Fe_(3)O_(4)/CNTs纳米复合材料用水热法在乙醇和丙二醇的混合溶液中合成,尺寸为5~15 nm的四氧化三铁纳米颗粒均匀附着在碳纳米管表面。作为锂电池负极材料,合成的Fe_(3)O_(4)/CNTs纳米复合材料展现出了优异的长循环特性和倍率循环特性...Fe_(3)O_(4)/CNTs纳米复合材料用水热法在乙醇和丙二醇的混合溶液中合成,尺寸为5~15 nm的四氧化三铁纳米颗粒均匀附着在碳纳米管表面。作为锂电池负极材料,合成的Fe_(3)O_(4)/CNTs纳米复合材料展现出了优异的长循环特性和倍率循环特性。在电流密度100 mA g^(-1)的条件下,在300次循环充放电后容量仍然能够保持在605 mAh g^(-1)。酸处理碳纳米管的加入为四氧化三铁提供了大量的生长点,显著减小了四氧化三铁颗粒的尺寸,阻止了充放电过程中颗粒的团聚,构建了独特的三维导电网,使复合材料展现出了优异的电化学性能。展开更多
针对水系镁离子电池正极材料循环不稳定及电化学性能差的问题,采用Mn_(3)O_(4)作为水系镁离子电池正极材料,通过简单的溶液共沉淀法将Mn_(3)O_(4)与碳纳米管(CNTs)原位复合形成Mn_(3)O_(4)/CNTs。经X射线粉末衍射仪(X-ray diffractomete...针对水系镁离子电池正极材料循环不稳定及电化学性能差的问题,采用Mn_(3)O_(4)作为水系镁离子电池正极材料,通过简单的溶液共沉淀法将Mn_(3)O_(4)与碳纳米管(CNTs)原位复合形成Mn_(3)O_(4)/CNTs。经X射线粉末衍射仪(X-ray diffractometer,XRD)、扫描电子显微镜(scanning electron microscopy,SEM)、通射电子显微镜(transmission electron microscopy,TEM)和循环伏安(cyclic voltammetry,CV)及充放电测试等表征,结果表明CNTs表面均匀附着尖晶石型Mn_(3)O_(4)纳米颗粒,提高了Mn_(3)O_(4)电极的导电性和电化学性能。Mn_(3)O_(4)/CNTs正极材料在100 mA/g下表现出305 mAh/g的比容量及长循环寿命,远高于Mn_(3)O_(4)的电池性能。Mn_(3)O_(4)/CNTs材料作为水系镁离子电池正极材料具有潜在的应用价值。展开更多
Constructing heterojunctions and hollow multi-shelled structures can render materials with fascinating physicochemical properties,and have been regarded as two promising strategies to overcome the severe shuttling and...Constructing heterojunctions and hollow multi-shelled structures can render materials with fascinating physicochemical properties,and have been regarded as two promising strategies to overcome the severe shuttling and sluggish kinetics of polysulfide in lithium-sulfur(Li-S)batteries.However,a single strategy can only take limited effect.Modulating catalytic hosts with synergistic effects are urgently desired.Herein,Mn_(3)O_(4)-MnS heterogeneous multi-shelled hollow spheres are meticulously designed by controlled sulfuration of Mn2O3 hollow spheres,and then applied as advanced encapsulation hosts for Li-S batteries.Benefiting from the separated spatial confinement by hollow multi-shelled structure,ample exposed active sites and built-in electric field by heterogeneous interface,and synergistic effects between Mn_(3)O_(4)(strong adsorption)and MnS(fast conversion)components,the assembled battery achieves prominent rate capability and decent cyclability(0.016%decay per cycle at 2 C,1000 cycles).More crucially,satisfactory areal capacity reaches up to 7.1 mAh cm^(-2)even with high sulfur loading(8.0 mg cm^(-2))and lean electrolyte(E/S=4.0 pL mg^(-1))conditions.This work will provide inspiration for the rational design of hollow multi-shelled heterostructure for various electrocatalysis applications.展开更多
Because of their large volume variation and inferior electrical conductivity,Mn_(3)O_(4)-based oxide anode materials have short cyclic lives and poor rate capability,which obstructs their development.In this study,we ...Because of their large volume variation and inferior electrical conductivity,Mn_(3)O_(4)-based oxide anode materials have short cyclic lives and poor rate capability,which obstructs their development.In this study,we successfully prepared a Mn_(3)O_(4)/N-doped honeycomb carbon composite using a smart and facile synthetic method.The Mn_(3)O_(4)nanopolyhedra are grown on N-doped honeycomb carbon,which evidently mitigates the volume change in the charging and discharging processes but also improves the electrochemical reaction kinetics.More importantly,the Mn-O-C bond in the Mn_(3)O_(4)/N-doped honeycomb carbon composite benefits electrochemical reversibility.These features of the Mn_(3)O_(4)/N-doped honeycomb carbon(NHC)composite are responsible for its superior electrochemical performance.When used for Li-ion batteries,the Mn_(3)O_(4)/N-doped honeycomb carbon anode exhibits a high reversible capacity of 598 mAh·g^(−1)after 350 cycles at 1 A·g^(−1).Even at 2 A·g^(−1),the Mn_(3)O_(4)/NHC anode still delivers a high capacity of 472 mAh·g^(−1).This work provides a new prospect for synthesizing and developing manganese-based oxide materials for energy storage.展开更多
Transition metal oxides are regarded as promising candidates of anode for next-generation lithium-ion batteries(LIBs)due to their ultrahigh theoretical capacity and low cost,but are restricted by their low conductivit...Transition metal oxides are regarded as promising candidates of anode for next-generation lithium-ion batteries(LIBs)due to their ultrahigh theoretical capacity and low cost,but are restricted by their low conductivity and large volume expansion during Li^(+)intercalation.Herein,we designed and constructed a structurally integrated 3D carbon tube(3D-CT)grid film with Mn_(3)O_(4)nanoparticles(Mn_(3)O_(4)-NPs)and carbon nanotubes(CNTs)filled in the inner cavity of CTs(denoted as Mn_(3)O_(4)-NPs/CNTs@3D-CT)as high-performance free-standing anode for LIBs.The Mn_(3)O_(4)-NPs/CNTs@3D-CT grid with Mn_(3)O_(4)-NPs filled in the inner cavity of 3D-CT not only afford sufficient space to overcome the damage caused by the volume expansion of Mn_(3)O_(4)-NPs during charge and discharge processes,but also achieves highly efficient channels for the fast transport of both electrons and Li+during cycling,thus offering outstanding electrochemical performance(865 mAh g^(-1)at 1 A g^(-1)after 300 cycles)and excellent rate capability(418 mAh g^(-1)at 4 A g^(-1))based on the total mass of electrode.The unique 3D-CT framework structure would open up a new route to the highly stable,high-capacity,and excellent cycle and high-rate performance free-standing electrodes for highperformance Li-ion storage.展开更多
Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_...Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_(2)O_(4) coating and Mg,Fe co-doping were constructed simultaneously by Mg,Fe surface treatment to suppress lattice oxygen evolution and P2-O2 phase transformation of P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)at deep charging.Through ex-situ X-ray diffraction(XRD)tests,we found that the Mg,Fe bulk co-doping could reduce the repulsion between transition metals and Na+/vacancies ordering,thus inhibiting the P2-O2 phase transition and significantly reducing the irreversible volume change of the material.Meanwhile,the internal electric field formed by the dielectric polarization of Mg Fe_(2)O_(4) effectively inhibits the outward migration of oxidized O^(a-)(a<2),thereby suppressing the lattice oxygen evolution at deep charging,confirmed by in situ Raman and ex situ XPS techniques.P2-Na NM@MF-3 shows enhanced high-voltage cycling performance with capacity retentions of 84.8% and 81.3%at 0.1 and 1 C after cycles.This work sheds light on regulating the surface chemistry for Na-layered oxide materials to enhance the high-voltage performance of Na-ion batteries.展开更多
文摘Fe_(3)O_(4)/CNTs纳米复合材料用水热法在乙醇和丙二醇的混合溶液中合成,尺寸为5~15 nm的四氧化三铁纳米颗粒均匀附着在碳纳米管表面。作为锂电池负极材料,合成的Fe_(3)O_(4)/CNTs纳米复合材料展现出了优异的长循环特性和倍率循环特性。在电流密度100 mA g^(-1)的条件下,在300次循环充放电后容量仍然能够保持在605 mAh g^(-1)。酸处理碳纳米管的加入为四氧化三铁提供了大量的生长点,显著减小了四氧化三铁颗粒的尺寸,阻止了充放电过程中颗粒的团聚,构建了独特的三维导电网,使复合材料展现出了优异的电化学性能。
文摘针对水系镁离子电池正极材料循环不稳定及电化学性能差的问题,采用Mn_(3)O_(4)作为水系镁离子电池正极材料,通过简单的溶液共沉淀法将Mn_(3)O_(4)与碳纳米管(CNTs)原位复合形成Mn_(3)O_(4)/CNTs。经X射线粉末衍射仪(X-ray diffractometer,XRD)、扫描电子显微镜(scanning electron microscopy,SEM)、通射电子显微镜(transmission electron microscopy,TEM)和循环伏安(cyclic voltammetry,CV)及充放电测试等表征,结果表明CNTs表面均匀附着尖晶石型Mn_(3)O_(4)纳米颗粒,提高了Mn_(3)O_(4)电极的导电性和电化学性能。Mn_(3)O_(4)/CNTs正极材料在100 mA/g下表现出305 mAh/g的比容量及长循环寿命,远高于Mn_(3)O_(4)的电池性能。Mn_(3)O_(4)/CNTs材料作为水系镁离子电池正极材料具有潜在的应用价值。
基金The support from the National Natural Science Foundation of China(No.51971083)the Natural Science Foundation of Heilongjiang Province,China(YQ 2020E007)is gratefully acknowledgedfinancially sponsored by Heilongjiang Touyan Team Program.
文摘Constructing heterojunctions and hollow multi-shelled structures can render materials with fascinating physicochemical properties,and have been regarded as two promising strategies to overcome the severe shuttling and sluggish kinetics of polysulfide in lithium-sulfur(Li-S)batteries.However,a single strategy can only take limited effect.Modulating catalytic hosts with synergistic effects are urgently desired.Herein,Mn_(3)O_(4)-MnS heterogeneous multi-shelled hollow spheres are meticulously designed by controlled sulfuration of Mn2O3 hollow spheres,and then applied as advanced encapsulation hosts for Li-S batteries.Benefiting from the separated spatial confinement by hollow multi-shelled structure,ample exposed active sites and built-in electric field by heterogeneous interface,and synergistic effects between Mn_(3)O_(4)(strong adsorption)and MnS(fast conversion)components,the assembled battery achieves prominent rate capability and decent cyclability(0.016%decay per cycle at 2 C,1000 cycles).More crucially,satisfactory areal capacity reaches up to 7.1 mAh cm^(-2)even with high sulfur loading(8.0 mg cm^(-2))and lean electrolyte(E/S=4.0 pL mg^(-1))conditions.This work will provide inspiration for the rational design of hollow multi-shelled heterostructure for various electrocatalysis applications.
基金financially supported by the Natural Science Foundation of Henan Province of China(No.222300420252)Nanyang Normal University(Nos.2020ZX013 and 2020ZX014).
文摘Because of their large volume variation and inferior electrical conductivity,Mn_(3)O_(4)-based oxide anode materials have short cyclic lives and poor rate capability,which obstructs their development.In this study,we successfully prepared a Mn_(3)O_(4)/N-doped honeycomb carbon composite using a smart and facile synthetic method.The Mn_(3)O_(4)nanopolyhedra are grown on N-doped honeycomb carbon,which evidently mitigates the volume change in the charging and discharging processes but also improves the electrochemical reaction kinetics.More importantly,the Mn-O-C bond in the Mn_(3)O_(4)/N-doped honeycomb carbon composite benefits electrochemical reversibility.These features of the Mn_(3)O_(4)/N-doped honeycomb carbon(NHC)composite are responsible for its superior electrochemical performance.When used for Li-ion batteries,the Mn_(3)O_(4)/N-doped honeycomb carbon anode exhibits a high reversible capacity of 598 mAh·g^(−1)after 350 cycles at 1 A·g^(−1).Even at 2 A·g^(−1),the Mn_(3)O_(4)/NHC anode still delivers a high capacity of 472 mAh·g^(−1).This work provides a new prospect for synthesizing and developing manganese-based oxide materials for energy storage.
基金supported by the Natural Science Foundation of China(91963202 and 52072372)the Key Research Program of Frontier Sciences(CAS,Grant,QYZDJ-SSW-SLH046)the CAS/SAFEA International Partnership Program for Creative Research Teams,and the Hefei Institutes of Physical Science,Chinese Academy of Sciences Director’s Fund(YZJ ZX202018)
文摘Transition metal oxides are regarded as promising candidates of anode for next-generation lithium-ion batteries(LIBs)due to their ultrahigh theoretical capacity and low cost,but are restricted by their low conductivity and large volume expansion during Li^(+)intercalation.Herein,we designed and constructed a structurally integrated 3D carbon tube(3D-CT)grid film with Mn_(3)O_(4)nanoparticles(Mn_(3)O_(4)-NPs)and carbon nanotubes(CNTs)filled in the inner cavity of CTs(denoted as Mn_(3)O_(4)-NPs/CNTs@3D-CT)as high-performance free-standing anode for LIBs.The Mn_(3)O_(4)-NPs/CNTs@3D-CT grid with Mn_(3)O_(4)-NPs filled in the inner cavity of 3D-CT not only afford sufficient space to overcome the damage caused by the volume expansion of Mn_(3)O_(4)-NPs during charge and discharge processes,but also achieves highly efficient channels for the fast transport of both electrons and Li+during cycling,thus offering outstanding electrochemical performance(865 mAh g^(-1)at 1 A g^(-1)after 300 cycles)and excellent rate capability(418 mAh g^(-1)at 4 A g^(-1))based on the total mass of electrode.The unique 3D-CT framework structure would open up a new route to the highly stable,high-capacity,and excellent cycle and high-rate performance free-standing electrodes for highperformance Li-ion storage.
基金supported by the Special Project for the Central Government to Guide Local Technological Development (GUIKE ZY20198008)the Guangxi Technology Base and talent Subject (GUIKE AD20238012,AD20297086)+5 种基金the Natural Science Foundation of Guangxi Province (2021GXNSFDA075012)the National Natural Science Foundation of China (51902108,52104298,22169004)the National Natural Science Foundation of China (U20A20249)the Regional Innovation and Development Joint Fundthe Guangxi Innovation Driven Development Subject (GUIKE AA19182020,19254004)the Special Fund for Guangxi Distinguished Expert。
文摘Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_(2)O_(4) coating and Mg,Fe co-doping were constructed simultaneously by Mg,Fe surface treatment to suppress lattice oxygen evolution and P2-O2 phase transformation of P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)at deep charging.Through ex-situ X-ray diffraction(XRD)tests,we found that the Mg,Fe bulk co-doping could reduce the repulsion between transition metals and Na+/vacancies ordering,thus inhibiting the P2-O2 phase transition and significantly reducing the irreversible volume change of the material.Meanwhile,the internal electric field formed by the dielectric polarization of Mg Fe_(2)O_(4) effectively inhibits the outward migration of oxidized O^(a-)(a<2),thereby suppressing the lattice oxygen evolution at deep charging,confirmed by in situ Raman and ex situ XPS techniques.P2-Na NM@MF-3 shows enhanced high-voltage cycling performance with capacity retentions of 84.8% and 81.3%at 0.1 and 1 C after cycles.This work sheds light on regulating the surface chemistry for Na-layered oxide materials to enhance the high-voltage performance of Na-ion batteries.
