on anions,displays retarded O3-P3-O1 multiple phase transitions and obviously reduced lattice strains upon cycling as directly revealed by a combination of ex situ X-ray absorption spectroscopy,in situ X-ray diffraction and geometric phase analysis.Meanwhile,the stable Na-storage lattice structure leads to a superior cycling stability with an excellent capacity retention of 84%and ultralow voltage decay of 0.2 mV/cycle after 300 cycles.More broadly,our work highlights an intrinsically structure-regulation strategy to enable a stable cycling structure of layered oxides meanwhile increasing the materials’redox activity and Nadiffusion kinetics.

Simulation of Corrosion-Induced Cracking of Reinforced Concrete Based on Fracture Phase Field Method

Accurate simulation of the cracking process caused by rust expansion of reinforced concrete(RC)structures plays an intuitive role in revealing the corrosion-induced failure mechanism.Considering the quasi-brittle fracture of concrete,the fracture phase field driven by the compressive-shear term is constructed and added to the traditional brittle fracture phase field model.The rationality of the proposed model is verified by a mixed fracture example under a shear displacement load.Then,the extended fracture phase model is applied to simulate the corrosion-induced cracking process of RC.The cracking patterns caused by non-uniform corrosion expansion are discussed for RC specimens with homogeneous macroscopically or heterogeneous with different polygonal aggregate distributions at the mesoscopic scale.Then,the effects of the protective layer on the crack propagation trajectory and cracking resistance are investigated,illustrating that the cracking angle and cracking resistance increase with the increase of the protective layer thickness,consistent with the experimental observation.Finally,the corrosion-induced cracking process of concrete specimens with large and small spacing rebars is simulated,and the interaction of multiple corrosion cracking is easily influenced by the reinforcement spacing,which increases with the decrease of the steel bar interval.These conclusions play an important role in the design of engineering anti-corrosion measures.The fracture phase field model can provide strong support for the life assessment of RC structures.

Dual-function protective layer for highly reversible Zn anode

The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.

Determination of Melamine in Fresh Milk by Electrochemistry with Solid Phase Microextraction at Bismuthyl Chloride Modified Graphite Epoxy Composite Electrode

Melamine as an important chemical raw material and a harmful additive in foods has attracted many people’s attention. In the present paper, The graphite-epoxy composited solid phase electrode was modified with bismuth layer by cyclic voltammetric deposition of bismuth from Bi(NO3)3 aqueous solution including 0.10 M HNO3, and hydrolyzed into micro bismuthyl chloride on-sites. Melamine in fresh milk was extracted with solid phase micro-extraction on the bismuthyl chloride modified graphite-epoxy composited solid electrode. The adsorption of melamine on bismuthyl chloride particle surfaces follows a Freundlich adsorption model, and results in the decrease of the reduction peak current of bismuth in bismuthyl chloride, and determined by differential pulse voltammetry from fresh milk in a larger concentration range of 10–4 ? 10–12 M with detection limit of 2.5 ? 10–12 M and relative standard deviation of 2.7%. The method is sensitive, convenient and was applied in the detection of melamine in fresh milk with relative deviation of 4.2% in content of 0.45 mg/kg melamine in the fresh milk.

Modified Layer-Removal Method for Measurement of Residual Stress in Pre-stretched Aluminium Alloy Plate

Residual stress is one of the factors affecting the machining deformation of monolithic structure parts in the aviation industry. Thus, the studies on machining deformation rules induced by residual stresses largely depend on correctly and efficiently measuring the residual stresses of workpieccs. A modified layer-removal method is proposed to measure residual stress by analysing the characteristics of a traditional, layer-removal method. The coefficients of strain release are then deduced according to the simulation results using the finite element method （FEM）. Moreover, the residual stress in a 7075T651 aluminium alloy plate is measured using the proposed method, and the results are then analyzed and compared with the data obtained by the traditional methods. The analysis indicates that the modified layer-removal method is effective and practical for measuring the residual stress distribution in pre-stretched aluminium alloy plates.

Properties of Phase Transformation of Ferroelectric Thin Films with Surface Layers

Using the generalized Ginzburg-Landau-Devonshire theory, the characteristics of phase transformation of a ferroelectric thin film with surface layers are investigated. We study the effect of the surface layer on the properties (coercive field, critical thickness) of a ferroelectric thin film. Our theoretical results show that the surface layer is likely to answer for the emergence of phase transformation.

Bacteria adherence property of molybdenum nitride modified layer on Ti6Al4V alloy

Molybdenum nitride(Mo-N) modified layer on Ti6Al4V alloy was obtained by the plasma surface alloying technique. The bacteria adherence property of the Mo-N modified layer on Ti6Al4V alloy on the oral bacteria Streptococcus Mutans was investigated and compared with that of Ti6Al4V alloy by fluorescence microscopy. The mechanism of the bacteria adherence was discussed. The sample was characterized by X-ray diffractometry(XRD),X-ray photoelectron spectroscopy(XPS) and rough-meter. The results show that the Mo-N modified layer is composed of phase Mo2N(fcc) and Mo2N(tetr). There are Mo 3d,N 1s,C 1s and O 1s in the Mo-N modified layer Ti 2p,O 1s,C 1s,in the Ti6Al4V alloy. The surface roughness(Ra) of Ti6Al4V alloy and the Mo-N modified layer is(0.06±0.01) μm and(0.16±0.01) μm,respectively. The Mo-N modified layer inhibits the bacteria adherence. Mo and N on surface of modified layer play a vital role in inhibiting the bacteria adherence.

Elastic strain response in the modified phase-field-crystal model

To understand and develop new nanostructure materials with specific mechanical properties, a good knowledge of the elastic strain response is mandatory. Here we investigate the linear elasticity response in the modified phase-field-crystal（MPFC） model. The results show that two different propagation modes control the elastic interaction length and time, which determine whether the density waves can propagate or not. By quantitatively calculating the strain field, we find that the strain distribution is indeed extremely uniform in case of elasticity. Further, we present a detailed theoretical analysis for the orientation dependence and temperature dependence of shear modulus. The simulation results show that the shear modulus reveals strong anisotropy and the one-mode analysis provides a good guideline for determining elastic shear constants until the system temperature falls below a certain value.