The Sr/F co-doped CaP(Sr/F-CaP)coatings were prepared by micro-arc oxidation(MAO)under different voltages to modify the microstructure and corrosion behavior of Mg-4Zn-1Mn alloy.The surface and interface characteristi...The Sr/F co-doped CaP(Sr/F-CaP)coatings were prepared by micro-arc oxidation(MAO)under different voltages to modify the microstructure and corrosion behavior of Mg-4Zn-1Mn alloy.The surface and interface characteristics investigated using scanning electron microscopy(SEM)and energy dispersive X-ray spectrometer(EDS)showed that the MAO coatings displayed uneven crater-like holes and tiny cracks under lower voltage,while they exhibited relatively homogeneous crater-like holes without cracks under higher voltage.The thickness of MAO coatings increased with increasing voltage.The corrosion behavior of Mg-4Zn-1Mn alloy was improved by the MAO coatings.The MAO coatings prepared under 450 V and 500 V voltages possessed the best corrosion resistance with regard to the electrochemical corrosion tests and immersion corrosion tests,respectively.The MAO coatings fabricated under 450-500 V could provide a better corrosion protection effect for the substrate.展开更多
P2-Na_(0.67)N_(i0.33)Mn_(0.67)O_(2)is considered as a promising cathode material for sodium-ion battery (SIBs)because of its high capacity and discharge potential.However,its practical use is limited by Na^(+)/vacancy...P2-Na_(0.67)N_(i0.33)Mn_(0.67)O_(2)is considered as a promising cathode material for sodium-ion battery (SIBs)because of its high capacity and discharge potential.However,its practical use is limited by Na^(+)/vacancy ordering and P2-O2 phase transition.Herein,a Ti^(4+)/F^(-) co-doping strategy is developed to address these issues.The optimal P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) exhibits much enhanced sodium storage performance in the high voltage range of 2.0–4.4 V,including a cycling stability of 77.2%over 300cycles at a rate of 2 C and a high-rate capability of 87.7 m Ah g^(-1) at 6 C.Moreover,the P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) delivers reversible capacities of 82.7 and 128.1 m Ah g^(-1) at-10 and 50℃ at a rate of 2 C,respectively.The capacity retentions over 200 cycles at-10℃ is 94.2%,implying more opportunity for practical application.In-situ X-ray diffraction analysis reveals that both P2-O2 phase transitions and Na^(+)/vacancy ordering is suppressed by Ti^(4+)/F^(-) co-doping,which resulting in fast Na^(+) diffusion and stable phase structure.The hard carbon//P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) full cell exhibits a high energy density of 310.2 Wh kg^(-1) and remarkable cyclability with 82.1%retention after 300 cycles at 1 C in the voltage range of 1.5–4.2 V.These results demonstrate that the co-doping Ti^(4+)/F^(-) is a promising strategy to improve the electrochemical properties of P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2),providing a facile tactic to develop high performance cathode materials for SIBs.展开更多
Hollow nanostructures with external shells and inner voids have been proved to greatly shorten the transport distance of ions/electrons and buffer volume change,especially for the large-sized potassium-ions in seconda...Hollow nanostructures with external shells and inner voids have been proved to greatly shorten the transport distance of ions/electrons and buffer volume change,especially for the large-sized potassium-ions in secondary batteries.In this work,hollow carbon(HC) nanospheres embedded with S,P co-doped NiSe_(2)nanoparticles are fabricated by "drop and dry" and "dissolving and precipitation" processes to form Ni(OH)2nanocrystals followed by annealing with S and P dopants to form nanoparticles.The resultant S,P-NiSe_(2)/HC composite exhibits excellent cyclic performance with 131.6 mA h g^(-1)at1000 mA g^(-1)after 3000 cycles for K^(+)storage and a capacity of 417.1 mA h g^(-1)at 1000 mA g^(-1)after1000 cycles for Li^(+)storage.K-ion full cells are assembled and deliver superior cycling stability with a ca pacity of 72.5 mA h g^(-1)at 200 mA g^(-1)after 500 cycles.The hollow carbon shell with excellent electrical conductivity effectively promotes the transporta tion and tolerates large volume variation for both K^(+)and Li^(+).Density functional theory calculations confirm that the S and P co-doping NiSe_(2) enables stronger adsorption of K^(+)ions and higher electrical conductivity that contributes to the improved electrochemical performance.展开更多
Developing highly efficient and stable platinum-based electrocatalyst for oxygen reduction reaction(ORR) is critical to expediting commercialization of fuel cells.Herein,several PtCu alloy nanocatalysts supported on N...Developing highly efficient and stable platinum-based electrocatalyst for oxygen reduction reaction(ORR) is critical to expediting commercialization of fuel cells.Herein,several PtCu alloy nanocatalysts supported on N,P co-doped carbon(PtCu/NPC) were prepared by microbial-sorption and carbonization-reduction.Among them,PtCu/NPC-700 ℃ exhibits excellent catalytic performance for ORR with a mass activity of 0.895 A mg_(pt)^(-1)(@0.9 V) which is 8.29 folds of commercial Pt/C.Additionally,the ECSA and MA of PtCu/NPC-700℃ only decrease by 14.2% and 18.7% respectively,while Pt/C decreases by 35.2% and 52.8% after 10,000 cycles of ADT test.Moreover,the PtCu/NPC-700℃ catalyst emanates a maximum power density of 715 mW cm^(-2) and only 11.1% loss of maximum power density after 10,000 ADTs in single-cell test,indicating PtCu/NPC-700℃ also manifests higher activity and durability in actual single-cell operation than Pt/C.This research provides an easy and novel strategy for developing highly active and durable Pt-based alloy catalyst.展开更多
Lithium (Li) metal batteries have attracted much attention owing to its ultra-high energy density.However,as important part of Li metal batteries,Li anodes still face many challenges,mainly including uncontrolled dend...Lithium (Li) metal batteries have attracted much attention owing to its ultra-high energy density.However,as important part of Li metal batteries,Li anodes still face many challenges,mainly including uncontrolled dendritic Li formation,dramatical volume variation and serious pulverization.Herein,manganese dioxide (MnO_(2)) nanosheet modified nitrogen (N),phosphorus (P) co-doping carbon nanofibers(NPC) on carbon cloth (CC)(MnO_(2)@NPC-CC) is successfully fabricated through electrodeposition approach and further treated with Li by the molten-infusion method to prepare Li based Mn@NPC-CC(Li-Mn@NPC-CC) electrode.The synergy of MnO_(2) and NPC obviously increases the reaction rate between MnO_(2)@NPC-CC and Li and guides even Li distribution over infusion process.Additionally,theoretical calculation,simulation and experimental results further indicate that N,P,Mn multi-doping effectively improves the superior lithiophilicity of Li-Mn@NPC-CC,which induces uniform Li deposition/dissolution to suppress dendrite growth over cycles.Moreover,conductive and porous NPC matrix not only effectively improves the stability of Li-Mn@NPC-CC,but also provides abundant spaces to accelerate the transfer of ion/electron and buffer electrode dimension variation during cycling.Hence,Li-Mn@NPC-CC-based symmetric cells exhibit extra-long cycling life (over 2200 h) with small hysteresis of 20 mV.When the LiMn@NPC-CC anode couples with air,Li iron phosphate (LiFePO_(4)),or hard carbon (C) cathode,the assembled full cells exhibit outstanding performance with low hysteresis and stable cycling properties.Especially,the corresponding pouch-typed Li–air cells also exhibit good performance at different bending angles and even power a series of electronic devices.展开更多
文摘The Sr/F co-doped CaP(Sr/F-CaP)coatings were prepared by micro-arc oxidation(MAO)under different voltages to modify the microstructure and corrosion behavior of Mg-4Zn-1Mn alloy.The surface and interface characteristics investigated using scanning electron microscopy(SEM)and energy dispersive X-ray spectrometer(EDS)showed that the MAO coatings displayed uneven crater-like holes and tiny cracks under lower voltage,while they exhibited relatively homogeneous crater-like holes without cracks under higher voltage.The thickness of MAO coatings increased with increasing voltage.The corrosion behavior of Mg-4Zn-1Mn alloy was improved by the MAO coatings.The MAO coatings prepared under 450 V and 500 V voltages possessed the best corrosion resistance with regard to the electrochemical corrosion tests and immersion corrosion tests,respectively.The MAO coatings fabricated under 450-500 V could provide a better corrosion protection effect for the substrate.
基金supported by the National Natural Science Foundation of China(21901146,51907110,22078179)the Key Research and Development Program of Shandong Province(2019GGX103027)+2 种基金the Natural Science Foundation of Shandong Province(ZR2019MB034)the Taishan Scholar Foundation(tsqn201812063)the 111 Project(B12015)。
文摘P2-Na_(0.67)N_(i0.33)Mn_(0.67)O_(2)is considered as a promising cathode material for sodium-ion battery (SIBs)because of its high capacity and discharge potential.However,its practical use is limited by Na^(+)/vacancy ordering and P2-O2 phase transition.Herein,a Ti^(4+)/F^(-) co-doping strategy is developed to address these issues.The optimal P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) exhibits much enhanced sodium storage performance in the high voltage range of 2.0–4.4 V,including a cycling stability of 77.2%over 300cycles at a rate of 2 C and a high-rate capability of 87.7 m Ah g^(-1) at 6 C.Moreover,the P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) delivers reversible capacities of 82.7 and 128.1 m Ah g^(-1) at-10 and 50℃ at a rate of 2 C,respectively.The capacity retentions over 200 cycles at-10℃ is 94.2%,implying more opportunity for practical application.In-situ X-ray diffraction analysis reveals that both P2-O2 phase transitions and Na^(+)/vacancy ordering is suppressed by Ti^(4+)/F^(-) co-doping,which resulting in fast Na^(+) diffusion and stable phase structure.The hard carbon//P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) full cell exhibits a high energy density of 310.2 Wh kg^(-1) and remarkable cyclability with 82.1%retention after 300 cycles at 1 C in the voltage range of 1.5–4.2 V.These results demonstrate that the co-doping Ti^(4+)/F^(-) is a promising strategy to improve the electrochemical properties of P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2),providing a facile tactic to develop high performance cathode materials for SIBs.
基金financially supported by the Shenzhen Science and Technology Program(JCYJ20220530141012028),ChinaThe National Natural Science Foundation of China(22005178),China+2 种基金The Key Research and Development Program of Shandong Province(2021ZLGX01),ChianThe fellowship of China Postdoctoral Science Foundation(2022M722333),Chianthe Jiangsu Funding Program for Excellent Postdoctoral Talent,Chian。
文摘Hollow nanostructures with external shells and inner voids have been proved to greatly shorten the transport distance of ions/electrons and buffer volume change,especially for the large-sized potassium-ions in secondary batteries.In this work,hollow carbon(HC) nanospheres embedded with S,P co-doped NiSe_(2)nanoparticles are fabricated by "drop and dry" and "dissolving and precipitation" processes to form Ni(OH)2nanocrystals followed by annealing with S and P dopants to form nanoparticles.The resultant S,P-NiSe_(2)/HC composite exhibits excellent cyclic performance with 131.6 mA h g^(-1)at1000 mA g^(-1)after 3000 cycles for K^(+)storage and a capacity of 417.1 mA h g^(-1)at 1000 mA g^(-1)after1000 cycles for Li^(+)storage.K-ion full cells are assembled and deliver superior cycling stability with a ca pacity of 72.5 mA h g^(-1)at 200 mA g^(-1)after 500 cycles.The hollow carbon shell with excellent electrical conductivity effectively promotes the transporta tion and tolerates large volume variation for both K^(+)and Li^(+).Density functional theory calculations confirm that the S and P co-doping NiSe_(2) enables stronger adsorption of K^(+)ions and higher electrical conductivity that contributes to the improved electrochemical performance.
基金supported by funding from the National Natural Science Foundation of China (12074435 and 52001335)the Science and Technology Innovation Program of Hunan Province (2021RC4001)the Natural Science Foundation of Yunnan Province (202201AT070259)。
文摘Developing highly efficient and stable platinum-based electrocatalyst for oxygen reduction reaction(ORR) is critical to expediting commercialization of fuel cells.Herein,several PtCu alloy nanocatalysts supported on N,P co-doped carbon(PtCu/NPC) were prepared by microbial-sorption and carbonization-reduction.Among them,PtCu/NPC-700 ℃ exhibits excellent catalytic performance for ORR with a mass activity of 0.895 A mg_(pt)^(-1)(@0.9 V) which is 8.29 folds of commercial Pt/C.Additionally,the ECSA and MA of PtCu/NPC-700℃ only decrease by 14.2% and 18.7% respectively,while Pt/C decreases by 35.2% and 52.8% after 10,000 cycles of ADT test.Moreover,the PtCu/NPC-700℃ catalyst emanates a maximum power density of 715 mW cm^(-2) and only 11.1% loss of maximum power density after 10,000 ADTs in single-cell test,indicating PtCu/NPC-700℃ also manifests higher activity and durability in actual single-cell operation than Pt/C.This research provides an easy and novel strategy for developing highly active and durable Pt-based alloy catalyst.
基金funding support from the National Natural Science Foundation of China (21905151 and 51772162)the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions, China (2019KJC004)+1 种基金the Outstanding Youth Foundation of Shandong Province, China (ZR2019JQ14)the Taishan Scholar Young Talent Program, Major Scientific and Technological Innovation Project (2019JZZY020405)。
文摘Lithium (Li) metal batteries have attracted much attention owing to its ultra-high energy density.However,as important part of Li metal batteries,Li anodes still face many challenges,mainly including uncontrolled dendritic Li formation,dramatical volume variation and serious pulverization.Herein,manganese dioxide (MnO_(2)) nanosheet modified nitrogen (N),phosphorus (P) co-doping carbon nanofibers(NPC) on carbon cloth (CC)(MnO_(2)@NPC-CC) is successfully fabricated through electrodeposition approach and further treated with Li by the molten-infusion method to prepare Li based Mn@NPC-CC(Li-Mn@NPC-CC) electrode.The synergy of MnO_(2) and NPC obviously increases the reaction rate between MnO_(2)@NPC-CC and Li and guides even Li distribution over infusion process.Additionally,theoretical calculation,simulation and experimental results further indicate that N,P,Mn multi-doping effectively improves the superior lithiophilicity of Li-Mn@NPC-CC,which induces uniform Li deposition/dissolution to suppress dendrite growth over cycles.Moreover,conductive and porous NPC matrix not only effectively improves the stability of Li-Mn@NPC-CC,but also provides abundant spaces to accelerate the transfer of ion/electron and buffer electrode dimension variation during cycling.Hence,Li-Mn@NPC-CC-based symmetric cells exhibit extra-long cycling life (over 2200 h) with small hysteresis of 20 mV.When the LiMn@NPC-CC anode couples with air,Li iron phosphate (LiFePO_(4)),or hard carbon (C) cathode,the assembled full cells exhibit outstanding performance with low hysteresis and stable cycling properties.Especially,the corresponding pouch-typed Li–air cells also exhibit good performance at different bending angles and even power a series of electronic devices.
