Li-rich layered oxide materials have attracted increasing attention because of their high specific capacity(>250 mAh g^(-1)). However, these materials typically suffer from poor cycling stability and low rate performance. Herein, we propose a facile and novel metal-organic-framework(MOF) shell-derived surface modification strategy to construct NiCo nanodots decorated(~5 nm in diameter) carbon-confined Li_(1.2)Mn_(0.54) Ni_(0.13)Co_(0.13)O_2 nanoparticles(LLO@C&NiCo). The MOF shell is firstly formed on the surface of as-prepared Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2 nanoparticles via low-pressure vapor superassembly and then is in situ converted to the NiCo nanodots decorated carbon shell after subsequent controlled pyrolysis.The obtained LLO@C&NiCo cathode exhibits enhanced cycling and rate capability with a capacity retention of 95% after 100 cycles at 0.4 C and a high capacity of 159 mAh g^(-1) at 5 C, respectively, compared with those of LLO(75% and 105 mAh g^(-1)). The electrochemical impedance spectroscopy and selected area electron diffraction analyses after cycling demonstrate that the thin C&NiCo shell can endow LLO with high electronic conductivity and structural stability, indicating the undesired formation of the spinel phase initiated from the particle surface is efficiently suppressed. Therefore, this presented strategy may open a new avenue on the design of high-performance electrode materials for energy storage.
Zhitong XiaoJiashen MengQi LiXuanpeng WangMeng HuangZiang LiuChunhua HanLiqiang Mai
The exploration for post-carbon electrode ma- terials for lithium-ion batteries has been a crucial way to satisfy the ever-growing demands for better performance with higher energy/power densities, enhanced safety, and longer cycle life. Transition metal oxides have recently re- ceived a great deal of attention as very promising anode materials due to their high theoretical capacity, good safety, eco-benignity, and huge abundance. The present work re- views the latest advances in developing novel transition metal oxides, including FeeO3, Fe3O4, CO3O4, CoO, NiO, MnO, Mn203, Mn3O4, MnO2, MOO3, Cr2O3, Nb2O5, and some binary oxides such as NiCO2O4, ZnCO2O4, MnCO2O4 and CoMn2O4. Nanostructuring and hybrid strategies ap- plicable to transition metal oxides are summarized and analyzed. Furthermore, the impacts of binder choice and heat treatment on electrochemical performance are discussed.
In this work, a fast(0.5 h), green microwave-assisted synthesis of single crystalline Sb_2Se_3 nanowires was developed. For the first time we demonstrated a facile solvent-mediated process, whereby intriguing nanostructures including antimony selenide(Sb_2Se_3) nanowires and selenium(Se) microrods can be achieved by merely varying the volume ratio of ethylene glycol(EG) and H_2O free from expensive chemical and additional surfactant. The achieved uniform Sb_2Se_3 nanowire is single crystalline along [001]growth direction with a diameter of 100 nm and a length up to tens of micrometers. When evaluated as an anode of lithium-ion battery, Sb_2Se_3 nanowire can deliver a high reversible capacity of 650.2 m Ah g^(-1) at 100 mA g^(-1) and a capacity retention of 63.8% after long-term 1000 cycles at 1000 mA g^(-1), as well as superior rate capability(389.5 m Ah g^(-1) at 2000 mA g^(-1)). This easy solvent-mediated microwave synthesis approach exhibits its great universe and importance towards the fabrication of high-performance metal chalcogenide electrode materials for future low-cost, large-scale energy storage systems.
Wen LuoJean-Jacques GaumetPierre MagriSébastien DilibertoFeng LiPascal FranchettiJaafar GhanbajaLiqiang Mai
In the last decade, pyrolyzed-carbon-based composites have attracted much attention for their applications in micro-supercapacitors. Although various methods have been investigated to improve the performance of pyrolyzed carbons, such as conductivity, energy storage density and cycling performance, effective methods for the integration and mass-production of pyrolyzed-carbon- based composites on a large scale are lacking. Here, we report the development of an optimized photolithographic technique for the fine micropatterning of photoresist/chitosan-coated carbon nanotube （CHIT-CNT） composite. After subsequent pyrolysis, the fabricated carbon/CHIT-CNT microelectrode-based micro-supercapacitor has a high capacitance （6.09 mF.cm-2） and energy density （4.5 mWh.cm-3） at a scan rate of 10 mV.s-L Additionally, the micro-supercapacitor has a remarkable long-term cyclability, with 99.9% capacitance retention after 10,000 cyclic voltammetry cycles. This design and microfabrication process allow the application of carbon microelectromechanical system （C-MEMS）-based micro-supercapacitors due to their high potential for enhancing the mechanical and electrochemical performance of micro-supercapacitors.
Nonmetal elements strictly govern the electrochemical performance of molybdenum compounds.Yet,the exact role played by nonmetals during electrocatalysis remains largely obscure.With intermetallic MoSi_2comprising silicene subunits,we present an unprecedented hydrogen evolution reaction(HER)behavior in aqueous alkaline solution.Under continuous operation,the HER activity of MoSi_2shows a more than one order of magnitude improvement in current density from 1.1 to 21.5 mA cm^(à2)at 0.4 V overpotential.Meanwhile,this activation behavior is highly reversible,such that voltage withdrawal leads to catalyst inactivation but another operation causes reactivation.Thus,the system shows dynamics strikingly analogous to the legendary Sisyphus’labor,which drops and recovers in a stepwise manner repeatedly,but never succeeds in reaching the top of the mountain.Isomorphic WSi_2behaves almost the same as MoSi_2,whereas other metal silicides with silicyne subunits,including CrSi_2and TaSi_2,do not exhibit any anomalous behavior.A thin amorphous shell of MoSi_2is observed after reaction,within which the Si remains partially oxidized while the oxidation state of Mo is basically unchanged.First-principles calculations further reveal that the adsorption of hydroxide ions on silicene subunit edges and the subsequent Si vacancy formation in MoSi_2jointly lead to the anomalous HER kinetics of the adjacent Mo active centers.This work demonstrates that the role of nonmetal varies dramatically with the electronic and crystallographic structures of silicides and that silicene structural subunit may serve as a promoter for boosting HER in alkaline media.
Zechao ZhuangYong LiJiazhao HuangZilan LiKangning ZhaoYunlong ZhaoLin XuLiang ZhouLyudmila V. MoskalevaLiqiang Mai
The high specific capacity and energy density of lithium-sulfur batteries have attracted strong considerations on their fundamental mechanism and energy applications.However,polysulfide shuttle is still the key issue that impedes the development of Li-S batteries.Exploring nanocrystal hosts for polysulfide immobilization and conversion is a promising way.In this contribution,we have investigated well-dispersed Co9S8 nanocrystals grown on graphene oxide(GO)nanosheets with different degrees of dispersion as cathode host materials for Li-S batteries.The Co9S8-GO composite with 1 wt%GO(GCS1)has an average crystal size of 76 nm and shows the strongest adsorption capability toward lithium polysulfides.When used as the host material for the cathode of Li-S batteries,the GCS1-sulfur composite exhibits an initial specific capacity of^-1000 mAh g^-1 at 0.5 C and shows an average decay rate of 0.11%for 500 cycles.This work on the dispersion control of Co9S8 nanocrystals may inspire more investigations on well-dispersed nanocrystal based hosts for Li-S batteries.
Lithium nickel manganese oxide spinel(Li Ni0.5-Mn1.5O4, LNMO) has attracted much attention as the cathode material for rechargeable lithium-ion batteries due to its high energy density and low cost. However, the short cycle life and poor high-rate capability hinder its commercialization. In this study, we synthesized hollow spherical LNMO built from polyhedral particles. The LNMO hollow structure guarantees sufficient contact with electrolyte and rapid diffusion of lithium ions. To enhance the conductivity, we use carbon nanotubes(CNTs) to modify the surface of the cathode. After CNT modification, the LNMO hollow structure manifests outstanding cycling stability and high-rate capability. It delivers a discharge capacity of 127 m A h g-1 at 5 C, maintaining 104 m A h g-1 after 500 cycles. Even at a high rate of 20 C, a capacity of 121 m A h g-1 can be obtained. The excellent electrochemical performance is ascribed to the unique structure and the enhanced conductivity through CNT modification. It is demonstrated that the CNTmodified hollow spherical LNMO is a promising cathode for lithium ion batteries.
The development of alternative electrode materials with high energy densities and power densities for batteries has been actively pursued to satisfy the power demands for electronic devices and hybrid electric vehicles. Recently, antimony（Sb）-based intermetallic compounds have attracted considerable research interests as new candidate anode materials for high-performance lithium-ion batteries（LIBs） and sodium-ion batteries（SIBs） due to their high theoretical capacity and suitable operating voltage. However, these intermetallic systems undergo large volume change during charge and discharge processes, which prohibits them from practical application. The rational construction of advanced anode with unique structures has been proved to be an effective approach to enhance its electrochemical performance. This review highlights the recent progress in improving and understanding the electrochemical performances of various Sb-based intermetallic compound anodes. The developments of synthesis and construction of Sb-based intermetallic compounds are systematically summarized. The electrochemical performances of various Sb-based intermetallic compound anodes are compared in its typical applications（LIBs or SIBs）.
