随着全球人口数量快速增长和科技不断进步,对能源需求逐步增加,但化石能源日渐枯竭,同时环境问题日趋严重.因此,亟需开发新型、绿色、高效的能源以及能源装置,以保障清洁能源的可持续利用.锂-氧电池因其能量密度高、环境友好等优点受到...随着全球人口数量快速增长和科技不断进步,对能源需求逐步增加,但化石能源日渐枯竭,同时环境问题日趋严重.因此,亟需开发新型、绿色、高效的能源以及能源装置,以保障清洁能源的可持续利用.锂-氧电池因其能量密度高、环境友好等优点受到了人们的广泛关注,并被认为是替代锂离子电池的新储能系统之一.然而,对于锂-氧电池仍需解决诸如能量密度低于理论值、倍率性能差和循环寿命短等难题.开发高效稳定的氧电极催化剂是解决上述问题的关键手段之一.在众多潜在的过渡金属氧化物催化剂中,四氧化三钴因其地壳丰度高、成本低和性能优异等优点成为研究热点.本文采用静电纺丝技术,结合热处理技术,成功制备了中空四氧化三钴纳米球镶嵌的多孔碳纳米纤维复合催化剂(H-Co_(3)O_(4)-CNFs),系统地研究了其氧还原反应(ORR)和析氧反应(OER)的电催化性能,以及作为锂-氧电池正极催化剂的电化学性能.结果表明,在碱性电解质中,H-Co_(3)O_(4)-CNFs具有较好的ORR/OER活性,展现出较好的双功能催化性能.H-Co_(3)O_(4)-CNFs作为锂-氧电池的氧电极催化剂材料,在100 mA g^(‒1)电流密度下的过电位为1.35 V,电池的放电比容量达到6134 mAh g^(‒1);当电流密度增加至800 mA g^(‒1)时,放电比容量仍能保持68.5%.在充放电电流密度为100 mA g^(‒1),限制容量为500 mAh g‒1的条件下,电池能保持150圈的稳定循环.H-Co3O4-CNFs催化剂较好的催化性能可归因于:(1)氮掺杂的多孔碳纤维具有良好的导电性和快速的电子传输能力;(2)多孔结构增大了电解液和催化剂活性位点的接触面积,并为放电产物过氧化锂的形成和分解提供了场所.另外,其良好的循环性能得益于裸露的Co_(3)O_(4)和嵌入纤维中的Co_(3)O_(4)形成的两种独立活性位点,这使其在ORR和OER过程中均有可用的催化活性位点,并在放电和充电过程中交替发挥作用.综上,本文研究结果为高效氧电极催化剂的设计提供了新思路。展开更多
Taking advantage of the nitrogen(N)-participation and large surface area of N-doped carbon nanocages(NCNCs),the Co Ox nanocrystals are conveniently immobilized onto the NCNCs with high dispersion.The Co Ox/NCNCs hybri...Taking advantage of the nitrogen(N)-participation and large surface area of N-doped carbon nanocages(NCNCs),the Co Ox nanocrystals are conveniently immobilized onto the NCNCs with high dispersion.The Co Ox/NCNCs hybrid exists in the mixed valence with predominant Co O over Co3O4 and demonstrates superb oxygen reduction reaction activity and stability remaining^94%current density even after operation over 100 h.These results suggest a promising strategy to develop advanced electrocatalysts with the novel NCNCs or even beyond.展开更多
Single-crystalline Li-doped Co3O4 truncated octahedra with different doping contents were synthesized by a simple combustion method with the fuel of multi-walled carbon nanotubes(MWCNTs).Controlled experiments showed ...Single-crystalline Li-doped Co3O4 truncated octahedra with different doping contents were synthesized by a simple combustion method with the fuel of multi-walled carbon nanotubes(MWCNTs).Controlled experiments showed that the pristine well-defined Co3O4 octahedra were obtained with exposed surfaces of {111} planes without lithium doping.In comparison with the octahedra,the truncated Co3O4 octahedra were composed of original {111} planes and extra {100} planes.It could be attributable to the selective adsorption of lithium ions on the {100} planes,making these planes with higher surface energy coexist with the crystal faces of {111}.Furthermore,the Li-doped truncated octahedra and undoped octahedra were used as catalysts in CO oxidation and as anode materials for Li-ion batteries(LIBs).The measurements exhibited that the Li-doped octahedra with added {100} crystal faces showed improved catalytic activity and electrochemical property because of the exposure of the higher energy faces of {100} and enhanced conductivity by Li doping.展开更多
文摘随着全球人口数量快速增长和科技不断进步,对能源需求逐步增加,但化石能源日渐枯竭,同时环境问题日趋严重.因此,亟需开发新型、绿色、高效的能源以及能源装置,以保障清洁能源的可持续利用.锂-氧电池因其能量密度高、环境友好等优点受到了人们的广泛关注,并被认为是替代锂离子电池的新储能系统之一.然而,对于锂-氧电池仍需解决诸如能量密度低于理论值、倍率性能差和循环寿命短等难题.开发高效稳定的氧电极催化剂是解决上述问题的关键手段之一.在众多潜在的过渡金属氧化物催化剂中,四氧化三钴因其地壳丰度高、成本低和性能优异等优点成为研究热点.本文采用静电纺丝技术,结合热处理技术,成功制备了中空四氧化三钴纳米球镶嵌的多孔碳纳米纤维复合催化剂(H-Co_(3)O_(4)-CNFs),系统地研究了其氧还原反应(ORR)和析氧反应(OER)的电催化性能,以及作为锂-氧电池正极催化剂的电化学性能.结果表明,在碱性电解质中,H-Co_(3)O_(4)-CNFs具有较好的ORR/OER活性,展现出较好的双功能催化性能.H-Co_(3)O_(4)-CNFs作为锂-氧电池的氧电极催化剂材料,在100 mA g^(‒1)电流密度下的过电位为1.35 V,电池的放电比容量达到6134 mAh g^(‒1);当电流密度增加至800 mA g^(‒1)时,放电比容量仍能保持68.5%.在充放电电流密度为100 mA g^(‒1),限制容量为500 mAh g‒1的条件下,电池能保持150圈的稳定循环.H-Co3O4-CNFs催化剂较好的催化性能可归因于:(1)氮掺杂的多孔碳纤维具有良好的导电性和快速的电子传输能力;(2)多孔结构增大了电解液和催化剂活性位点的接触面积,并为放电产物过氧化锂的形成和分解提供了场所.另外,其良好的循环性能得益于裸露的Co_(3)O_(4)和嵌入纤维中的Co_(3)O_(4)形成的两种独立活性位点,这使其在ORR和OER过程中均有可用的催化活性位点,并在放电和充电过程中交替发挥作用.综上,本文研究结果为高效氧电极催化剂的设计提供了新思路。
基金supported by the National Natural Science Foundation of China(51232003,21473089,21373108,21173115)the National Basic Research Program of China(2013CB932902)+2 种基金Jiangsu Province Science and Technology Support Project(BE2012159)Suzhou Science and Technology Plan projects(ZXG2013025)National Science Fund for Talent Training in Basic Science(J1103310)
文摘Taking advantage of the nitrogen(N)-participation and large surface area of N-doped carbon nanocages(NCNCs),the Co Ox nanocrystals are conveniently immobilized onto the NCNCs with high dispersion.The Co Ox/NCNCs hybrid exists in the mixed valence with predominant Co O over Co3O4 and demonstrates superb oxygen reduction reaction activity and stability remaining^94%current density even after operation over 100 h.These results suggest a promising strategy to develop advanced electrocatalysts with the novel NCNCs or even beyond.
基金supported by China National Funds for Distinguished Young Scientists (Grant No. 50725208)National Natural Science Foundation of China (Grant Nos. 11079002,20973019,and 51102005)+2 种基金Research Fund for the Doctoral Program of Higher Education of China (Grant No.20101102120045)Beijing Natural Science Foundation (Grant No.2113048)the Fundamental Research Funds for the Central Universities
文摘Single-crystalline Li-doped Co3O4 truncated octahedra with different doping contents were synthesized by a simple combustion method with the fuel of multi-walled carbon nanotubes(MWCNTs).Controlled experiments showed that the pristine well-defined Co3O4 octahedra were obtained with exposed surfaces of {111} planes without lithium doping.In comparison with the octahedra,the truncated Co3O4 octahedra were composed of original {111} planes and extra {100} planes.It could be attributable to the selective adsorption of lithium ions on the {100} planes,making these planes with higher surface energy coexist with the crystal faces of {111}.Furthermore,the Li-doped truncated octahedra and undoped octahedra were used as catalysts in CO oxidation and as anode materials for Li-ion batteries(LIBs).The measurements exhibited that the Li-doped octahedra with added {100} crystal faces showed improved catalytic activity and electrochemical property because of the exposure of the higher energy faces of {100} and enhanced conductivity by Li doping.
