Studies on three-dimensional structured carbon templates have focused on how to guide homogeneous lithium metal nucleation and growth for lithium metal anodes(LMAs).However,there is still insufficient evidence for a k...Studies on three-dimensional structured carbon templates have focused on how to guide homogeneous lithium metal nucleation and growth for lithium metal anodes(LMAs).However,there is still insufficient evidence for a key factor to achieve their high electrochemical performance.Here,the effects of nanopores and sulfur doping on carbon-based nanoporous host(CNH)electrode materials for LMAs were investigated using natural polymer-derived CNHs.Homogeneous pore-filling behaviors of lithium metal in the nanopores of the CNH electrode materials were first observed by ex situ scanning electron microscopy analysis,where the protective lithium metal nucleation and growth process led to significantly high Coulombic efficiency(CE)of~99.4%and stable 600 cycles.In addition,a comparison study of CNH and sulfurdoped CNH(S-CNH)electrodes,which differ only in the presence or absence of sulfur,revealed that sulfur doping can cause lower electrochemical series resistance,higher CE value,and better cycling stability in a wide range of current densities and number of cycles.Moreover,S-CNH-based LMAs showed high electrochemical performance in full-cell Li-S battery tests using a sulfur copolymer cathode,where a high energy density of 1370Wh kgelectrode−1 and an excellent power density of 4120Wkgelectrode−1 were obtained.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 solid-solution reaction between an alkali cation and an active host material is known as a singlephase redox mechanism,and it is typically accompanied by a continuous voltage change.It is distinct from the typical...The solid-solution reaction between an alkali cation and an active host material is known as a singlephase redox mechanism,and it is typically accompanied by a continuous voltage change.It is distinct from the typical alkali cation intercalation reaction at an equivalent site of the active host material,which exhibits a voltage plateau.Herein,we report an unusual solid-solution potassium-ion intercalation mechanism with a low-voltage plateau capacity on multilayered turbostratic graphene nanosheets(T-GNSs).Despite the disordered graphitic structure with a broad range of d-spacings(3.65–4.18À),the T-GNSs showed a reversible plateau capacity of~200 m A h g^(-1),which is higher than that of a well-ordered graphite nanoplate(~120 m A h g^(-1)).In addition,a sloping capacity of~220 m A h g^(-1)was delivered with the plateau capacity,and higher rate capabilities,better reversibility,and a more stable cycling performance were confirmed on the turbostratic microstructure.First-principles calculations suggest that the multitudinous lattice domains of the T-GNSs contain diverse intercalation sites with strong binding energies,which could be the origin of the high-performance solid-solution potassium-ion intercalation behavior when the turbostratic graphene stacks have a d-spacing smaller than that of equilibrium potassium–graphite intercalation compounds(5.35À).展开更多
Bifunctional hybrid anodes(BHAs),which are both a high-performance active host material for lithium-ion storage as well as a guiding agent for homogeneous lithium metal nucleation and growth,exhibit significant potent...Bifunctional hybrid anodes(BHAs),which are both a high-performance active host material for lithium-ion storage as well as a guiding agent for homogeneous lithium metal nucleation and growth,exhibit significant potential as anodes for next-generation high-energy-density lithium-ion batteries(LIBs).In this study,sulfur-doped hard carbon nanosphere assemblies(S-HCNAs)were prepared through a hydrothermal treatment of a liquid organic precursor,followed by high-temperature thermal annealing with elemental sulfur for application as BHAs for LIBs.In a carbonate-based electrolyte containing fluoroethylene carbonate additive,the S-HCNAs showed high lithium-ion storage capacities in sloping as well as plateau voltage sections,good rate capabilities,and stable cyclabilities.In addition,high average Coulombic efficiencies(CEs)of~96.9%were achieved for dual lithium-ion and lithium metal storage cycles.In the LIB full-cell tests with typical NCM811 cathodes,the S-HCNA-based BHAs containing~400 mA h g^(−1) of excess lithium led to high energy and power densities of~500Wh kg^(−1) and~1695Wkg^(−1),respectively,and a stable cycling performance with~100%CEs was achieved.展开更多
Thick cathodes can overcome the low capacity issues,which mostly hamper the performance of the conventional active cathode materials,used in rechargeable Li batteries.However,the typical slurry-based method induces cr...Thick cathodes can overcome the low capacity issues,which mostly hamper the performance of the conventional active cathode materials,used in rechargeable Li batteries.However,the typical slurry-based method induces cracking and flaking during the fabrication of thick electrodes.In addition,a significant increase in the charge-transfer resistance and local cur-rent overload results in poor rate capabilities and cycling stabilities,thereby limiting electrode thickening.In this study,a synergistic dual-network combination strategy based on a conductive nanofibrillar network(CNN)and a nano-bridging amor-phous polyhydroxyalkanoate(aPHA)binder is used to demonstrate the feasibility of constructing a high-performance thick cathode.The CNN and aPHA dual network facilitates the fabrication of a thick cathode(≥250μm thickness and≥90 wt%active cathode material)by a mass-producible slurry method.The thick cathode exhibited a high rate capability and excel-lent cycling stability.In addition,the thick cathode and thin Li metal anode pair(Li//t-NCM)exhibited an optimal energy performance,affording high-performance Li metal batteries with a high areal energy of~25.3 mW h cm^(-2),a high volumetric power density of~1720 W L^(-1),and an outstanding specific energy of~470 W h kg^(-1)at only 6 mA h cm^(-2).展开更多
Currently,most of the materials for oil-water separation membranes are limited to fluorine-based polymers with low surface energy.However,it is not biodegradable and requires large amounts of organic and toxic solvent...Currently,most of the materials for oil-water separation membranes are limited to fluorine-based polymers with low surface energy.However,it is not biodegradable and requires large amounts of organic and toxic solvents in the membrane manufacturing process.Therefore,interest in the development of a new eco-friendly oil-water separation membrane that does not cause secondary pollution and exhibits selective wettability characteristics in water or oil is increasing.The biopolymeric nanofibrous membranes inspired by fish skin can provide specific underwater oleophobicity,which is effective for excellent oil-water separation efficiency and prevention of secondary contamination.Fish gelatin,which is highly soluble in water and has a low gelation temperature,can be electrospun in an aqueous solution and has the same polar functional groups as the hydrophilic mucilage of fish skin.In addition,the micro/nanostructure of fish skin,which induces superoleophobicity in water,introduces a bead-on-string structure using the Rayleigh instability of electrospinning.The solubility of fish gelatin in water was removed using an eco-friendly crosslinking method using reducing sugars.Fish skin-mimicking materials successfully separated suspended oil and emulsified oil,with a maximum flux of 2086 Lm^(−2) h^(−1) and a separation efficiency of more than 99%.The proposed biopolymeric nanofibrous membranes use fish gelatin,which can be extracted from fish waste and has excellent biodegradability with excellent oil-water separation performance.In addition,polymer material processing,including membrane manufacturing and crosslinking,can be realized through eco-friendly processes.Therefore,fish skin-inspired biopolymeric membrane is expected to be a promising candidate for a sustainable and effective oil-water separation membrane in the future.展开更多
基金National Research Foundation of Korea,Grant/Award Numbers:2019R1A2C1084836,2021R1A4A2001403。
文摘Studies on three-dimensional structured carbon templates have focused on how to guide homogeneous lithium metal nucleation and growth for lithium metal anodes(LMAs).However,there is still insufficient evidence for a key factor to achieve their high electrochemical performance.Here,the effects of nanopores and sulfur doping on carbon-based nanoporous host(CNH)electrode materials for LMAs were investigated using natural polymer-derived CNHs.Homogeneous pore-filling behaviors of lithium metal in the nanopores of the CNH electrode materials were first observed by ex situ scanning electron microscopy analysis,where the protective lithium metal nucleation and growth process led to significantly high Coulombic efficiency(CE)of~99.4%and stable 600 cycles.In addition,a comparison study of CNH and sulfurdoped CNH(S-CNH)electrodes,which differ only in the presence or absence of sulfur,revealed that sulfur doping can cause lower electrochemical series resistance,higher CE value,and better cycling stability in a wide range of current densities and number of cycles.Moreover,S-CNH-based LMAs showed high electrochemical performance in full-cell Li-S battery tests using a sulfur copolymer cathode,where a high energy density of 1370Wh kgelectrode−1 and an excellent power density of 4120Wkgelectrode−1 were obtained.
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supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(NRF-2019R1A2C1084836,and NRF-2021R1A4A2001403)supported by the KU-KIST School Program。
文摘The solid-solution reaction between an alkali cation and an active host material is known as a singlephase redox mechanism,and it is typically accompanied by a continuous voltage change.It is distinct from the typical alkali cation intercalation reaction at an equivalent site of the active host material,which exhibits a voltage plateau.Herein,we report an unusual solid-solution potassium-ion intercalation mechanism with a low-voltage plateau capacity on multilayered turbostratic graphene nanosheets(T-GNSs).Despite the disordered graphitic structure with a broad range of d-spacings(3.65–4.18À),the T-GNSs showed a reversible plateau capacity of~200 m A h g^(-1),which is higher than that of a well-ordered graphite nanoplate(~120 m A h g^(-1)).In addition,a sloping capacity of~220 m A h g^(-1)was delivered with the plateau capacity,and higher rate capabilities,better reversibility,and a more stable cycling performance were confirmed on the turbostratic microstructure.First-principles calculations suggest that the multitudinous lattice domains of the T-GNSs contain diverse intercalation sites with strong binding energies,which could be the origin of the high-performance solid-solution potassium-ion intercalation behavior when the turbostratic graphene stacks have a d-spacing smaller than that of equilibrium potassium–graphite intercalation compounds(5.35À).
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 and NRF-2021R1A4A2001403)supported by 2018 Research Grant(PoINT)from Kangwon National University。
文摘Bifunctional hybrid anodes(BHAs),which are both a high-performance active host material for lithium-ion storage as well as a guiding agent for homogeneous lithium metal nucleation and growth,exhibit significant potential as anodes for next-generation high-energy-density lithium-ion batteries(LIBs).In this study,sulfur-doped hard carbon nanosphere assemblies(S-HCNAs)were prepared through a hydrothermal treatment of a liquid organic precursor,followed by high-temperature thermal annealing with elemental sulfur for application as BHAs for LIBs.In a carbonate-based electrolyte containing fluoroethylene carbonate additive,the S-HCNAs showed high lithium-ion storage capacities in sloping as well as plateau voltage sections,good rate capabilities,and stable cyclabilities.In addition,high average Coulombic efficiencies(CEs)of~96.9%were achieved for dual lithium-ion and lithium metal storage cycles.In the LIB full-cell tests with typical NCM811 cathodes,the S-HCNA-based BHAs containing~400 mA h g^(−1) of excess lithium led to high energy and power densities of~500Wh kg^(−1) and~1695Wkg^(−1),respectively,and a stable cycling performance with~100%CEs was achieved.
基金supported by the Basic Science Research Program of the National Research Foundation of Korea(NRF)funded by the Ministry of Education(RS-2023-00302689 and NRF-2021R1A4A2001403)funded by the Korea Institute of Science and Technology(KIST)Institutional Program(2V09840).
文摘Thick cathodes can overcome the low capacity issues,which mostly hamper the performance of the conventional active cathode materials,used in rechargeable Li batteries.However,the typical slurry-based method induces cracking and flaking during the fabrication of thick electrodes.In addition,a significant increase in the charge-transfer resistance and local cur-rent overload results in poor rate capabilities and cycling stabilities,thereby limiting electrode thickening.In this study,a synergistic dual-network combination strategy based on a conductive nanofibrillar network(CNN)and a nano-bridging amor-phous polyhydroxyalkanoate(aPHA)binder is used to demonstrate the feasibility of constructing a high-performance thick cathode.The CNN and aPHA dual network facilitates the fabrication of a thick cathode(≥250μm thickness and≥90 wt%active cathode material)by a mass-producible slurry method.The thick cathode exhibited a high rate capability and excel-lent cycling stability.In addition,the thick cathode and thin Li metal anode pair(Li//t-NCM)exhibited an optimal energy performance,affording high-performance Li metal batteries with a high areal energy of~25.3 mW h cm^(-2),a high volumetric power density of~1720 W L^(-1),and an outstanding specific energy of~470 W h kg^(-1)at only 6 mA h cm^(-2).
基金supported by the Technology Innovation Program(20018540)funded by the Ministry of Trade,Industry and Energy(MOTIE,Korea)+1 种基金supported by the Basic Science Research Program of the National Research Foundation of Korea(NRF)funded by the Ministry of Education(NRF-2021R1A4A2001403).
文摘Currently,most of the materials for oil-water separation membranes are limited to fluorine-based polymers with low surface energy.However,it is not biodegradable and requires large amounts of organic and toxic solvents in the membrane manufacturing process.Therefore,interest in the development of a new eco-friendly oil-water separation membrane that does not cause secondary pollution and exhibits selective wettability characteristics in water or oil is increasing.The biopolymeric nanofibrous membranes inspired by fish skin can provide specific underwater oleophobicity,which is effective for excellent oil-water separation efficiency and prevention of secondary contamination.Fish gelatin,which is highly soluble in water and has a low gelation temperature,can be electrospun in an aqueous solution and has the same polar functional groups as the hydrophilic mucilage of fish skin.In addition,the micro/nanostructure of fish skin,which induces superoleophobicity in water,introduces a bead-on-string structure using the Rayleigh instability of electrospinning.The solubility of fish gelatin in water was removed using an eco-friendly crosslinking method using reducing sugars.Fish skin-mimicking materials successfully separated suspended oil and emulsified oil,with a maximum flux of 2086 Lm^(−2) h^(−1) and a separation efficiency of more than 99%.The proposed biopolymeric nanofibrous membranes use fish gelatin,which can be extracted from fish waste and has excellent biodegradability with excellent oil-water separation performance.In addition,polymer material processing,including membrane manufacturing and crosslinking,can be realized through eco-friendly processes.Therefore,fish skin-inspired biopolymeric membrane is expected to be a promising candidate for a sustainable and effective oil-water separation membrane in the future.
