The critical role of carbon in marrying silicon and graphite anodes for high-energy lithium-ion batteries

Increasing the energy density of conventional lithium-ion batteries(LIBs)is important for satisfying the demands of electric vehicles and advanced electronics.Silicon is considered as one of the most-promising anodes to replace the traditional graphite anode for the realization of high-energy LIBs due to its extremely high theoretical capacity,although its severe volume changes during lithiation/delithiation have led to a big challenge for practical application.In contrast,the co-utilization of Si and graphite has been well recognized as one of the preferred strategies for commercialization in the near future.In this review,we focus on different carbonaceous additives,such as carbon nanotubes,reduced graphene oxide,and pyrolyzed carbon derived from precursors such as pitch,sugars,heteroatom polymers,and so forth,which play an important role in constructing micrometersized hierarchical structures of silicon/graphite/carbon(Si/G/C)composites and tailoring the morphology and surface with good structural stability,good adhesion,high electrical conductivity,high tap density,and good interface chemistry to achieve high capacity and long cycling stability simultaneously.We first discuss the importance and challenge of the co-utilization of Si and graphite.Then,we carefully review and compare the improved effects of various types of carbonaceous materials and their associated structures on the electrochemical performance of Si/G/C composites.We also review the diverse synthesis techniques and treatment methods,which are also significant factors for optimizing Si/G/C composites.Finally,we provide a pertinent evaluation of these forms of carbon according to their suitability for commercialization.We also make far-ranging suggestions with regard to the selection of proper carbonaceous materials and the design of Si/G/C composites for further development.

Controlling of coordination state of Ru_(x)N_(y) clusters for efficient oxygen reduction electrocatalysis

Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series of well-dispersed nitrogen-coordinated Ru-clusters on carbon black(Ru_(x)N_(y)/C)were prepared by pyrolyzing different Ru-containing sandwich compounds as the Ru sources.The higher thermal stability of these complexed sandwich precursors(bis(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)monomer,dichloro(p-cymene)Ru(II)dimer,and chloro(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)tetramer)affords the control of coordinated state for the resulting Ru-clusters,in comparison of that derived from ruthenium chlorides.After the pyrolysis treatment,the Ru coordinated state in Ru_(x)N_(y)/C,with the Ru–N and Ru–Ru bonds,still showed the structural inheritance from the Ru(II)monomer,dimer,and tetramer,but using ruthenium chlorides as the Ru source resulted in the nanoscale Ru agglomerations.The ORR testing exhibited that the Ru_(x)N_(y)/C sample derived from the Ru(II)tetramer(Ru_(x)N_(y)/C-T)presents the higher catalytic activity than the other obtained samples in either alkaline or acidic electrolytes.Even in the acidic electrolyte,Ru_(x)N_(y)/C-T shows the comparable ORR activity to that of Pt/C catalysts,and it shows the superior tolerance against methanol and CO.The X-ray absorption spectroscopy and density functional theory calculations demonstrate that these tetra-nuclear Ru-clusters could be the most active site due to their broadened d-orbital bands and lower energy d-band center than those of other subnano species and nanocrystals,and their favorable Yeager-type adsorption of O_(2)-molecules is also contributed to promoting O–O bond cleavage and accelerating the ORR process.

Highly active porous nickel-film electrode via polystyrene microsphere template-assisted composite electrodeposition for hydrogen-evolution reaction in alkaline medium

A highly porous nickel-film electrode with satisfactory mechanical strength was prepared by a facile vertical template-assisted composite electrodeposition method using polystyrene(PS) microspheres templates, with the aim of improving the electrocatalytic activity for the hydrogen-evolution reaction(HER). During the composite electrodeposition process, the hydrophobic PS microspheres were highly dispersed in the electrolyte with the help of a surfactant, and then co-deposited with Ni to form the film electrode. After removing the PS templates by annealing, a porous Ni film containing large amount of uniformly dispersed pores with narrow size distribution was obtained, and then applied as the electrode for the HER in an alkaline medium. As evidenced by the electrochemical analysis, the porous Ni film electrode exhibits higher catalytic activity as compared to a dense Ni film electrode and is superior to a Ni/Ru O2/Ce O2 commercial electrode. The effect of temperature on the catalytic properties of the porous Ni film electrode was also investigated; the activation energy was calculated as 17.26 k J/mol. The enhanced activity toward the HER was attributed to the improved electrochemical surface area and mass transportation facilitated by the high porosity of the synthesized Ni film electrode.