Nanostructured N-doped carbon materials derived from expandable biomass with superior electrocatalytic performance towards V^(2+)/V^(3+) redox reaction for vanadium redox flow battery

Vanadium redox flow battery(VRFB)is one of the most promising large-scale energy storage systems,which ranges from kilowatt to megawatt.Nevertheless,poor electrochemical activity of electrode for two redox couples still restricts the extensive applications of VRFB.Compared with V^(2+)/V^(3+)redox reaction,V^(2+)/V^(3+)reaction plays a more significant role in voltage loss of VRFB owing to slow heterogeneous electron transfer rate.Herein,N-doped carbon materials derived from scaphium scaphigerum have been developed as negative electrocatalyst by hydrothermal carbonization and high-temperature nitridation treatments.The undoped carbon material hardly has electrocatalytic ability for V^(2+)/V^(3+)reaction.Based on this,N-doped carbon materials with urea as nitrogen source exhibit excellent electrocatalytic properties.And the material nitrided at 850°C(SSC/N-850)exhibits the best performance among those from700 to 1000℃.SSC/N-850 can accelerate the electrode process including V^(2+)/V^(3+)reaction and mass transfer of active ions due to the large reaction place,more active sites,and good hydrophilicity.The effect of catalyst on comprehensive performance of cell was evaluated.SSC/N-850 can improve the charge-discharge performance greatly.Utilization of SSC/N-850 can lessen the electrochemical polarization of cell,further resulting in increased discharge capacity and energy efficiency.Discharge capacity and energy efficiency increase by 81.5%and 9.8%by using SSC/N-850 as negative catalyst at 150 m A cm^(-2),respectively.Our study reveals that the developed biomass-derived carbon materials are the low-cost and efficient negative electrocatalyst for VRFB system.

Functional carbon materials for high-performance Zn metal anodes

The realization of“carbon peak”and“carbon neutralization”highly depends on the efficient utilization of renewable energy sources.Exploring reliable and low-cost electrochemical energy storage systems is an ever-growing demand for renewable energy integration.Among available candidates,aqueous zinc-ion batteries(AZIBs)receive extensive researchers'attention because of their material abundance,high capacity,high safety,and environmental friendliness.However,the irreversible issues of Zn anode in terms of notorious dendric Zn growth,Zn corrosion/hydrogen evolution,and passivation significantly impede the commercialization of high-performance AZIBs.Carbon materials have advantages of large specific surface area,low cost,high electrical conductivity,controllable structure,and good stability.Their application provides remedies for improving the comprehensive performance of Zn anodes.In this review,the fundamentals and issues of Zn anodes,and the research progress with functional carbon materials for Zn anodes in recent years are presented.Three major strategies are described in detail,including the use of carbon materials(carbon nanotubes,graphene,carbon fiber,metal-organic framework(MOF)derived host,etc.)as Zn plating/stripping substrates,as protective coating layers on Zn,and as electrolyte additives.Finally,the remaining challenges and perspectives of carbon materials in high-performance AZIBs are outlined.

Effect of Adding Microwave Absorber on Structures and Properties of Hypercoal-Based Activated Carbons

Using lignite-based hypercoal as raw material, KOH as activator and CuO as microwave absorber, we prepared hypercoal-based activated carbons by microwave-assisted activation. The pore structure and the electrochemical performance of the activated carbons were tested, and the effects of adding CuO in the activation reaction process were also investigated. The activated carbons prepared were characterized by nitrogen adsorption-desorption, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The specific surface area and mesoporous ratio of the hypercoal-based activated carbon are 1257 m2/g and 55.4%, respectively. When the activated carbons are used as the electrode materials, the specific capacitance reaches 309 F/g in 3 M KOH electrolyte. In comparison with those prepared without CuO absorber, the specific capacitance increases by 11.6%. It was proved that the addition of microwave absorber in microwave-assisted activation was a low-cost method for rapidly preparing activated carbon, and it could effectively promote the development of the pore structure and improve its electrochemical performance.

KHCO_3 activated carbon microsphere as excellent electrocatalyst for VO^(2+)/VO_2^+ redox couple for vanadium redox flow battery

In this paper,carbon microsphere prepared by hydrothermal treatment was activated by KHCO_3 at high temperature,and employed as the catalyst for VO^(2+)/VO_2^+redox reaction for vanadium redox flow battery(VRFB).Carbon microsphere can be etched by KHCO_3 due to the reaction between the pyrolysis products of KHCO_3 and carbon atoms.Moreover,KHCO_3 activation can bring many oxygen functional groups on carbon microsphere,further improving the wettability of catalyst and increasing the active sites.The electrocatalytic properties of carbon microsphere from hydrothermal treatment are improved by high temperature carbonization,and can further be enhanced by KHCO_3 activation.Among carbon microsphere samples,the VO^(2+)/VO_2^+redox reaction exhibits the highest electrochemical kinetics on KHCO_3 activated sample.The cell using KHCO_3 activated carbon microsphere as the positive catalyst demonstrates higher energy efficiency and larger discharge capacity,especially at high current density.The results reveal that KHCO_3 activated carbon microsphere is an efficient,low-cost carbon-based catalyst for VO^(2+)/VO_2^+redox reaction for VRFB system.

Recent advances in metals and metal oxides as catalysts for vanadium redox flow battery:Properties,structures,and perspectives

Vanadium redox flow battery(VRFB)is a kind of battery with wide application prospect.Electrode material is one of the key components of VRFB,and its stability directly affects the performance of battery.Among all kinds of electrode materials,carbon-based material has the best comprehensive properties.However,carbon-based electrodes still have disadvantages such as poor hydrophilicity and low electrochemical activity which need to be improved.One of the effective ways to improve the performance of electrode is to modify carbon-based material with metals and metal oxides.The metal catalysts have excellent electrical conductivity and high catalytic activity.The metal oxide catalysts have the advantages of low cost,wide variety and strong oxidizing properties.This work introduced the application of metal and metal oxide modified electrodes in VRFB in recent years,classified the catalysts,studied their catalytic performance and mechanism.The metal catalysts were reviewed from precious metals and base metals.The metal oxide catalysts were classified and discussed according to the similar properties of the same group elements.This work compared different modification methods,summarized the research progress of metal and metal oxide modification,and proposes the future development direction of electrodes and catalysts.

Ultrafine SnO_(2)in situ modified graphite felt derived from metal-organic framework as a superior electrode for vanadium redox flow battery

Metal-organic framework(MOF)and its derivatives have low-cost,controllable structure,and good catalytic performance,which are often used in the electrochemical field.In this work,SnO_(2)in situ modified graphite felt(SnO_(2)/GF)is prepared by hydrothermal method then simple thermal treatment using Sn-based MOF(Sn-MOF)as precursor.SnO_(2)is uniformly and firmly distributed on the GF surface rather than the common agglomeration and poor bonding of metal oxides on carbon-based electrodes,providing stable active centers for the VO^(2+)/VO_(2)^(+)and V^(2+)/V^(3+)redox reactions.At250 mA·cm^(-2),the energy efficiency of the battery with SnO_(2)/GF remains at 63.2%,while the blank one has failed.The former battery,at 100 mA·cm^(-2),has higher energy efficiency and good cycle stability(over 200 cycles).The battery performance of this study is better than that of most previous report in metal oxide-related work.This work obtains high-performance composite electrode by simple treatment of MOF,which provides a reference for the application of MOF in vanadium redox flow battery.