Li-O_(2) batteries provide an attractive and potential strategy for energy conversion and storage with high specific energy densities.However,large over-potential in oxygen evolution reactions (OER) caused by the deco...Li-O_(2) batteries provide an attractive and potential strategy for energy conversion and storage with high specific energy densities.However,large over-potential in oxygen evolution reactions (OER) caused by the decomposition obstacles of Li_(2)O_(2) seriously impedes its electrochemical performances.Herein,a novel N,O,S and F co-doping vesicular carbon was prepared by self-template pyrolysis method and used in LiO_(2) battery to tune the nucleation and decomposition of Li_(2)O_(2).The introduction of F in the carbon matrix with suitable content can regulate the adsorption of intermediates,through which the morphology of Li_(2)O_(2) can be controlled to film,favorable to its decomposition in charge process.The cathode based on the optimized F doped carbon vesicle exhibits improved electrochemical performances including a low over-potential,large capacity and a long-term stability.Density functional theory (DFT) results show that F and C in C–F bond hasve a strong interaction to Li and O in Li_(2)O_(2),respectively,which can enhance the transfer of electrons from Li_(2)O_(2) to the carbon matrix to generate hole polaron and thus accelerate the delithiation and decomposition of Li_(2)O_(2).This work provides a new sight into understanding the mechanism of nucleation and decomposition of Li_(2)O_(2) for the development of high-performance Li-O_(2) batteries.展开更多
Li-CO_(2) batteries provide an attractive and potential strategy for CO_(2) utilization as well as energy conversion and storage with high specific energy densities.However,the poor reversibility caused by the decompo...Li-CO_(2) batteries provide an attractive and potential strategy for CO_(2) utilization as well as energy conversion and storage with high specific energy densities.However,the poor reversibility caused by the decomposition obstacles of Li_(2)CO_(3) and C products is still a challenge for Li-CO_(2) batteries,which seriously influences its electrochemical performances.Herein,a free-standing MnOOH arrays cathode has been prepared and employed in Li-CO_(2) battery,which realizes a great improvement of electrochemical performances by adjusting the discharge products distribution.Experiments coupled with theoretical calculations verifies that the formation of Li-containing carbonaceous species(LiCO_(2),LiCO and Li_(2) CO_(3))bonded with MnOOH through Li ion regulates the nucleation behavior of Li_(2)CO_(3) and C,making them grown on MnOOH uniformly.The fine Li_(2) CO_(3) grains(with a size about 5 nm)embedded into carbon matrix greatly enlarges the contact interface between them,facilitating the transmission of electrons through the discharge products and finally improves CO_(2) evolution activity.This ingenious design strategy of regulating discharge products distribution to improve electrochemical performances provides a promising way to develop advanced Li-CO_(2) batteries.展开更多
High electrochemically active bimessite is always desirable pseudocapacitive material for supercapacitor.Here,two-dimensional(2D)compulsive malposition parallel bimessite standing on β-MnO_(2) interconnected networks...High electrochemically active bimessite is always desirable pseudocapacitive material for supercapacitor.Here,two-dimensional(2D)compulsive malposition parallel bimessite standing on β-MnO_(2) interconnected networks have been designed.Due to the retrition of β-MnO_(2),compulsi ve malposition,slippage of MnO6 slab,occured in bimessite resulting in weaken bi nding force between bimessi te slab and interlayer cations,which enhanced their electrochemical performances.Additionally,the electrical conductivity of the structure was largely promoted by the 2D charge transfer route and double-exchange mechanism in bimessite,also leading to desirable electro-chemical properties.Based on the fraction of as-prepared nanostructure,the par all bimessite exhibited good pseudocapacitance performance(660 F g^(-1))with high rate capability.In addition,the asymmetrice supercapacitor assembled by reduced graphene oxide(RGO)and as-prepared nanostructure,which respectively served as the negative and positive eletrode,delivered an energy density of 33.1 Wh kg^(-1) and a mad mum power density of 64.0 kW kg^(-1) with excellent cyeling stability(95.8% after 10000 cycles).Finally,the study opens new avenwes for synthesizing high eletrochemically actiwe bimessite structure for high-performance energy storage devices.展开更多
Aprotic Li-CO_(2)batteries have attracted growing interest due to their high theoretical energy density and its ability to use green house gas CO_(2)for energy storage.However,the poor ability of activating CO_(2)in o...Aprotic Li-CO_(2)batteries have attracted growing interest due to their high theoretical energy density and its ability to use green house gas CO_(2)for energy storage.However,the poor ability of activating CO_(2)in organic electrolyte often leads to the premature termination of CO_(2)reduction reaction(CO_(2)RR)directly.Here in this work,cetyl trimethyl ammonium bromide(CTAB)was introduced into a dimethyl sulfoxide(DMSO)based Li-CO_(2)battery for the first time to enhance the CO_(2)RR.Significantly improved electrochemical performances,including reduced discharge over-potential and increased discharge capacity,can be achieved with the addition of CTAB.Ab initio molecular dynamics(AIMD)simulations show that quaternary ammonium group CTA^(+) can accelerate CO_(2)reduction process by forming more stable contact ion pair(CIP)with CO_(2)^(–),reducing the energy barrier for CO_(2)RR,thus improving the CO_(2)reduction process.In addition,adding CTA^(+) is also favorable for the solution-phase growth of discharge products because of the improved migration ability of stable CTA^(+)-CO_(2)^(–) CIP in the electrolyte,which is beneficial for improving the utilization ratio of cathode.This work could facilitate the development of CO_(2)RR by providing a novel understanding of CO_(2)RR mechanism in organic system.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant No.21701145)the China Postdoctoral Science Foundation(Grant Nos.2017M610459,2018T110739)。
文摘Li-O_(2) batteries provide an attractive and potential strategy for energy conversion and storage with high specific energy densities.However,large over-potential in oxygen evolution reactions (OER) caused by the decomposition obstacles of Li_(2)O_(2) seriously impedes its electrochemical performances.Herein,a novel N,O,S and F co-doping vesicular carbon was prepared by self-template pyrolysis method and used in LiO_(2) battery to tune the nucleation and decomposition of Li_(2)O_(2).The introduction of F in the carbon matrix with suitable content can regulate the adsorption of intermediates,through which the morphology of Li_(2)O_(2) can be controlled to film,favorable to its decomposition in charge process.The cathode based on the optimized F doped carbon vesicle exhibits improved electrochemical performances including a low over-potential,large capacity and a long-term stability.Density functional theory (DFT) results show that F and C in C–F bond hasve a strong interaction to Li and O in Li_(2)O_(2),respectively,which can enhance the transfer of electrons from Li_(2)O_(2) to the carbon matrix to generate hole polaron and thus accelerate the delithiation and decomposition of Li_(2)O_(2).This work provides a new sight into understanding the mechanism of nucleation and decomposition of Li_(2)O_(2) for the development of high-performance Li-O_(2) batteries.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.21701145 and 21701146,21671176)China Postdoctoral Science Foundation(Grant Nos.2017M610459 and 2018T110739)。
文摘Li-CO_(2) batteries provide an attractive and potential strategy for CO_(2) utilization as well as energy conversion and storage with high specific energy densities.However,the poor reversibility caused by the decomposition obstacles of Li_(2)CO_(3) and C products is still a challenge for Li-CO_(2) batteries,which seriously influences its electrochemical performances.Herein,a free-standing MnOOH arrays cathode has been prepared and employed in Li-CO_(2) battery,which realizes a great improvement of electrochemical performances by adjusting the discharge products distribution.Experiments coupled with theoretical calculations verifies that the formation of Li-containing carbonaceous species(LiCO_(2),LiCO and Li_(2) CO_(3))bonded with MnOOH through Li ion regulates the nucleation behavior of Li_(2)CO_(3) and C,making them grown on MnOOH uniformly.The fine Li_(2) CO_(3) grains(with a size about 5 nm)embedded into carbon matrix greatly enlarges the contact interface between them,facilitating the transmission of electrons through the discharge products and finally improves CO_(2) evolution activity.This ingenious design strategy of regulating discharge products distribution to improve electrochemical performances provides a promising way to develop advanced Li-CO_(2) batteries.
基金the National Natural Science Foundation of China(Grant No.51908092)Projects(No.2020CDJXZ001,2020CDCGJ006 and 2020CDCGCL004)supported by the Fundamental Research Funds for the Central Universities,the Joint Funds of the National Natural Science Foundation of China-Guangdong(Grant No.U1801254)+5 种基金the project funded by Chongqing Special Postdoctoral Science Foundation(XmT2018043)the Chongqing Research Program of Basic Research and Frontier Technology(cstc2017jcyjBX0080)Natural Science Foundation Project of Chongqing for Post-doctor(cstc2019jcyjbsh0079,cstc2019jcyjbshX0085)Technological projects of Chongqing Municipal Education Commission(KJZDK201800801)the Innovative Research Team of Chongqing(CXTDG201602014)the Innovative technology of New materials and metallurgy(2019CDXYCL0031).
文摘High electrochemically active bimessite is always desirable pseudocapacitive material for supercapacitor.Here,two-dimensional(2D)compulsive malposition parallel bimessite standing on β-MnO_(2) interconnected networks have been designed.Due to the retrition of β-MnO_(2),compulsi ve malposition,slippage of MnO6 slab,occured in bimessite resulting in weaken bi nding force between bimessi te slab and interlayer cations,which enhanced their electrochemical performances.Additionally,the electrical conductivity of the structure was largely promoted by the 2D charge transfer route and double-exchange mechanism in bimessite,also leading to desirable electro-chemical properties.Based on the fraction of as-prepared nanostructure,the par all bimessite exhibited good pseudocapacitance performance(660 F g^(-1))with high rate capability.In addition,the asymmetrice supercapacitor assembled by reduced graphene oxide(RGO)and as-prepared nanostructure,which respectively served as the negative and positive eletrode,delivered an energy density of 33.1 Wh kg^(-1) and a mad mum power density of 64.0 kW kg^(-1) with excellent cyeling stability(95.8% after 10000 cycles).Finally,the study opens new avenwes for synthesizing high eletrochemically actiwe bimessite structure for high-performance energy storage devices.
基金National Science Foundation of China(Nos.21701145 and 21701146)China Postdoctoral Science Foundation(Nos.2017M610459 and 2018T110739)。
文摘Aprotic Li-CO_(2)batteries have attracted growing interest due to their high theoretical energy density and its ability to use green house gas CO_(2)for energy storage.However,the poor ability of activating CO_(2)in organic electrolyte often leads to the premature termination of CO_(2)reduction reaction(CO_(2)RR)directly.Here in this work,cetyl trimethyl ammonium bromide(CTAB)was introduced into a dimethyl sulfoxide(DMSO)based Li-CO_(2)battery for the first time to enhance the CO_(2)RR.Significantly improved electrochemical performances,including reduced discharge over-potential and increased discharge capacity,can be achieved with the addition of CTAB.Ab initio molecular dynamics(AIMD)simulations show that quaternary ammonium group CTA^(+) can accelerate CO_(2)reduction process by forming more stable contact ion pair(CIP)with CO_(2)^(–),reducing the energy barrier for CO_(2)RR,thus improving the CO_(2)reduction process.In addition,adding CTA^(+) is also favorable for the solution-phase growth of discharge products because of the improved migration ability of stable CTA^(+)-CO_(2)^(–) CIP in the electrolyte,which is beneficial for improving the utilization ratio of cathode.This work could facilitate the development of CO_(2)RR by providing a novel understanding of CO_(2)RR mechanism in organic system.