Due to their low cost,environmental friendliness and high energy density,the lithium-sulfur batteries(LSB)have been regarded as a promising alternative for the next generation of rechargeable battery systems.However,t...Due to their low cost,environmental friendliness and high energy density,the lithium-sulfur batteries(LSB)have been regarded as a promising alternative for the next generation of rechargeable battery systems.However,the practical application of LSB is seriously hampered by its short cycle life and high self-charge owing to the apparent shuttle effect of soluble lithium polysulfides.Using MgSO_(4)@MgO composite as both template and dopant,template-guided S-doped mesoporous graphene(SMG)is prepared via the fluidized-bed chemical vapor deposition method.As the polypropylene(PP)modifier,SMG with high specific surface area,abundant mesoporous structures and moderate S doping content offers a wealth of physical and chemical adsorptive sites and reduced interfacial contact resistance,thereby restraining the serious shuttle effects of lithium polysulfides.Consequently,the LSB configured with mesoporous graphene(MG)as S host material and SMG as a separator modifier exhibits an enhanced electrochemical performance with a high average capacity of 955.64 mA h g^(-1) at 1C and a small capacity decay rate of 0.109%per cycle.Additionally,the density functional theory(DFT)calculation models have been rationally constructed and demonstrated that the doped S atoms in SMG possess higher binding energy to lithium polysulfides than that in MG,indicating that the SMG/PP separator can effectively capture soluble lithium polysulfides via chemical binding forces.This work would provide valuable insight into developing a versatile carbon-based separator modifier for LSB.展开更多
The conversion of waste tire pyrolysis oil(WTPO)into S-doped porous carbon nanorods(labeled as WPCNs)with hierarchical pore structure is realized by a simple template-directed approach.The specific surface area of as-...The conversion of waste tire pyrolysis oil(WTPO)into S-doped porous carbon nanorods(labeled as WPCNs)with hierarchical pore structure is realized by a simple template-directed approach.The specific surface area of as-obtained porous carbon nanorods can reach up to 1448 m^(2) g^(−1) without the addition of any activating agent.As the capacitive electrode,WPCNs possess the extraordinary compatibility to capacitance,different electrolyte systems as well as long-term cycle life even at a commercial-level areal mass loading(10 mg cm^(−2)).Besides,only an extremely small capacitance fluctuation is observed under the extreme circumstance(−40 to 80℃),reflecting the excellent high-and low-temperature performance.The relationship between the pore structure and capacitive behavior is analyzed by comparing WPCNs with mesopores-dominated asphalt-derived porous carbon nanorods(APCNs)and micropores-dominated activated carbon.The molecular dynamics simulation further reveals the ion diffusion and transfer ability of the as-prepared carbon materials under different pore size distribution.The total ion flow(NT)of WPCNs calculated by the simulation is obviously larger than APCNs and the N_(T) ratio between them is similar with the experimental average capacitance ratio.Furthermore,this work also provides a valuable strategy to prepare the electrode material with high capacitive energy storage ability through the high value-added utilization of WTPO.展开更多
The commercial graphite(CG)is the conventional anode material for lithium ion batteries(LIBs)due to its low delithiation voltage plateau(below 0.5 V)and extraordinary durability.Nevertheless,the further promotion of e...The commercial graphite(CG)is the conventional anode material for lithium ion batteries(LIBs)due to its low delithiation voltage plateau(below 0.5 V)and extraordinary durability.Nevertheless,the further promotion of energy density of LIBs is restricted by the limited capacity below 0.5 V of CG.Here,based on the supercritical CO2 exfoliation technique,the production of multi-layered graphene(MLG)is achieved from the pilot scale production line.The great merit of the exfoliated MLG anode is that the voltage plateau below 0.5 V is broadened obviously as compared to those of natural graphite and CG.Additionally,no obvious lithium dendrites are observed for MLG during the lithiation process.The large delithiation capacity under the low voltage plateau of MLG is mainly benefited from the combination of Li intercalation and boundary storage mechanism,which is further confirmed by the density functional theory calculations.The LiFePO4/MLG full cell can afford the satisfactory electrochemical property with respect to the capacity,energy density and ultralong cycling stability(90%capacity retention after 500 cycles at 2 C),significantly better than that of LiFePO4/CG.Besides,this developed technique not only dedicates to producing the high-performance anode for LIBs but also opens a door for the mass production of MLG in the industrial scale.展开更多
Porous carbon spheres derived from the facile hydrothermal treatment associated with the calcination process exhibit the good spherical morphology and unique porous structure.For the Li-based half-cell test,porous car...Porous carbon spheres derived from the facile hydrothermal treatment associated with the calcination process exhibit the good spherical morphology and unique porous structure.For the Li-based half-cell test,porous carbon spheres electrode not only exhibits larger reversible capacities and better compatibility as compared to the widely-used graphite,but also provides stable delithiation plateaus under different current density.Additionally,the delithiation ratio below 1 V almost accounts for a constant value(around 70%)with the increase of current density,evidencing that Li intercalation storage is the dominant model and Li insertion/extraction processes are propitious.The lithium ion hybrid capacitor configured with S-doped mesoporous graphene and porous carbon spheres as cathode and anode,delivers satisfied energy and power densities(up to 177 Wh kg^(−1) and 12,303 W kg^(−1),respectively)as well as long-term cyclability,which is superior to the corresponding S-doped mesoporous graphene//graphite and activated carbon//porous carbon spheres.In addition,the developed synthesis strategy is in favor of the realization of the scalable production of porous carbon spheres.展开更多
Nanomesh graphene (NMG) obtained by template chemical vapor deposition was used to synthesize the binder-free graphene monoliths by simple tablet pressing. The stacking manner of the NMG sheets was crucial to the co...Nanomesh graphene (NMG) obtained by template chemical vapor deposition was used to synthesize the binder-free graphene monoliths by simple tablet pressing. The stacking manner of the NMG sheets was crucial to the cohesion interaction between the graphene sheets, only the NMG materials with a loosely stacking manner could be pressed into binder-free monoliths. At the tableting pressure of 2-8 MPa, both the bulk densities and the specific surface areas of the monoliths keep nearly constant as the tableting pressure increases, indicating that the NMG monoliths have obvious elasticity and a porous structure due to the large corrugations and the mesh structures of the graphene sheets. As a result, an extraordinary methane storage capacity of 236 (v/v) at 9 MPa was obtained in the graphene monolith prepared by tabletin~ at 4 MPa.展开更多
基金supported by the Science Foundation of China University of Petroleum,Beijing(No.ZX20230047)Open Research Fund of State Key Laboratory of Coking Coal Exploitation and Comprehensive Utilization,China Pingmei Shenma Group(No.41040220201308).
文摘Due to their low cost,environmental friendliness and high energy density,the lithium-sulfur batteries(LSB)have been regarded as a promising alternative for the next generation of rechargeable battery systems.However,the practical application of LSB is seriously hampered by its short cycle life and high self-charge owing to the apparent shuttle effect of soluble lithium polysulfides.Using MgSO_(4)@MgO composite as both template and dopant,template-guided S-doped mesoporous graphene(SMG)is prepared via the fluidized-bed chemical vapor deposition method.As the polypropylene(PP)modifier,SMG with high specific surface area,abundant mesoporous structures and moderate S doping content offers a wealth of physical and chemical adsorptive sites and reduced interfacial contact resistance,thereby restraining the serious shuttle effects of lithium polysulfides.Consequently,the LSB configured with mesoporous graphene(MG)as S host material and SMG as a separator modifier exhibits an enhanced electrochemical performance with a high average capacity of 955.64 mA h g^(-1) at 1C and a small capacity decay rate of 0.109%per cycle.Additionally,the density functional theory(DFT)calculation models have been rationally constructed and demonstrated that the doped S atoms in SMG possess higher binding energy to lithium polysulfides than that in MG,indicating that the SMG/PP separator can effectively capture soluble lithium polysulfides via chemical binding forces.This work would provide valuable insight into developing a versatile carbon-based separator modifier for LSB.
基金supported by the National Key Research and Development Program of China(No.2018YFC1902603).
文摘The conversion of waste tire pyrolysis oil(WTPO)into S-doped porous carbon nanorods(labeled as WPCNs)with hierarchical pore structure is realized by a simple template-directed approach.The specific surface area of as-obtained porous carbon nanorods can reach up to 1448 m^(2) g^(−1) without the addition of any activating agent.As the capacitive electrode,WPCNs possess the extraordinary compatibility to capacitance,different electrolyte systems as well as long-term cycle life even at a commercial-level areal mass loading(10 mg cm^(−2)).Besides,only an extremely small capacitance fluctuation is observed under the extreme circumstance(−40 to 80℃),reflecting the excellent high-and low-temperature performance.The relationship between the pore structure and capacitive behavior is analyzed by comparing WPCNs with mesopores-dominated asphalt-derived porous carbon nanorods(APCNs)and micropores-dominated activated carbon.The molecular dynamics simulation further reveals the ion diffusion and transfer ability of the as-prepared carbon materials under different pore size distribution.The total ion flow(NT)of WPCNs calculated by the simulation is obviously larger than APCNs and the N_(T) ratio between them is similar with the experimental average capacitance ratio.Furthermore,this work also provides a valuable strategy to prepare the electrode material with high capacitive energy storage ability through the high value-added utilization of WTPO.
基金supported by the National Natural Science Foundation of China(Nos.21706283 and 21776308)Beijing Talents Foundation(No.2017000020124G010)+1 种基金Science Foundation of China University of Petroleum,Beijing(No.2462017YJRC003)the Joint Open Fund of Jiangsu Collaborative Innovation Center for Ecological Building Material and Environmental Protection Equipment and Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province(No.JH201812)。
文摘The commercial graphite(CG)is the conventional anode material for lithium ion batteries(LIBs)due to its low delithiation voltage plateau(below 0.5 V)and extraordinary durability.Nevertheless,the further promotion of energy density of LIBs is restricted by the limited capacity below 0.5 V of CG.Here,based on the supercritical CO2 exfoliation technique,the production of multi-layered graphene(MLG)is achieved from the pilot scale production line.The great merit of the exfoliated MLG anode is that the voltage plateau below 0.5 V is broadened obviously as compared to those of natural graphite and CG.Additionally,no obvious lithium dendrites are observed for MLG during the lithiation process.The large delithiation capacity under the low voltage plateau of MLG is mainly benefited from the combination of Li intercalation and boundary storage mechanism,which is further confirmed by the density functional theory calculations.The LiFePO4/MLG full cell can afford the satisfactory electrochemical property with respect to the capacity,energy density and ultralong cycling stability(90%capacity retention after 500 cycles at 2 C),significantly better than that of LiFePO4/CG.Besides,this developed technique not only dedicates to producing the high-performance anode for LIBs but also opens a door for the mass production of MLG in the industrial scale.
基金supported by the National Natural Science Foundation of China(No.52022109,51834008 and21706283)Beijing Municipal Natural Science Foundation(No.2202047)+1 种基金Beijing Talents Foundation(No.2017000020124G010)Science Foundation of China University of Petroleum,Beijing(No.2462020YXZZ016,2462018YJRC041 and2462017YJRC003).
文摘Porous carbon spheres derived from the facile hydrothermal treatment associated with the calcination process exhibit the good spherical morphology and unique porous structure.For the Li-based half-cell test,porous carbon spheres electrode not only exhibits larger reversible capacities and better compatibility as compared to the widely-used graphite,but also provides stable delithiation plateaus under different current density.Additionally,the delithiation ratio below 1 V almost accounts for a constant value(around 70%)with the increase of current density,evidencing that Li intercalation storage is the dominant model and Li insertion/extraction processes are propitious.The lithium ion hybrid capacitor configured with S-doped mesoporous graphene and porous carbon spheres as cathode and anode,delivers satisfied energy and power densities(up to 177 Wh kg^(−1) and 12,303 W kg^(−1),respectively)as well as long-term cyclability,which is superior to the corresponding S-doped mesoporous graphene//graphite and activated carbon//porous carbon spheres.In addition,the developed synthesis strategy is in favor of the realization of the scalable production of porous carbon spheres.
基金supported by Science Foundation of China University of Petroleum,Beijing(QD-2010-03)
文摘Nanomesh graphene (NMG) obtained by template chemical vapor deposition was used to synthesize the binder-free graphene monoliths by simple tablet pressing. The stacking manner of the NMG sheets was crucial to the cohesion interaction between the graphene sheets, only the NMG materials with a loosely stacking manner could be pressed into binder-free monoliths. At the tableting pressure of 2-8 MPa, both the bulk densities and the specific surface areas of the monoliths keep nearly constant as the tableting pressure increases, indicating that the NMG monoliths have obvious elasticity and a porous structure due to the large corrugations and the mesh structures of the graphene sheets. As a result, an extraordinary methane storage capacity of 236 (v/v) at 9 MPa was obtained in the graphene monolith prepared by tabletin~ at 4 MPa.