Metallic zinc(Zn)is one of the most attractive multivalent-metal anode materials in post-lithium batteries because of its high abundance,low cost and high theoretical capacity.However,it usually suffers from large vol...Metallic zinc(Zn)is one of the most attractive multivalent-metal anode materials in post-lithium batteries because of its high abundance,low cost and high theoretical capacity.However,it usually suffers from large voltage polarization,low Coulombic efficiency and high propensity for dendritic failure during Zn stripping/plating,hindering the practical application in aqueous rechargeable zinc-metal batteries(AR-ZMBs).Here we demonstrate that anionic surfactant-assisted in situ surface alloying of Cu and Zn remarkably improves Zn reversibility of 3D nanoporous Zn electrodes for potential use as high-performance AR-ZMB anode materials.As a result of the zincophilic ZnxCuy alloy shell guiding uniform Zn deposition with a zero nucleation overpotential and facilitating Zn stripping via the ZnxCuy/Zn galvanic couples,the self-supported nanoporous ZnxCuy/Zn electrodes exhibit superior dendrite-free Zn stripping/plating behaviors in ambient aqueous electrolyte,with ultralow polarizations under current densities up to 50 mA cm^(‒2),exceptional stability for 1900 h and high Zn utilization.This enables AR-ZMB full cells constructed with nanoporous ZnxCuy/Zn anode and K_(z)MnO_(2)cathode to achieve specific energy of as high as~430 Wh kg^(‒1)with~99.8%Coulombic efficiency,and retain~86%after long-term cycles for>700 h.展开更多
The coupling between electrochemically active material and conductive matrix is vitally important for high efficiency lithium ion batteries （LIBs）. By introducing oxygen groups into the nanoporous carbon framework, ...The coupling between electrochemically active material and conductive matrix is vitally important for high efficiency lithium ion batteries （LIBs）. By introducing oxygen groups into the nanoporous carbon framework, we accom- plish sustainably enhanced electrochemical performance for a SnO2/carbon LIB. 2-5 nm SnO2 nanoparticles are hydro- thermally grown in different nanoporous carbon frameworks, which are pristine, nitrogen- or oxygen-doped carbons. Compared with pristine and nitrogen-doped carbon hosts, the SnO2/oxygen-doped activated carbon （OAC） composite ex- hibits a higher discharge capacity of 1,122mAhg^-1 at 500 mA g^-1 after 320 cycles operation and a larger lithium storage capacity up to 680 mAhg-I at a high rate of 2,000 mA g^-1. The exceptional electrochemical performance originated from the oxygen groups, which could act as Lewis acid sites to attract electrons effectively from Sn during the charge process, thus accelerating reversible conversion of Sn to SnO2. Meanwhile, SnO2 nanoparticles are effectively bonded with carbon through such oxygen groups, thus preventing the electrochemical sintering and maintaining the cycling stability of the SnO2/OAC composite anode. The high electrochemical performance, low biomass cost, and facile preparation renders the SnO2/OAC composites a promising candidate for anode materials.展开更多
Rechargeable aluminum batteries(RABs),which use earth-abundant and high-volumetric-capacity metal anodes(8040 m Ah cm-3),have great potential as next-generation power sources because they use cheaper resources to deli...Rechargeable aluminum batteries(RABs),which use earth-abundant and high-volumetric-capacity metal anodes(8040 m Ah cm-3),have great potential as next-generation power sources because they use cheaper resources to deliver higher energies,compared to current lithium ion batteries.However,the mechanism of charge delivery in the newly developed,ionic liquid-based electrolytic system for RABs differs from that in conventional organic electrolytes.Thus,targeted research efforts are required to address the large overpotentials and cycling decay encountered in the ionic liquid-based electrolytic system.In this study,a nanoporous carbon(NPC)electrode with well-developed nanopores is used to develop a high-performance aluminum anode.The negatively charged nanopores can provide quenched dynamics of electrolyte molecules in the aluminum deposition process,resulting in an increased collision rate.The fast chemical equilibrium of anionic species induced by the facilitated anionic collisions leads to more favorable reduction reactions that form aluminum metals.The nanoconfinement effect causes separated nucleation and growth of aluminum nanoparticles in the multiple confined nanopores,leading to higher coulombic efficiencies and more stable cycling performance compared with macroporous carbon black and 2D stainless steel electrodes.展开更多
The effect of annealing of Ti foils before anodization on the morphology and electrochemical performance of resultant nanoporous anatase TiO2 （np-TiO2） as anode in rechargeable lithium-ion batteries （LIBs） was inv...The effect of annealing of Ti foils before anodization on the morphology and electrochemical performance of resultant nanoporous anatase TiO2 （np-TiO2） as anode in rechargeable lithium-ion batteries （LIBs） was investigated. The np-TiO2 anode fabricated from annealed Ti foils exhibited higher specific surface area and reduced pore diameter compared to np-TiO2 electrode fabricated from as-received Ti foils. The highly porous np-TiO2 anode fabricated from annealed Ti foils exhibited 1st discharge capacity of 453.25 mAh/g and reduced to 172.70 mAh/g at 1 C current rate after 300 cycles; whilst the np-TiO2 electrode fabricated from the as-received Ti foils exhibited 1st discharge capacity of 213.30 mAh/g and reduced to 160.0 mAh/g at 1 C current rate after 300cycles. Even after 400cycles, such np-TiO2 electrode exhibited a reversible capacity of 125.0 mAh/g at 2.5 C current rate. Compared to the untreated Ti foils, the enhanced electro- chemical performance of np-TiO2 anode fabricated from annealed Ti foils was ascribed to the annealing- induced removal of residual stress among the Ti atoms. The benefit of annealing process can reduce pore size of as-fabricated np-TiO2.展开更多
Sulfur doped carbonaceous materials are promising anodes for potassium-ion batteries because of their ability to bridge active sites and induce C/S electron coupling,resulting in increased ion storage capacitance Howe...Sulfur doped carbonaceous materials are promising anodes for potassium-ion batteries because of their ability to bridge active sites and induce C/S electron coupling,resulting in increased ion storage capacitance However,the large potassium ions could cause significant volume expansion and structure collapse during operation in sulfur doped carbonaceous anodes,which lead to rapidly capacity sacrifice during long-term cycling.Nanopore design for anchoring sulfur atom in carbon skeleton is a novel way to alleviate the structure collapse and maintain the cycling stability.Therefore,this study developed a controlled nanopore and sulfur doped carbon sphere structure(S-NPHCSs).In potassium-ion batteries S-NPHCSs anode demonstrated exceptional performance with a high reversible capacity of 247 mAh·g^(–1)after 50 cycles at 0.2 A·g^(–1)and delivered a long cycle stability of 600 cycles at a high current density of 1.0 A·g^(–1).Interconnected nanopores and doped sulfur structure not only expand the accumulation space and offer ample active sites for diffusion and adsorption of potassium ions,but also build stable channels through nanopore structure to ensure the cyclic stability.This finding provides a fundamental theory for designing nanopore structures and introducing sulfur doped carbonaceous materials to enhance capacitive potassium storage and long cycle stability.展开更多
基金supported by National Natural Science Foundation of China (No. 51871107, 52130101)Chang Jiang Scholar Program of China (Q2016064)+3 种基金the Program for JLU Science and Technology Innovative Research Team (JLUSTIRT, 2017TD-09)the Natural Science Foundation of Jilin Province (20200201019JC)the Fundamental Research Funds for the Central Universitiesthe Program for Innovative Research Team (in Science and Technology) in University of Jilin Province
文摘Metallic zinc(Zn)is one of the most attractive multivalent-metal anode materials in post-lithium batteries because of its high abundance,low cost and high theoretical capacity.However,it usually suffers from large voltage polarization,low Coulombic efficiency and high propensity for dendritic failure during Zn stripping/plating,hindering the practical application in aqueous rechargeable zinc-metal batteries(AR-ZMBs).Here we demonstrate that anionic surfactant-assisted in situ surface alloying of Cu and Zn remarkably improves Zn reversibility of 3D nanoporous Zn electrodes for potential use as high-performance AR-ZMB anode materials.As a result of the zincophilic ZnxCuy alloy shell guiding uniform Zn deposition with a zero nucleation overpotential and facilitating Zn stripping via the ZnxCuy/Zn galvanic couples,the self-supported nanoporous ZnxCuy/Zn electrodes exhibit superior dendrite-free Zn stripping/plating behaviors in ambient aqueous electrolyte,with ultralow polarizations under current densities up to 50 mA cm^(‒2),exceptional stability for 1900 h and high Zn utilization.This enables AR-ZMB full cells constructed with nanoporous ZnxCuy/Zn anode and K_(z)MnO_(2)cathode to achieve specific energy of as high as~430 Wh kg^(‒1)with~99.8%Coulombic efficiency,and retain~86%after long-term cycles for>700 h.
基金supported by the National High Technology Research and Development Program of China(2012AA053305 and 2014AA052501)the National Natural Science Foundation of China(21506224)
文摘The coupling between electrochemically active material and conductive matrix is vitally important for high efficiency lithium ion batteries （LIBs）. By introducing oxygen groups into the nanoporous carbon framework, we accom- plish sustainably enhanced electrochemical performance for a SnO2/carbon LIB. 2-5 nm SnO2 nanoparticles are hydro- thermally grown in different nanoporous carbon frameworks, which are pristine, nitrogen- or oxygen-doped carbons. Compared with pristine and nitrogen-doped carbon hosts, the SnO2/oxygen-doped activated carbon （OAC） composite ex- hibits a higher discharge capacity of 1,122mAhg^-1 at 500 mA g^-1 after 320 cycles operation and a larger lithium storage capacity up to 680 mAhg-I at a high rate of 2,000 mA g^-1. The exceptional electrochemical performance originated from the oxygen groups, which could act as Lewis acid sites to attract electrons effectively from Sn during the charge process, thus accelerating reversible conversion of Sn to SnO2. Meanwhile, SnO2 nanoparticles are effectively bonded with carbon through such oxygen groups, thus preventing the electrochemical sintering and maintaining the cycling stability of the SnO2/OAC composite anode. The high electrochemical performance, low biomass cost, and facile preparation renders the SnO2/OAC composites a promising candidate for anode materials.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)Funded by the Ministry of Education(NRF-2019R1A2C1084836,NRF-2018M1A2A2061994,and NRF-2021R1A4A2001403)the KU-KIST School Program。
文摘Rechargeable aluminum batteries(RABs),which use earth-abundant and high-volumetric-capacity metal anodes(8040 m Ah cm-3),have great potential as next-generation power sources because they use cheaper resources to deliver higher energies,compared to current lithium ion batteries.However,the mechanism of charge delivery in the newly developed,ionic liquid-based electrolytic system for RABs differs from that in conventional organic electrolytes.Thus,targeted research efforts are required to address the large overpotentials and cycling decay encountered in the ionic liquid-based electrolytic system.In this study,a nanoporous carbon(NPC)electrode with well-developed nanopores is used to develop a high-performance aluminum anode.The negatively charged nanopores can provide quenched dynamics of electrolyte molecules in the aluminum deposition process,resulting in an increased collision rate.The fast chemical equilibrium of anionic species induced by the facilitated anionic collisions leads to more favorable reduction reactions that form aluminum metals.The nanoconfinement effect causes separated nucleation and growth of aluminum nanoparticles in the multiple confined nanopores,leading to higher coulombic efficiencies and more stable cycling performance compared with macroporous carbon black and 2D stainless steel electrodes.
基金the financially support to this research by the Australian Research Council (ARC) through the ARC Discovery Project DP170102557
文摘The effect of annealing of Ti foils before anodization on the morphology and electrochemical performance of resultant nanoporous anatase TiO2 （np-TiO2） as anode in rechargeable lithium-ion batteries （LIBs） was investigated. The np-TiO2 anode fabricated from annealed Ti foils exhibited higher specific surface area and reduced pore diameter compared to np-TiO2 electrode fabricated from as-received Ti foils. The highly porous np-TiO2 anode fabricated from annealed Ti foils exhibited 1st discharge capacity of 453.25 mAh/g and reduced to 172.70 mAh/g at 1 C current rate after 300 cycles; whilst the np-TiO2 electrode fabricated from the as-received Ti foils exhibited 1st discharge capacity of 213.30 mAh/g and reduced to 160.0 mAh/g at 1 C current rate after 300cycles. Even after 400cycles, such np-TiO2 electrode exhibited a reversible capacity of 125.0 mAh/g at 2.5 C current rate. Compared to the untreated Ti foils, the enhanced electro- chemical performance of np-TiO2 anode fabricated from annealed Ti foils was ascribed to the annealing- induced removal of residual stress among the Ti atoms. The benefit of annealing process can reduce pore size of as-fabricated np-TiO2.
基金supported by the Key R&D Plan of Jihua Laboratory(Nos.X200191TL200 and X220301XS220)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515110052)+1 种基金Foshan Postdoctoral Science Foundation(Nos.X221071MS210)Numerical computations were performed on Hefei advanced computing center。
文摘Sulfur doped carbonaceous materials are promising anodes for potassium-ion batteries because of their ability to bridge active sites and induce C/S electron coupling,resulting in increased ion storage capacitance However,the large potassium ions could cause significant volume expansion and structure collapse during operation in sulfur doped carbonaceous anodes,which lead to rapidly capacity sacrifice during long-term cycling.Nanopore design for anchoring sulfur atom in carbon skeleton is a novel way to alleviate the structure collapse and maintain the cycling stability.Therefore,this study developed a controlled nanopore and sulfur doped carbon sphere structure(S-NPHCSs).In potassium-ion batteries S-NPHCSs anode demonstrated exceptional performance with a high reversible capacity of 247 mAh·g^(–1)after 50 cycles at 0.2 A·g^(–1)and delivered a long cycle stability of 600 cycles at a high current density of 1.0 A·g^(–1).Interconnected nanopores and doped sulfur structure not only expand the accumulation space and offer ample active sites for diffusion and adsorption of potassium ions,but also build stable channels through nanopore structure to ensure the cyclic stability.This finding provides a fundamental theory for designing nanopore structures and introducing sulfur doped carbonaceous materials to enhance capacitive potassium storage and long cycle stability.
