The relationship between the specific surface area（SSA） of rust and the electrochemical behavior of rusted steel under wet-dry acid corrosion conditions was investigated. The results showed that the corrosion curren...The relationship between the specific surface area（SSA） of rust and the electrochemical behavior of rusted steel under wet-dry acid corrosion conditions was investigated. The results showed that the corrosion current density first increased and then decreased with increasing SSA of the rust during the corrosion process. The structure of the rust changed from single-layer to double-layer, and the γ-FeOOH content decreased in the inner layer of the rust with increasing corrosion time; by contrast, the γ-FeOOH content in the outer layer was constant. When the SSA of the rust was lower than the critical SSA corresponding to the relative humidity during the drying period, condensed water in the micropores of the rust could evaporate, which prompted the diffusion of O_2 into the rust and the following formation process of γ-FeOOH, leading to an increase of corrosion current density with increasing corrosion time. However, when the SSA of the rust reached or exceeded the critical SSA, condensate water in the micro-pores of the inner layer of the rust could not evaporate which inhibited the diffusion of O_2 and decreased the γ-FeOOH content in the inner rust, leading to a decrease of corrosion current density with increasing corrosion time.展开更多
Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,t...Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,this work reports a feasible procedure to achieve the controllably partial removal of thiolate ligands from unsupported[Au_(25)(PET)_(18)]-nanoclusters with the preservation of the core structure.This procedure shortens the processing duration by rapid heating and cooling on the basis of traditional annealing treatment,avoiding the reconfiguration or agglomeration of Au_(25)nanoclusters,where the degree of dethiolation can be regulated by the control of duration.This work finds that a moderate degree of dethiolation can expose the Au active sites while maintaining the suppression of the competing hydrogen evolution reaction.Consequently,the activity and selectivity towards CO formation in electrochemical CO_(2)reduction reaction of Au_(25)nanoclusters can be promoted.This work provides a new approach for the removal of thiolate ligands from atomically precise gold nanoclusters.展开更多
A novel C/Pb composite has been successfully prepared by electmless plating to reduce the hydrogenevolution and achieve the high reversibility of the anode of lead-carbon battery （LCB）. The depositedlead on the surf...A novel C/Pb composite has been successfully prepared by electmless plating to reduce the hydrogenevolution and achieve the high reversibility of the anode of lead-carbon battery （LCB）. The depositedlead on the surface of C/Pb composite was found to be uniform and adherent to carbon surface. Becauselead has been stuck on the surface of C/Pb composite, the embedded structure suppresses the hydrogenevolution of lead-carbon anode and strengthens the connection between carbon additive and sponge lead.Compared with the blank anode, the lead-carbon anode with C/Pb composite displays excellent charge-discharge reversibility, which is attributed to the good connection between carbon additives and leadthat has been stuck on the surface of C/Pb composite during the preparation process. The addition of CIPb composite maintains a solid anode structure with high specific surface area and power volume, andthereby, it plays a significant role in the highly reversible lead-carbon anode.展开更多
Carbon-sulfur nano-composite cathodes for lithium rechargeable batteries were investigated by electrochemical impedance spectroscopy (EIS). The novel carbon-sulfur nano-composite material was synthesized by heating su...Carbon-sulfur nano-composite cathodes for lithium rechargeable batteries were investigated by electrochemical impedance spectroscopy (EIS). The novel carbon-sulfur nano-composite material was synthesized by heating sublimed sulfur and high surface area activated carbon (HSAAC) in certain conditions. Equivalent circuits were used to fit the spectra at different discharge states. The variations of impedance spectra, charge-transfer resistance and double layer capacitance were discussed. The changes of EIS with potential were analyzed based on a plausible electrical equivalent circuit model, and some parameters were measured and analyzed about electrochemical performance and state of charge and discharge of the electrode. The good accuracy in fitting values of the model to the experimental data indicates that the mathematical model gives out a satisfying description upon the mechanism of high rate of capacity fade in lithium-sulfur battery.展开更多
Nickel-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM,1-x-y≥0.6)is known as a promising cathode material for lithium-ion batteries since its superiority of high voltage and large capacity.However,polycrystalline Ni-rich NCMs...Nickel-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM,1-x-y≥0.6)is known as a promising cathode material for lithium-ion batteries since its superiority of high voltage and large capacity.However,polycrystalline Ni-rich NCMs suffer from poor cycle stability,limiting its further application.Herein,single crystal and polycrystalline LiNi_(0.84)Co_(0.07)Mn_(0.09)O_(2)cathode materials are compared to figure out the relation of the morphology and the electrochemical storage performance.According to the Li^(+)diffusion coefficient,the lower capacity of single crystal samples is mainly ascribed to the limited Li+diffusion in the large bulk.In situ XRD illustrates that the polycrystalline and single crystal NCMs show a virtually identical manner and magnitude in lattice contraction and expansion during cycling.Also,the electrochemically active surface area(ECSA)measurement is employed in lithium-ion battery study for the first time,and these two cathodes show huge discrepancy in the ECSA after the initial cycle.These results suggest that the single crystal sample exhibits reduced cracking,surface side reaction,and Ni/Li mixing but suffers the lower Li^(+)diffusion kinetics.This work offers a view of how the morphology of Ni-rich NCM effects the electrochemical performance,which is instructive for developing a promising strategy to achieve good rate performance and excellent cycling stability.展开更多
Modifying electrochemical surface area(ECSA)and surface chemistry are promising approaches to enhance the capacities of oxygen cathodes for lithium-oxygen(Li-O_(2))batteries.Although various chemical approaches have b...Modifying electrochemical surface area(ECSA)and surface chemistry are promising approaches to enhance the capacities of oxygen cathodes for lithium-oxygen(Li-O_(2))batteries.Although various chemical approaches have been successfully used to tune the cathode surface,versatile physical techniques including plasma etching etc.could be more effortless and effective than arduous chemical treatments.Herein,for the first time,we propose a facile oxygen plasma treatment to simultaneously etch and modify the surface of Co_(3)O_(4)nanosheet arrays(NAs)cathode for Li-O_(2)batteries.The oxygen plasma not only etches Co_(3)O_(4)nanosheets to enhance the ECSA but also lowers the oxygen vacancy concentration to enable a Co^(3+)-rich surface.In addition,the NA architecture enables the full exposure of oxygen vacancies and surface Co^(3+)that function as the catalytically active sites.Thus,the synergistic effects of enhanced ECSA,modest oxygen vacancy and high surface Co^(3+)achieve a significantly enhanced reversible capacity of 3.45 mAh/cm^(2)for Co_(3)O_(4)NAs.This work not only develops a promising high-capacity cathode for Li-O_(2)batteries,but also provides a facile physical method to simultaneously tune the nanostructure and surface chemistry of energy storage materials.展开更多
The electrochemical surface area (ESA) of the half-membrane electrode assembly (HMEA) and dimethyl-ether (DME) electrooxidation on the HMEA were examined by cyclic voltammetry (CV). The ESAs of the electrode before an...The electrochemical surface area (ESA) of the half-membrane electrode assembly (HMEA) and dimethyl-ether (DME) electrooxidation on the HMEA were examined by cyclic voltammetry (CV). The ESAs of the electrode before and after DME electrooxidation were calculated from the integrated charge during the adsorption (and/or desorption) of atomic hydrogen minus the charge for the double layer charging in 0.5 mol·L-1 H2SO4. The increase in ESA was observed, and this was attributed to the change of catalyst layer structure, leading to a more effective contact between catalysts and the electrolyte Nafion.展开更多
研究了Pt/CNT（碳纳米管）电极在动电位和恒电位两种情况下的电化学稳定性. 在动电位条件（0.05～1.2 V vs RHE（可逆氢电极）循环伏安940次, 60 h）下, Pt/CNT电极的电化学表面积下降18.8%;在恒电位条件（1.2 V vs RHE, 60 h）下, Pt/...研究了Pt/CNT（碳纳米管）电极在动电位和恒电位两种情况下的电化学稳定性. 在动电位条件（0.05～1.2 V vs RHE（可逆氢电极）循环伏安940次, 60 h）下, Pt/CNT电极的电化学表面积下降18.8%;在恒电位条件（1.2 V vs RHE, 60 h）下, Pt/CNT电极的电化学表面积仅下降5.2%. 这表明Pt/CNT电极在动电位条件下性能衰减得更迅速. X射线光电子能谱分析表明,恒电位条件下载体碳纳米管被氧化的程度较大. X射线衍射分析计算表明,动电位和恒电位氧化后, Pt颗粒的平均粒径从3.8 nm分别增大到4.9和3.9 nm. Pt颗粒的长大可能是Pt/CNT电极性能衰减的主要原因之一,而载体的氧化不是Pt/CNT电极性能衰减的主要原因.展开更多
基金the National Natural Science Foundation of China(Project No.51571027)for funding support
文摘The relationship between the specific surface area（SSA） of rust and the electrochemical behavior of rusted steel under wet-dry acid corrosion conditions was investigated. The results showed that the corrosion current density first increased and then decreased with increasing SSA of the rust during the corrosion process. The structure of the rust changed from single-layer to double-layer, and the γ-FeOOH content decreased in the inner layer of the rust with increasing corrosion time; by contrast, the γ-FeOOH content in the outer layer was constant. When the SSA of the rust was lower than the critical SSA corresponding to the relative humidity during the drying period, condensed water in the micropores of the rust could evaporate, which prompted the diffusion of O_2 into the rust and the following formation process of γ-FeOOH, leading to an increase of corrosion current density with increasing corrosion time. However, when the SSA of the rust reached or exceeded the critical SSA, condensate water in the micro-pores of the inner layer of the rust could not evaporate which inhibited the diffusion of O_2 and decreased the γ-FeOOH content in the inner rust, leading to a decrease of corrosion current density with increasing corrosion time.
基金the financial support of the Training Program of the Major Research Plan of the National Natural Science Foundation of China(92061124)the National Natural Science Foundation of China(21975292,21978331,22068008,and 52101186)+3 种基金the Guangdong Basic and Applied Basic Research Foundation(2021A1515010167 and 2022A1515011196)the Guangzhou Key R&D Program/Plan Unveiled Flagship Project(20220602JBGS02)the Guangzhou Basic and Applied Basic Research Project(202201011449)the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202220 and FC202216)。
文摘Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,this work reports a feasible procedure to achieve the controllably partial removal of thiolate ligands from unsupported[Au_(25)(PET)_(18)]-nanoclusters with the preservation of the core structure.This procedure shortens the processing duration by rapid heating and cooling on the basis of traditional annealing treatment,avoiding the reconfiguration or agglomeration of Au_(25)nanoclusters,where the degree of dethiolation can be regulated by the control of duration.This work finds that a moderate degree of dethiolation can expose the Au active sites while maintaining the suppression of the competing hydrogen evolution reaction.Consequently,the activity and selectivity towards CO formation in electrochemical CO_(2)reduction reaction of Au_(25)nanoclusters can be promoted.This work provides a new approach for the removal of thiolate ligands from atomically precise gold nanoclusters.
基金the financial support provided by the National Natural Science Foundation of China (No.21573093)the National Key Research and Development Program (No.2017YFB0307501)Guangdong Innovative and Entrepreneurial Research Team Program (No.2013C092)
文摘A novel C/Pb composite has been successfully prepared by electmless plating to reduce the hydrogenevolution and achieve the high reversibility of the anode of lead-carbon battery （LCB）. The depositedlead on the surface of C/Pb composite was found to be uniform and adherent to carbon surface. Becauselead has been stuck on the surface of C/Pb composite, the embedded structure suppresses the hydrogenevolution of lead-carbon anode and strengthens the connection between carbon additive and sponge lead.Compared with the blank anode, the lead-carbon anode with C/Pb composite displays excellent charge-discharge reversibility, which is attributed to the good connection between carbon additives and leadthat has been stuck on the surface of C/Pb composite during the preparation process. The addition of CIPb composite maintains a solid anode structure with high specific surface area and power volume, andthereby, it plays a significant role in the highly reversible lead-carbon anode.
文摘Carbon-sulfur nano-composite cathodes for lithium rechargeable batteries were investigated by electrochemical impedance spectroscopy (EIS). The novel carbon-sulfur nano-composite material was synthesized by heating sublimed sulfur and high surface area activated carbon (HSAAC) in certain conditions. Equivalent circuits were used to fit the spectra at different discharge states. The variations of impedance spectra, charge-transfer resistance and double layer capacitance were discussed. The changes of EIS with potential were analyzed based on a plausible electrical equivalent circuit model, and some parameters were measured and analyzed about electrochemical performance and state of charge and discharge of the electrode. The good accuracy in fitting values of the model to the experimental data indicates that the mathematical model gives out a satisfying description upon the mechanism of high rate of capacity fade in lithium-sulfur battery.
基金supported by the National Natural Science Foundation of China(Nos.51872157,52072208)Shenzhen Technical Plan Project(JCYJ20170817161753629)+1 种基金Fundamental Research Project of Shenzhen(No.JCYJ20190808153609561)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01N111).
文摘Nickel-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM,1-x-y≥0.6)is known as a promising cathode material for lithium-ion batteries since its superiority of high voltage and large capacity.However,polycrystalline Ni-rich NCMs suffer from poor cycle stability,limiting its further application.Herein,single crystal and polycrystalline LiNi_(0.84)Co_(0.07)Mn_(0.09)O_(2)cathode materials are compared to figure out the relation of the morphology and the electrochemical storage performance.According to the Li^(+)diffusion coefficient,the lower capacity of single crystal samples is mainly ascribed to the limited Li+diffusion in the large bulk.In situ XRD illustrates that the polycrystalline and single crystal NCMs show a virtually identical manner and magnitude in lattice contraction and expansion during cycling.Also,the electrochemically active surface area(ECSA)measurement is employed in lithium-ion battery study for the first time,and these two cathodes show huge discrepancy in the ECSA after the initial cycle.These results suggest that the single crystal sample exhibits reduced cracking,surface side reaction,and Ni/Li mixing but suffers the lower Li^(+)diffusion kinetics.This work offers a view of how the morphology of Ni-rich NCM effects the electrochemical performance,which is instructive for developing a promising strategy to achieve good rate performance and excellent cycling stability.
基金supported by grants from the National Natural Science Foundation of China(Nos.22075219 and 51972257)the National Key Research Program of China(No.2016YFA0202602)the Research Start-Up Fund from Wuhan University of Technology.
文摘Modifying electrochemical surface area(ECSA)and surface chemistry are promising approaches to enhance the capacities of oxygen cathodes for lithium-oxygen(Li-O_(2))batteries.Although various chemical approaches have been successfully used to tune the cathode surface,versatile physical techniques including plasma etching etc.could be more effortless and effective than arduous chemical treatments.Herein,for the first time,we propose a facile oxygen plasma treatment to simultaneously etch and modify the surface of Co_(3)O_(4)nanosheet arrays(NAs)cathode for Li-O_(2)batteries.The oxygen plasma not only etches Co_(3)O_(4)nanosheets to enhance the ECSA but also lowers the oxygen vacancy concentration to enable a Co^(3+)-rich surface.In addition,the NA architecture enables the full exposure of oxygen vacancies and surface Co^(3+)that function as the catalytically active sites.Thus,the synergistic effects of enhanced ECSA,modest oxygen vacancy and high surface Co^(3+)achieve a significantly enhanced reversible capacity of 3.45 mAh/cm^(2)for Co_(3)O_(4)NAs.This work not only develops a promising high-capacity cathode for Li-O_(2)batteries,but also provides a facile physical method to simultaneously tune the nanostructure and surface chemistry of energy storage materials.
文摘The electrochemical surface area (ESA) of the half-membrane electrode assembly (HMEA) and dimethyl-ether (DME) electrooxidation on the HMEA were examined by cyclic voltammetry (CV). The ESAs of the electrode before and after DME electrooxidation were calculated from the integrated charge during the adsorption (and/or desorption) of atomic hydrogen minus the charge for the double layer charging in 0.5 mol·L-1 H2SO4. The increase in ESA was observed, and this was attributed to the change of catalyst layer structure, leading to a more effective contact between catalysts and the electrolyte Nafion.
