LiNi0.8Co0.1Mn0.1O2(NCM811)|SiOx-graphite(SiO-Gr.)battery chemistry is of intensive attention because its achievable practical energy density is approaching impressively 300 Wh Kg^(-1).However,it still suffers rapid c...LiNi0.8Co0.1Mn0.1O2(NCM811)|SiOx-graphite(SiO-Gr.)battery chemistry is of intensive attention because its achievable practical energy density is approaching impressively 300 Wh Kg^(-1).However,it still suffers rapid capacity fades during repeated cycles,both chemical,electrochemical and mechanical irreversibility contribute.A comprehensive understanding behind the fading behavior of the cell chemistry is required before fully realize the benefits of this chemistry.Herein,the in-situ thickness variation is introduced as a diagnostic technique and is performed on 5-55 Ah NCM811|SiO-Gr cells.With the help of Li reference electrode and in-situ X-ray diffraction device,the correspondence between thickness variation and the electrode potential is carefully investigated.Firstly,the NCM811|SiO-Gr cell is characterized with the maximum cell thickness at around 80%state-of-charge(SOC)in the discharge process,rather than at 100%SOC.Secondly,the electrochemical behaviors during rate charge/discharge are diagnosed,and a Li platting signal is resolved from thickness variation profile at 2C.This work confirms that the thickness monitoring is a nondestructive and informative complement to conventional diagnostic techniques for failure analysis of pouch cells.展开更多
In this work,the discharge properties and electrochemical behaviors of as-cast AZ80-La-Gd anode for Mg-air battery have been investigated and compared with the AZ80 anode.The microstructure evolution,electrochemical b...In this work,the discharge properties and electrochemical behaviors of as-cast AZ80-La-Gd anode for Mg-air battery have been investigated and compared with the AZ80 anode.The microstructure evolution,electrochemical behaviors and surface morphologies after discharge have been discussed to connect the discharge properties.The results indicate that the modified AZ80-La-Gd is an outstanding candidate for anode for Mg-air batter,which has high cell voltage,stable discharge curves,good specific capacity and energy,and good anodic efficiency.It exhibits the best anodic efficiency,specific capacity and energy of 76.45%,1703.6 mAh·g^(-1)and 2186.3 mWh·g^(-1),respectively,which are20.24%,18.92%and 25.71%higher than values for AZ80 anode.Such excellent discharge performance is attributed to the Al-RE particles.They refine the Mg_(17)Al_(12)phase and therefore improve the self-corrosion resistance and desorption ability of AZ80 anode.展开更多
Cyclic voltammetry, chronoamperometry and chronopotentiometry were used toinvestigate the electrochemical behaviors of Bi(III) in Bi(NO_3)_3-LiClO_4-DMSO (dimethylsulfoxide)system on Pt and Cu electrodes. Experimental...Cyclic voltammetry, chronoamperometry and chronopotentiometry were used toinvestigate the electrochemical behaviors of Bi(III) in Bi(NO_3)_3-LiClO_4-DMSO (dimethylsulfoxide)system on Pt and Cu electrodes. Experimental results indicated that the electroreducation of Bi(III)to Bi(0) was irreversible on Pt and Cu electrodes. The diffusion coefficient and electron transfercoefficient of Bi(III) in 0.01 mol.L^(-1) Bi(NO_3)_3-0.l mol.L^(-1) LiClO_4-DMSO system at 303 Kwere 1.75 X 10^(-6) cm^2.s^1 and 0.147 respectively.展开更多
The effects of chromium on the corrosion and the electrochemical behaviors of ultra high strength steels were studied by the salt spray test and electrochemical methods. The results show that ultra high strength steel...The effects of chromium on the corrosion and the electrochemical behaviors of ultra high strength steels were studied by the salt spray test and electrochemical methods. The results show that ultra high strength steels remain martensite structures and have anodic dissolution characteristic with an increase of chromium content. There is no typical passive region on the polarization curves of an ultra high strength stainless steel, AerMet 100 steel, and 300M steel. However, chromium improves the corrosion resistance of the stainless steel remarkably. It has the slowest corrosion rate in the salt spray test, one order of magnitude less than that of AerMet 100 and 300M steels. With the increase of chromium content, the polarization resistance becomes larger, the corrosion potential shifts towards the positive direction with a value of 545 mV, and the corrosion current density decreases in electrochemical measures in 3.5wt% NaCl solutions. Because of the higher content of chromium, the ultra high strength stainless steel has a better corrosion resistance than AerMet 100 and 300M steels.展开更多
Electrochemical behaviors of Zn-Fe alloy and Zn-Fe-TiO2 composite electrodeposition in alkaline zincatesolutions were studied respectively by the methods of linear potential sweep and cyclic voltammetry. From the re-s...Electrochemical behaviors of Zn-Fe alloy and Zn-Fe-TiO2 composite electrodeposition in alkaline zincatesolutions were studied respectively by the methods of linear potential sweep and cyclic voltammetry. From the re-sults it can be concluded that Zn shows under potential deposition, Zn-Fe alloy codeposition is anomalous codeposi-tion and Zn-Fe alloy cathode polarization is increased with the introduction of additive. From the view point of elec-trochemistry, the reasons that the content of Fe in the Zn-Fe coating changes with the composition of the electrolyteand the process conditions altering and the relationship between the content of Fe and the appearance of the coatingare interpreted. The cathode polarization of Zn-Fe alloy codeposition is enhanced obviously with addition of additive.In the course of composite electrodeposition, TiO2 has less promotion to electrodeposition of zinc ions than to iron i-ons, while the electrodeposition of iron ions improves the content of TiO2 in composite coating, which is inagreement with the results of process experiments.展开更多
The characteristics of N-propyl-N′-ethoxycarbonyl thiourea(PECTU) were studied in the flotation experiments of chalcopyrite and pyrite compared with butyl xanthate(BX). The interaction mechanism between mineral a...The characteristics of N-propyl-N′-ethoxycarbonyl thiourea(PECTU) were studied in the flotation experiments of chalcopyrite and pyrite compared with butyl xanthate(BX). The interaction mechanism between mineral and PECTU was investigated according to zeta potential and electrochemistry measurements in the presence of PECTU. The results proved that PECTU performed a stronger ability to capture chalcopyrite and a better selectivity against pyrite. The zeta potential of chalcopyrite was positively shifted after interacting with PECTU, which indicated that the collector PECTU was obviously adsorbed on chalcopyrite surface. The cyclic voltammetry and Tafel curves results indicated that the oxidation and corrosion rates of chalcopyrite surface were limited in the presence of PECTU, while the effect of PECTU on pyrite in weak alkaline solution can be neglected basically according to the results of zeta potential and electrochemical tests.展开更多
The effects of yttrium(Y)and yttrium+calcium(Y+Ca)additions on the electrochemical properties and discharge performance of the as-extruded Mg−8Al−0.5Zn−0.2Mn(AZ80)anodes for Mg−air batteries were investigated.The resu...The effects of yttrium(Y)and yttrium+calcium(Y+Ca)additions on the electrochemical properties and discharge performance of the as-extruded Mg−8Al−0.5Zn−0.2Mn(AZ80)anodes for Mg−air batteries were investigated.The results show that the addition of 0.2 wt.%Y increased the corrosion resistance and discharge activity of AZ80 anode.This was attributed to the fine and sphericalβ-Mg_17)Al_(12) phases dispersing evenly in AZ80+0.2Y alloy,which suppressed the localized corrosion and severe“chunk effect”,and facilitated the rapid activation ofα-Mg.Combinative addition of 0.2 wt.%Y and 0.15 wt.%Ca generated grain refinement and a reduction of theβ-Mg_17)Al_(12) phase,resulting in a further enhancement in discharge voltage.However,the incorporation of Ca in Mg_17)Al_(12) and Al_(2)Y compounds compromised the corrosion resistance and anodic efficiency of AZ80+0.2Y+0.15Ca anode.Consequently,AZ80+0.2Y anode exhibited excellent overall discharge performance,with the peak discharge capacity and anodic efficiency of 1525 mA·h·g^(−1) and 67%at 80 mA/cm^(2),13%and 14%higher than those of AZ80 anode,respectively.展开更多
Mg-Zn binary alloys fabricated by the gas-phase alloying technique under vacuum condition were investigated in the state of initial state and after heat treatment for the microstructure and electrochemical behaviors.D...Mg-Zn binary alloys fabricated by the gas-phase alloying technique under vacuum condition were investigated in the state of initial state and after heat treatment for the microstructure and electrochemical behaviors.Different from the traditional Mg-Zn alloys preparation methods,alloys prepared by gas-phase alloying have a large number of intermetallic compounds,such as MgZn,Mg7Zn3 and MgZn2.After solution treatment,the boundary of the eutectic disappeared and the size ofα-Mg increased from 100μm to 150μm.At the same time,the value of the resistance of charge transfer increased,which indicates that the resistance of the charge transfer and the corrosion resistance of the alloys increased.After artificial aging treatment,the distribution ofα-Mg was more uniform and its size was reduced to about 50μm,and there was new eutectic structure formed.The newly formed eutectic structure forms galvanic cells with the alloy matrix,which makes the corrosion resistance of the alloy weaken.展开更多
X-ray photoelectron spectroscopy(XPS)and Raman spectroscopy were used to analyze the complexes in LiCl−KCl eutectic salt containing VCl_(3) and KF.The additional fluoride ions would replace chloride ions and combine w...X-ray photoelectron spectroscopy(XPS)and Raman spectroscopy were used to analyze the complexes in LiCl−KCl eutectic salt containing VCl_(3) and KF.The additional fluoride ions would replace chloride ions and combine with V(Ⅲ)to form VF_(6)^(3-).The electrochemical behavior of V(Ⅲ)was evaluated under condition of the molar concentration ratio of F−to Vn+(α)equal to 0:1,1:1,2:1,5:1,20:1 and 50:1,respectively.The results showed that a new reduction step appeared:VF_(6)^(3-)→V^(2+),and the reduction mechanism of vanadium ions became more complicated.The metallic vanadium was deposited on the tungsten electrode at−2.90 V in the LiCl−KCl melts for 6 h,and the products were characterized by SEM−EDS.It was indicated that the particle size of the product decreased with adding fluoride ions for the forming of the coordination compound VF_(6)^(3-).展开更多
The electrochemical behaviors of n-type silicon wafers pH value and solid content of the slurry on the corrosion of silicon in silica-based slurry were investigated, and the influences of the wafers were studied by us...The electrochemical behaviors of n-type silicon wafers pH value and solid content of the slurry on the corrosion of silicon in silica-based slurry were investigated, and the influences of the wafers were studied by using electrochemical DC polarization and AC impedance techniques. The results revealed that these factors affected the corrosion behaviors of silicon wafers to different degrees and had their suitable parameters that made the maximum corrosion rate of the wafers. The corrosion potential of (100) sttrface was lower than that of(111), whereas the current density of (100) was much higher than that of(111).展开更多
A new kind of comblike copolymer film composed of acrylic acid-polyethylene glycol monomethyl ether acrylate copolymer(AA-PEGMA copolymer) was successfully synthesized to immobilize hemoglobin(Hb). FTIR, UV-Vis an...A new kind of comblike copolymer film composed of acrylic acid-polyethylene glycol monomethyl ether acrylate copolymer(AA-PEGMA copolymer) was successfully synthesized to immobilize hemoglobin(Hb). FTIR, UV-Vis and CD spectra suggest that Hb kept its original structure in the AA-PEGMA copolymer film without denaturation. A pair of well-defined, quasi-reversible cyclic voltammetric peaks at around –270 mV vs. saturated calomel electrode(SCE) for the Hb Fe(III)/Fe(II) redox couple was observed on the film-modified electrode in phos phate buffer solution(PBS, pH=7.0). The formal potential of Hb/AA-PEGMA copolymer film-modified electrode is linearly dependent on solution pH with a slope of –46.3 mV/pH, illustrating that one-proton transfer was accompa nied with each electron transfer. Furthermore, the modified electrode displayed electrocatalytic response to the reduc tion of H2O2 with a linear range of 3.5―126 μmol/L and a detection limit of 1.17 μmol/L. In conclusion, the AA-PEGMA copolymer film was proved to be an excellent matrix for the immobilization and electrochemistry of proteins.展开更多
The high-temperature requirement for liquid iron smelting via molten oxide electrolysis presents significant challenges.This study investigates the electrochemical reduction of Fe(Ⅲ)in a novel low-temperature electro...The high-temperature requirement for liquid iron smelting via molten oxide electrolysis presents significant challenges.This study investigates the electrochemical reduction of Fe(Ⅲ)in a novel low-temperature electrolyte,Na_(2)SiO_(3)-SiO_(2)-Fe_(2)O_(3),utilizing cyclic voltammetry and square wave voltammetry techniques.The results show that Fe(Ⅲ)reduction occurs in two steps:Fe(Ⅲ)+e^(−)→Fe(Ⅱ),Fe(Ⅱ)+2e^(−)→Fe,and that the redox process of Fe(Ⅲ)/Fe(Ⅱ)at the tungsten electrode is an irreversible reaction controlled by diffusion.The diffusion coefficients of Fe(Ⅲ)in the molten Na_(2)SiO_(3)-SiO_(2)-Fe_(2)O_(3)in the temperature range of 1248–1278 K are between 1.86×10^(−6)cm^(2)/s and 1.58×10^(−4)cm^(2)/s.The diffusion activation energy of Fe(Ⅲ)in the molten salt is 1825.41 kJ/mol.As confirmed by XRD analysis,potentiostatic electrolysis at−0.857 V(vs.O_(2)/O_(complex)^(2-))for 6 h produces metallic iron on the cathode.展开更多
Biphasic layered oxide cathodes,known for their superior electrochemical performance,are prime candidates for commercializing in Na-ion batteries.Herein,we unveil a series of P3/P2 monophasic and biphasic Al-substitut...Biphasic layered oxide cathodes,known for their superior electrochemical performance,are prime candidates for commercializing in Na-ion batteries.Herein,we unveil a series of P3/P2 monophasic and biphasic Al-substituted Na_(3/4)Mn_(5-x/8)Al_(2x/8)Ni_(3-x/8)O_(2)layered oxide cathodes that lie along the‘zero Mn^(3+)line’in the Na_(3/4)(Mn-Al-Ni)O_(2)pseudo-ternary system.The structural analysis showed a larger Na^(+)conduction bottleneck area in both P3 and P2 structures with a higher Al3+content,which enhanced their rate performance.In each composition,the P3/P2 biphasic compound with nearly equal fractions of P3 and P2 phases outperformed their monophasic counterparts in almost all electrochemical performance parameters.Operando synchrotron XRD measurements obtained for the monophasic P3 and biphasic P2/P3 samples revealed the absence of the O3 phase during cycling.The high structure stability and faster Na^(+)transport kinetics in the biphasic samples underpins the enhancement of electrochemical properties in the Al-substituted P3/P2 cathodes.These results highlight fixed oxidation state lines as a novel tool to identify and design layered oxide cathodes for Na-ion batteries in pseudo-ternary diagrams involving Jahn-Teller active cations.展开更多
The electrochemical behaviors and corrosion resistance of the wrought Mg–Y–Zn based alloys with high Y/Zn mole ratio have been investigated in details.The results show that the corrosion resistance of the investigat...The electrochemical behaviors and corrosion resistance of the wrought Mg–Y–Zn based alloys with high Y/Zn mole ratio have been investigated in details.The results show that the corrosion resistance of the investigated Mg–Y–Zn based alloys are dependent on the modified arrangement of LPSO phase by adjusting Y/Zn mole ratios.Increasing the Y/Zn mole ratio not only greatly decreases the size of LPSO phase plates,but also leads to the precipitation of Mg_(24)Y_(5) phase.The corrosion rate of Mg–Y–Zn based alloys greatly increases from 7.4 mg·cm^(−2)·day^(−1) to 11.3 mg·cm^(−2)·day^(−1) with increasing the Y/Zn mole ratio up to 3.It should be attributed to the decreasing size of LPSO phase plates as cathodes,further increasing the hydrogen evolution kinetics.The related corrosion mechanism is discussed in details.展开更多
A composite conversion coating was prepared on magnesium alloy by the only one-step immersion treatment. The characteristics of the conversion coating were investigated by scanning electron microscopy (SEM) and X-ra...A composite conversion coating was prepared on magnesium alloy by the only one-step immersion treatment. The characteristics of the conversion coating were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the composite conversion coating consists of magnesium hydroxide, magnesium phosphate and man- ganese phosphate. The electrochemical behavior of the conversion coating was investigated systematically by electrochemical impedance spectroscopy (EIS) and poten- tiodynamic polarization measurement in different NaC1 solutions. Polarization measurements and EIS results reveal that the magnesium alloy with the conversion coating have better corrosion resistance compared to the bare magnesium alloy in these conditions. And the corro- sion rate of the magnesium alloy with conversion coating increases consistently with the chloride ion concentration. In alkaline conditions, the magnesium alloy with conver- sion coating has superior corrosion resistance by the syn- ergistic effects between Mg(OH)2 film and conversion coating. Moreover, the electrochemical corrosion mechanism of the magnesium alloy was analyzed with respect to the conversion coating in a Cl^- containing environment.展开更多
To address the issues of large volume change and low conductivity of silicon(Si)materials,carbon coatings have been widely employed as surface protection agent and conductive medium to encapsulate the Si materials,whi...To address the issues of large volume change and low conductivity of silicon(Si)materials,carbon coatings have been widely employed as surface protection agent and conductive medium to encapsulate the Si materials,which can improve the electrochemical performance of Si-based electrodes.There has been a strong demand to gain a deeper understanding of the impact of efficient carbon coating over the lithiation and delithiation process of Si materials.Here,we report the first observation of the extended two-phase transformation of carbon-coated Si nanoparticles(Si/C)during electrochemical processes.The Si/C nanoparticles were prepared by sintering Si nanoparticles with polyvinylidene chloride precursor.The Si/C electrode underwent a two-phase transition during the first 20 cycles at 0.2 C,but started to engage in solid solution reaction when the ordered compact carbon coating began to crack.Under higher current density conditions,the electrode was also found to be involved in solid solution reaction,which,however,was due to the overwhelming demand of kinetic property rather than the breaking of the carbon coating.In comparison,the Si/C composites prepared with sucrose possessed more disordered and porous carbon structures,and presented solid solution reaction throughout the entire cycling process.展开更多
Porous Al-Mg alloys with different nominal compositions were successfully fabricated via elemental powder reactive synthesis, and the phase composition, pore structure, and corrosion resistance were characterized with...Porous Al-Mg alloys with different nominal compositions were successfully fabricated via elemental powder reactive synthesis, and the phase composition, pore structure, and corrosion resistance were characterized with X-ray diffractometer, scanning electron microscope and electrochemical analyzer. The volume expansion ratio, open porosity and corrosion resistance in 3.5%(mass fraction) Na Cl aqueous solution of the alloys increase at first and then decrease with the increase of Mg content. The maxima of volume expansion ratio and open porosity are 18.3% and 28.1% for the porous Al-56%Mg(mass fraction) alloy, while there is the best corrosion resistance for the porous Al-37.5% Mg(mass fraction) alloy. The pore formation mechanism can be explained by Kirkendall effect, and the corrosion resistance can be mainly affected by the phase composition for the porous Al-Mg alloys. They would be of the potential application for filtration in the chloride environment.展开更多
Heterocyclic compounds are the promising biological compounds as nature-friendly for the corrosion protection of metallic surface.In this work,three heterocyclic compounds such as 1-azanaphthalene-8-ol(8-AN),2-methylq...Heterocyclic compounds are the promising biological compounds as nature-friendly for the corrosion protection of metallic surface.In this work,three heterocyclic compounds such as 1-azanaphthalene-8-ol(8-AN),2-methylquinoline-8-ol(8-MQ),and 8-quinolinol-5-sulfonic acid(8-QSA)were used as green compounds,and their anti-corrosion performance for AZ31 Mg in saline water was discussed on the basis of impedance interpretation and surface analysis.Findings found that the electrochemical performance was improved in the order of 8-AN>8-MQ>8-QSA,demonstrating the electron donor effect of N-heterocycles to form coordination complexes on the magnesium surface.From the electrochemical performance,the protective layer constructed at the optimal concentration reinforces the barrier against aggressive environments,with potential inhibition efficiency of 87.4%,99.0%,and 99.9%for 8-QSA,8-MQ,and 8-AN,respectively.Quantum chemical parameters and electron density distribution for free organic species in the absence and presence of Mg^(2+)cation were evaluated using density functional theory(DFT).Upon the formation of coordination complexes between organic compound and Mg^(2+),energy gap underwent change about ΔE=5.7 eV in the 8-AN/Mg^(2+)system.Furthermore,the adsorption of heterocyclic compounds on Mg surface reveals the formation of strong covalent bonds with Mg atoms,which further confirmed by the electron density difference and projected density of states analyses.Based on theoretical calculations,three inhibitors can adsorb on the metal surface in both parallel and perpendicular orientations via C,O and N atoms.In the parallel configuration,the C-Mg,N-Mg and O-Mg bond distances are between 2.11 and 2.25˚A,whereas the distances in the case of perpendicular adsorption are between 2.20 and 2.40˚A(covalent bonds via O and N atoms).The results indicated that parallel configurations are energetically more stable,in which the adsorption energies are-4.48 eV(8-AN),-4.28 eV(8-MQ)and-3.82 eV(8-QSA)compared to that of perpendicular adsorption(-3.65,-3.40,and-2.63 eV).As a result,experimental and theoretical studies were in well agreement and confirm that the nitrogen and oxygen atoms will be the main adsorption sites.展开更多
Selenium(Se),as an important quasi-metal element,has attracted much attention in the fields of thin-film solar cells,electrocatalysts and energy storage applications,due to its unique physical and chemical properties....Selenium(Se),as an important quasi-metal element,has attracted much attention in the fields of thin-film solar cells,electrocatalysts and energy storage applications,due to its unique physical and chemical properties.However,the electrochemical behavior of Se in different systems from electrolytic cell to battery are complex and not fully understood.In this article,we focus on the electrochemical processes of Se in aqueous solutions,molten salts and ionic liquid electrolytes,as well as the application of Se-containing materials in energy storage.Initially,the electrochemical behaviors of Se-containing species in different systems are comprehensively summarized to understand the complexity of the kinetic processes and guide the Se electrodeposition.Then,the relationship between the deposition conditions and resulting structure and morphology of electrodeposited Se is discussed,so as to regulate the morphology and composition of the products.Finally,the advanced energy storage applications of Se in thin-film solar cells and secondary batteries are reviewed,and the electrochemical reaction processes of Se are systematically comprehended in monovalent and multivalent metal-ion batteries.Based on understanding the fundamental electrochemistry mechanism,the future development directions of Se-containing materials are considered in view of the in-depth review of reaction kinetics and energy storage applications.展开更多
The influence of micro-Ca/In alloying on the microstructural charac teristics,electrochemical behaviors and discharge properties of extruded dilute Mg-0.5Bi-0.5Sn-based(wt.%)alloys as anodes for Mg-air batteries are e...The influence of micro-Ca/In alloying on the microstructural charac teristics,electrochemical behaviors and discharge properties of extruded dilute Mg-0.5Bi-0.5Sn-based(wt.%)alloys as anodes for Mg-air batteries are evaluated.The grain size and texture intensity of the Mg-Bi-Sn-based alloys are significantly decreased after the Ca/In alloying,particularly for the In-containing alloy.Note that,in addition to nanoscale Mg_(3)Bi_(2)phase,a new microscale Mg_(2)Bi_(2)Ca phase forms in the Ca-containing alloy.The electrochemical test results demonstrate that Ca/In micro-alloying can enhance the electrochemical activity.Using In to alloy the Mg-Bi-Sn-based alloy is effective in restricting the cathodic hydrogen evolution(CHE)kinetics,leading to a low self-corrosion rate,while severe CHE occurred after Ca alloying.The micro-alloying of Ca/In to Mg-Bi-Sn-based alloy strongly deteriorates the compactness of discharge products film and mitigates the"chunk effect"(CE),hence the cell voltage,anodic efficiency as well as discharge capacity are greatly improved.The In-containing alloy exhibits outstanding discharge performance under the combined effect of the modified microstructure and discharge products,thus making it a potential anode material for primary Mg-air battery.展开更多
基金funded by the Ministry of Science and Technology of China(No.2019YFE0100200,2019YFA0705703)the National Natural Science Foundation of China(No.22075064,No.21875057,U1564205 and 51706117)+1 种基金the Key-Area Research and Development Program of Guangdong Province(No.2020B090919005)the Tsinghua University Initiative Scientific Research Program(No.2019Z02UTY06).
文摘LiNi0.8Co0.1Mn0.1O2(NCM811)|SiOx-graphite(SiO-Gr.)battery chemistry is of intensive attention because its achievable practical energy density is approaching impressively 300 Wh Kg^(-1).However,it still suffers rapid capacity fades during repeated cycles,both chemical,electrochemical and mechanical irreversibility contribute.A comprehensive understanding behind the fading behavior of the cell chemistry is required before fully realize the benefits of this chemistry.Herein,the in-situ thickness variation is introduced as a diagnostic technique and is performed on 5-55 Ah NCM811|SiO-Gr cells.With the help of Li reference electrode and in-situ X-ray diffraction device,the correspondence between thickness variation and the electrode potential is carefully investigated.Firstly,the NCM811|SiO-Gr cell is characterized with the maximum cell thickness at around 80%state-of-charge(SOC)in the discharge process,rather than at 100%SOC.Secondly,the electrochemical behaviors during rate charge/discharge are diagnosed,and a Li platting signal is resolved from thickness variation profile at 2C.This work confirms that the thickness monitoring is a nondestructive and informative complement to conventional diagnostic techniques for failure analysis of pouch cells.
基金financially supported by the National Natural Science Foundation of China(Grant No.51974082)the Programme of Introducing Talents of Discipline Innovation to Universities 2.0(the 111 Project of China 2.0,No.BP0719037)
文摘In this work,the discharge properties and electrochemical behaviors of as-cast AZ80-La-Gd anode for Mg-air battery have been investigated and compared with the AZ80 anode.The microstructure evolution,electrochemical behaviors and surface morphologies after discharge have been discussed to connect the discharge properties.The results indicate that the modified AZ80-La-Gd is an outstanding candidate for anode for Mg-air batter,which has high cell voltage,stable discharge curves,good specific capacity and energy,and good anodic efficiency.It exhibits the best anodic efficiency,specific capacity and energy of 76.45%,1703.6 mAh·g^(-1)and 2186.3 mWh·g^(-1),respectively,which are20.24%,18.92%and 25.71%higher than values for AZ80 anode.Such excellent discharge performance is attributed to the Al-RE particles.They refine the Mg_(17)Al_(12)phase and therefore improve the self-corrosion resistance and desorption ability of AZ80 anode.
基金This project is financially supported by the Thousand-Hundred-Ten-talent Project Foundation of Guangdong Province Education Office (No. 00-079-421005)
文摘Cyclic voltammetry, chronoamperometry and chronopotentiometry were used toinvestigate the electrochemical behaviors of Bi(III) in Bi(NO_3)_3-LiClO_4-DMSO (dimethylsulfoxide)system on Pt and Cu electrodes. Experimental results indicated that the electroreducation of Bi(III)to Bi(0) was irreversible on Pt and Cu electrodes. The diffusion coefficient and electron transfercoefficient of Bi(III) in 0.01 mol.L^(-1) Bi(NO_3)_3-0.l mol.L^(-1) LiClO_4-DMSO system at 303 Kwere 1.75 X 10^(-6) cm^2.s^1 and 0.147 respectively.
基金supported by the National Science and Technology Infrastructure Platforms Construction Projects of China (Grant No2005DKA10400)the National Science Foundation of China (No50871021)
文摘The effects of chromium on the corrosion and the electrochemical behaviors of ultra high strength steels were studied by the salt spray test and electrochemical methods. The results show that ultra high strength steels remain martensite structures and have anodic dissolution characteristic with an increase of chromium content. There is no typical passive region on the polarization curves of an ultra high strength stainless steel, AerMet 100 steel, and 300M steel. However, chromium improves the corrosion resistance of the stainless steel remarkably. It has the slowest corrosion rate in the salt spray test, one order of magnitude less than that of AerMet 100 and 300M steels. With the increase of chromium content, the polarization resistance becomes larger, the corrosion potential shifts towards the positive direction with a value of 545 mV, and the corrosion current density decreases in electrochemical measures in 3.5wt% NaCl solutions. Because of the higher content of chromium, the ultra high strength stainless steel has a better corrosion resistance than AerMet 100 and 300M steels.
文摘Electrochemical behaviors of Zn-Fe alloy and Zn-Fe-TiO2 composite electrodeposition in alkaline zincatesolutions were studied respectively by the methods of linear potential sweep and cyclic voltammetry. From the re-sults it can be concluded that Zn shows under potential deposition, Zn-Fe alloy codeposition is anomalous codeposi-tion and Zn-Fe alloy cathode polarization is increased with the introduction of additive. From the view point of elec-trochemistry, the reasons that the content of Fe in the Zn-Fe coating changes with the composition of the electrolyteand the process conditions altering and the relationship between the content of Fe and the appearance of the coatingare interpreted. The cathode polarization of Zn-Fe alloy codeposition is enhanced obviously with addition of additive.In the course of composite electrodeposition, TiO2 has less promotion to electrodeposition of zinc ions than to iron i-ons, while the electrodeposition of iron ions improves the content of TiO2 in composite coating, which is inagreement with the results of process experiments.
基金Project(51374249)supported by the National Natural Science Foundation of China
文摘The characteristics of N-propyl-N′-ethoxycarbonyl thiourea(PECTU) were studied in the flotation experiments of chalcopyrite and pyrite compared with butyl xanthate(BX). The interaction mechanism between mineral and PECTU was investigated according to zeta potential and electrochemistry measurements in the presence of PECTU. The results proved that PECTU performed a stronger ability to capture chalcopyrite and a better selectivity against pyrite. The zeta potential of chalcopyrite was positively shifted after interacting with PECTU, which indicated that the collector PECTU was obviously adsorbed on chalcopyrite surface. The cyclic voltammetry and Tafel curves results indicated that the oxidation and corrosion rates of chalcopyrite surface were limited in the presence of PECTU, while the effect of PECTU on pyrite in weak alkaline solution can be neglected basically according to the results of zeta potential and electrochemical tests.
基金financial supports from the Key Development Project of Sichuan Province,China (No.2017GZ0399)the National Natural Science Foundation of China (No.52061040)the Open Projects of the Key Laboratory of Advanced Technologies of Materials,Ministry of Education,Southwest Jiaotong University,China (No.KLATM202003)。
文摘The effects of yttrium(Y)and yttrium+calcium(Y+Ca)additions on the electrochemical properties and discharge performance of the as-extruded Mg−8Al−0.5Zn−0.2Mn(AZ80)anodes for Mg−air batteries were investigated.The results show that the addition of 0.2 wt.%Y increased the corrosion resistance and discharge activity of AZ80 anode.This was attributed to the fine and sphericalβ-Mg_17)Al_(12) phases dispersing evenly in AZ80+0.2Y alloy,which suppressed the localized corrosion and severe“chunk effect”,and facilitated the rapid activation ofα-Mg.Combinative addition of 0.2 wt.%Y and 0.15 wt.%Ca generated grain refinement and a reduction of theβ-Mg_17)Al_(12) phase,resulting in a further enhancement in discharge voltage.However,the incorporation of Ca in Mg_17)Al_(12) and Al_(2)Y compounds compromised the corrosion resistance and anodic efficiency of AZ80+0.2Y+0.15Ca anode.Consequently,AZ80+0.2Y anode exhibited excellent overall discharge performance,with the peak discharge capacity and anodic efficiency of 1525 mA·h·g^(−1) and 67%at 80 mA/cm^(2),13%and 14%higher than those of AZ80 anode,respectively.
基金Project(2015DFR50990-01)supported by the International Cooperation Project of Ministry of Science and Technology of ChinaProject(2016KF-01)supported by the Shaanxi Key Laboratory of Nano-materials and Technology,ChinaProject(2015CXY-01)supported by the Cooperation Project on the Integration of Industry,Education and Research of Yulin Science and Technology Bureau,China。
文摘Mg-Zn binary alloys fabricated by the gas-phase alloying technique under vacuum condition were investigated in the state of initial state and after heat treatment for the microstructure and electrochemical behaviors.Different from the traditional Mg-Zn alloys preparation methods,alloys prepared by gas-phase alloying have a large number of intermetallic compounds,such as MgZn,Mg7Zn3 and MgZn2.After solution treatment,the boundary of the eutectic disappeared and the size ofα-Mg increased from 100μm to 150μm.At the same time,the value of the resistance of charge transfer increased,which indicates that the resistance of the charge transfer and the corrosion resistance of the alloys increased.After artificial aging treatment,the distribution ofα-Mg was more uniform and its size was reduced to about 50μm,and there was new eutectic structure formed.The newly formed eutectic structure forms galvanic cells with the alloy matrix,which makes the corrosion resistance of the alloy weaken.
基金supports from the National Key Research and Development Program of China (No.2021YFC2901600)supported by the State Key Laboratory of Special Rare Metal Materials (No.SKL2020K004)。
文摘X-ray photoelectron spectroscopy(XPS)and Raman spectroscopy were used to analyze the complexes in LiCl−KCl eutectic salt containing VCl_(3) and KF.The additional fluoride ions would replace chloride ions and combine with V(Ⅲ)to form VF_(6)^(3-).The electrochemical behavior of V(Ⅲ)was evaluated under condition of the molar concentration ratio of F−to Vn+(α)equal to 0:1,1:1,2:1,5:1,20:1 and 50:1,respectively.The results showed that a new reduction step appeared:VF_(6)^(3-)→V^(2+),and the reduction mechanism of vanadium ions became more complicated.The metallic vanadium was deposited on the tungsten electrode at−2.90 V in the LiCl−KCl melts for 6 h,and the products were characterized by SEM−EDS.It was indicated that the particle size of the product decreased with adding fluoride ions for the forming of the coordination compound VF_(6)^(3-).
基金This study was financially supported by the National Natural Science Foundation of China (No.59925412)the Natural Science Foundation of Hunan Province of China (No.03JJY3015).
文摘The electrochemical behaviors of n-type silicon wafers pH value and solid content of the slurry on the corrosion of silicon in silica-based slurry were investigated, and the influences of the wafers were studied by using electrochemical DC polarization and AC impedance techniques. The results revealed that these factors affected the corrosion behaviors of silicon wafers to different degrees and had their suitable parameters that made the maximum corrosion rate of the wafers. The corrosion potential of (100) sttrface was lower than that of(111), whereas the current density of (100) was much higher than that of(111).
基金Supported by the National Natural Science Foundation of China(No.21076065)
文摘A new kind of comblike copolymer film composed of acrylic acid-polyethylene glycol monomethyl ether acrylate copolymer(AA-PEGMA copolymer) was successfully synthesized to immobilize hemoglobin(Hb). FTIR, UV-Vis and CD spectra suggest that Hb kept its original structure in the AA-PEGMA copolymer film without denaturation. A pair of well-defined, quasi-reversible cyclic voltammetric peaks at around –270 mV vs. saturated calomel electrode(SCE) for the Hb Fe(III)/Fe(II) redox couple was observed on the film-modified electrode in phos phate buffer solution(PBS, pH=7.0). The formal potential of Hb/AA-PEGMA copolymer film-modified electrode is linearly dependent on solution pH with a slope of –46.3 mV/pH, illustrating that one-proton transfer was accompa nied with each electron transfer. Furthermore, the modified electrode displayed electrocatalytic response to the reduc tion of H2O2 with a linear range of 3.5―126 μmol/L and a detection limit of 1.17 μmol/L. In conclusion, the AA-PEGMA copolymer film was proved to be an excellent matrix for the immobilization and electrochemistry of proteins.
基金Project(52074084)supported by the National Natural Science Foundation of China。
文摘The high-temperature requirement for liquid iron smelting via molten oxide electrolysis presents significant challenges.This study investigates the electrochemical reduction of Fe(Ⅲ)in a novel low-temperature electrolyte,Na_(2)SiO_(3)-SiO_(2)-Fe_(2)O_(3),utilizing cyclic voltammetry and square wave voltammetry techniques.The results show that Fe(Ⅲ)reduction occurs in two steps:Fe(Ⅲ)+e^(−)→Fe(Ⅱ),Fe(Ⅱ)+2e^(−)→Fe,and that the redox process of Fe(Ⅲ)/Fe(Ⅱ)at the tungsten electrode is an irreversible reaction controlled by diffusion.The diffusion coefficients of Fe(Ⅲ)in the molten Na_(2)SiO_(3)-SiO_(2)-Fe_(2)O_(3)in the temperature range of 1248–1278 K are between 1.86×10^(−6)cm^(2)/s and 1.58×10^(−4)cm^(2)/s.The diffusion activation energy of Fe(Ⅲ)in the molten salt is 1825.41 kJ/mol.As confirmed by XRD analysis,potentiostatic electrolysis at−0.857 V(vs.O_(2)/O_(complex)^(2-))for 6 h produces metallic iron on the cathode.
基金the Science and Engineering Research Board(SERB),Govt.of India,for the financial support(grant number:CRG/2021/005548).
文摘Biphasic layered oxide cathodes,known for their superior electrochemical performance,are prime candidates for commercializing in Na-ion batteries.Herein,we unveil a series of P3/P2 monophasic and biphasic Al-substituted Na_(3/4)Mn_(5-x/8)Al_(2x/8)Ni_(3-x/8)O_(2)layered oxide cathodes that lie along the‘zero Mn^(3+)line’in the Na_(3/4)(Mn-Al-Ni)O_(2)pseudo-ternary system.The structural analysis showed a larger Na^(+)conduction bottleneck area in both P3 and P2 structures with a higher Al3+content,which enhanced their rate performance.In each composition,the P3/P2 biphasic compound with nearly equal fractions of P3 and P2 phases outperformed their monophasic counterparts in almost all electrochemical performance parameters.Operando synchrotron XRD measurements obtained for the monophasic P3 and biphasic P2/P3 samples revealed the absence of the O3 phase during cycling.The high structure stability and faster Na^(+)transport kinetics in the biphasic samples underpins the enhancement of electrochemical properties in the Al-substituted P3/P2 cathodes.These results highlight fixed oxidation state lines as a novel tool to identify and design layered oxide cathodes for Na-ion batteries in pseudo-ternary diagrams involving Jahn-Teller active cations.
文摘The electrochemical behaviors and corrosion resistance of the wrought Mg–Y–Zn based alloys with high Y/Zn mole ratio have been investigated in details.The results show that the corrosion resistance of the investigated Mg–Y–Zn based alloys are dependent on the modified arrangement of LPSO phase by adjusting Y/Zn mole ratios.Increasing the Y/Zn mole ratio not only greatly decreases the size of LPSO phase plates,but also leads to the precipitation of Mg_(24)Y_(5) phase.The corrosion rate of Mg–Y–Zn based alloys greatly increases from 7.4 mg·cm^(−2)·day^(−1) to 11.3 mg·cm^(−2)·day^(−1) with increasing the Y/Zn mole ratio up to 3.It should be attributed to the decreasing size of LPSO phase plates as cathodes,further increasing the hydrogen evolution kinetics.The related corrosion mechanism is discussed in details.
基金financially supported by the National Natural Science Foundation of China(No.51222106)the Fundamental Research Funds for the Central Universities(No. 230201306500002)the National Basic Research Program of China(No.2014CB643300)
文摘A composite conversion coating was prepared on magnesium alloy by the only one-step immersion treatment. The characteristics of the conversion coating were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the composite conversion coating consists of magnesium hydroxide, magnesium phosphate and man- ganese phosphate. The electrochemical behavior of the conversion coating was investigated systematically by electrochemical impedance spectroscopy (EIS) and poten- tiodynamic polarization measurement in different NaC1 solutions. Polarization measurements and EIS results reveal that the magnesium alloy with the conversion coating have better corrosion resistance compared to the bare magnesium alloy in these conditions. And the corro- sion rate of the magnesium alloy with conversion coating increases consistently with the chloride ion concentration. In alkaline conditions, the magnesium alloy with conver- sion coating has superior corrosion resistance by the syn- ergistic effects between Mg(OH)2 film and conversion coating. Moreover, the electrochemical corrosion mechanism of the magnesium alloy was analyzed with respect to the conversion coating in a Cl^- containing environment.
基金This study is funded by the Assistant Secretary for Energy Efficiency,Vehicle Technologies Office of the U.S.Department of Energy,under the Si Consortium Program.Electron microscopy experiments are conducted at the National Centre for Electron Microscopy and the Molecular Foundry located at Lawrence Berkeley National Laboratory is supported by the Director,Office of Science,Office of Basic Energy Sciences,the U.S.Department of Energy under Contract No.DE-AC02-05CH11231.
文摘To address the issues of large volume change and low conductivity of silicon(Si)materials,carbon coatings have been widely employed as surface protection agent and conductive medium to encapsulate the Si materials,which can improve the electrochemical performance of Si-based electrodes.There has been a strong demand to gain a deeper understanding of the impact of efficient carbon coating over the lithiation and delithiation process of Si materials.Here,we report the first observation of the extended two-phase transformation of carbon-coated Si nanoparticles(Si/C)during electrochemical processes.The Si/C nanoparticles were prepared by sintering Si nanoparticles with polyvinylidene chloride precursor.The Si/C electrode underwent a two-phase transition during the first 20 cycles at 0.2 C,but started to engage in solid solution reaction when the ordered compact carbon coating began to crack.Under higher current density conditions,the electrode was also found to be involved in solid solution reaction,which,however,was due to the overwhelming demand of kinetic property rather than the breaking of the carbon coating.In comparison,the Si/C composites prepared with sucrose possessed more disordered and porous carbon structures,and presented solid solution reaction throughout the entire cycling process.
基金Project(IRT_14R48)supported by the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education of ChinaProjects(51271158,51272158,51401175,51504213)supported by the National Natural Science Foundation of China+2 种基金Project([2009]17)supported by the Changjiang Scholar Incentive Program,ChinaProject(CX2015B224)supported by the Hunan Provincial Innovation Foundation for Postgraduate,ChinaProject(2015WK3021)supported by the Hunan Provincial Key Research Program,China
文摘Porous Al-Mg alloys with different nominal compositions were successfully fabricated via elemental powder reactive synthesis, and the phase composition, pore structure, and corrosion resistance were characterized with X-ray diffractometer, scanning electron microscope and electrochemical analyzer. The volume expansion ratio, open porosity and corrosion resistance in 3.5%(mass fraction) Na Cl aqueous solution of the alloys increase at first and then decrease with the increase of Mg content. The maxima of volume expansion ratio and open porosity are 18.3% and 28.1% for the porous Al-56%Mg(mass fraction) alloy, while there is the best corrosion resistance for the porous Al-37.5% Mg(mass fraction) alloy. The pore formation mechanism can be explained by Kirkendall effect, and the corrosion resistance can be mainly affected by the phase composition for the porous Al-Mg alloys. They would be of the potential application for filtration in the chloride environment.
基金financially supported by the National Research Laboratory Project of the National Research Foundation funded by the Ministry of Science and ICT,Republic of Korea(NRF-2020R1A2C2004192)G.Y.H.for research support via the YGY Project(YGY20150627000)supported by National Research Foundation(NRF)of South Korea(2022R1A2C1004392)。
文摘Heterocyclic compounds are the promising biological compounds as nature-friendly for the corrosion protection of metallic surface.In this work,three heterocyclic compounds such as 1-azanaphthalene-8-ol(8-AN),2-methylquinoline-8-ol(8-MQ),and 8-quinolinol-5-sulfonic acid(8-QSA)were used as green compounds,and their anti-corrosion performance for AZ31 Mg in saline water was discussed on the basis of impedance interpretation and surface analysis.Findings found that the electrochemical performance was improved in the order of 8-AN>8-MQ>8-QSA,demonstrating the electron donor effect of N-heterocycles to form coordination complexes on the magnesium surface.From the electrochemical performance,the protective layer constructed at the optimal concentration reinforces the barrier against aggressive environments,with potential inhibition efficiency of 87.4%,99.0%,and 99.9%for 8-QSA,8-MQ,and 8-AN,respectively.Quantum chemical parameters and electron density distribution for free organic species in the absence and presence of Mg^(2+)cation were evaluated using density functional theory(DFT).Upon the formation of coordination complexes between organic compound and Mg^(2+),energy gap underwent change about ΔE=5.7 eV in the 8-AN/Mg^(2+)system.Furthermore,the adsorption of heterocyclic compounds on Mg surface reveals the formation of strong covalent bonds with Mg atoms,which further confirmed by the electron density difference and projected density of states analyses.Based on theoretical calculations,three inhibitors can adsorb on the metal surface in both parallel and perpendicular orientations via C,O and N atoms.In the parallel configuration,the C-Mg,N-Mg and O-Mg bond distances are between 2.11 and 2.25˚A,whereas the distances in the case of perpendicular adsorption are between 2.20 and 2.40˚A(covalent bonds via O and N atoms).The results indicated that parallel configurations are energetically more stable,in which the adsorption energies are-4.48 eV(8-AN),-4.28 eV(8-MQ)and-3.82 eV(8-QSA)compared to that of perpendicular adsorption(-3.65,-3.40,and-2.63 eV).As a result,experimental and theoretical studies were in well agreement and confirm that the nitrogen and oxygen atoms will be the main adsorption sites.
基金supported by the Fundamental Research Funds for the Central Universities(FRF-TP-19-079A1)National Natural Science Foundation of China(51804022,51725401)
文摘Selenium(Se),as an important quasi-metal element,has attracted much attention in the fields of thin-film solar cells,electrocatalysts and energy storage applications,due to its unique physical and chemical properties.However,the electrochemical behavior of Se in different systems from electrolytic cell to battery are complex and not fully understood.In this article,we focus on the electrochemical processes of Se in aqueous solutions,molten salts and ionic liquid electrolytes,as well as the application of Se-containing materials in energy storage.Initially,the electrochemical behaviors of Se-containing species in different systems are comprehensively summarized to understand the complexity of the kinetic processes and guide the Se electrodeposition.Then,the relationship between the deposition conditions and resulting structure and morphology of electrodeposited Se is discussed,so as to regulate the morphology and composition of the products.Finally,the advanced energy storage applications of Se in thin-film solar cells and secondary batteries are reviewed,and the electrochemical reaction processes of Se are systematically comprehended in monovalent and multivalent metal-ion batteries.Based on understanding the fundamental electrochemistry mechanism,the future development directions of Se-containing materials are considered in view of the in-depth review of reaction kinetics and energy storage applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.:51901153)Shanxi Scholarship Council of China(Grant No.:2019032)+1 种基金Natural Science Foundation of Shanxi(Grant No.:202103021224049)the Science and Technology Major Project of Shanxi Province(Grant No.:20191102008,20191102007)。
文摘The influence of micro-Ca/In alloying on the microstructural charac teristics,electrochemical behaviors and discharge properties of extruded dilute Mg-0.5Bi-0.5Sn-based(wt.%)alloys as anodes for Mg-air batteries are evaluated.The grain size and texture intensity of the Mg-Bi-Sn-based alloys are significantly decreased after the Ca/In alloying,particularly for the In-containing alloy.Note that,in addition to nanoscale Mg_(3)Bi_(2)phase,a new microscale Mg_(2)Bi_(2)Ca phase forms in the Ca-containing alloy.The electrochemical test results demonstrate that Ca/In micro-alloying can enhance the electrochemical activity.Using In to alloy the Mg-Bi-Sn-based alloy is effective in restricting the cathodic hydrogen evolution(CHE)kinetics,leading to a low self-corrosion rate,while severe CHE occurred after Ca alloying.The micro-alloying of Ca/In to Mg-Bi-Sn-based alloy strongly deteriorates the compactness of discharge products film and mitigates the"chunk effect"(CE),hence the cell voltage,anodic efficiency as well as discharge capacity are greatly improved.The In-containing alloy exhibits outstanding discharge performance under the combined effect of the modified microstructure and discharge products,thus making it a potential anode material for primary Mg-air battery.