Effect of LiTFSI and LiFSI on Cycling Performance of Lithium Metal Batteries Using Thermoplastic Polyurethane/Halloysite Nanotubes Solid Electrolyte

All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrolyte still faces challenges.In this study,a thin solid polymer composite electrolyte(SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane(TPU),lithium salt(LiTFSI or LiFSI),and halloysite nanotubes(HNTs) in a porous framework of polyethylene separator(PE)(TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE).The composition,electrochemical performance,and especially the effect of anions(TFSI~-and FSI~-) on cycling performance are investigated.The results reveal that the flexible TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V(vs.Li+/Li) at 60℃,respectively.Reduction in FSI~-tends to form more LiF and sulfur compounds at the interface between TPU-HNTs-LiFSI-PE and Li metal anode,thus enhancing the interfacial stability.As a result,cell composed of TPU-HNTs-LiFSI-PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase(SEI) with a distinct decrease in charge-transfer resistance during cycling.Li|Li symmetric cell with TPU-HNTs-LiFSI-PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately39 mV at a current density of 0.1 mA cm~(-2),while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU-HNTs-LiTFSI-PE.The initial capacities of NCMITPU-HNTs-LiTFSIPEILi and NCMITPU-HNTs-LiFSI-PEILi cells were 149 and 114 mAh g~(-1),with capacity retention rates of 83.52% and89.99% after 300 cycles at 0.5 C,respectively.This study provides a valuable guideline for designing flexible SPCE,which shows great application prospect in the practice of ASSLB.     

Machine learning of phases and mechanical properties in complex concentrated alloys

The mechanical properties of complex concentrated alloys (CCAs) depend on their formed phases and corresponding microstructures.The data-driven prediction of the phase formation and associated mechanical properties is essential to discovering novel CCAs.The present work collects 557 samples of various chemical compositions,comprising 61 amorphous,167 single-phase crystalline,and 329 multi-phases crystalline CCAs.Three classification models are developed with high accuracies to category and understand the formed phases of CCAs.Also,two regression models are constructed to predict the hard-ness and ultimate tensile strength of CCAs,and the correlation coefficient of the random forest regression model is greater than 0.9 for both of two targeted properties.Furthermore,the Shapley additive expla-nation (SHAP) values are calculated,and accordingly four most important features are identified.A significant finding in the SHAP values is that there exists a critical value in each of the top four fea-tures,which provides an easy and fast assessment in the design of improved mechanical properties of CCAs.The present work demonstrates the great potential of machine learning in the design of advanced CCAs.     

Highly active sites of low spin FeⅡN4species:The identification and the ORR performance

Over recent years,catalytic materials of Fe-N-C species have been recognized being active for oxygen reduction reaction(ORR).However,the identification of active site remains challenging as it generally involves a pyrolysis process and mixed components being obtained.Herein Fe₃C/C and Fe₂N/C samples were synthesized by temperature programmed reduction of Fe precursors in 15%CH₄/H₂and pure NH₃,respectively.By acid leaching of Fe₂N/C sample,only single sites of FeN₄species were presented,providing an ideal model for identification of catalytic functions of the single sites of FeN₄in ORR.A correlation was conducted between the concentration of Fe^ⅡN₄in low spin state by Mossbauer spectra and the kinetic current density at 0.8 V in alkaline media,and such a structure-performance correlation assures the catalytic roles of low spin Fe^ⅡN₄ species as highly active sites for the ORR.     

An operation optimization method of a fully mechanized coal mining face based on semi-physical virtual simulation

A mathematical hydraulic support self-tracking model for three-machine cooperative mining is proposed to address low efficiency and difficulties in strategy evaluation of a fully mechanized coal face.The proposed model uses the coordinates and traction speed of the shearer to calculate the frequency of the circular hydraulic support and realize the coordinated operation of the three-machine mining technology.A unity3d hardware-in-the-loop simulation experimental hearer and hydraulic support platform was used to validate the model of autonomous follow-up.The results indicate that collaborative control of coal mining allowed for an efficiency 3.76%higher than under automatic operation mode and 46.03%higher than under manual control;thus,The mathematical model provided an improved production efficiency of the fully mechanized mining face.The mathematical model also provides a more intelligent and reliable security support,and improves the intelligent level of hydraulic support follow-up control.     

Albumin mediated reactive oxygen species scavenging and targeted delivery of methotrexate for rheumatoid arthritis therapy

Rheumatoid arthritis(RA)is a common chronic systemic autoimmune disease.Although there are a variety of treatments for RA,the substantial clinical therapies are still limited to disease-modifying anti-rheumatic drugs(DMARD),which would induce obvious side-effect in patients after long-term administration.Herein,an uncomplicated drug-induced self-assembly strategy was proposed to fabricate enzyme-loaded albumin nanomedicine.The hydrophobic drug methotrexate(MTX)could induce self-assembly of superoxide dismutase(SOD)and human serum albumin(HSA)to form HSA-SOD-MTX nanoparticle.After intravenous injection,dual-modal imaging including fluorescence imaging or single-photon emission computed tomography(SPECT)/CT imaging exhibits high accumulation of cyanine 5.5(Cy5.5)or 125l labeled HSA-SOD-MTX nanoparticles in the joints of collagen-induced arthritis(CIA)mice.Importantly,using the synergy therapy of SOD enzyme to scavenge the reactive oxygen species(ROS)and MTX to suppress inflammation,HSA-SOD-MTX nanoparticles exhibit excellent therapeutic efficiency of RA in CIA mice compared with the other groups.Micro-CT and clinical arthritis score of RA mice further demonstrate that RA symptoms of mice treated with HSA-SOD-MTX nanoparticles is significantly relived,which was further demonstrated by the histological analysis and the inflammatory factors measurement.The synergy therapy of inflammation by MTX and SOD enzyme based on HSA-SOD-MTX nanoparticles show excellent therapeutic effects of RA without inducing obvious side effects.Therefore,our strategy may further promote the highly efficient therapy of RA using SOD enzyme to scavenge the ROS and decreasing the side-effect of MTX,which may provide the reference for clinical RA treatment.     

Microfluidic-enabled ambient-temperature synthesis of ultrasmall bimetallic nanoparticles

The production of bimetallic nanoparticles with ultrasmall sizes is the constant pursuit in chemistry and materials science because of their promising applications in catalysis,electronics and sensing.Here we report ambient-temperature preparation of bimetallic NPs with tunable size and composition using microfluidic-controlled co-reduction of two metal precursors on silicon surface.Instead of free diffusion of metal ions in bulk system,microfluidic flow could well control the local ions concentration,thus leading to homogenous and controllable reduction rate among different nucleation sites.By controlling precursor concentration,flow rate and reaction time,we rationally design a series of bimetallic NPs including Ag-Cu,Ag-Pd,Cu-Pt,Cu-Pd and Pt-Pd NPs with ultrasmall sizes(~3.0 nm),tight size distributions(relative standard deviation(RSD)<21%),clean surface,and homogenous elemental compositions among particles(standard deviation(SD)of weight ratios<3.5%).This approach provides a facile,green and scalable method toward the synthesis of diverse bimetallic NPs with excellent activity.     

煤 /重油加氢共炼中SDBS对煤担载铁镍催化剂的改性效果

以广西褐煤为载体煤,铁盐和镍盐为活性组分,考察了以十二烷基苯磺酸钠(SDBS)作为表面活性剂,对沉淀-氧化法制备煤担载型铁镍催化剂(FeNi/C)的影响以及制备的催化剂在煤/重油加氢共炼中的反应性能。采用XRD和TEM分析了FeNi和FeNi-SDBS的物相组成与微观形貌变化,并以SEM-mapping手段对比了Fe元素和Ni元素在FeNi/C及FeNi-SDBS/C表面的分散效果,采用高压釜实验评价了不同催化剂的反应性能,并对反应后的固体产物采用元素分析、FTIR和SEM进行组成和结构性质研究。结果表明:SDBS的加入显著降低了催化剂的平均粒径,α/γ-FeOOH和Fe0.67Ni0.33OOH等活性相的晶体结构特征减弱,在载体煤上得到了更好的分散效果;FeNi-SDBS/C催化剂相比FeNi/C催化剂有更高的油收率和干基无灰煤转化率,催化活性明显提高;采用SDBS改性的催化剂反应后得到固体产物的n(H)∶n(C)高、脂肪链长度低、芳环取代度大、结构疏松且平均粒径小,表面改性后的FeNi-SDBS/C催化剂拥有更强的促进煤加氢转化和抑制体系缩合生焦的作用。     

煤溶胀对煤/油加氢共炼中煤转化率的影响及机理研究

选取安徽褐煤为原料煤,在不同温度下用催化裂化油浆对其进行溶胀处理,再将体系进行加氢共炼反应,以考察煤的溶胀对煤/油加氢共炼反应中干基无灰煤转化率的影响,并通过激光粒度仪、比表面和孔隙度仪、SEM、XRD、FT-IR等分析手段对比了溶胀前后褐煤及反应残渣的组成和结构变化。结果表明:油煤浆中的褐煤在200℃和300℃下均出现溶胀现象,伴随有轻微的转化,但在300℃下褐煤的溶胀现象更为明显,且300℃溶胀处理后进行加氢共炼反应,体系的干基无灰煤转化率由88.67%增至94.58%,反应残渣含量由4.12%降至2.73%。由表征分析可知,溶胀处理后褐煤的平均粒径、比表面积和孔体积增大,表面粗糙程度增加,孔隙结构增多。此外,溶胀处理后的反应残渣与未溶胀处理的反应残渣相比脂肪链变短,支链化程度降低,缩合程度降低,且300℃溶胀后残渣的芳香环取代度提高。证实溶胀处理增加了褐煤与活化氢的接触面积,增多了褐煤的加氢活性位点,有利于促进煤中有机质组分的转化并抑制稠环烃类的缩合,从而提高了转化率,降低了残渣含量。     

Microstructure and mechanical properties in the TLP joint of FeCoNiTiAl and Inconel 718 alloys using BNi2 filler

High entropy alloy(HEA) of Fe Co Ni Ti Al and Inconel 718 superalloy were firstly transient liquid phase(TLP) bonded by BNi2 filler due to the diffusion of Si and B in the filler to the base metals. The effects of bonding time on microstructure evolution and mechanical properties of the TLP joints were investigated.Owing to the complete isothermal solidification of the joints bonded for 30 min 120 min at 1100°C,no athermally solidified zones(ASZs) formed by eutectic phases were observed in the welded zone. Thus the TLP joints were only composed by the isothermally solidified zone(ISZ) and two diffusion affected zone(DAZ) adjacent to the dissimilar base metals and the negative effect of the ASZ on joint properties can be avoided. In addition, the increase of the bonding time can also make the Ti B2 borides precipitated in the DAZ near HEA and the brittle borides or carbides in the DAZ near IN718 alloy decrease and reduce the possibility of the stress concentration happened in the joints under loading. Therefore, the highest shear strength(632.1 MPa) of the TLP joints was obtained at 1100°C for 120 min, which was higher than that of the joint bonded for 30 min, 404.2 MPa. Furthermore, the extension of the bonding time made the fracture mechanism of the joint be transformed from the intergranular fracture to the transgranular fracture. However, as the brittle borides in the DAZ near IN718 can not be eliminated completely and refining of grains also happened in such region, all the TLP joints fractured inner the DAZ near IN718 alloy.     

Minimising non-selective defects in ultrathin reduced graphene oxide membranes with graphene quantum dots for enhanced water and NaCl separation

Reduced graphene oxide (rGO) membranes have been intensively evaluated for desalination and ionic sieving applications,benefiting from their stable and well-confined interlayer channels.However,rGO membranes generally suffer from low permeability due to the high transport resistance resulting from the narrowed two-dimensional (2D) channels.Although high permeability can be realized by reducing membrane thickness,membrane selectivity normally declines because of the formation of non-selective defects,in particular pinholes.In this study,we demonstrate that the non-selective defects in ultrathin rGO membranes can be effectively minimised by a facile posttreatment via surface-deposition of graphene quantum dots (GQDs).The resultant GQDs/rGO membranes obtained a good trade-off between water permeance (14 L·m-2·h-1·MPa-1) and NaCl rejection (91％).This work provides new insights into the design of high quality ultrathin 2D laminar membranes for desalination,molecular/ionic sieving and other separation applications.