Lithium metal(LM)is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential.Nonetheless,side reactions,volume change,and unwanted lithium dendrite growth seriou...Lithium metal(LM)is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential.Nonetheless,side reactions,volume change,and unwanted lithium dendrite growth seriously limit the practical application of LM.Herein,with the aid of a hard template approach,a novel lithiophilic CoF_(2)-carbon hollow sphere(CoF_(2)@C-HS)composite material is successfully prepared via a facile in-situ fluorination and etching strategy.The lithiophilic CoF_(2) acts as nucleation sites to reduce nucleation overpotential as well as induces the spatial Li deposition and the formation of LiFrich solid electrolyte interphase(SEI),and the hollow carbon matrix can enhance the electrical conductivity and offer free space for LM deposition.Theoretical simulations reveal that the synergistic effect of lithiophilic CoF_(2) and hollow carbon matrix homogenizes the electric field distribution and Li~+flux.Benefiting from these advantages,the CoF_(2)@C-HS-modified copper substrate electrode delivers an enhanced Coulombic efficiency(CE)of 93.7%for 280 cycles at 1 mA cm^(-2)and 1 mA h cm^(-2).The symmetrical cell using CoF_(2)@C-HS can stably cycle more than 1800 h with a low voltage hysteresis of 11 mV at a current density of 0.5 MA cm^(-2)and an areal capacity of 0.5 mA h cm^(-2).Moreover,the Li@CoF_(2)@C-HS composite anode enables more than 300 stable cycles at 1 C with a capacity retention of 95%in LiFePO_(4)-based full cell and 110 stable cycles at 1 C in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)-based highvoltage full cell.This work might shed a new light on designing lithiophilic hosts to spatially confine LM deposition,realizing dendrite-free LM anodes and the practical applications of LM batteries.展开更多
The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein...The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.展开更多
TiAIC metal gate for the metal-oxide-semiconductor field-effect-transistor (MOSFET) is grown by the atorr/ic layer deposition method using TiCI4 and AI(CH3) 3 (TMA) as precursors. It is found that the major PrOd...TiAIC metal gate for the metal-oxide-semiconductor field-effect-transistor (MOSFET) is grown by the atorr/ic layer deposition method using TiCI4 and AI(CH3) 3 (TMA) as precursors. It is found that the major PrOduct of the TIC14 and TMA reaction is TiA1C, and the components of C and A1 are found to increase with higher growth temperature. The reaction mechanism is investigated by using x-ray photoemission spectroscopy (XPS), Fourier transform infrared spectroscopy (FFIR), and scanning electron microscope (SEM). The reaction mechanism is as follows. Ti is generated through the reduction of TiCI4 by TMA. The reductive behavior of TMA involves the formation of ethane. The Ti from the reduction of TIC14 by TMA reacts with ethane easily forming heterogenetic TiCH2, TiCH=CH2 and TiC fragments. In addition, TMA thermally decomposes, driving A1 into the TiC film and leading to TiA1C formation. With the growth temperature increasing, TMA decomposes more severely, resulting in more C and A1 in the TiA1C film. Thus, the film composition can be controlled by the growth temperature to a certain extent.展开更多
A new class of activated mesoporous Al-MCM-41 layers was deposited on Fe-CrAl metallic foils in the presence of cationic surfactant cetyltrimethylammonium bromide under basic conditions by an in-situ hydrothermal meth...A new class of activated mesoporous Al-MCM-41 layers was deposited on Fe-CrAl metallic foils in the presence of cationic surfactant cetyltrimethylammonium bromide under basic conditions by an in-situ hydrothermal method. The characterization techniques including X-ray diffraction, nitrogen adsorption and transmission electron microscopy, as well as field-emission scanning electron microscopy were performed to investigate the pore structure and surface morphology of the Al-MCM-41 layers. The Al-MCM-41 materials are of amorphous structure but exhibit large BET surface area (up to 757.0 m2/g) and pore volume (up to 0.72 cm3/g), as well as a mean pore diameter of 3 nm. The layers deposited on the FeCrAl foils are continuous despite with a few of holes on the surface.展开更多
The effect of Al in Ti-microalloyed welding wire on microstructure and toughness of deposited metals is studied.The results show that the deposited metal toughness worsens with increasing Al in wire' The mechanis...The effect of Al in Ti-microalloyed welding wire on microstructure and toughness of deposited metals is studied.The results show that the deposited metal toughness worsens with increasing Al in wire' The mechanism of Al is as follows:(1) Al makes oxygen content in deposited metal increase.(2)Al restrains the formation of Ti-rich oxide inclusion, which causes granular bainite microstructure in deposited metal.(3)The content of solute Ti in deposited metal increases with Al content in welding wire,as a result,a part of carbonrich constitution in deposited metal is in the form of twin martensite.展开更多
In order to reduce sulphur ( S ) and phosphorus ( P ) impurities in deposited metal, a small amount of rare earth (RE) lanthanum ( La) and yttrium (Y) were added into the coating ofE4303 electrode, a low car...In order to reduce sulphur ( S ) and phosphorus ( P ) impurities in deposited metal, a small amount of rare earth (RE) lanthanum ( La) and yttrium (Y) were added into the coating ofE4303 electrode, a low carbon steel electrode. The microstructures of deposited metal were analyzed with metalloscope, and then the content of S and P was examined by energy dispenive X-ray spectrometer ( EDXS ), and by wavelength dispersive X-ray fluorescence (XRF) spectrometer for further examination. The results show that the proper addition of La and Y can be beneficial to the desulfurization and dephosphorization of the deposited metal. Certainly, difference in the addition amount of La and Y could lead to various desulfurization and dephosphorization efficiency, in which the former is more obvious than the latter. With the proper amount of La attd Y, there is finer microstructure in deposited metal, and mechanical properties are improved as well. The S content in deposited metal with added La and Y decreases by 44. 44 wt. % , while the P content 6. 67 wt. %, compared with that in deposited metal without La and II.展开更多
The 25 road-deposited sediments were collected from five different land-use zones (industrial, residential, commercial, park, and countryside) in Hangzhou, China. The concentrations of metals (Cd, Co, Cr, Cu, Fe, M...The 25 road-deposited sediments were collected from five different land-use zones (industrial, residential, commercial, park, and countryside) in Hangzhou, China. The concentrations of metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in these samples were determined using ICP-AES after digestion with the mixture of HNO3-HF-HC1 (aqua regia), and chemically fractionated according to the modified BCR (the European Community Bureau of Reference) sequential extraction procedure. The high metal concentration levels were detected in the sample from industrial zone and commercial zone having heavy traffic. While the low metal levels were noted in the street dust sample from residential zone, park, and countryside zone. The mobility sequence based on the sum of the BCR sequential extraction stages was: Zn (80.28%), Pb (78.68%), Cd (77.66%) 〉 Cu (73.34%) 〉 Mn (67.92%) 〉 Co (41.66%) 〉 Ni (30.36%) 〉 Cr (21.56%), Fe (20.86%). Correlation analysis and principal component analysis were applied to the data matrix to evaluate the analytical results and to identify the possible pollution sources of metals. Factor analysis showed that these areas were mainly contaminated by three sources, namely lithology, traffic, and industry.展开更多
Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-me...Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-metal batteries.To address these challenges,we report in this study a functional nitro-cellulose interfacial layer(NCIL)on the surface of Zn anodes enlightened by a nitro-coordination chemistry strategy.The NCIL exhibits strong zincophilicity and superior coordination capability with Zn^(2+)due to the highly electronegative and highly nucleophilic nature of the nitro functional group.This characteristic facilitates a rapid Zn-ion desolvation process and homogeneous Zn plating,effectively preventing H_(2) evolution and dendrite formation.Additionally,the negatively charged surface of NCIL acts as a shield,repelling SO_(4)^(2-)anions and inhibiting corrosive reactions on the Zn surface.Remarkably,reversible and stable Zn plating/stripping is achieved for over 5100 h at a current density of 1 mA cm^(-2),which is nearly 30 times longer than that of bare Zn anodes.Furthermore,the Zn/V_(2)O_(5) full cells with the functional interface layer deliver a high-capacity retention of 80.3%for over 10,000 cycles at 5 A g^(-1).This research offers valuable insights for the rational development of advanced protective interface layers in order to achieve ultra-long-lifeZnmetal batteries.展开更多
Piezoelectric ceramic and polymeric separators have been proposed to effectively regulate Li deposition and suppress dendrite growth,but such separators still fail to satisfactorily support durable operation of lithiu...Piezoelectric ceramic and polymeric separators have been proposed to effectively regulate Li deposition and suppress dendrite growth,but such separators still fail to satisfactorily support durable operation of lithium metal batteries owing to the fragile ceramic layer or low-piezoelectricity polymer as employed.Herein,by combining PVDF-HFP and ferroelectric BaTiO_(3),we develop a homogeneous,single-layer composite separator with strong piezoelectric effects to inhibit dendrite growth while maintaining high mechanical strength.As squeezed by local protrusion,the polarized PVDF-HFP/BaTiO_(3)composite separator generates a local voltage to suppress the local-intensified electric field and further deconcentrate regional lithium-ion flux to retard lithium deposition on the protrusion,hence enabling a smoother and more compact lithium deposition morphology than the unpoled composite separator and the pure PVDF-HFP separator,especially at high rates.Remarkably,the homogeneous incorporation of BaTiO_(3)highly improves the piezoelectric performances of the separator with residual polarization of 0.086 pC cm^(-2)after polarization treatment,four times that of the pure PVDF-HFP separator,and simultaneously increases the transference number of lithium-ion from 0.45 to 0.57.Beneficial from the prominent piezoelectric mechanism,the polarized PVDF-HFP/BaTiO_(3)composite separator enables stable cyclic performances of Li||LiFePO_(4)cells for 400 cycles at 2 C(1 C=170 mA g^(-1))with a capacity retention above 99%,and for 600 cycles at 5 C with a capacity retention over 85%.展开更多
This work adopts a multi⁃step etching⁃heat treatment strategy to prepare porous silicon microsphere com⁃posite with Sb⁃Sn surface modification and carbon coating(pSi/Sb⁃Sn@C),using industrial grade SiAl alloy micro⁃sp...This work adopts a multi⁃step etching⁃heat treatment strategy to prepare porous silicon microsphere com⁃posite with Sb⁃Sn surface modification and carbon coating(pSi/Sb⁃Sn@C),using industrial grade SiAl alloy micro⁃spheres as a precursor.pSi/Sb⁃Sn@C had a 3D structure with bimetallic(Sb⁃Sn)modified porous silicon micro⁃spheres(pSi/Sb⁃Sn)as the core and carbon coating as the shell.Carbon shells can improve the electronic conductivi⁃ty and mechanical stability of porous silicon microspheres,which is beneficial for obtaining a stable solid electrolyte interface(SEI)film.The 3D porous core promotes the diffusion of lithium ions,increases the intercalation/delithia⁃tion active sites,and buffers the volume expansion during the intercalation process.The introduction of active met⁃als(Sb⁃Sn)can improve the conductivity of the composite and contribute to a certain amount of lithium storage ca⁃pacity.Due to its unique composition and microstructure,pSi/Sb⁃Sn@C showed a reversible capacity of 1247.4 mAh·g^(-1) after 300 charge/discharge cycles at a current density of 1.0 A·g^(-1),demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.展开更多
The undesirable dendrite growth induced by non-planar zinc(Zn)deposition and low Coulombic efficiency resulting from severe side reactions have been long-standing challenges for metallic Zn anodes and substantially im...The undesirable dendrite growth induced by non-planar zinc(Zn)deposition and low Coulombic efficiency resulting from severe side reactions have been long-standing challenges for metallic Zn anodes and substantially impede the practical application of rechargeable aqueous Zn metal batteries(ZMBs).Herein,we present a strategy for achieving a high-rate and long-cycle-life Zn metal anode by patterning Zn foil surfaces and endowing a Zn-Indium(Zn-In)interface in the microchannels.The accumulation of electrons in the microchannel and the zincophilicity of the Zn-In interface promote preferential heteroepitaxial Zn deposition in the microchannel region and enhance the tolerance of the electrode at high current densities.Meanwhile,electron aggregation accelerates the dissolution of non-(002)plane Zn atoms on the array surface,thereby directing the subsequent homoepitaxial Zn deposition on the array surface.Consequently,the planar dendrite-free Zn deposition and long-term cycling stability are achieved(5,050 h at 10.0 mA cm^(−2) and 27,000 cycles at 20.0 mA cm^(−2)).Furthermore,a Zn/I_(2) full cell assembled by pairing with such an anode can maintain good stability for 3,500 cycles at 5.0 C,demonstrating the application potential of the as-prepared ZnIn anode for high-performance aqueous ZMBs.展开更多
Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition be...Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition behavior still occurs at the top of 3D frameworks owing to the local accumulation of Li ions.To promote uniform Li deposition without top dendrite growth,herein,a layered multifunctional framework based on oxidation-treated polyacrylonitrile(OPAN) and metal-organic framework(MOF) derivatives was proposed for rationally regulating the distribution of Li ions flux,nucleation sites,and electrical conductivity.Profiting from these merits,the OPAN/carbon nano fiber-MOF(CMOF) composite framework demonstrated a reversible Li plating/stripping behavior for 500 cycles with a stable Coulombic efficiency of around 99.0% at the current density of 2 mA/cm~2.Besides,such a Li composite anode exhibited a superior cycle lifespan of over 1300 h under a low polarized voltage of 18 mV in symmetrical cells.When the Li composite anode was paired with LiFePO_(4)(LFP) cathode,the obtained full cell exhibited a stable cycling over 500 cycles.Moreover,the COMSOL Multiphysics simulation was conducted to reveal the effects on homogeneous Li ions distribution derived from the above-mentioned OPAN/CMOF framework and electrical insulation/conduction design.These electrochemical and simulated results shed light on the difficulties of designing stable and safe Li metal anode via optimizing the 3D frameworks.展开更多
The microstructure of E911 deposited metal was observed and the effect of heat input and postweld heat treatment on microstructure and impact toughness was investigated. The microstructure consists of tempered martens...The microstructure of E911 deposited metal was observed and the effect of heat input and postweld heat treatment on microstructure and impact toughness was investigated. The microstructure consists of tempered martensite and residual δ- ferrite. The morphology of tempered martensite is columnar and the residual δ-ferrite is polygonal. With the increase in heat input, the width of columnar martensite grain and the size of residual δ-ferrite increased, whereas the volume fraction of residual δ-ferrite varied slightly. The impact toughness decreased as heat input increased. The result reveals that coarsening columnar martensite grain and δ-ferrite have greater effect on impact toughness than volume fraction of residual δ-ferrite. As the time of postweld heat treatment is exceeded 8h, aggregation of M23 C6occurs in some grain boundaries or lath interfaces. The partial aggregation of M23 C6 results in the decrease in impact toughness.展开更多
The single solid source precursor, cobalt (Ⅱ) acetylacetonate was prepared and characterized by infrared spectroscopy. Thin films of cobalt oxide were deposited on soda lime glass substrates through the pyrolysis ...The single solid source precursor, cobalt (Ⅱ) acetylacetonate was prepared and characterized by infrared spectroscopy. Thin films of cobalt oxide were deposited on soda lime glass substrates through the pyrolysis (metal organic chemical vapour deposition (MOCVD)) of single solid source precursor, cobalt acetylacetonate, Co[C5H7O2]2 at a temperature of 420℃. The compositional characterization carried out by rutherford backscattering spectroscopy and X-ray diffraction (XRD), showed that the films have a stoichiometry of Co2O3 and an average thickness of 227±0.2 nm. A direct energy gap of 2,15±0.01 eV was calculated by the data obtained by optical absorption spectroscopy. The morphology of the films obtained by scanning electron microscopy, showed that the grains were continuous and uniformly distributed at various magnifications, while the average grain size was less than i micron for the deposited thin films of cobalt oxide.展开更多
The microstractures of 9Cr-lMo multipass deposited metal were observed. The effect of microstructure on impact toughness of 9Cr-lMo multipass deposited metal with varying heat inputs was investigated. Result shows tha...The microstractures of 9Cr-lMo multipass deposited metal were observed. The effect of microstructure on impact toughness of 9Cr-lMo multipass deposited metal with varying heat inputs was investigated. Result shows that fine-grained microstructure occurs in reheated zones. The absorbed energy increases with the increase of volume fraction of fine-grained microstructure , suggesting that the volume fraction of fine-grained microstracture influences directly on impact toughness. The increasing ratio of fine-grained zone thickness to weld layer thickness is responsible for improving impact toughness after PWHT.展开更多
The laser metal deposition (LMD) was conducted on copper by varying the processing parameters in order to achieve the best possible settings. Two sets of experiments were conducted. The deposited composites were cha...The laser metal deposition (LMD) was conducted on copper by varying the processing parameters in order to achieve the best possible settings. Two sets of experiments were conducted. The deposited composites were characterized through the evolving microstructure, microhardness profiling and mechanical properties. It was found that the evolving microstructures of the deposited composites were characterized with primary, secondary and tertiary arms dendrites, acicular microstructure as well as the alpha and beta eutectic structures. From the two sets of experiments performed, it was found that Sample E produced at a laser power of 1200 W and a scanning speed of 1.2 m/min has the highest hardness of HV (190±42) but exhibits some lateral cracks due to its brittle nature, while Sample B produced at laser power of 1200 W and a scanning speed of 0.3 m/min shows no crack and a good microstructure with an increase in dendrites. The strain hardening coefficient of the deposited copper composite obtained in this experiment is 3.35.展开更多
The effect of electropulsing treatment on microstructure and mechanical strength of laser metal deposited Ti−6Al−4V alloy was investigated in order to eliminate the anisotropy in strength of laser metal deposited Ti−6...The effect of electropulsing treatment on microstructure and mechanical strength of laser metal deposited Ti−6Al−4V alloy was investigated in order to eliminate the anisotropy in strength of laser metal deposited Ti−6Al−4V alloy by tensile tests,optical microscopy,scanning electron microscopy,electron back-scattered diffraction analyses and transmission electron microscopy.With increasing applied voltages from 0 to 130 V,the evolution of microstructure within columnarβgrains followed the sequence ofα′martensite→colonyαstructure→basket-weaveαstructure.The electropulsing treated at 130 V weakened the texture of martensite withinβgrains.The as-built Ti−6Al−4V alloy showed an anisotropy in yield strength(6.2%).After processing at 130 V,the anisotropy in yield strength was reduced to 0.6%,which was attributed to the almost equivalent distribution of Schmid factor in the samples deformed along different orientations.展开更多
By means of metallographic microscope(OM),scanning electron microscope(SEM),back scattering electron diffraction(EBSD)and transmission electron microscope(TEM),the effect of Cu on microstructure transformation and mec...By means of metallographic microscope(OM),scanning electron microscope(SEM),back scattering electron diffraction(EBSD)and transmission electron microscope(TEM),the effect of Cu on microstructure transformation and mechanical properties of deposited metal of 590MPa class steel welding wire was studied.The results show that the microstructure of deposited metal is composed of acicular ferrite,lamellar bainite,granular bainite and residual austenite.With the increase of Cu content,the phase transition temperature of the deposited metal decreases,making the phase transition region of ferrite and pearlite shift to the right,expanding the phase transition region of bainite and shrinking the phase transition region of ferrite and pearlite.The microstructure of deposited metal changed,the content of M-A elements increased but the size decreased,and the ferrite-bainite biphasic microstructure was matched.The reduction of M-A component content in strips and blocks and the reduction of effective grain size will reduce the nucleation probability of microcracks,increase crack growth resistance,and improve the impact toughness of the deposited metal.展开更多
Chromium (Cr) doped Zinc oxide ZnO thin films were deposited onto glass substrates by Metal Organic Chemical Vapour Deposition (MOCVD) technique with varying dopant concentration at a temperature of 420°C. The ef...Chromium (Cr) doped Zinc oxide ZnO thin films were deposited onto glass substrates by Metal Organic Chemical Vapour Deposition (MOCVD) technique with varying dopant concentration at a temperature of 420°C. The effect of the chromium concentration on morphological, structural, optical, electrical and gas sensing properties of the films were investigated. The scanning electron microscopy results revealed that the Cr concentration has great influence on the crystallinity, surface smoothness and grain size. X-ray diffraction (XRD) studies shows that films were polycrystalline in nature and grown as a hexagonal wurtzite structure. A direct optical band energy gap of 3.32 to 3.10 eV was obtained from the optical measurements. The transmission was found to decrease with increasing Cr doping concentration. Rutherford Backscattering Spectroscopy (RBS) analysis also demonstrates that Cr ions are substitutionally incorporated into ZnO. I-V characteristic of the film shows a resistivity ranges from 1.134 × 10-2 · cm to 1.24 × 10-2 · cm at room temperature. The gas sensing response of the films were enhanced with incorporation of Cr as a dopant with optimum operating temperature around 200°C.展开更多
Firstly, the concept, sources and damage of atmospheric deposition were introduced, and then the relation between atmospheric deposition and accumulation of heavy metals in rice in Guangxi was analyzed to provide refe...Firstly, the concept, sources and damage of atmospheric deposition were introduced, and then the relation between atmospheric deposition and accumulation of heavy metals in rice in Guangxi was analyzed to provide reference for the implementation of effective risk early warning of pollution from heavy metal deposition and safe production of rice in mining areas of Guangxi.展开更多
基金supported by the Natural Science Foundation of China (52277218)the Hubei Provincial Natural Science Foundation of China (2024AFA094)+1 种基金the Excellent Discipline Cultivation Project by JHUN (2023XKZ009)supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,Materials Sciences and Engineering Division under contract number DE-AC05-00OR22725。
文摘Lithium metal(LM)is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential.Nonetheless,side reactions,volume change,and unwanted lithium dendrite growth seriously limit the practical application of LM.Herein,with the aid of a hard template approach,a novel lithiophilic CoF_(2)-carbon hollow sphere(CoF_(2)@C-HS)composite material is successfully prepared via a facile in-situ fluorination and etching strategy.The lithiophilic CoF_(2) acts as nucleation sites to reduce nucleation overpotential as well as induces the spatial Li deposition and the formation of LiFrich solid electrolyte interphase(SEI),and the hollow carbon matrix can enhance the electrical conductivity and offer free space for LM deposition.Theoretical simulations reveal that the synergistic effect of lithiophilic CoF_(2) and hollow carbon matrix homogenizes the electric field distribution and Li~+flux.Benefiting from these advantages,the CoF_(2)@C-HS-modified copper substrate electrode delivers an enhanced Coulombic efficiency(CE)of 93.7%for 280 cycles at 1 mA cm^(-2)and 1 mA h cm^(-2).The symmetrical cell using CoF_(2)@C-HS can stably cycle more than 1800 h with a low voltage hysteresis of 11 mV at a current density of 0.5 MA cm^(-2)and an areal capacity of 0.5 mA h cm^(-2).Moreover,the Li@CoF_(2)@C-HS composite anode enables more than 300 stable cycles at 1 C with a capacity retention of 95%in LiFePO_(4)-based full cell and 110 stable cycles at 1 C in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)-based highvoltage full cell.This work might shed a new light on designing lithiophilic hosts to spatially confine LM deposition,realizing dendrite-free LM anodes and the practical applications of LM batteries.
基金the financial support from the National Natural Science Foundation of China(Nos.22205191 and 52002346)the Science and Technology Innovation Program of Hunan Province(No.2021RC3109)+1 种基金the Natural Science Foundation of Hunan Province,China(No.2022JJ40446)Guangxi Key Laboratory of Low Carbon Energy Material(No.2020GXKLLCEM01)。
文摘The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.
基金Project supported by the Key Technology Study for 16/14 nm Program of the Ministry of Science and Technology of China(Grant No.2013ZX02303)
文摘TiAIC metal gate for the metal-oxide-semiconductor field-effect-transistor (MOSFET) is grown by the atorr/ic layer deposition method using TiCI4 and AI(CH3) 3 (TMA) as precursors. It is found that the major PrOduct of the TIC14 and TMA reaction is TiA1C, and the components of C and A1 are found to increase with higher growth temperature. The reaction mechanism is investigated by using x-ray photoemission spectroscopy (XPS), Fourier transform infrared spectroscopy (FFIR), and scanning electron microscope (SEM). The reaction mechanism is as follows. Ti is generated through the reduction of TiCI4 by TMA. The reductive behavior of TMA involves the formation of ethane. The Ti from the reduction of TIC14 by TMA reacts with ethane easily forming heterogenetic TiCH2, TiCH=CH2 and TiC fragments. In addition, TMA thermally decomposes, driving A1 into the TiC film and leading to TiA1C formation. With the growth temperature increasing, TMA decomposes more severely, resulting in more C and A1 in the TiA1C film. Thus, the film composition can be controlled by the growth temperature to a certain extent.
基金Funded by the National Natural Science Foundation of China (No.50502002)Scientific Research Common Program of Beijing Municipal Commission of Education (No. KM200610005016)Youth Foundation of Beijing University of Technology (No.00190)
文摘A new class of activated mesoporous Al-MCM-41 layers was deposited on Fe-CrAl metallic foils in the presence of cationic surfactant cetyltrimethylammonium bromide under basic conditions by an in-situ hydrothermal method. The characterization techniques including X-ray diffraction, nitrogen adsorption and transmission electron microscopy, as well as field-emission scanning electron microscopy were performed to investigate the pore structure and surface morphology of the Al-MCM-41 layers. The Al-MCM-41 materials are of amorphous structure but exhibit large BET surface area (up to 757.0 m2/g) and pore volume (up to 0.72 cm3/g), as well as a mean pore diameter of 3 nm. The layers deposited on the FeCrAl foils are continuous despite with a few of holes on the surface.
文摘The effect of Al in Ti-microalloyed welding wire on microstructure and toughness of deposited metals is studied.The results show that the deposited metal toughness worsens with increasing Al in wire' The mechanism of Al is as follows:(1) Al makes oxygen content in deposited metal increase.(2)Al restrains the formation of Ti-rich oxide inclusion, which causes granular bainite microstructure in deposited metal.(3)The content of solute Ti in deposited metal increases with Al content in welding wire,as a result,a part of carbonrich constitution in deposited metal is in the form of twin martensite.
基金This project is supported by National Natural Science Foundation of China ( Grant No. 51305178) Xuzhou City Science and Technology Plan Projects (Grant No. XC12A013).
文摘In order to reduce sulphur ( S ) and phosphorus ( P ) impurities in deposited metal, a small amount of rare earth (RE) lanthanum ( La) and yttrium (Y) were added into the coating ofE4303 electrode, a low carbon steel electrode. The microstructures of deposited metal were analyzed with metalloscope, and then the content of S and P was examined by energy dispenive X-ray spectrometer ( EDXS ), and by wavelength dispersive X-ray fluorescence (XRF) spectrometer for further examination. The results show that the proper addition of La and Y can be beneficial to the desulfurization and dephosphorization of the deposited metal. Certainly, difference in the addition amount of La and Y could lead to various desulfurization and dephosphorization efficiency, in which the former is more obvious than the latter. With the proper amount of La attd Y, there is finer microstructure in deposited metal, and mechanical properties are improved as well. The S content in deposited metal with added La and Y decreases by 44. 44 wt. % , while the P content 6. 67 wt. %, compared with that in deposited metal without La and II.
基金supported by the Natural Science Foun-dation of Zhejiang Province, China (No. R306011)the National Basic Research Program (973) of China (No.2005CB121104)the National Natural Science Foundation of China (No. 40771090).
文摘The 25 road-deposited sediments were collected from five different land-use zones (industrial, residential, commercial, park, and countryside) in Hangzhou, China. The concentrations of metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in these samples were determined using ICP-AES after digestion with the mixture of HNO3-HF-HC1 (aqua regia), and chemically fractionated according to the modified BCR (the European Community Bureau of Reference) sequential extraction procedure. The high metal concentration levels were detected in the sample from industrial zone and commercial zone having heavy traffic. While the low metal levels were noted in the street dust sample from residential zone, park, and countryside zone. The mobility sequence based on the sum of the BCR sequential extraction stages was: Zn (80.28%), Pb (78.68%), Cd (77.66%) 〉 Cu (73.34%) 〉 Mn (67.92%) 〉 Co (41.66%) 〉 Ni (30.36%) 〉 Cr (21.56%), Fe (20.86%). Correlation analysis and principal component analysis were applied to the data matrix to evaluate the analytical results and to identify the possible pollution sources of metals. Factor analysis showed that these areas were mainly contaminated by three sources, namely lithology, traffic, and industry.
基金supported by the National Natural Science Foundation of China (No. 22005216 and 52172241)the General Research Fund of Hong Kong (No. CityU 11308321)Tianjin Research Innovation Project for Postgraduate Students (No.2022BKY130)
文摘Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-metal batteries.To address these challenges,we report in this study a functional nitro-cellulose interfacial layer(NCIL)on the surface of Zn anodes enlightened by a nitro-coordination chemistry strategy.The NCIL exhibits strong zincophilicity and superior coordination capability with Zn^(2+)due to the highly electronegative and highly nucleophilic nature of the nitro functional group.This characteristic facilitates a rapid Zn-ion desolvation process and homogeneous Zn plating,effectively preventing H_(2) evolution and dendrite formation.Additionally,the negatively charged surface of NCIL acts as a shield,repelling SO_(4)^(2-)anions and inhibiting corrosive reactions on the Zn surface.Remarkably,reversible and stable Zn plating/stripping is achieved for over 5100 h at a current density of 1 mA cm^(-2),which is nearly 30 times longer than that of bare Zn anodes.Furthermore,the Zn/V_(2)O_(5) full cells with the functional interface layer deliver a high-capacity retention of 80.3%for over 10,000 cycles at 5 A g^(-1).This research offers valuable insights for the rational development of advanced protective interface layers in order to achieve ultra-long-lifeZnmetal batteries.
基金supported by the Science Foundation of National Key Laboratory of Science and Technology on Advanced Composites in Special Environmentsthe National Natural Science Foundation of China(12002109)
文摘Piezoelectric ceramic and polymeric separators have been proposed to effectively regulate Li deposition and suppress dendrite growth,but such separators still fail to satisfactorily support durable operation of lithium metal batteries owing to the fragile ceramic layer or low-piezoelectricity polymer as employed.Herein,by combining PVDF-HFP and ferroelectric BaTiO_(3),we develop a homogeneous,single-layer composite separator with strong piezoelectric effects to inhibit dendrite growth while maintaining high mechanical strength.As squeezed by local protrusion,the polarized PVDF-HFP/BaTiO_(3)composite separator generates a local voltage to suppress the local-intensified electric field and further deconcentrate regional lithium-ion flux to retard lithium deposition on the protrusion,hence enabling a smoother and more compact lithium deposition morphology than the unpoled composite separator and the pure PVDF-HFP separator,especially at high rates.Remarkably,the homogeneous incorporation of BaTiO_(3)highly improves the piezoelectric performances of the separator with residual polarization of 0.086 pC cm^(-2)after polarization treatment,four times that of the pure PVDF-HFP separator,and simultaneously increases the transference number of lithium-ion from 0.45 to 0.57.Beneficial from the prominent piezoelectric mechanism,the polarized PVDF-HFP/BaTiO_(3)composite separator enables stable cyclic performances of Li||LiFePO_(4)cells for 400 cycles at 2 C(1 C=170 mA g^(-1))with a capacity retention above 99%,and for 600 cycles at 5 C with a capacity retention over 85%.
文摘This work adopts a multi⁃step etching⁃heat treatment strategy to prepare porous silicon microsphere com⁃posite with Sb⁃Sn surface modification and carbon coating(pSi/Sb⁃Sn@C),using industrial grade SiAl alloy micro⁃spheres as a precursor.pSi/Sb⁃Sn@C had a 3D structure with bimetallic(Sb⁃Sn)modified porous silicon micro⁃spheres(pSi/Sb⁃Sn)as the core and carbon coating as the shell.Carbon shells can improve the electronic conductivi⁃ty and mechanical stability of porous silicon microspheres,which is beneficial for obtaining a stable solid electrolyte interface(SEI)film.The 3D porous core promotes the diffusion of lithium ions,increases the intercalation/delithia⁃tion active sites,and buffers the volume expansion during the intercalation process.The introduction of active met⁃als(Sb⁃Sn)can improve the conductivity of the composite and contribute to a certain amount of lithium storage ca⁃pacity.Due to its unique composition and microstructure,pSi/Sb⁃Sn@C showed a reversible capacity of 1247.4 mAh·g^(-1) after 300 charge/discharge cycles at a current density of 1.0 A·g^(-1),demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.
基金supported by the National Research Foundation of Korea Grant funded by the Korean government(MSIP)(No.2018R1A6A1A03025708).
文摘The undesirable dendrite growth induced by non-planar zinc(Zn)deposition and low Coulombic efficiency resulting from severe side reactions have been long-standing challenges for metallic Zn anodes and substantially impede the practical application of rechargeable aqueous Zn metal batteries(ZMBs).Herein,we present a strategy for achieving a high-rate and long-cycle-life Zn metal anode by patterning Zn foil surfaces and endowing a Zn-Indium(Zn-In)interface in the microchannels.The accumulation of electrons in the microchannel and the zincophilicity of the Zn-In interface promote preferential heteroepitaxial Zn deposition in the microchannel region and enhance the tolerance of the electrode at high current densities.Meanwhile,electron aggregation accelerates the dissolution of non-(002)plane Zn atoms on the array surface,thereby directing the subsequent homoepitaxial Zn deposition on the array surface.Consequently,the planar dendrite-free Zn deposition and long-term cycling stability are achieved(5,050 h at 10.0 mA cm^(−2) and 27,000 cycles at 20.0 mA cm^(−2)).Furthermore,a Zn/I_(2) full cell assembled by pairing with such an anode can maintain good stability for 3,500 cycles at 5.0 C,demonstrating the application potential of the as-prepared ZnIn anode for high-performance aqueous ZMBs.
基金supported by the National Natural Science Foundation of China (52302292, 52302058, 52302085)the China Postdoctoral Science Foundation (2021M702225)+1 种基金the Anhui Province University Natural Science Research Project (2023AH030093, 2023AH040301)the Startup Research Fund of Chaohu University (KYQD-2023005, KYQD-2023051)。
文摘Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition behavior still occurs at the top of 3D frameworks owing to the local accumulation of Li ions.To promote uniform Li deposition without top dendrite growth,herein,a layered multifunctional framework based on oxidation-treated polyacrylonitrile(OPAN) and metal-organic framework(MOF) derivatives was proposed for rationally regulating the distribution of Li ions flux,nucleation sites,and electrical conductivity.Profiting from these merits,the OPAN/carbon nano fiber-MOF(CMOF) composite framework demonstrated a reversible Li plating/stripping behavior for 500 cycles with a stable Coulombic efficiency of around 99.0% at the current density of 2 mA/cm~2.Besides,such a Li composite anode exhibited a superior cycle lifespan of over 1300 h under a low polarized voltage of 18 mV in symmetrical cells.When the Li composite anode was paired with LiFePO_(4)(LFP) cathode,the obtained full cell exhibited a stable cycling over 500 cycles.Moreover,the COMSOL Multiphysics simulation was conducted to reveal the effects on homogeneous Li ions distribution derived from the above-mentioned OPAN/CMOF framework and electrical insulation/conduction design.These electrochemical and simulated results shed light on the difficulties of designing stable and safe Li metal anode via optimizing the 3D frameworks.
基金Acknowledgements The authors acknowledge gratefully to the financial support for this work from National Natural Science Foundation of China and Baosteel (No. 50734004) and the assistance of Welding Laboratory of Baosteel Group.
文摘The microstructure of E911 deposited metal was observed and the effect of heat input and postweld heat treatment on microstructure and impact toughness was investigated. The microstructure consists of tempered martensite and residual δ- ferrite. The morphology of tempered martensite is columnar and the residual δ-ferrite is polygonal. With the increase in heat input, the width of columnar martensite grain and the size of residual δ-ferrite increased, whereas the volume fraction of residual δ-ferrite varied slightly. The impact toughness decreased as heat input increased. The result reveals that coarsening columnar martensite grain and δ-ferrite have greater effect on impact toughness than volume fraction of residual δ-ferrite. As the time of postweld heat treatment is exceeded 8h, aggregation of M23 C6occurs in some grain boundaries or lath interfaces. The partial aggregation of M23 C6 results in the decrease in impact toughness.
基金the Third World Academy of Science (TWAS, Grant #93-058 R6/PHYS/AF/AC)Obafemi Awolowo University(University Research Committee URC) for supporting this project
文摘The single solid source precursor, cobalt (Ⅱ) acetylacetonate was prepared and characterized by infrared spectroscopy. Thin films of cobalt oxide were deposited on soda lime glass substrates through the pyrolysis (metal organic chemical vapour deposition (MOCVD)) of single solid source precursor, cobalt acetylacetonate, Co[C5H7O2]2 at a temperature of 420℃. The compositional characterization carried out by rutherford backscattering spectroscopy and X-ray diffraction (XRD), showed that the films have a stoichiometry of Co2O3 and an average thickness of 227±0.2 nm. A direct energy gap of 2,15±0.01 eV was calculated by the data obtained by optical absorption spectroscopy. The morphology of the films obtained by scanning electron microscopy, showed that the grains were continuous and uniformly distributed at various magnifications, while the average grain size was less than i micron for the deposited thin films of cobalt oxide.
文摘The microstractures of 9Cr-lMo multipass deposited metal were observed. The effect of microstructure on impact toughness of 9Cr-lMo multipass deposited metal with varying heat inputs was investigated. Result shows that fine-grained microstructure occurs in reheated zones. The absorbed energy increases with the increase of volume fraction of fine-grained microstructure , suggesting that the volume fraction of fine-grained microstracture influences directly on impact toughness. The increasing ratio of fine-grained zone thickness to weld layer thickness is responsible for improving impact toughness after PWHT.
基金supported by the Council of Scientific and Industrial Research(CSIR),National Laser Centre,Rental Pool Programme,Pretoria,South Africa and also for the award of the Africa Laser Centre bursary to the main author
文摘The laser metal deposition (LMD) was conducted on copper by varying the processing parameters in order to achieve the best possible settings. Two sets of experiments were conducted. The deposited composites were characterized through the evolving microstructure, microhardness profiling and mechanical properties. It was found that the evolving microstructures of the deposited composites were characterized with primary, secondary and tertiary arms dendrites, acicular microstructure as well as the alpha and beta eutectic structures. From the two sets of experiments performed, it was found that Sample E produced at a laser power of 1200 W and a scanning speed of 1.2 m/min has the highest hardness of HV (190±42) but exhibits some lateral cracks due to its brittle nature, while Sample B produced at laser power of 1200 W and a scanning speed of 0.3 m/min shows no crack and a good microstructure with an increase in dendrites. The strain hardening coefficient of the deposited copper composite obtained in this experiment is 3.35.
基金financial supports from the National Key R&D Program of China (No.2017YFE0123500)。
文摘The effect of electropulsing treatment on microstructure and mechanical strength of laser metal deposited Ti−6Al−4V alloy was investigated in order to eliminate the anisotropy in strength of laser metal deposited Ti−6Al−4V alloy by tensile tests,optical microscopy,scanning electron microscopy,electron back-scattered diffraction analyses and transmission electron microscopy.With increasing applied voltages from 0 to 130 V,the evolution of microstructure within columnarβgrains followed the sequence ofα′martensite→colonyαstructure→basket-weaveαstructure.The electropulsing treated at 130 V weakened the texture of martensite withinβgrains.The as-built Ti−6Al−4V alloy showed an anisotropy in yield strength(6.2%).After processing at 130 V,the anisotropy in yield strength was reduced to 0.6%,which was attributed to the almost equivalent distribution of Schmid factor in the samples deformed along different orientations.
文摘By means of metallographic microscope(OM),scanning electron microscope(SEM),back scattering electron diffraction(EBSD)and transmission electron microscope(TEM),the effect of Cu on microstructure transformation and mechanical properties of deposited metal of 590MPa class steel welding wire was studied.The results show that the microstructure of deposited metal is composed of acicular ferrite,lamellar bainite,granular bainite and residual austenite.With the increase of Cu content,the phase transition temperature of the deposited metal decreases,making the phase transition region of ferrite and pearlite shift to the right,expanding the phase transition region of bainite and shrinking the phase transition region of ferrite and pearlite.The microstructure of deposited metal changed,the content of M-A elements increased but the size decreased,and the ferrite-bainite biphasic microstructure was matched.The reduction of M-A component content in strips and blocks and the reduction of effective grain size will reduce the nucleation probability of microcracks,increase crack growth resistance,and improve the impact toughness of the deposited metal.
文摘Chromium (Cr) doped Zinc oxide ZnO thin films were deposited onto glass substrates by Metal Organic Chemical Vapour Deposition (MOCVD) technique with varying dopant concentration at a temperature of 420°C. The effect of the chromium concentration on morphological, structural, optical, electrical and gas sensing properties of the films were investigated. The scanning electron microscopy results revealed that the Cr concentration has great influence on the crystallinity, surface smoothness and grain size. X-ray diffraction (XRD) studies shows that films were polycrystalline in nature and grown as a hexagonal wurtzite structure. A direct optical band energy gap of 3.32 to 3.10 eV was obtained from the optical measurements. The transmission was found to decrease with increasing Cr doping concentration. Rutherford Backscattering Spectroscopy (RBS) analysis also demonstrates that Cr ions are substitutionally incorporated into ZnO. I-V characteristic of the film shows a resistivity ranges from 1.134 × 10-2 · cm to 1.24 × 10-2 · cm at room temperature. The gas sensing response of the films were enhanced with incorporation of Cr as a dopant with optimum operating temperature around 200°C.
基金Supported by Foundation for Scientific and Technological Development of Guangxi Academy of Agricultural Sciences(2017JM06)Special Funds for Basic Scientific Research of Guangxi Academy of Agricultural Sciences(2015YT32)+1 种基金Key Planning Project for Research and Development of Guangxi,China(AB16380084)National Major Research Development Program of China(2016YFD0800700)~~
文摘Firstly, the concept, sources and damage of atmospheric deposition were introduced, and then the relation between atmospheric deposition and accumulation of heavy metals in rice in Guangxi was analyzed to provide reference for the implementation of effective risk early warning of pollution from heavy metal deposition and safe production of rice in mining areas of Guangxi.