This paper invesitages the synergetic effect between high-surface-area carbons, such as Ketjan Black(KB) or Super P(SP) carbon materials, and low-surface-area carbon paper(CP) current collectors and it also examines t...This paper invesitages the synergetic effect between high-surface-area carbons, such as Ketjan Black(KB) or Super P(SP) carbon materials, and low-surface-area carbon paper(CP) current collectors and it also examines their influence on the discharge performance of nonaqueous Li–O2cells. Ultra-large specific discharge capacities are found in the KB/CP cathodes, which are much greater than those observed in the individual KB or CP cathodes. Detailed analysis indicates that such unexpectedly large capacities result from the synergetic effect between the two components. During the initial discharges of KB or SP materials, a large number of superoxide radical(O·-2) species in the electrolytes and Li2O2 nuclei at the CP surfaces are formed, which activate the CP current collectors to contribute considerable capacities. These results imply that CP could be a superior material for current collectors in terms of its contribution to the overall discharge capacity.On the other hand, we should be careful to calculate the specific capacities of the oxygen cathodes when using CP as a current collector; i.e., ignoring the contribution from the CP may cause overstated discharge capacities.展开更多
Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and of...Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.展开更多
The hierarchically porous carbons （HPCs） were prepared by sol-gel selassembly technology in different surfactant concentrations and were used as the potential electrode for lithium oxygen batteries. The physical and...The hierarchically porous carbons （HPCs） were prepared by sol-gel selassembly technology in different surfactant concentrations and were used as the potential electrode for lithium oxygen batteries. The physical and electrochemical properties of the as-prepared HPCs were investigated by filed emission scanning electron microscopy （FE-SEM）, transmission electron microscopy （TEM）, nitrogen adsorption-desorption isotherm and galvanostatic charge/discharge. The results indicate that all of the HPCs mainly possess mesoporous structure with nearly similar pore size distribution. Using the HPCs as the electrode, a high discharge capacity for lithium oxygen battery can be achieved, and the discharge capacity increases with the specific surface area. Especially, the HPCs-3 oxygen electrode with CTAB concentration of 0.27 mol/L exhibits good capacity retention through controlling discharge depth to 800 mA·h/g and the highest discharge capacity of 2050 mA·h/g at a rate of 0.1 mA/cm2.展开更多
Aprotic lithium-oxygen batteries possess ultrahigh energy density but suffer from the sluggish decomposition of discharge product,quick depletion of Li anode and cleavage of electrolyte,in close association with oxyge...Aprotic lithium-oxygen batteries possess ultrahigh energy density but suffer from the sluggish decomposition of discharge product,quick depletion of Li anode and cleavage of electrolyte,in close association with oxygen reduction reaction at the cathode.Herein,highly dispersed silver nanoparticles are used to enhance the lithium-oxygen battery with 1.0 M lithium perchlorate in dimethyl sulfoxide.It is observed that film-like amorphous lithium peroxide is formed through surface pathway instead of bulk crystals,due to the incorporation of silver nanoparticles dispersed in the electrolyte,which subsequently accelerates the decomposition of the discharge product by offering more active sites and improved conductivity.The released silver nanoparticles after battery charging can be re-used in the following cycles.Experiments and theoretical calculation further indicate that the suspended silver nanoparticles can adsorb the soluble oxygen reduction intermediates,which are responsible for the alleviation of oxidative cleavage of electrolyte and corrosion of lithium anode.The lifespan of lithium oxygen batteries is therefore significantly extended from 55 to 390 cycles,and the rate performance and full-discharge capacity are also largely enhanced.The battery failure is attributed to the coalescence and growth of silver nanoparticles in the electrolyte,and further improvement on colloid stability is underway.展开更多
Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult...Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.展开更多
Lithium-oxygen batteries are among the most promising electrochemical energy storage systems,which have attracted significant attention in the past few years duo to its far more energy density than lithium-ion batteri...Lithium-oxygen batteries are among the most promising electrochemical energy storage systems,which have attracted significant attention in the past few years duo to its far more energy density than lithium-ion batteries.Lithium oxygen battery energy storage is a reactive storage mechanism,and the discharge and charge processes are usually called oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Consequently,complex systems usually create complex problems,lithium oxygen batteries also face many problems,such as excessive accumulation of discharge products(Li_(2)O_(2))in the cathode pores,resulting in reduced capacity,unstable cycling performance and so on.Cathode catalyst,which could influence the kinetics of OER and ORR in lithium oxygen(Li-O_(2))battery,is one of the decisive factors to determine the electrochemical performance of the battery,so the design of cathode catalyst is vitally important.This review discusses the catalytic cathode materials,which are divided into four parts,carbon based materials,metals and metal oxides,composite materials and other materials.展开更多
Rechargeable lithium–oxygen batteries have been considered as a promising energy storage technology because of their ultra-high theoretical energy densities which are comparable to gasoline. In order to improve the e...Rechargeable lithium–oxygen batteries have been considered as a promising energy storage technology because of their ultra-high theoretical energy densities which are comparable to gasoline. In order to improve the electrochemical properties of lithium–oxygen batteries(LOBs), especially the cycling performance, a high-efficiency cathode catalyst is the most important component.Hence, we aim to demonstrate that CuCr_2O_4@rGO(CCO@rGO) nanocomposites, which are synthesized using a facile hydrothermal method and followed by a series of calcination processes, are an effective cathode catalyst. The obtained CCO@rGO nanocomposites which served as the cathode catalyst of the LOBs exhibited an outstanding cycling performance for over 100 cycles with a fixed capacity of 1000 mAh g^(-1) at a current density of 200 mA g^(-1). The enhanced properties were attributed to the synergistic effect between the high catalytic efficiency of the spinel-structured CCO nanoparticles, the high specific surface area, and high conductivity of the rGO.展开更多
In recent years, as one of the most promising chemical power sources for future society, lithium–oxygen (Li–O2) battery receives great attention due to its extremely high theoretical energy density of 3505 Wh kg^(–...In recent years, as one of the most promising chemical power sources for future society, lithium–oxygen (Li–O2) battery receives great attention due to its extremely high theoretical energy density of 3505 Wh kg^(–1)[1–4]. In practice, large polarization and consequent low energy efficiency currently still hinder the application of Li–O2batteries, which mainly results from the sluggish electrochemical reaction kinetics of oxygen diffusion electrodes in aprotic electrolytes [5]. On one hand, oxygen reduction reaction (ORR)in aprotic electrolytes is intrinsically sluggish due to the difficult charge transfer, the low solubility of oxygen.展开更多
The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,mo...The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme（SNG）. In contrast with routine N-doped graphene framework（NGF） with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^（-1）, a large surface area of 1531 m^2 g^（-1）, a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.展开更多
The development of highly efficient catalysts in the cathodes of rechargeable Li-O_(2) batteries is a considerable challenge.To enhance the electrochemical performance of the Li-O_(2) battery,it is essential to choose...The development of highly efficient catalysts in the cathodes of rechargeable Li-O_(2) batteries is a considerable challenge.To enhance the electrochemical performance of the Li-O_(2) battery,it is essential to choose a suitable catalyst material.Copper selenide(CuSe)is considered as a more promising cathode catalyst material for Li-O_(2) battery due to its better conductivity and rich electrochemical active sites.However,its electrochemical reaction and fundamental catalytic mechanism remain unclear till now.Herein,in-situ environmental transmission electron microscopy technique was used to study the catalysis mechanism of the CuSe nanosheets in Li-O_(2) batteries during discharge and charge processes.It is found that Li_(2)O was formed and decomposed around the ultrafine-grained Cu during the discharge and charge processes,respectively,demonstrating excellent cycling.This indicate that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter four-electron-transfer oxygen reduction reaction,leading to the formation of Li_(2)O.Our study provides important understanding of the electrochemistry of the LiO_(2) nanobatteries,which will aid the development of high-performance Li-O_(2) batteries for energy storage applications.展开更多
Among the intrinsically conductive polymers, polyanilines have been of great interest in the past decades due to their wide applications in many fields, thanks to their reasonably good conductivity, easy preparation, ...Among the intrinsically conductive polymers, polyanilines have been of great interest in the past decades due to their wide applications in many fields, thanks to their reasonably good conductivity, easy preparation, and special redox properties. Ever-increasing environmental corsiderations make the processing of polyanilines shift from toxic organic solvent-based system to eco-friendly water-based system. The present paper reviews the synthesis of water-borne conducting polyanilines, and possible applications are discussed including supercapacitor electrode material, metal free corrosion protection coating, lithium oxygen battery cathode material and ultraviolet curable resin.展开更多
Nanostructured materials have received tremendous interest due to their unique mechanical/electrical properties and overall behavior contributed by the complex synergy of bulk and interfacial properties for efficient ...Nanostructured materials have received tremendous interest due to their unique mechanical/electrical properties and overall behavior contributed by the complex synergy of bulk and interfacial properties for efficient and effective energy conversion and storage. The booming development of nanotechnology affords emerging but effective tools in designing advanced energy material. We reviewed the significant progress and dominated nanostructured energy materials in electrochemical energy conversion and storage devices, including lithium ion batteries, lithium-sulfur batteries, lithium-oxygen batteries, lithium metal batteries, and supercapacitors. The use of nanostructured electrocatalyst for effective electrocatalysis in oxygen reduction and oxygen evolution reactions for fuel cells and metal-air batteries was also included. The challenges in the undesirable side reactions between electrolytes and electrode due to high electrode/electrolyte contact area, low volumetric energy density of electrode owing to low tap density, and uniform production of complex energy materials in working devices should be overcome to fully demonstrate the advanced energy nanostructures for electrochemical energy conversion and storage. The energy chemistry at the interfaces of nanostructured electrode/electrolyte is highly expected to guide the rational design and full demonstration of energy materials in a working device. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
Understanding and regulating the electronic states of single-atom sites near the Fermi energy level are essential for developing effective electrocatalysts for lithium–oxygen batteries(LOBs).In this study,we introduc...Understanding and regulating the electronic states of single-atom sites near the Fermi energy level are essential for developing effective electrocatalysts for lithium–oxygen batteries(LOBs).In this study,we introduce an axial oxygen ligand at the metal center of cobalt porphyrin(CoPP)to adjust the electronic state of the Co center.Theoretical calculations and experimental findings show that this axial interaction disrupts the planar tetragonal crystal field of CoPP,resulting in enhanced spin polarization and electronic rearrangement.This rearrangement of d orbitals causes an upward shift in the frontier orbitals,which facilitates electron exchange during reactions.Additionally,the increased number of unpaired electrons in the d orbitals enhances the adsorption of CoPPO-MXene to various oxygen species,promoting the formation of a thin film-like Li2O2.These thin film-like discharge products improve contact with the electrode surfaces,leading to easier decomposition during the charging process.Consequently,CoPP-OMXene-based LOBs demonstrate a high discharge capacity of 11035mAh g−1,a low overpotential of 0.76 V,and remarkable cycling stability(445 cycles).展开更多
Alkaline zinc manganese dioxide（Zn–MnO2）batteries are widely used in everyday life. Recycling of waste alkaline Zn–MnO2 batteries has always been a hot environmental concern. In this study, a simple and costeffect...Alkaline zinc manganese dioxide（Zn–MnO2）batteries are widely used in everyday life. Recycling of waste alkaline Zn–MnO2 batteries has always been a hot environmental concern. In this study, a simple and costeffective process for synthesizing Mn3O4/carbon nanotube（CNT） nanocomposites from recycled alkaline Zn–MnO2 batteries is presented. Manganese oxide was recovered from spent Zn–MnO2 battery cathodes. The Mn3O4/CNT nanocomposites were produced by ball milling the recovered manganese oxide in a commercial multi-wall carbon nanotubes（MWCNTs） solution. Scanning electron microscopy（SEM） analysis demonstrates that the nanocomposite has a unique three-dimensional（3D） bird nest structure. Mn3O4 nanoparticles are homogeneously distributed on MWCNT framework. Mn3O4/CNT nanocomposites were evaluated as an anode material for lithium-ion batteries, exhibiting a highly reversible specific capacitance of -580 mA h·g^-1 after 100 cycles. Moreover, Mn3O4/CNT nanocomposite also shows a fairly positive onset potential of -0.15 V and quite high oxygen reducibility when considered as an electrocatalyst for oxygen reduction reaction.展开更多
Boron-doped Ketjenblack is attempted as cathode catalyst for non-aqueous rechargeable Li–O2 batteries. The boron-doped Ketjenblack delivers an extremely high discharge capacity of 7193 m Ah/g at a current density of ...Boron-doped Ketjenblack is attempted as cathode catalyst for non-aqueous rechargeable Li–O2 batteries. The boron-doped Ketjenblack delivers an extremely high discharge capacity of 7193 m Ah/g at a current density of 0.1 m A/cm2, and the capacity is about 2.3 times as that of the pristine KB. When the batteries are cycled with different restricted capacity, the boron-doped Ketjenblack based cathodes exhibits higher discharge platform and longer cycle life than Ketjenblack based cathodes. Additionally, the boron-doped Ketjenblack also shows a superior electrocatalytic activity for oxygen reduction in 0.1 mol/L KOH aqueous solution. The improvement in catalytic activity results from the defects and activation sites introduced by boron doping.展开更多
Understanding alkali metal ions’(e.g.,Li^(+)/Na^(+)/K^(+))transport mechanism is challenging but critical to improving the performance of alkali metal batteries.Herein using a-MnO_(2)nanowires as cathodes,the transpo...Understanding alkali metal ions’(e.g.,Li^(+)/Na^(+)/K^(+))transport mechanism is challenging but critical to improving the performance of alkali metal batteries.Herein using a-MnO_(2)nanowires as cathodes,the transport kinetics of Li^(+)/Na^(+)/K^(+)in the 2×2 channels of a-MnO_(2)with a growth direction of[001]is revealed.We show that ion radius plays a decisive role in determining the ion transport and electrochemistry.Regardless of the ion radii,Li^(+)/Na^(+)/K^(+)can all go through the 2×2 channels of a-MnO_(2),generating large stress and causing channel merging or opening.However,smaller ions such as Li^(+)and Na^(+)cannot only transport along the[001]direction but also migrate along the<110>direction to the nanowire surface;for large ion such as K^(+),diffusion along the<110>direction is prohibited.The different ion transport behavior has grand consequences in the electrochemistry of metal oxygen batteries(MOBs).For Li-O_(2)battery,Li^(+)transports uniformly to the nanowire surface,forming a uniform layer of oxide;Na^(+)also transports to the nanowire surface but may be clogged locally due to its larger radius,therefore sporadic pearl-like oxides form on the nanowire surface;K^(+)cannot transport to the nanowire surface due to its large radius,instead,it breaks the nanowire locally,causing local deposition of potassium oxides.The study provides atomic scale understanding of the alkali metal ion transport mechanism which may be harnessed to improve the performance of MOBs.展开更多
Microbes are microscopic living organisms that surround us which include bacteria, archaea, most protozoa, and some fungi and algae. In recent years, microbes have been explored as novel precursors to synthesize carbo...Microbes are microscopic living organisms that surround us which include bacteria, archaea, most protozoa, and some fungi and algae. In recent years, microbes have been explored as novel precursors to synthesize carbon-based（nano）materials and as substrates or templates to produce carbon-containing（nano）composites. Being greener and more affordable, microbe-derived carbons（MDCs） offer good potential for energy applications. In this review, we describe the unique advantages of MDCs and outline the common procedures to prepare them. We also extensively discuss the energy applications of MDCs including their use as electrodes in supercapacitors and lithium-ion batteries, and as electrocatalysts for processes such as oxygen reduction, oxygen evolution, and hydrogen evolution reactions which are essential for fuel cell and water electrochemical splitting cells. Based on the literature trend and our group＇s expertise, we propose potential research directions for developing new types of MDCs. This review, therefore, provides the state-of-the-art of a new energy chemistry concept. We expect to stimulate future research on the applications of MDCs that may address energy and environmental challenges that our societies are facing.展开更多
The shift to clean energy is crucial in mitigating the harmful effects of fossil fuels on the environment.Nevertheless,as we embrace clean energy sources,particularly solar and wind energies,high-energy-density storag...The shift to clean energy is crucial in mitigating the harmful effects of fossil fuels on the environment.Nevertheless,as we embrace clean energy sources,particularly solar and wind energies,high-energy-density storage devices like lithium and sodium-oxygen batteries are essential.However,challenges such as the irreversibility of lithium and sodium peroxides and their non-conductivity nature on the cathode electrode hinder practical use.2D materials,particularlyβ_(12)-borophene,show promise in addressing these challenges.In this study,we used density functional theory to thoroughly investigate the adsorption mechanisms of alkali-metal peroxides and their impact on the electronic properties of theβ_(12)-borophene.Our results revealed adsorption energies of-3.71 and-3.54 eV for Li_(2)O_(2)and Na_(2)O_(2),respectively,showing that the adsorbed peroxides are stable and unlikely to decompose into the electrolyte.The calculated Gibbs free energy changes that revealed low overpotentials of 1.03 V for Li_(2)O_(2)and 1.61 V for Na_(2)O_(2).Moreover,even with increased concentrations of peroxides on the surface,β_(12)-borophene retained its ability to adsorb additional peroxides,achieving theoretical voltages of 2.60 V for Li_(2)O_(2)and 2.04 V for Na_(2)O_(2).Notably,the metallic nature ofβ_(12)remained stable despite the adsorption of peroxides,evidenced by an increase in electronic states around the Fermi level and the overlap of the valence and conduction bands.Furthermore,thermal stability analysis at 300 K confirmed that the structure ofβ_(12)-borophene remained intact,reinforcing its suitability as a cathode at standard temperature of the battery.The low diffusion energy barriers of 1.04 and 0.92 eV were obtained for Li_(2)O_(2)and Na_(2)O_(2),respectively,suggesting a high rate of peroxides migration on the substrate surface.The dissociation energy barriers for Li_(2)O_(2)and Na_(2)O_(2)were found to be minimal at 1.86 and 1.69 eV,respectively,indicating the catalytic effects and enhancing electrochemical processes.Our findings suggest thatβ_(12)-borophene can be a potential cathode electrode for the next-generation lithium and sodium-oxygen batteries.展开更多
The development of an ideal cathode for Li-O_(2)battery(LOB)has been a great challenge in achieving high discharge capacity,enhanced stability,and longevity.The formation of undesired and irreversible discharge produc...The development of an ideal cathode for Li-O_(2)battery(LOB)has been a great challenge in achieving high discharge capacity,enhanced stability,and longevity.The formation of undesired and irreversible discharge products on the surface of current cathode materials limit the life span of the LOB.In this study,we report the systematic electrochemical study to compare the performance of LOB employing a unique graphitic nanostructured carbon architecture,i.e.,vertically aligned carbon nanofiber(VACNF)arrays,as the cathode materials.Transition metal(Ni)and noble metal alloy(PtRu)are further deposited on the VACNF array as electrocatalysts to improve the discharge/charge processes at the cathode.The structure of as-prepared electrodes was examined with the field emission scanning electron microscopy,high-resolution transmission electron microscopy,and X-ray photoelectron spectroscopy(XPS).The LOB with VACNF-Ni electrode delivered the highest specific and areal discharge capacities(14.92 Ah·g^(−1),4.32 mAh·cm^(−2))at 0.1 mA·cm^(−2)current density as compared with VACNF-PtRu(9.07 Ah·g^(−1),2.62 mAh·cm^(−2)),bare VACNF(5.55 Ah·g^(−1),1.60 mAh·cm^(−2))and commercial Vulcan XC(3.83 Ah·g^(−1),1.91 mAh·cm^(−2)).Cycling stability tests revealed the superior performance of VACNF-PtRu with 27 cycles as compared with VACNF-Ni(13 cycles),VACNF(8 cycles),and Vulcan XC(3 cycles).The superior cycling stability of VACNF-PtRu can be attributed to its ability to suppress the formation of Li2CO3 during the discharge cycle,as elucidated by XPS analysis of discharged samples.We also investigated the impact of carbon cloth and carbon fiber as cathode electrode substrate on the performance of LOB.展开更多
Oxygen reduction reactions(ORRs)with one-or two-electron-transfer pathways are the essential process for aprotic metal-oxygen batteries,in which the stability of superoxide intermediates/products(O_(2)^(-),LiO_(2),NaO...Oxygen reduction reactions(ORRs)with one-or two-electron-transfer pathways are the essential process for aprotic metal-oxygen batteries,in which the stability of superoxide intermediates/products(O_(2)^(-),LiO_(2),NaO_(2),etc.)mainly dominates the ORR activity/stability and battery performance.However,little success in regulating the stability of the superoxides has been achieved due to their highly reactive characteristics.Herein,we identified and modulated the stability of superoxides by introducing anthraquinone derivatives as cocatalysts which functioned as superoxide trapper adsorbing the superoxides generated via surface-mediated ORR and then transferring them from the solid catalyst surface into electrolyte.Among the studied trappers,1,4-difluoroanthraquinone(DFAQ)with electron-withdrawing groups showed the highest adsorption towards superoxides and could efficiently stabilize LiO_(2)in electrolyte,which greatly promoted the surface-mediated ORR rate and stability.This highlighted the magnitude of adsorption between the trapper and LiO_(2)on the ORR activity/stability.Using an aprotic Li-O_(2)battery as a model metal-O_(2)battery,the overall performance of the cell with DFAQ was substantially improved in terms of cell capacity,rate capability and cyclic stability.These results represent a significant advance in the understanding of ORR mechanisms and promoting the performance of metal-O_(2)batteries.展开更多
基金supported by the Natural Science Foundation of the Chinese Academy of Sciences(Grant No.KGZD-EW-202-2)the National Key Basic Research Program of China(Grant No.2014CB921004)the National Natural Science Foundation of China(Grant No.U1232111)
文摘This paper invesitages the synergetic effect between high-surface-area carbons, such as Ketjan Black(KB) or Super P(SP) carbon materials, and low-surface-area carbon paper(CP) current collectors and it also examines their influence on the discharge performance of nonaqueous Li–O2cells. Ultra-large specific discharge capacities are found in the KB/CP cathodes, which are much greater than those observed in the individual KB or CP cathodes. Detailed analysis indicates that such unexpectedly large capacities result from the synergetic effect between the two components. During the initial discharges of KB or SP materials, a large number of superoxide radical(O·-2) species in the electrolytes and Li2O2 nuclei at the CP surfaces are formed, which activate the CP current collectors to contribute considerable capacities. These results imply that CP could be a superior material for current collectors in terms of its contribution to the overall discharge capacity.On the other hand, we should be careful to calculate the specific capacities of the oxygen cathodes when using CP as a current collector; i.e., ignoring the contribution from the CP may cause overstated discharge capacities.
基金supported by Basic Science Research Program(Priority Research Institute)through the NRF of Korea funded by the Ministry of Education(2021R1A6A1A10039823)by the Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education(2020R1A6C101B194)。
文摘Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.
基金Projects (51272221,51072173,21203161) supported by the National Natural Science Foundation of ChinaProject (10CY005) supported by Industrial Project of Colleges and Universities of Hunan Province,China
文摘The hierarchically porous carbons （HPCs） were prepared by sol-gel selassembly technology in different surfactant concentrations and were used as the potential electrode for lithium oxygen batteries. The physical and electrochemical properties of the as-prepared HPCs were investigated by filed emission scanning electron microscopy （FE-SEM）, transmission electron microscopy （TEM）, nitrogen adsorption-desorption isotherm and galvanostatic charge/discharge. The results indicate that all of the HPCs mainly possess mesoporous structure with nearly similar pore size distribution. Using the HPCs as the electrode, a high discharge capacity for lithium oxygen battery can be achieved, and the discharge capacity increases with the specific surface area. Especially, the HPCs-3 oxygen electrode with CTAB concentration of 0.27 mol/L exhibits good capacity retention through controlling discharge depth to 800 mA·h/g and the highest discharge capacity of 2050 mA·h/g at a rate of 0.1 mA/cm2.
基金financially supported by the National Natural Science Foundation of China(Nos.51874051 and 21163004)the Natural Science Foundation of Guangxi(No.2018GXNSFAA281184 and 2019GXNSFAA245046)the Bagui Scholar Program of Guangxi Province。
文摘Aprotic lithium-oxygen batteries possess ultrahigh energy density but suffer from the sluggish decomposition of discharge product,quick depletion of Li anode and cleavage of electrolyte,in close association with oxygen reduction reaction at the cathode.Herein,highly dispersed silver nanoparticles are used to enhance the lithium-oxygen battery with 1.0 M lithium perchlorate in dimethyl sulfoxide.It is observed that film-like amorphous lithium peroxide is formed through surface pathway instead of bulk crystals,due to the incorporation of silver nanoparticles dispersed in the electrolyte,which subsequently accelerates the decomposition of the discharge product by offering more active sites and improved conductivity.The released silver nanoparticles after battery charging can be re-used in the following cycles.Experiments and theoretical calculation further indicate that the suspended silver nanoparticles can adsorb the soluble oxygen reduction intermediates,which are responsible for the alleviation of oxidative cleavage of electrolyte and corrosion of lithium anode.The lifespan of lithium oxygen batteries is therefore significantly extended from 55 to 390 cycles,and the rate performance and full-discharge capacity are also largely enhanced.The battery failure is attributed to the coalescence and growth of silver nanoparticles in the electrolyte,and further improvement on colloid stability is underway.
基金This work was supported by National Key R&D Program of China(2021YFF0500503)National Natural Science Foundation of China(21925202,U22B2071)International Joint Mission on Climate Change and Carbon Neutrality.
文摘Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.
基金We thank the financial support from the National Natural Science Foundation of China(52172173,51872071)Anhui Provincial Natural Science Foundation for Distinguished Young Scholar(2108085J25)+2 种基金Anhui Provincial Natural Science Foundation for Outstanding Young Scholar(2208085Y05)Anhui Province Key Laboratory of Environment-Friendly Polymer Materials,the Natural Science Research Projects of Universities in Anhui Province(KJ2020A0021)Guangxi Key Laboratory of Low Carbon Energy Materials(2021GXKLLCEM04).
文摘Lithium-oxygen batteries are among the most promising electrochemical energy storage systems,which have attracted significant attention in the past few years duo to its far more energy density than lithium-ion batteries.Lithium oxygen battery energy storage is a reactive storage mechanism,and the discharge and charge processes are usually called oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Consequently,complex systems usually create complex problems,lithium oxygen batteries also face many problems,such as excessive accumulation of discharge products(Li_(2)O_(2))in the cathode pores,resulting in reduced capacity,unstable cycling performance and so on.Cathode catalyst,which could influence the kinetics of OER and ORR in lithium oxygen(Li-O_(2))battery,is one of the decisive factors to determine the electrochemical performance of the battery,so the design of cathode catalyst is vitally important.This review discusses the catalytic cathode materials,which are divided into four parts,carbon based materials,metals and metal oxides,composite materials and other materials.
基金jointly supported by National Science Foundation of China (Grant Numbers: 11572271 and 51302236)the Principal Fund of Xiamen University (Hosted by Guanghui Yue, 2018)
文摘Rechargeable lithium–oxygen batteries have been considered as a promising energy storage technology because of their ultra-high theoretical energy densities which are comparable to gasoline. In order to improve the electrochemical properties of lithium–oxygen batteries(LOBs), especially the cycling performance, a high-efficiency cathode catalyst is the most important component.Hence, we aim to demonstrate that CuCr_2O_4@rGO(CCO@rGO) nanocomposites, which are synthesized using a facile hydrothermal method and followed by a series of calcination processes, are an effective cathode catalyst. The obtained CCO@rGO nanocomposites which served as the cathode catalyst of the LOBs exhibited an outstanding cycling performance for over 100 cycles with a fixed capacity of 1000 mAh g^(-1) at a current density of 200 mA g^(-1). The enhanced properties were attributed to the synergistic effect between the high catalytic efficiency of the spinel-structured CCO nanoparticles, the high specific surface area, and high conductivity of the rGO.
基金supported by grants from the National Natural Science Foundation of China (Nos. 21673169, 51672205, 51972257)the National Key Research Program of China (No. 2016YFA0202602)+1 种基金the Research Start-Up Fund from Wuhan University of Technologythe Fundamental Research Funds for the Central Universities (WUT: No. 2019IB003)。
文摘In recent years, as one of the most promising chemical power sources for future society, lithium–oxygen (Li–O2) battery receives great attention due to its extremely high theoretical energy density of 3505 Wh kg^(–1)[1–4]. In practice, large polarization and consequent low energy efficiency currently still hinder the application of Li–O2batteries, which mainly results from the sluggish electrochemical reaction kinetics of oxygen diffusion electrodes in aprotic electrolytes [5]. On one hand, oxygen reduction reaction (ORR)in aprotic electrolytes is intrinsically sluggish due to the difficult charge transfer, the low solubility of oxygen.
基金supported by the National Key Research and Development Program(2016YFA0202500 and 2016YFA0200102)the Natural Scientific Foundation of China(21776019)
文摘The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme（SNG）. In contrast with routine N-doped graphene framework（NGF） with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^（-1）, a large surface area of 1531 m^2 g^（-1）, a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.
基金financially supported by the National Natural Science Foundation of China(Nos.52022088,51971245)Natural Science Foundation of Hebei Province(No.F2021203097)China Postdoctoral Science Foundation(No.2021M702756)。
文摘The development of highly efficient catalysts in the cathodes of rechargeable Li-O_(2) batteries is a considerable challenge.To enhance the electrochemical performance of the Li-O_(2) battery,it is essential to choose a suitable catalyst material.Copper selenide(CuSe)is considered as a more promising cathode catalyst material for Li-O_(2) battery due to its better conductivity and rich electrochemical active sites.However,its electrochemical reaction and fundamental catalytic mechanism remain unclear till now.Herein,in-situ environmental transmission electron microscopy technique was used to study the catalysis mechanism of the CuSe nanosheets in Li-O_(2) batteries during discharge and charge processes.It is found that Li_(2)O was formed and decomposed around the ultrafine-grained Cu during the discharge and charge processes,respectively,demonstrating excellent cycling.This indicate that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter four-electron-transfer oxygen reduction reaction,leading to the formation of Li_(2)O.Our study provides important understanding of the electrochemistry of the LiO_(2) nanobatteries,which will aid the development of high-performance Li-O_(2) batteries for energy storage applications.
基金supported by the National Natural Science Foundation of China (Nos. 51073156 and 51021003)Program of Scientific Development of Jilin Province (No. 20116024)
文摘Among the intrinsically conductive polymers, polyanilines have been of great interest in the past decades due to their wide applications in many fields, thanks to their reasonably good conductivity, easy preparation, and special redox properties. Ever-increasing environmental corsiderations make the processing of polyanilines shift from toxic organic solvent-based system to eco-friendly water-based system. The present paper reviews the synthesis of water-borne conducting polyanilines, and possible applications are discussed including supercapacitor electrode material, metal free corrosion protection coating, lithium oxygen battery cathode material and ultraviolet curable resin.
基金supported by the National Key Research and Development Program (no.2016YFA0202500)National Basic Research Program of China (2015CB932500)the Natural Scientific Foundation of China (nos.21306102 and 21422604)
文摘Nanostructured materials have received tremendous interest due to their unique mechanical/electrical properties and overall behavior contributed by the complex synergy of bulk and interfacial properties for efficient and effective energy conversion and storage. The booming development of nanotechnology affords emerging but effective tools in designing advanced energy material. We reviewed the significant progress and dominated nanostructured energy materials in electrochemical energy conversion and storage devices, including lithium ion batteries, lithium-sulfur batteries, lithium-oxygen batteries, lithium metal batteries, and supercapacitors. The use of nanostructured electrocatalyst for effective electrocatalysis in oxygen reduction and oxygen evolution reactions for fuel cells and metal-air batteries was also included. The challenges in the undesirable side reactions between electrolytes and electrode due to high electrode/electrolyte contact area, low volumetric energy density of electrode owing to low tap density, and uniform production of complex energy materials in working devices should be overcome to fully demonstrate the advanced energy nanostructures for electrochemical energy conversion and storage. The energy chemistry at the interfaces of nanostructured electrode/electrolyte is highly expected to guide the rational design and full demonstration of energy materials in a working device. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
基金supported by The National Natural Science Foundation of China(Grant Nos.21905033,52271201)the Science and Technology Department of Sichuan Province(Grant Nos.2025NSFTD0005,2022YFG0100,2022ZYD0045).
文摘Understanding and regulating the electronic states of single-atom sites near the Fermi energy level are essential for developing effective electrocatalysts for lithium–oxygen batteries(LOBs).In this study,we introduce an axial oxygen ligand at the metal center of cobalt porphyrin(CoPP)to adjust the electronic state of the Co center.Theoretical calculations and experimental findings show that this axial interaction disrupts the planar tetragonal crystal field of CoPP,resulting in enhanced spin polarization and electronic rearrangement.This rearrangement of d orbitals causes an upward shift in the frontier orbitals,which facilitates electron exchange during reactions.Additionally,the increased number of unpaired electrons in the d orbitals enhances the adsorption of CoPPO-MXene to various oxygen species,promoting the formation of a thin film-like Li2O2.These thin film-like discharge products improve contact with the electrode surfaces,leading to easier decomposition during the charging process.Consequently,CoPP-OMXene-based LOBs demonstrate a high discharge capacity of 11035mAh g−1,a low overpotential of 0.76 V,and remarkable cycling stability(445 cycles).
基金financially supported by the National Natural Science Foundation of China(Nos.21671096 and 21603094)the Shenzhen Peacock Plan(No.KQCX2014052215 0815065)+1 种基金the Natural Science Foundation of Shenzhen(Nos.JCYJ20150630145302231 and JCYJ20150331101823677)the Science and Technology Innovation Foundation for the Undergraduates of South University of Science and Technology of China(Nos.2016S10,2016S20,2015x19 and 2015x12)
文摘Alkaline zinc manganese dioxide（Zn–MnO2）batteries are widely used in everyday life. Recycling of waste alkaline Zn–MnO2 batteries has always been a hot environmental concern. In this study, a simple and costeffective process for synthesizing Mn3O4/carbon nanotube（CNT） nanocomposites from recycled alkaline Zn–MnO2 batteries is presented. Manganese oxide was recovered from spent Zn–MnO2 battery cathodes. The Mn3O4/CNT nanocomposites were produced by ball milling the recovered manganese oxide in a commercial multi-wall carbon nanotubes（MWCNTs） solution. Scanning electron microscopy（SEM） analysis demonstrates that the nanocomposite has a unique three-dimensional（3D） bird nest structure. Mn3O4 nanoparticles are homogeneously distributed on MWCNT framework. Mn3O4/CNT nanocomposites were evaluated as an anode material for lithium-ion batteries, exhibiting a highly reversible specific capacitance of -580 mA h·g^-1 after 100 cycles. Moreover, Mn3O4/CNT nanocomposite also shows a fairly positive onset potential of -0.15 V and quite high oxygen reducibility when considered as an electrocatalyst for oxygen reduction reaction.
基金supported by the MOST(Grant nos.2013CB934000and 2014DFG71590)Beijing Municipal Program(Grant no.YETP0157)
文摘Boron-doped Ketjenblack is attempted as cathode catalyst for non-aqueous rechargeable Li–O2 batteries. The boron-doped Ketjenblack delivers an extremely high discharge capacity of 7193 m Ah/g at a current density of 0.1 m A/cm2, and the capacity is about 2.3 times as that of the pristine KB. When the batteries are cycled with different restricted capacity, the boron-doped Ketjenblack based cathodes exhibits higher discharge platform and longer cycle life than Ketjenblack based cathodes. Additionally, the boron-doped Ketjenblack also shows a superior electrocatalytic activity for oxygen reduction in 0.1 mol/L KOH aqueous solution. The improvement in catalytic activity results from the defects and activation sites introduced by boron doping.
基金financially supported by the National Natural Science Foundation of China(22279112,52022088,51971245,51772262,21406191,U20A20336,21935009)the Natural Science Foundation of Hebei Province,China(B2022203018,F2021203097,B2020203037,B2018203297)+2 种基金the Hunan Innovation Team,China(2018RS3091)the Beijing Natural Science Foundation,China(2202046)the Fok Ying-Tong Education Foundation of China(171064)。
文摘Understanding alkali metal ions’(e.g.,Li^(+)/Na^(+)/K^(+))transport mechanism is challenging but critical to improving the performance of alkali metal batteries.Herein using a-MnO_(2)nanowires as cathodes,the transport kinetics of Li^(+)/Na^(+)/K^(+)in the 2×2 channels of a-MnO_(2)with a growth direction of[001]is revealed.We show that ion radius plays a decisive role in determining the ion transport and electrochemistry.Regardless of the ion radii,Li^(+)/Na^(+)/K^(+)can all go through the 2×2 channels of a-MnO_(2),generating large stress and causing channel merging or opening.However,smaller ions such as Li^(+)and Na^(+)cannot only transport along the[001]direction but also migrate along the<110>direction to the nanowire surface;for large ion such as K^(+),diffusion along the<110>direction is prohibited.The different ion transport behavior has grand consequences in the electrochemistry of metal oxygen batteries(MOBs).For Li-O_(2)battery,Li^(+)transports uniformly to the nanowire surface,forming a uniform layer of oxide;Na^(+)also transports to the nanowire surface but may be clogged locally due to its larger radius,therefore sporadic pearl-like oxides form on the nanowire surface;K^(+)cannot transport to the nanowire surface due to its large radius,instead,it breaks the nanowire locally,causing local deposition of potassium oxides.The study provides atomic scale understanding of the alkali metal ion transport mechanism which may be harnessed to improve the performance of MOBs.
基金supported by the Ministry of Education, Singapore (2013-T1-002132)the iFood program of Nanyang Technological UniversityThe University of Sydney for financial support
文摘Microbes are microscopic living organisms that surround us which include bacteria, archaea, most protozoa, and some fungi and algae. In recent years, microbes have been explored as novel precursors to synthesize carbon-based（nano）materials and as substrates or templates to produce carbon-containing（nano）composites. Being greener and more affordable, microbe-derived carbons（MDCs） offer good potential for energy applications. In this review, we describe the unique advantages of MDCs and outline the common procedures to prepare them. We also extensively discuss the energy applications of MDCs including their use as electrodes in supercapacitors and lithium-ion batteries, and as electrocatalysts for processes such as oxygen reduction, oxygen evolution, and hydrogen evolution reactions which are essential for fuel cell and water electrochemical splitting cells. Based on the literature trend and our group＇s expertise, we propose potential research directions for developing new types of MDCs. This review, therefore, provides the state-of-the-art of a new energy chemistry concept. We expect to stimulate future research on the applications of MDCs that may address energy and environmental challenges that our societies are facing.
基金support from the University of Pretoria,Department of Innovation and Research.
文摘The shift to clean energy is crucial in mitigating the harmful effects of fossil fuels on the environment.Nevertheless,as we embrace clean energy sources,particularly solar and wind energies,high-energy-density storage devices like lithium and sodium-oxygen batteries are essential.However,challenges such as the irreversibility of lithium and sodium peroxides and their non-conductivity nature on the cathode electrode hinder practical use.2D materials,particularlyβ_(12)-borophene,show promise in addressing these challenges.In this study,we used density functional theory to thoroughly investigate the adsorption mechanisms of alkali-metal peroxides and their impact on the electronic properties of theβ_(12)-borophene.Our results revealed adsorption energies of-3.71 and-3.54 eV for Li_(2)O_(2)and Na_(2)O_(2),respectively,showing that the adsorbed peroxides are stable and unlikely to decompose into the electrolyte.The calculated Gibbs free energy changes that revealed low overpotentials of 1.03 V for Li_(2)O_(2)and 1.61 V for Na_(2)O_(2).Moreover,even with increased concentrations of peroxides on the surface,β_(12)-borophene retained its ability to adsorb additional peroxides,achieving theoretical voltages of 2.60 V for Li_(2)O_(2)and 2.04 V for Na_(2)O_(2).Notably,the metallic nature ofβ_(12)remained stable despite the adsorption of peroxides,evidenced by an increase in electronic states around the Fermi level and the overlap of the valence and conduction bands.Furthermore,thermal stability analysis at 300 K confirmed that the structure ofβ_(12)-borophene remained intact,reinforcing its suitability as a cathode at standard temperature of the battery.The low diffusion energy barriers of 1.04 and 0.92 eV were obtained for Li_(2)O_(2)and Na_(2)O_(2),respectively,suggesting a high rate of peroxides migration on the substrate surface.The dissociation energy barriers for Li_(2)O_(2)and Na_(2)O_(2)were found to be minimal at 1.86 and 1.69 eV,respectively,indicating the catalytic effects and enhancing electrochemical processes.Our findings suggest thatβ_(12)-borophene can be a potential cathode electrode for the next-generation lithium and sodium-oxygen batteries.
基金S.S.H.Z.and X.L.L.highly appreciate the support from the National Science Foundation(Nos.1833048 and 1941083)The work by J.L.’s group is partially supported by the National Science Foundation under grant(No.CBET-2054754).
文摘The development of an ideal cathode for Li-O_(2)battery(LOB)has been a great challenge in achieving high discharge capacity,enhanced stability,and longevity.The formation of undesired and irreversible discharge products on the surface of current cathode materials limit the life span of the LOB.In this study,we report the systematic electrochemical study to compare the performance of LOB employing a unique graphitic nanostructured carbon architecture,i.e.,vertically aligned carbon nanofiber(VACNF)arrays,as the cathode materials.Transition metal(Ni)and noble metal alloy(PtRu)are further deposited on the VACNF array as electrocatalysts to improve the discharge/charge processes at the cathode.The structure of as-prepared electrodes was examined with the field emission scanning electron microscopy,high-resolution transmission electron microscopy,and X-ray photoelectron spectroscopy(XPS).The LOB with VACNF-Ni electrode delivered the highest specific and areal discharge capacities(14.92 Ah·g^(−1),4.32 mAh·cm^(−2))at 0.1 mA·cm^(−2)current density as compared with VACNF-PtRu(9.07 Ah·g^(−1),2.62 mAh·cm^(−2)),bare VACNF(5.55 Ah·g^(−1),1.60 mAh·cm^(−2))and commercial Vulcan XC(3.83 Ah·g^(−1),1.91 mAh·cm^(−2)).Cycling stability tests revealed the superior performance of VACNF-PtRu with 27 cycles as compared with VACNF-Ni(13 cycles),VACNF(8 cycles),and Vulcan XC(3 cycles).The superior cycling stability of VACNF-PtRu can be attributed to its ability to suppress the formation of Li2CO3 during the discharge cycle,as elucidated by XPS analysis of discharged samples.We also investigated the impact of carbon cloth and carbon fiber as cathode electrode substrate on the performance of LOB.
基金the National Natural Science Foundation of China(21773055,U1604122,51702086,21203055and 21805070)the Program for Science&Technology Innovation Talents in Universities of Henan Province(18HASTIT004)China Postdoctoral Science Foundation(2020M672201)。
文摘Oxygen reduction reactions(ORRs)with one-or two-electron-transfer pathways are the essential process for aprotic metal-oxygen batteries,in which the stability of superoxide intermediates/products(O_(2)^(-),LiO_(2),NaO_(2),etc.)mainly dominates the ORR activity/stability and battery performance.However,little success in regulating the stability of the superoxides has been achieved due to their highly reactive characteristics.Herein,we identified and modulated the stability of superoxides by introducing anthraquinone derivatives as cocatalysts which functioned as superoxide trapper adsorbing the superoxides generated via surface-mediated ORR and then transferring them from the solid catalyst surface into electrolyte.Among the studied trappers,1,4-difluoroanthraquinone(DFAQ)with electron-withdrawing groups showed the highest adsorption towards superoxides and could efficiently stabilize LiO_(2)in electrolyte,which greatly promoted the surface-mediated ORR rate and stability.This highlighted the magnitude of adsorption between the trapper and LiO_(2)on the ORR activity/stability.Using an aprotic Li-O_(2)battery as a model metal-O_(2)battery,the overall performance of the cell with DFAQ was substantially improved in terms of cell capacity,rate capability and cyclic stability.These results represent a significant advance in the understanding of ORR mechanisms and promoting the performance of metal-O_(2)batteries.
