Development of Integrated Computational Materials Engineering(ICME)Model for Mg Alloy Design and Process Optimization

Integrated computational materials engineering(ICME)has emerged to be one of the most powerful materials genome engineering(MGE)approaches in designing new materials and manufacturing processes in recent years.It has successfully deployed many new products for the electronic,automotive,and aerospace industries.This paper reviews the current status of research on first principles in the design of high-strength Mg alloys,discusses the application of crystal plasticity finite element models to the microscale slip,twinning,microstructure morphology,texture evolution,and macroscopic forming of Mg alloys,and introduces the research progress of crystal plasticity finite element models and phase field models,meta cellular automata models and first principles coupled models respectively,around the need for multi-scale coupled simulations of Mg alloys.The key technology obstacles of integrating the first principles,crystal plasticity finite element,and microstructure models for Mg alloys have been solved.This paper can provide a reference for the design of new Mg alloy compositions and the development of high-performance Mg alloys.

Integrated Computational Materials Engineering for the Development and Design of High Modulus Al Alloys

Integrated computational materials engineering(ICME)is to integrate multi-scale computational simulations and key experimental methods such as macroscopic,mesoscopic,and microscopic into the whole process of Al alloys design and development,which enables the design and development of Al alloys to upgrade from traditional empirical to the integration of compositionprocess-structure-mechanical property,thus greatly accelerating its development speed and reducing its development cost.This study combines calculation of phase diagram(CALPHAD),Finite element calculations,first principle calculations,and microstructure characterization methods to predict and regulate the formation and structure of composite precipitates from the design of highmodulus Al alloy compositions and optimize the casting process parameters to inhibit the formation of micropore defects in the casting process,and the final tensile strength of Al alloys reaches420 MPa and Young's modulus reaches more than 88 GPa,which achieves the design goal of the high strength and modulus Al alloys,and establishes a new mode of the design and development of the strength/modulus Al alloys.

Micro-aluminum powder with bi-or tri-component alloy coating as a promising catalyst:Boosting pyrolysis and combustion of ammonium perchlorate

A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.

Insight into the capacity degradation and structural evolution of single-crystal Ni-rich cathodes

Single-crystal Ni-rich cathodes are a promising candidate for high-energy lithium-ion batteries due to their higher structural and cycling stability than polycrystalline materials.However,the phase evolution and capacity degradation of these single-crystal cathodes during continuous lithation/delithation cycling remains unclear.Understanding the mapping relationship between the macroscopic electrochemical properties and the material physicochemical properties is crucial.Here,we investigate the correlation between the physical-chemical characteristics,phase transition,and capacity decay using capacity differential curve feature identification and in-situ X-ray spectroscopic imaging.We systematically clarify the dominant mechanism of phase evolution in aging cycling.Appropriately high cut-off voltages can mitigate the slow kinetic and electrochemical properties of single-crystal cathodes.We also find that second-order differential capacity discharge characteristic curves can be used to identify the crystal structure disorder of Ni-rich cathodes.These findings constitute a step forward in elucidating the correlation between the electrochemical extrinsic properties and the physicochemical intrinsic properties and provide new perspectives for failure analysis of layered electrode materials.

Phase-field simulations of the effect of temperature and interface for zirconiumδ-hydrides

Hydride precipitation in zirconium cladding materials can damage their integrity and durability.Service temperature and material defects have a significant effect on the dynamic growth of hydrides.In this study,we have developed a phasefield model based on the assumption of elastic behaviour within a specific temperature range(613 K-653 K).This model allows us to study the influence of temperature and interfacial effects on the morphology,stress,and average growth rate of zirconium hydride.The results suggest that changes in temperature and interfacial energy influence the length-to-thickness ratio and average growth rate of the hydride morphology.The ultimate determinant of hydride orientation is the loss of interfacial coherency,primarily induced by interfacial dislocation defects and quantifiable by the mismatch degree q.An escalation in interfacial coherency loss leads to a transition of hydride growth from horizontal to vertical,accompanied by the onset of redirection behaviour.Interestingly,redirection occurs at a critical mismatch level,denoted as qc,and remains unaffected by variations in temperature and interfacial energy.However,this redirection leads to an increase in the maximum stress,which may influence the direction of hydride crack propagation.This research highlights the importance of interfacial coherency and provides valuable insights into the morphology and growth kinetics of hydrides in zirconium alloys.

Anti-aging performance improvement and enhanced combustion efficiency of boron via the coating of PDA

Boron is an ambitious fuel in energetic materials since its high heat release values,but its application is prohibited by low combustion efficiency and oxidization during storage.The polydopamine(PDA)was introduced into boron particles,investigating the impact of PDA content on the energetic behavior of boron.The results indicated that the PDA coating formed a fishing net structure on the surface of boron particles.The heat release results showed that the combustion calorific value of B@PDA was higher than that of the raw boron.Specifically,the actual combustion heat of boron powder in B@10%PDA increased by 38.08%.Meanwhile,the DSC peak temperature decreased by 100.65℃under similar oxidation rate compared to raw boron.Simultaneously,the B@PDA@AP and B@AP composites were prepared,and their combustion properties were evaluated.It was demonstrated that B@10%PDA@AP exhibited superior performance in terms of peak pressure and burning time,respectively.The peak pressure is 12.43 kPa more than B@AP and burning time is 2.22 times higher than B@AP.Therefore,the coating of PDA effectively inhibits the oxidization of boron during storage and enhances the energetic behavior of boron and corresponding composites.

Boosting High-Voltage and Ultralong-Cycling Performance of Single-Crystal LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) Cathode Materials via Three-in-One Modification

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.

Evolution of the porous structure for phosphoric acid etching carbon as cathodes in Li–O_(2) batteries:Pyrolysis temperature-induced characteristics changes

Although biomass-derived carbon(biochar)has been widely used in the energy field,the relation between the carbonization condition and the physical/chemical property of the product remains elusive.Here,we revealed the carbonization condition's effect on the morphology,surface property,and electrochemical performance of the obtained carbon.An open slit pore structure with shower-puff-like nanoparticles can be obtained by finely tuning the carbonization temperature,and its unique pore structure and surface properties enable the Li–O_(2) battery with cycling longevity(221 cycles with 99.8%Coulombic efficiency at 0.2 mA cm^(−2) and controlled discharge–charge depths of 500 mAh g^(−1))and high capacity(16,334 mAh g^(−1) at 0.02 mA cm^(−2)).This work provides a greater understanding of the mechanism of the biochar carbonization procedure under various pyrolysis conditions,paving the way for future study of energy storage devices.

Carbon-based interface engineering and architecture design for high-performance lithium metal anodes

Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electrochemical potential.However,owing to inhomogeneous Li-ion flux,Li anodes undergo uncontrollable Li deposition,leading to limited power output and practical applications.Carbon materials and their composites with controllable structures and properties have received extensive attention to guide the homogeneous growth of Li to achieve high-performance Li anodes.In this review,the correlation between the behavior of Li anode and the properties of carbon materials is proposed.Subsequently,we review emerging strategies for rationally designing high-performance Li anodes with carbon materials,including interface engineering(stabilizing solid electrolyte interphase layer and other functionalized interfacial layer)and architecture design of host carbon(constructing three-dimension structure,preparing hollow structure,introducing lithiophilic sites,optimizing geometric effects,and compositing with Li).Based on the insights,some prospects on critical challenges and possible future research directions in this field are concluded.It is anticipated that further innovative works on the fundamental chemistry and theoretical research of Li anodes are needed.

Tuning microstructures of TC4 ELI to improve explosion resistance

A reasonable heat treatment process for TC4 ELI titanium alloy is crucial to tune microstructures to improve its explosion resistance.However,there is limited investigation on tuning microstructures of TC4 ELI to improve explosion resistance.Moreover,the current challenge is quantifying microstructural changes'effects on explosion resistance and incorporating microstructural changes into finite element models.This work aims to tune microstructures to improve explosion resistance and elucidate their anti-explosion mechanism,and find a suitable method to incorporate microstructural changes into finite element models.In this work,we systematically study the deformation and failure characteristics of TC4 ELI plates with varying microstructures using an air explosion test and LS-DYNA finite element modeling.The Johnson-Cook(JC)constitutive parameters are used to quantify the effects of microstructural changes on explosion resistance and incorporate microstructural changes into finite element models.Because of the heat treatment,one plate has equiaxed microstructure and the other has bimodal microstructure.The convex of the plate after the explosion has a quadratic relationship with the charge mass,and the simulation results demonstrate high reliability,with the error less than 17.5%.Therefore,it is feasible to obtain corresponding JC constitutive parameters based on the differences in microstructures and mechanical properties and characterize the effects of microstructural changes on explosion resistance.The bimodal target exhibits excellent deformation resistance.The response of bimodal microstructure to the shock wave may be more intense under explosive loading.The well-coordinated structure of the bimodal target enhances its resistance to deformation.

Fabrication and Modification Strategies of Metal Halide Perovskite Absorbers

Due to the long carrier lifetime,high carrier mobility,and high absorption coefficient of perovskite materials,the power conversion efficiency(PCE)of perovskite solar cells(PSCs)has increased from 3.8%in 2009 to 25.7%in 2021,which have already surpassed the PCE of thin-film solar cells and closes to the efficiency of Si-based photovoltaics(26.7%).Therefore,PSCs have become a promising clean energy technology for commercialization.However,the low defect formation energy of perovskite leads to a higher defect density than other conventional photovoltaic materials.It results in severe non-radiative recombination,limiting its further development and the commercialization.In this review,we summarize the mechanism and strategies for high-quality perovskite absorber fabrications to minimize the bulk and surface/interface defects of halide perovskite,including film quality development and interface modification.Strategies are proposed for further promoting the film quality and the corresponding device performance.Finally,we highlight the challenges that need to be overcome to control over the defect properties of halide perovskite.

Fabrication of combustion pyrotechnics for laser and electromagnetic interference shielding

The contradiction between flammability and packing density is the technical bottleneck for combustible smoke agent.Herein,polyurethane(PU)foams with flammability and resilience were prepared with polyol and isocyanate as raw materials by chemical foaming method,then compounded with metal powders,polytetrafluoroethylene(PTFE),phthalic annychide(PA),etc.in a certain proportion and pressed into pyrotechnic grain to obtain eco-friendly combustion aerosols with compact density of about1.15 g/cm^(3).The resulting combustion smoke agent combined the advantages of PU foam and pyrotechnic with easy ignition,large smoke production,long duration and low environmental pollution.The transmittance of aerosols for 532 nm and 1064 nm lasers was close to 0,and the EMI SE reached up to65 d B and 35 d B in GPS band and X band,respectively.In addition,the resulting pyrotechnic grains exhibited good mechanical strength and elasticity for sample 1:25,with a compressive strength of22 MPa and an elastic modulus of 195 MPa.The resulting combustion smoke agent is expected to play a potential role in the field of electromagnetic damage and protection.

Surface Molecular Encapsulation with Cyclodextrin in Promoting the Activity and Stability of Fe Single-Atom Catalyst for Oxygen Reduction Reaction

Fe single-atom catalysts(Fe-SACs)have been extensively studied as a highly efficient electrocatalyst toward the oxygen reduction reaction(ORR).Nonetheless,they suffer from stability issue induced by dissolution of Fe metal center and the OH^(−)blocking.Herein,a surface molecular engineering strategy is developed by usingβ-cyclodextrins(CDs)as a localized molecular encapsulation.The CD-modified Fe-SAC(Fe-SNC-β-CD)shows obviously improved activity toward the ORR with 0.90 V,4.10 and 4.09 mA cm^(-2)for E_(1/2),J_(0)and Jk0.9,respectively.Meanwhile,the Fe-SNC-β-CD shows the excellent long-term stability against aggressive stress and the poisoning.It is confirmed through electrochemical investigation that modification ofβ-CD can,on one hand,regulate the atomic Fe coordination chemistry through the interaction between the CD and FeN_(x) moiety,while on the other mitigate the strong adsorption of OH^(−)and function as protective barrier against the poisoning molecules leading to enhanced ORR activity and stability for the Fe-SACs.The molecular encapsulation strategy demonstrates the uniqueness of post-pyrolysis surface molecular engineering for the design of single-atom catalyst.

Effects of inorganic ions,organic particles,blood cells,and cyclic loading on in vitro corrosion of Mg–Al alloys

Recently,magnesium(Mg)alloys have attracted extensive attention as biodegradable implant materials.However,cyclic loading and the corrosive environment of the body are significant challenges for the practical use of alloys,and there are few studies on this topic.In this study,we conducted a four-point bending fatigue test for 86,400 cycles(12 h)in simulated body fluid(SBF),plasma,and whole blood with an AZ series alloy Mg-9Al-0.5Zn-0.27Mn-0.12Ag,to examine the effects of inorganic ions,organic particles,blood cells,and cyclic loading on Mg alloy corrosion.The Mg^(2+)concentration and solution pH were measured before and after experimentation,and the sample surfaces were characterized by 3D digital microscopy,scanning electron microscopy(SEM),energy-dispersive X-ray spectroscopy(EDS),Fourier-transform infrared(FTIR)spectroscopy,Raman spectroscopy,and X-ray photoelectron spectroscopy(XPS).Our results showed that in the non-loading condition,a porous and weak inorganic product layer(mainly Mg/Ca phosphate and carbonate)formed on the surface of the Mg alloy sample immersed in SBF,which hardly had a protective effect on Mg alloy corrosion.For the samples immersed in plasma,the organic particles promoted the formation of an organic and more compact product layer,which protected the Mg alloy from severe corrosion.For the sample immersed in whole blood,the blood cells affected organic particle deposition on the product layer and thus interfered with the formation of an organic compact product layer,which slightly accelerated the corrosion process.Furthermore,cyclic loading damaged the layer integrity and significantly increased the corrosion rates of all the studied materials compared to the samples not subjected to cyclic loading.Nonetheless,under cyclic loading,blood cells adsorbed on the Mg alloy surfaces,and formed films,which protected the Mg alloy substrate and delayed Mg alloy corrosion.

A Nano-Micro Engineering Nanofiber for Electromagnetic Absorber,Green Shielding and Sensor

It is extremely unattainable for a material to simultaneously obtain efficient electromagnetic(EM)absorption and green shielding performance,which has not been reported due to the competition between conduction loss and reflection.Herein,by tailoring the internal structure through nano-micro engineering,a NiCo2O4 nanofiber with integrated EM absorbing and green shielding as well as strain sensing functions is obtained.With the improvement of charge transport capability of the nanofiber,the performance can be converted from EM absorption to shielding,or even coexist.Particularly,as the conductivity rising,the reflection loss declines from −52.72 to −10.5 dB,while the EM interference shielding effectiveness increases to 13.4 dB,suggesting the coexistence of the two EM functions.Furthermore,based on the high EM absorption,a strain sensor is designed through the resonance coupling of the patterned NiCo2O4 structure.These strategies for tuning EM performance and constructing devices can be extended to other EM functional materials to promote the development of electromagnetic driven devices.

Environmental and economic assessment of structural repair technologies for spent lithium-ion battery cathode materials

The existing recycling and regeneration technologies have problems,such as poor regeneration effect and low added value of products for lithium(Li)-ion battery cathode materials with a low state of health.In this work,a targeted Li replenishment repair technology is proposed to improve the discharge-specific capacity and cycling stability of the repaired LiCoO_(2) cathode materials.Compared with the spent cathode material with>50%Li deficiency,the Li/Co molar ratio of the regenerated LiCoO_(2) cathode is>0.9,which completely removes the Co_(3)O_(4) impurity phase formed by the decomposition of LixCoO_(2) in the failed cathode material after repair.The repaired LiCoO_(2) cathode mater-ials exhibit better cycling stability,lower electrochemical impedance,and faster Li^(+)diffusion than the commercial materials at both 1 and 10 C.Meanwhile,Li_(1.05)CoO_(2) cathodes have higher Li replenishment efficiency and cycling stability.The energy consumption and greenhouse gas emissions of LiCoO_(2) cathodes produced by this repair method are significantly reduced compared to those using pyrometallurgical and hydro-metallurgical recycling processes.

Enhanced thermal- and impact-initiated reactions of PTFE/Al energetic materials through ultrasonic-assisted core-shell construction

A facile and economical approach was developed for the large-scale production of powdered core-shell structured PTFE/Al (CS-PA) energetic materials through ultrasonic-assisted mixing. The low-cost micrometer-sized PTFE and Al particles were used as starting materials. Under high-power ultrasonic waves, the PTFE powder was dispersed into nano-to sub-micrometer-sized particles and then encapsulated the Al microparticles to form the core-shell structure. The heat of combustion, burning rate, and pressurization rate of the powdered CS-PA were measured. The thermal-initiated reaction behavior was further evaluated using thermogravimetry-differential scanning calorimetry. Subsequently, the bulk CS-PA with a uniform microstructure was obtained via cold isostatic pressing of the powdered CS-PA followed by vacuum sintering. For the bulk CS-PA, the quasi-static compression behavior was characterized, and the impact-initiated reaction processes were conducted using the Split Hopkinson Pressure Bar (SHPB) and evaluated by a high-speed camera. Compared to physically mixed PTFE/Al materials, the powdered and bulk CS-PA demonstrated enhanced thermal- and impact-initiated reaction characteristics respectively, proving the effectiveness of our approach for constructing core-shell structures.

Gelation of Hole Transport Layer to Improve the Stability of Perovskite Solar Cells

To achieve high power conversion efficiency(PCE) and long-term stability of perovskite solar cells(PSCs), a hole transport layer(HTL) with persistently high conductivity, good moisture/oxygen barrier ability, and adequate passivation capability is important. To achieve enough conductivity and effective hole extraction, spiro-OMe TAD, one of the most frequently used HTL in optoelectronic devices, often needs chemical doping with a lithium compound(LiTFSI). However, the lithium salt dopant induces crystallization and has a negative impact on the performance and lifetime of the device due to its hygroscopic nature. Here, we provide an easy method for creating a gel by mixing a natural small molecule additive(thioctic acid, TA) with spiro-OMe TAD. We discover that gelation effectively improves the compactness of resultant HTL and prevents moisture and oxygen infiltration. Moreover, the gelation of HTL improves not only the conductivity of spiro-OMe TAD, but also the operational robustness of the devices in the atmospheric environment. In addition, TA passivates the perovskite defects and facilitates the charge transfer from the perovskite layer to HTL. As a consequence, the optimized PSCs based on the gelated HTL exhibit an improved PCE(22.52%) with excellent device stability.

Nano silica aerogel-induced formation of an organic/alloy biphasic interfacial layer enables construction of stable high-energy lithium metal batteries

Lithium metal batteries represent promising candidates for high-energy-density batteries, however, many challenges must still be overcome,e.g., interface instability and dendrite growth. In this work, nano silica aerogel was employed to generate a hybrid film with high lithium ion conductivity(0.6 mS cm^(-1)at room temperature) via an in situ crosslinking reaction. TOF-SIMS profile analysis has revealed conversion mechanism of hybrid film to Li–Si alloy/Li F biphasic interface layer, suggesting that the Li–Si alloy and Li F-rich interface layer promoted rapid Li+transport and shielded the Li anodes from corrosive reactions with electrolyte-derived products. When coupled with nickel-cobalt-manganese-based cathodes, the batteries achieve outstanding capacity retention over 1000 cycles at 1 C. Additionally the developed film coated on Li enabled high coulombic efficiency(99.5%) after long-term cycling when coupled with S cathodes. Overall, the results presented herein confirm an effective strategy for the development of high-energy batteries.

A review on the failure and regulation of solid electrolyte interphase in lithium batteries

Solid electrolyte interphase(SEI)has been widely recognized as the most important and the least understood component in lithium batteries.Considering the intrinsic instability in both chemical and mechanical,the failure of SEI is inevitable and strongly associated with the performance decay of practical working batteries.In this Review,the failure mechanisms and the corresponding regulation strategies of SEI are focused.Firstly,the fundamental properties of SEI,including the formation principles,and the typical composition and structures are briefly introduced.Moreover,the common SEI failure modes involving thermal failure,chemical failure,and mechanical failure are classified and discussed,respectively.Beyond that,the regulation strategies of SEI with respect to different failure modes are further concluded.Finally,the future endeavor in further disclosing the mysteries of SEI is prospected.