Low-platinum(Pt)alloy catalysts hold promising application in oxygen reduction reaction(ORR)electrocatalysis of protonexchange-membrane fuel cells(PEMFCs).Although significant progress has been made to boost the kinet...Low-platinum(Pt)alloy catalysts hold promising application in oxygen reduction reaction(ORR)electrocatalysis of protonexchange-membrane fuel cells(PEMFCs).Although significant progress has been made to boost the kinetic ORR mass activity at low current densities in liquid half-cells,little attention was paid to the performance of Pt-based catalysts in realistic PEMFCs particularly at high current densities for high power density,which remains poorly understood.In this paper,we show that,regardless of the kinetic mass activity at the low current density region,the high current density performance of the low-Pt alloy catalysts is dominantly controlled by the total Pt surface area,particularly in low-Pt-loading H_(2)–air PEMFCs.To this end,we propose two different strategies to boost the specific Pt surface area,the post-15-nm dealloyed nanoporous architecture and the sub-5-nm solid core–shell nanoparticles(NPs)through fluidic-bed synthesis,both of which bring in comparably high mass activity and high Pt surface area for large-current-density performance.At medium current density,the dealloyed porous NPs provide substantially higher H_(2)–air PEMFC performance compared to solid core–shell catalysts,despite their similar mass activity in liquid half-cells.Scanning transmission electron microscopy images combined with electron energy loss spectroscopic imaging evidence a previously unreported“semi-immersed nanoporous-Pt/ionomer”structure in contrast to a“fully-immersed core–shellPt/ionomer”structure,thus favoring O_(2) transport and improving the fuel cell performance.Our results provide new insights into the role of Pt nanostructures in concurrently optimizing the mass activity,Pt surface area and Pt/Nafion interface for high power density fuel cells.展开更多
LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)secondary particles with high tap density have a great potential for high volumetric energy density lithium(Li)-ion power bat-tery.However,the ionic conductivity mechanism of NCA ...LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)secondary particles with high tap density have a great potential for high volumetric energy density lithium(Li)-ion power bat-tery.However,the ionic conductivity mechanism of NCA with compact structure is still a suspense,especially the function of grain boundaries.Herein,we sys-tematically investigate the Li-ion transport behavior in both the primitive NCA(PNCA)secondary sphere densely grown by single-crystal primary grains and ball-milled NCA(MNCA)nanosized particle to reveal the role of grain bound-aries for Li-ion transport.The PNCA and MNCA have comparable Li-ion dif-fusion coefficients and rate performance.Moreover,the graphene nanosheet conductive additive only mildly affects the Li-ion diffusion in PNCA cathode,while which severely blocks the Li-ion transport in MNCA cathode.Through high-resolution transmission electron microscopy and electron energy loss spec-troscopy,we clearly observe Li-ion depletion at lower state of charge(SOC)and Li-ion aggregation at high SOC along the grain boundaries of PNCA secondary particles during high-rate lithiation process.The grain boundaries can construct an interconnected Li-ion transport network for highly efficient Li-ion transport,which contributes to excellent high-rate performance of compact PNCA sec-ondary particles.These findings present new strategy and deep insight in design-ing compact materials with excellent high-rate performance.展开更多
基金supported by the National Science Fund for Distinguished Young Scholars(52125309)the National Natural Science Foundation of China(51991343,51920105002,51991340,52188101,and 11974156)+3 种基金Guangdong Innovative and Entrepreneurial Research Team Program(2017ZT07C341 and 2019ZT08C044)the Bureau of Industry and Information Technology of Shenzhen for the “2017 Graphene Manufacturing Innovation Center Project”(201901171523)Shenzhen Basic Research Project(JCYJ20200109144616617 and JCYJ20190809180605522)Shenzhen Science and Technology Program(KQTD20190929173815000 and 20200925161102001)。
基金supported by the National Natural Science Foundation of China(Nos.52173222,51622103 and 22109088)the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01N111)+1 种基金Key Area Research and Development Program of Guangdong Province(No.2020B0909040003)Shenzhen Science and Technology Innovation Committee(Nos.WDZ20200819115243002 and JCYJ20190809172617313).
文摘Low-platinum(Pt)alloy catalysts hold promising application in oxygen reduction reaction(ORR)electrocatalysis of protonexchange-membrane fuel cells(PEMFCs).Although significant progress has been made to boost the kinetic ORR mass activity at low current densities in liquid half-cells,little attention was paid to the performance of Pt-based catalysts in realistic PEMFCs particularly at high current densities for high power density,which remains poorly understood.In this paper,we show that,regardless of the kinetic mass activity at the low current density region,the high current density performance of the low-Pt alloy catalysts is dominantly controlled by the total Pt surface area,particularly in low-Pt-loading H_(2)–air PEMFCs.To this end,we propose two different strategies to boost the specific Pt surface area,the post-15-nm dealloyed nanoporous architecture and the sub-5-nm solid core–shell nanoparticles(NPs)through fluidic-bed synthesis,both of which bring in comparably high mass activity and high Pt surface area for large-current-density performance.At medium current density,the dealloyed porous NPs provide substantially higher H_(2)–air PEMFC performance compared to solid core–shell catalysts,despite their similar mass activity in liquid half-cells.Scanning transmission electron microscopy images combined with electron energy loss spectroscopic imaging evidence a previously unreported“semi-immersed nanoporous-Pt/ionomer”structure in contrast to a“fully-immersed core–shellPt/ionomer”structure,thus favoring O_(2) transport and improving the fuel cell performance.Our results provide new insights into the role of Pt nanostructures in concurrently optimizing the mass activity,Pt surface area and Pt/Nafion interface for high power density fuel cells.
基金National Natural Science Founda-tion of China,Grant/Award Number:U2001220Local Innovative Research Teams Project of Guangdong Pearl River Talents Program,Grant/Award Number:2017BT01N111+2 种基金Shenzhen Technical Plan Project,Grant/Award Numbers:JCYJ20180508152135822,JCYJ20180508152210821,JCYJ20170412170706047Shenzhen graphene manufacturing innova-tion center,Grant/Award Number:201901161513Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center,Grant/Award Number:XMHT20200203006。
文摘LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)secondary particles with high tap density have a great potential for high volumetric energy density lithium(Li)-ion power bat-tery.However,the ionic conductivity mechanism of NCA with compact structure is still a suspense,especially the function of grain boundaries.Herein,we sys-tematically investigate the Li-ion transport behavior in both the primitive NCA(PNCA)secondary sphere densely grown by single-crystal primary grains and ball-milled NCA(MNCA)nanosized particle to reveal the role of grain bound-aries for Li-ion transport.The PNCA and MNCA have comparable Li-ion dif-fusion coefficients and rate performance.Moreover,the graphene nanosheet conductive additive only mildly affects the Li-ion diffusion in PNCA cathode,while which severely blocks the Li-ion transport in MNCA cathode.Through high-resolution transmission electron microscopy and electron energy loss spec-troscopy,we clearly observe Li-ion depletion at lower state of charge(SOC)and Li-ion aggregation at high SOC along the grain boundaries of PNCA secondary particles during high-rate lithiation process.The grain boundaries can construct an interconnected Li-ion transport network for highly efficient Li-ion transport,which contributes to excellent high-rate performance of compact PNCA sec-ondary particles.These findings present new strategy and deep insight in design-ing compact materials with excellent high-rate performance.
