Seed-mediated growth is the most general way to controllably synthesize bimetal nano-heterostructures. Despite successful instances through trial and error were reported, the way for second metal depositing on the see...Seed-mediated growth is the most general way to controllably synthesize bimetal nano-heterostructures. Despite successful instances through trial and error were reported, the way for second metal depositing on the seed. namely whether the symmetry of resulted nano-heterostructure follows the original crystal symmetry of seed metal, remains an unpredictable issue to date. In this work, we propose that the ther- modynamic factor, i.e., the difference of equilibrium electrochemical potentials （corresponding to their Fermi levels） of two metals in the growth solution, plays a key role for the symmetry breaking of bimetal nano-heterostructures during the seed-mediated growth. As a proof-of-principle experiment, by revers- ing the relative position of Fermi levels of the Pd nanocube seeds and the second metal Au with changing the concentration of reductant （L-ascorbic acid） in the growth solution, the structure of as-prepared prod- ucts successfully evolved from centrosymmetric Pd@Au core-shell trisoctabedra to asymmetric Pd-Au hetero-dimers. The idea was further demonstrated by the growth of Ag on the Pd seeds. The present work intends to reveal the origin of symmetry breaking in the seed-mediated growth of nano-heterostructures from the viewpoint of thermodynamics, and these new insights will in turn help to achieve rational con- struction of bimetal nano-heterostructures with soecific functions.展开更多
Potassium ion batteries(PIBs)with high-volumetric energy densities are promising for next-generation low-cost energy storage devices.Metallic bismuth(Bi)with a structure similar to graphite,is a promising anode materi...Potassium ion batteries(PIBs)with high-volumetric energy densities are promising for next-generation low-cost energy storage devices.Metallic bismuth(Bi)with a structure similar to graphite,is a promising anode material for PIBs due to its high theoretical volumetric capacity(3763 mA h cm^−3)and relatively low working potential(−2.93 V vs.standard hydrogen electrode).However,it experiences severe capacity decay caused by a huge volume expansion of Bi when alloying with potassium.This study reports a flexible and free-standing Bi nanosheet(BiNS)/reduced graphene oxide composite membrane with designed porosity close to the expansion ratio of BiNS after charging.The controlled pore structure improves the electron and ion transport during cycling,and strengthens the structural stability of the electrode during potassiation and depotassiation,leading to excellent electrochemical performance for potassium-ion storage.In particular,it delivers a high reversible volumetric capacity of 451 mA h cm^−3 at the current density of 0.5 A g^−1,which is much higher than the previously reported commercial graphite material.展开更多
基金supported by the National Basic Research Program of China(2015CB93230)the National Key Research and Development Program of China(2017YFA0206801)+1 种基金the National Natural Science Foundation of China(21333008,21671163,21721001,and 21773190)the Fundamental Research Funds for the Central Universities(20720160026)
文摘Seed-mediated growth is the most general way to controllably synthesize bimetal nano-heterostructures. Despite successful instances through trial and error were reported, the way for second metal depositing on the seed. namely whether the symmetry of resulted nano-heterostructure follows the original crystal symmetry of seed metal, remains an unpredictable issue to date. In this work, we propose that the ther- modynamic factor, i.e., the difference of equilibrium electrochemical potentials （corresponding to their Fermi levels） of two metals in the growth solution, plays a key role for the symmetry breaking of bimetal nano-heterostructures during the seed-mediated growth. As a proof-of-principle experiment, by revers- ing the relative position of Fermi levels of the Pd nanocube seeds and the second metal Au with changing the concentration of reductant （L-ascorbic acid） in the growth solution, the structure of as-prepared prod- ucts successfully evolved from centrosymmetric Pd@Au core-shell trisoctabedra to asymmetric Pd-Au hetero-dimers. The idea was further demonstrated by the growth of Ag on the Pd seeds. The present work intends to reveal the origin of symmetry breaking in the seed-mediated growth of nano-heterostructures from the viewpoint of thermodynamics, and these new insights will in turn help to achieve rational con- struction of bimetal nano-heterostructures with soecific functions.
基金This work was supported by the National Natural Science Foundation of China(51902176)China Postdoctoral Science Foundation(2018M631462)+1 种基金Guangdong Innovative and Entrepreneurial Research Team Program(2017ZT07C341)Shenzhen Municipal Development and Reform Commission and the Development and Reform Commission of Shenzhen Municipality for the development of the“Low-Dimensional Materials and Devices”Discipline.
文摘Potassium ion batteries(PIBs)with high-volumetric energy densities are promising for next-generation low-cost energy storage devices.Metallic bismuth(Bi)with a structure similar to graphite,is a promising anode material for PIBs due to its high theoretical volumetric capacity(3763 mA h cm^−3)and relatively low working potential(−2.93 V vs.standard hydrogen electrode).However,it experiences severe capacity decay caused by a huge volume expansion of Bi when alloying with potassium.This study reports a flexible and free-standing Bi nanosheet(BiNS)/reduced graphene oxide composite membrane with designed porosity close to the expansion ratio of BiNS after charging.The controlled pore structure improves the electron and ion transport during cycling,and strengthens the structural stability of the electrode during potassiation and depotassiation,leading to excellent electrochemical performance for potassium-ion storage.In particular,it delivers a high reversible volumetric capacity of 451 mA h cm^−3 at the current density of 0.5 A g^−1,which is much higher than the previously reported commercial graphite material.
