Pyrolytic graphite (PG) with highly aligned graphene layers,present anisotropic electrical and thermal transport behavior,which is attractive in electronic,electrocatalyst and energy storage.Such pristine PG could mee...Pyrolytic graphite (PG) with highly aligned graphene layers,present anisotropic electrical and thermal transport behavior,which is attractive in electronic,electrocatalyst and energy storage.Such pristine PG could meeting the limit of electrical conductivity (~2.5×10^(4) S·cm^(−1)),although efforts have been made for achieving high-purity sp^(2) hybridized carbon.For manipulating the electrical conductivity of PG,a facile and efficient electrochemical strategy is demonstrated to enhance electrical transport ability via reversible intercalation/de-intercalation of AlCl_(4)^(-)into the graphitic interlayers.With the stage evolution at different voltages,variable electrical and thermal transport behaviors could be achieved via controlling AlCl_(4)^(-)concentrations in the PG because of substantial variation in the electronic density of states.Such evolution leads to decoupled electrical and thermal transport (opposite variation trend) in the in-plane and out-of-plane directions,and the in-plane electrical conductivity of the pristine PG (1.25×10^(4) S·cm^(−1)) could be massively promoted to 4.09×10^(4) S·cm(AlCl_(4)^(-)intercalated PG),much better than the pristine bulk graphitic papers used for the electrical transport and electromagnetic shielding.The fundamental mechanism of decoupled transport feature and electrochemical strategy here could be extended into other anisotropic conductive bulks for achieving unusual behaviors.展开更多
Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and...Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and low cycle life due to the shuttle effect.To mitigate the shuttle effect induced by soluble selenium chloroaluminate compound that tends to migrate towards the negative electrode,a quasi-solid-state Al-Se battery was fabricated through the synthesis of a multi-aperture structure quasisolid-state electrolyte(MOF@GPE)based on metal-organic framework(MOF)material and gel-polymer electrolyte(GPE).The high ionic conductivity(1.13×10^(-3)S cm^(-1))of MOF@GPE at room temperature,coupled with its wide electrochemical stability window(2.45 V),can facilitate ion transport kinetics and enhance the electrochemical performance of Al-Se batteries.The MOF@GPE-based quasi-solidstate Al-Se batteries exhibit outstanding long-life cycling stability,delivering a high specific discharge capacity of 548 mA h g^(-1)with a maintained discharge specific capacity of 345 mA h g^(-1)after 500 cycles at a current density of 200 mA g^(-1).The stable ion transmission and high ion transport kinetics in MOF@GPE can be attributed to the stable structure and permeable channel of MOF,which effectively captures the soluble selenium chloroaluminate compound and further restrains the shuttle effect,resulting in improved cycling performance.展开更多
The properties of non-oxide materials are continuously revealed,and their applications in the fields of ceramics,energy,and catalysis are increasingly extensive.Regardless of the traditional binary materials or the MA...The properties of non-oxide materials are continuously revealed,and their applications in the fields of ceramics,energy,and catalysis are increasingly extensive.Regardless of the traditional binary materials or the MAX phases,the preparation methods,which are environmentally friendly,efficient,economical,and easy to scale-up,have always been the focus of attention.Molten salt synthesis has demonstrated unparalleled advantages in achieving non-oxide materials.In addition,with the development of the process in molten salt synthesis,it also shows great potential in scale-up production.In this review,the recent progress of molten salt synthesis in the preparation of binary non-oxide and MAX phase is reviewed,as well as some novel processes.The reaction mechanisms and the influence of synthetic conditions for certain materials are discussed in detail.The paper is finalized with the discussion of the application prospect and future research trends of molten salt synthesis in non-oxide materials.展开更多
Ti-bearing slag(TiO2>20 wt%)is a valuable titanium secondary resource.The extraction of titanium from the slag is difficult due to the complex composition and structure.Although molten oxide electrolysis is conside...Ti-bearing slag(TiO2>20 wt%)is a valuable titanium secondary resource.The extraction of titanium from the slag is difficult due to the complex composition and structure.Although molten oxide electrolysis is considered as a promising method,silicon will be preferentially electroreduced compared to titanium due to low theoretical decomposition voltage.In this work,a liquid copper cathode is used to selectively extract titanium from molten Al2O3-MgO-CaO-TiO2-SiO2 electrolyte.It is found that comparing to silicon,titanium can be preferentially reduced by one-step electron transfer due to the enhanced depolarization effect on a liquid copper cathode.So,Ti-Cu alloys are firstly obtained from molten Ti-bearing slag,and then Ti-Si alloys are co-electrodeposited in the molten oxide electrolyte with low TiO2 content.It may be ascribed to the larger binding force between titanium and copper than that between silicon and copper.It provides an effective strategy for the separation of titanium from of Ti-bearing slag.展开更多
The growing global demands of safe, low-cost and high working voltage energy storage devices trigger strong interests in novel battery concepts beyond state-of-art lithium-ion battery. Herein, a dualion battery based ...The growing global demands of safe, low-cost and high working voltage energy storage devices trigger strong interests in novel battery concepts beyond state-of-art lithium-ion battery. Herein, a dualion battery based on nanostructured Ni_3S_2/Ni foam@RGO(NSNR) composite anode is developed, utilizing graphite as cathode material and LiPF6-VC-based solvent as electrolyte. The battery operates at high working voltage of 4.2–4.5 V, with superior discharge capacity of ~90 m A h g^(-1) at 100 mA g^(-1), outstanding rate performance, and long-term cycling stability over 500 cycles with discharge capacity retention of ~85.6%. Moreover, the composite simultaneously acts as the anode material and the current collector, and the corrosion phenomenon can be greatly reduced compared to metallic Al anode. Thus, this work represents a significant step forward for practical safe, low-cost and high working voltage dual-ion batteries,showing attractive potential for future energy storage application.展开更多
For addressing the critical problems in current collectors in the aluminium batteries,a variety of carbonbased current collectors,including carbon fiber textiles and three-dimensional(3D)biomass-derivative carbon(BDC)...For addressing the critical problems in current collectors in the aluminium batteries,a variety of carbonbased current collectors,including carbon fiber textiles and three-dimensional(3D)biomass-derivative carbon(BDC)networks,are employed for serving as lightweight non-metal current collectors.The results indicate that all the carbon-based current collectors have electrochemical stability in the acidic electrolyte environments.In the assembled aluminium batteries with all-carbon positive electrodes,thermal annealing process on the carbon-based current collectors has substantially promoted the entire electrochemical energy storage performance.Additionally,both the structure configuration and chemical components of the current collectors have also great impact on the rate capability and cycling stability,implying that the 3D BDC networks are more favorable to offer promoted energy storage capability.Implication of the results from suggests that the carbon-based current collectors and all-carbon positive electrodes are able to deliver more advantages in energy storage behaviors in comparison with the traditional positive electrodes with metal Mo current collectors.Such novel strategy promises a new route for fabricating highperformance positive electrodes for stable advanced aluminium batteries.展开更多
Potassium-ion batteries(PIBs),also known as“novel post-lithium-ion batteries,”have promising energy storage and utilization prospects due to their abundant and inexpensive raw materials.Appropriate anode materials a...Potassium-ion batteries(PIBs),also known as“novel post-lithium-ion batteries,”have promising energy storage and utilization prospects due to their abundant and inexpensive raw materials.Appropriate anode materials are critical for realizing high-performance PIBs because they are an important component determining the energy and power densities.Two-dimensional(2D)layered anode materials with increased interlayer distances,specific surface areas,and more active sites are promising candidates for PIBs,which have a high reversible capacity in the energetic pathway.In this review,we briefly summarize K+storage behaviors in 2D layered carbon,transition metal chalcogenides,and MXene materials and provide some suggestions on how to select and optimize appropriate 2D anode materials to achieve ideal electrochemical performance.展开更多
Internal gases caused by side reactions are crucial signals for evaluating health and safety states of Li-ion batteries(LIBs)while it is still a great challenge to timely realize accurate monitoring.To address the iss...Internal gases caused by side reactions are crucial signals for evaluating health and safety states of Li-ion batteries(LIBs)while it is still a great challenge to timely realize accurate monitoring.To address the issues of implanting various gas sensors into commercial batteries,here a novel method is developed to fast operando monitoring gas evolution via equipping non-dispersive infrared multi-gases sensors into a sealed tank,where real commercial batteries with one open end could be settled for operating.The generated CO_(2)concentration is strongly linked with both voltage and temperature,while the concentrations of CH_(4) and C_(2)H_(4) are solely dependent on temperature.As a typical trace gas,evolution behaviors of CO_(2)have been related to 0_(2) generation from LiNi_(o.5)Mn_(0.3)CoO_(2)0_(2) positive electrode,implying stable CO_(2)release below a critical voltage of 4.5 V.By tracking CO_(2)concentration,an increased amount of Li_(2)CO_(3) was monitored on the surface of graphite negative electrode during discharge process at dfferent temperatures and cutoff voltages,which contributes to the component variation of solid electrolyte interfaces.Such operando techniques promise a plaform for well understanding the interaction of side reactions linked with gas evolution between positive and negative electrodes in commercial LIBs.展开更多
Aluminum batteries are attractive in electrochemical energy storage due to high energy density and lowcost aluminum,while the energy density is limited for the lack of favorable positive electrode materials to match a...Aluminum batteries are attractive in electrochemical energy storage due to high energy density and lowcost aluminum,while the energy density is limited for the lack of favorable positive electrode materials to match aluminum negative electrodes.Tellurium positive electrode is intrinsically electrically conductive among chalcogen and holds high theoretical specific capacity(1260.27 mAh g^(-1)) and discharge voltage plateau(~1,5 V).However,the chemical and electrochemical dissolution of Te active materials results in the low material utilization and poor cycling stability.To enhance the electrochemical performance,herein a nitrogen doped porous carbon(N-PC) is derived from zeolite imidazolate framework(ZIF-67)as an effective tellurium host to suppress the undesired shuttle effect.In order to inhibit the volume expansion of N-PC during the charge/discharge process,the reduced graphene oxide(rGO) nanosheets are introduced to form a stable host materials(N-PC-rGO) for stabilizing Te.The physical encapsulation and chemical confinement to soluble tellurium species are achieved.N-PC-rGO-Te positive electrode exhibits an improved initial specific capacity and long-term cycling performance at a current density of 500 mA g^(-1)(initial specific capacity:935.5 mAh g^(-1);after 150 cycles:467.5 mAh g^(-1)), highlighting a promising design strategy for inhibiting chemical and electrochemical dissolution of Te.展开更多
Carbon contamination and the formation of low-valence oxides limit the preparation of refractory metals by molten salt electrolysis.In this paper,a liquid Zn cathode is adopted for the electrochemical reduction of sol...Carbon contamination and the formation of low-valence oxides limit the preparation of refractory metals by molten salt electrolysis.In this paper,a liquid Zn cathode is adopted for the electrochemical reduction of soluble K2CrO4 to metallic Cr in CaCl2-KCl molten salt.It is found that CrO4^2-can be directly electrochemically reduced to Cr via a six-electron-transfer step and low-valence Cr oxides is hardly produced.The reduction rate is obviously increased from 16.7 mgCrh^-1cm^-2 on the solid Mo cathode to58.7 mgCrh-1cm-2on liquid Zn cathode.The electrodeposited Cr is distributed in liquid Zn cathode.Carbon contamination is effectively avoided due to the negligible solubility of carbon in the liquid Zn cathode.Furthermore,Cr can be effectively separated and enriched to the bottom of liquid Zn under supergravity field,realizing the efficient acquisition of metallic Cr and recycling of liquid Zn.The method herein provides a promising route for the preparation of refractory metals with high-purity by molten salt electrolysis.展开更多
Graphite has been currently considered as a promising cathode material in dual ion batteries(DIBs)due to its unique features of sp2 hybridized carbon and stacked two-dimensional layered structures.However,unexpected v...Graphite has been currently considered as a promising cathode material in dual ion batteries(DIBs)due to its unique features of sp2 hybridized carbon and stacked two-dimensional layered structures.However,unexpected volume/thickness changes in the graphite cathodes,induced by the intercalation/deintercalation of anions with large molecular size have been known to be a critical problem in designing DIB cells.To understand the volume/thickness changes in the DIB electrodes,in operando optical observing apparatus has been employed to observe the cross-section view of a graphite-based cathode upon cycles in the present work.The observation suggests that the cathode initially presented a huge irreversible thickness change(60%),and such thickness variation was prone to reduce and remain <20% in the following cycles.The results from both in operando observation and electrochemical characterizations collectively indicate that the greater thickness variation at initial cycle should be attributed to both anion intercalation into graphite-based cathodes and irreversible decomposition of chemical components in the DIB system.The method here highlights a universal route for fundamentally understanding the electrodes of huge volume variation.展开更多
Normal titanium oxycarbide exhibits an excellent electrical conductivity and a high carrier concentration of approximately 10^(21) cm^(-3);however,the low Seebeck coefficient limits the thermoelectric application.In t...Normal titanium oxycarbide exhibits an excellent electrical conductivity and a high carrier concentration of approximately 10^(21) cm^(-3);however,the low Seebeck coefficient limits the thermoelectric application.In this study,first-principle calculations demonstrate that the metal vacancy of titanium oxycarbide weakens the density of state passing through the valence band at the Fermi level,impairing the carrier concentration and enhancing carrier mobility.Thermodynamic analysis justifies the formation of titanium oxycarbide with metal vacancy through solid-state reaction.Transmission electron microscopic images demonstrate the segregation of metal vacancy based on the observation of the defect-rich and single-crystal face-centered cubic regions.Metal vacancy triggers the formation of vacancy-rich and single-crystal face-centered cubic regions.The aggregation of metal vacancy leads to the formation of the vacancy-rich region and other regions with a semi-coherent interface,suppressing the carrier concentration from 1.71×10^(21) to 4.5×10^(20) cm^(-3) and resulting in the Seebeck coefficient from -11μV/K of TiC_(0.5)O_(0.5) to -64μV/K at 1073 K.Meanwhile,vacancies accelerate electron migration from 1.65 to 4.22 cm^(-2)·V^(-1)·s^(-1),maintaining high conductivity.The figure of merit(ZT)increases more than five orders of magnitude via the introduction of metal vacancy,with the maximum figure of 2.11×10^(-2) at 1073 K.These results indicate the potential thermoelectric application of metal-oxycarbide materials through vacancy engineering.展开更多
With the advent of flexible/wearable electronic devices,flexible lithium-ion batteries(LIBs)have attracted significant attention as optimal power source candidates.Flexible LIBs with good flexibility,mechanical stabil...With the advent of flexible/wearable electronic devices,flexible lithium-ion batteries(LIBs)have attracted significant attention as optimal power source candidates.Flexible LIBs with good flexibility,mechanical stability,and high energy density are still an enormous challenge.In recent years,many complex and diverse design methods for flexible LIBs have been reported.The design and evaluation of ideal flexible LIBs must take into consideration both mechanical and electrochemical factors.In this review,the recent progress and challenges of flexible LIBs are reviewed from a mechano-electrochemical perspective.The recent progress in flexible LIB design is addressed concerning flexible material and configuration design.The mechanical and electrochemical evaluations of flexible LIBs are also summarized.Furthermore,mechano-electrochemical perspectives for the future direction of flexible LIBs are also discussed.Finally,the relationship between mechanical loading and the electrode process is analyzed from a mechano-electrochemical perspective.The evaluation of flexible LIBs should be based on mechano-electrochemical processes.Reviews and perspectives are of great significance to the design and practicality of flexible LIBs,which is contributed to bridging the gap between laboratory exploration and practical applications.展开更多
Structural deformation and dendrite formation, which would impact the electrochemical processes of rechargeable metal batteries, are usually observed in the high-energy density metal electrodes. Herein,we design an in...Structural deformation and dendrite formation, which would impact the electrochemical processes of rechargeable metal batteries, are usually observed in the high-energy density metal electrodes. Herein,we design an in-situ optical mechano-electrochemical system to study Al deposition on the Al electrode in non-aqueous Al batteries under non-uniform strain. Inhomogeneous distribution of applied strain is realized by creating an oval hole in the Al electrode. The results of the in-situ experiments suggest that the dense Al deposition, which is related to the evolution of surface morphology and increasing reactive sites, is achieved in the regions of stress concentration. The evolution of surface morphology is monitored by the in-situ tension experiments using scanning electron microscope and atomic force microscope.Besides, a qualitative mathematical model is employed to analyze the changes of the local reaction rate owing to the changed surface morphology and the cracks of oxide film under tensile stress. The results are useful to understand the Al deposition when the mechanical force is applied to the metal electrode.展开更多
Metal sulfides with high theoretical capacities are expected as promising cathode materials of Al batteries(AIBs). However, powdery active materials are mainly synthesized and loaded on current collector by insulating...Metal sulfides with high theoretical capacities are expected as promising cathode materials of Al batteries(AIBs). However, powdery active materials are mainly synthesized and loaded on current collector by insulating binder without capacity. Meanwhile, S as inert element in metal sulfides can not usually provide capacity. So, powdery metal sulfides only exhibit limiting practical capacity and poor cycling stability due to weak conductivity and low mass utilization. Herein, the novel self-supporting and dual-active Co-S nanosheets on carbon cloth (i.e. Co-S/CC) with hierarchically porous structure are constructed as cathode of AIBs. Co-S nanosheets are derived from ZIF-67 nanosheets on CC by a facile ligand replacement reaction. As a result, the binder-free Co-S/CC cathode with good conductivity delivers excellent initial discharge capacity of 383.4 m Ah g^(-1)(0.211 m Ah cm^(-2)) at current density of 200 m A g^(-1)and maintain reversible capacity of 156.9 m Ah g^(-1)(0.086 m Ah cm^(-2)) with Coulombic efficiency of 95.8% after 500 cycles,which are much higher than those of the traditional slurry-coating cathodes. Both Co and S as active elements in Co-S/CC contribute to capacity, which leads to a high mass utilization. This work provides a significant strategy for the construction of self-supporting metallic cathode for advanced high-energy density Al battery.展开更多
Metal aluminum batteries(MABs)are considered potential large-scale energy storage devices because of their high energy density,resource abundance,low cost,safety,and environmental friendliness.Given their high electri...Metal aluminum batteries(MABs)are considered potential large-scale energy storage devices because of their high energy density,resource abundance,low cost,safety,and environmental friendliness.Given their high electrical conductivity,high theoretical specific capacity,and high discharge potential,Te is considered a potential positive electrode material for MABs.Nonetheless,the critical issues induced by the chemical and electrochemical dissolution of tellurium and subsequent chemical precipitation on bare Al negative electrodes result in poor cycle stability and low discharge capacity of Al-Te batteries.Here an efficient TiB_(2)-based modified layer has been proposed to address bare Al electrodes(Al/TB).Consequently,the low-voltage hysteresis and long cycle life of the Al/TB negative electrode have been achieved.In addition,the electrochemical performance of the Al-Te battery based on the Al/TB negative electrode is dramatically improved.Furthermore,the modified separator technology is introduced to match with the as-designed Al/TB negative electrode.Therefore,the record-setting long-term cycle stability of up to 500 cycles has been achieved in the Al-Te battery.The facile strategy also opens a potential route for other high-energy density battery systems,such as Al-S and Al-Se batteries.展开更多
Aluminum-selenium(Al-Se)batteries have been considered as one of the most promising energy storage systems owing to their high capacity,energy density,and cost effectiveness,but Se falls challenges in addressing the s...Aluminum-selenium(Al-Se)batteries have been considered as one of the most promising energy storage systems owing to their high capacity,energy density,and cost effectiveness,but Se falls challenges in addressing the shuttle effect of soluble intermediate product and sluggish reaction kinetics in the solid-solid conversion process during cycling.Herein,we propose an unprecedented design concept for fabricating uniform Se/C hollow microspheres with controllable morphologies through low-temperature electro-deoxidation in neutral NaCl-AlCl3 molten salt system.Such Se/C hollow microspheres are demonstrated to hold a favorable hollow structure for hosting Se,which can not only suppress the dissolution of soluble intermediate products into the electrolyte,thereby maintaining the structural integrity and maximizing Se utilization of the active material,but also promote the electrical/ionic conductivity,thus facilitating the rapid reaction kinetics during cycling.Accordingly,the as-prepared Se/C hollow microspheres exhibit a high reversible capacity of 720.1 mAh g^(−1)at 500 mA g^(−1).Even at the high current density of 1000 mA g^(−1),Se/C delivers a high discharge capacity of 564.0 mAh g^(−1),long-term stability over 1100 cycles and high Coulombic efficiency of 98.6%.This present work provides valuable insights into short-process recovery of advanced Se-containingmaterials and value-added utilization for energy storage.展开更多
Despite its existence for more than 80 years,the titanium industry is still challenged by massive carbon emissions,high production costs,and large resource waste.More than one hundred million tons of Ti-bearing blast ...Despite its existence for more than 80 years,the titanium industry is still challenged by massive carbon emissions,high production costs,and large resource waste.More than one hundred million tons of Ti-bearing blast furnace slag(TB-slag)has been discarded in China because of the difficulty of reutilization,which requires efficient titanium extraction and recovery technologies.This paper describes a low-cost,carbon-emission-free method for Ti extraction and oxygen evolution via molten oxide electrolysis(MOE)vacuum distillation.After a comprehensive analysis of the binding energies and activities of liquid metals,the highlights of our study are as follows.1)Sb has the best preferential deposition of Ti among a series of high-Ti-affinitive liquid metal cathodes(Cu,Ni,Pb,Sn,and Sb).2)The Ir anode was first used in TB-slag with IrO_(2) formed on its surface to protect it from further corrosion.3)An alloy containing Ti and Ca can be obtained by MOE,and Ti and Ca metals can be refined by further vacuum distillation.4)A closed loop is formed in the overall process owing to the recyclable Sb cathode and continuous feeding of TB-slag into the electrolyte.This simple,low-cost,and environmentally friendly method can realize the efficient utilization of Ti resources and achieve carbon neutrality.展开更多
Aluminum-sulfur(Al-S)batteries are regarded as a desirable candidate for large-scale energy storage be-cause of their high energy density and abundant natural resources of electrode materials.To address the critical i...Aluminum-sulfur(Al-S)batteries are regarded as a desirable candidate for large-scale energy storage be-cause of their high energy density and abundant natural resources of electrode materials.To address the critical issues of low discharge voltage and rapid capacity decay in Al-S batteries,here an electrocatalyst-assisted gel-polymer electrolyte(GPE)-based Al-S battery is fabricated using platinum nanoparticles deco-rated platinum/nitrogen co-doped graphene(PtNG)as sulfur host for positive electrode and metal-organic frameworks(MOF)filled GPE(MOF@GPE)as solid electrolyte.Pt-based active sites derived from Pt nan-oclusters’surface and atomically dispersed Pt-N_(2) chemical bonds in PtNG can catalyze the decomposition of sulfur and polysulfides in the electrochemical process,greatly accelerating the sulfur redox kinetics.Furthermore,the MOF fillers in MOF@GPE electrolyte significantly inhibit the shuttle effect of polysul-fides,efficiently improving the utilization of sulfur.Consequently,the established Al-S battery delivers a specific capacity of 1009 mAh g^(−1) with a discharge plateau of∼0.95 V,along with a capacity retention of 65% after 300 cycles,revealing ultrahigh energy density and long cycle life.Such a strategy of combin-ing electrocatalyst and MOF-based gel electrolyte affords a fresh plateau for promoting the rechargeable ability of Al-S batteries,advancing remarkable routes for achieving efficient and stable energy storage devices.展开更多
Incorporating a selenium(Se)positive electrode into aluminum(Al)-ion batteries is an effective strategy for improving the overall battery performance.However,the cycling stability of Se positive electrodes has challen...Incorporating a selenium(Se)positive electrode into aluminum(Al)-ion batteries is an effective strategy for improving the overall battery performance.However,the cycling stability of Se positive electrodes has challenges due to the dissolution of intermediate reaction products.In this work,we aim to harness the advantages of Se while reducing its limitations by preparing a core-shell mesoporous carbon hollow sphere with a titanium nitride(C@TiN)host to load 63.9wt%Se as the positive electrode material for Al-Se batteries.Using the physical and chemical confinement offered by the hollow mesoporous carbon and TiN,the obtained core-shell mesoporous carbon hollow spheres coated with Se(Se@C@TiN)display superior utilization of the active material and remarkable cycling stability.As a result,Al-Se batteries equipped with the as-prepared Se@C@TiN composite positive electrodes show an initial discharge specific capacity of 377 mAh·g^(-1)at a current density of 1000 mA·g^(-1)while maintaining a discharge specific capacity of 86.0 mAh·g^(-1)over 200 cycles.This improved cycling performance is ascribed to the high electrical conductivity of the core-shell mesoporous carbon hollow spheres and the unique three-dimensional hierarchical architecture of Se@C@TiN.展开更多
基金financially supported by the National Key R&D Program of China (No. 2018YFB0104400)the National Natural Science Foundation of China (Nos. 52074036, 51725401, and 51874019)Beijing Municipal Science and Technology Commission (No. Z191100002719007)
文摘Pyrolytic graphite (PG) with highly aligned graphene layers,present anisotropic electrical and thermal transport behavior,which is attractive in electronic,electrocatalyst and energy storage.Such pristine PG could meeting the limit of electrical conductivity (~2.5×10^(4) S·cm^(−1)),although efforts have been made for achieving high-purity sp^(2) hybridized carbon.For manipulating the electrical conductivity of PG,a facile and efficient electrochemical strategy is demonstrated to enhance electrical transport ability via reversible intercalation/de-intercalation of AlCl_(4)^(-)into the graphitic interlayers.With the stage evolution at different voltages,variable electrical and thermal transport behaviors could be achieved via controlling AlCl_(4)^(-)concentrations in the PG because of substantial variation in the electronic density of states.Such evolution leads to decoupled electrical and thermal transport (opposite variation trend) in the in-plane and out-of-plane directions,and the in-plane electrical conductivity of the pristine PG (1.25×10^(4) S·cm^(−1)) could be massively promoted to 4.09×10^(4) S·cm(AlCl_(4)^(-)intercalated PG),much better than the pristine bulk graphitic papers used for the electrical transport and electromagnetic shielding.The fundamental mechanism of decoupled transport feature and electrochemical strategy here could be extended into other anisotropic conductive bulks for achieving unusual behaviors.
基金supported by the National Natural Science Foundation of China(51874019 and 51725401)the China Postdoctoral Science Foundation(2020M680347 and 2021T140051)the Fundamental Research Funds for the Central Universities(FRFTP-20-045A1)。
文摘Aluminum-selenium(Al-Se)batteries,which possess a high theoretical specific capacity of 1357 mA h g^(-1),represent a promising energy storage technology.However,they suffer from significant attenuation of capacity and low cycle life due to the shuttle effect.To mitigate the shuttle effect induced by soluble selenium chloroaluminate compound that tends to migrate towards the negative electrode,a quasi-solid-state Al-Se battery was fabricated through the synthesis of a multi-aperture structure quasisolid-state electrolyte(MOF@GPE)based on metal-organic framework(MOF)material and gel-polymer electrolyte(GPE).The high ionic conductivity(1.13×10^(-3)S cm^(-1))of MOF@GPE at room temperature,coupled with its wide electrochemical stability window(2.45 V),can facilitate ion transport kinetics and enhance the electrochemical performance of Al-Se batteries.The MOF@GPE-based quasi-solidstate Al-Se batteries exhibit outstanding long-life cycling stability,delivering a high specific discharge capacity of 548 mA h g^(-1)with a maintained discharge specific capacity of 345 mA h g^(-1)after 500 cycles at a current density of 200 mA g^(-1).The stable ion transmission and high ion transport kinetics in MOF@GPE can be attributed to the stable structure and permeable channel of MOF,which effectively captures the soluble selenium chloroaluminate compound and further restrains the shuttle effect,resulting in improved cycling performance.
基金the National Natural Science Foundation of China(Grant No.51804277)supported by the State Key Laboratory of Special Rare Metal Materials(No.SKL2020K004)Northwest Rare Metal Materials Research Institute.
文摘The properties of non-oxide materials are continuously revealed,and their applications in the fields of ceramics,energy,and catalysis are increasingly extensive.Regardless of the traditional binary materials or the MAX phases,the preparation methods,which are environmentally friendly,efficient,economical,and easy to scale-up,have always been the focus of attention.Molten salt synthesis has demonstrated unparalleled advantages in achieving non-oxide materials.In addition,with the development of the process in molten salt synthesis,it also shows great potential in scale-up production.In this review,the recent progress of molten salt synthesis in the preparation of binary non-oxide and MAX phase is reviewed,as well as some novel processes.The reaction mechanisms and the influence of synthetic conditions for certain materials are discussed in detail.The paper is finalized with the discussion of the application prospect and future research trends of molten salt synthesis in non-oxide materials.
基金supported by the National Natural Science Foundation of China(51725401)the Fundamental Research Funds for the Central Universities(FRF-TP-18-010B1).
文摘Ti-bearing slag(TiO2>20 wt%)is a valuable titanium secondary resource.The extraction of titanium from the slag is difficult due to the complex composition and structure.Although molten oxide electrolysis is considered as a promising method,silicon will be preferentially electroreduced compared to titanium due to low theoretical decomposition voltage.In this work,a liquid copper cathode is used to selectively extract titanium from molten Al2O3-MgO-CaO-TiO2-SiO2 electrolyte.It is found that comparing to silicon,titanium can be preferentially reduced by one-step electron transfer due to the enhanced depolarization effect on a liquid copper cathode.So,Ti-Cu alloys are firstly obtained from molten Ti-bearing slag,and then Ti-Si alloys are co-electrodeposited in the molten oxide electrolyte with low TiO2 content.It may be ascribed to the larger binding force between titanium and copper than that between silicon and copper.It provides an effective strategy for the separation of titanium from of Ti-bearing slag.
基金supported by the National Natural Science Foundation of China (No. 51725401)the Fundamental Research Funds for the Central Universities (FRF-TP-15-002C1 and FRF-TP17-002C2)
文摘The growing global demands of safe, low-cost and high working voltage energy storage devices trigger strong interests in novel battery concepts beyond state-of-art lithium-ion battery. Herein, a dualion battery based on nanostructured Ni_3S_2/Ni foam@RGO(NSNR) composite anode is developed, utilizing graphite as cathode material and LiPF6-VC-based solvent as electrolyte. The battery operates at high working voltage of 4.2–4.5 V, with superior discharge capacity of ~90 m A h g^(-1) at 100 mA g^(-1), outstanding rate performance, and long-term cycling stability over 500 cycles with discharge capacity retention of ~85.6%. Moreover, the composite simultaneously acts as the anode material and the current collector, and the corrosion phenomenon can be greatly reduced compared to metallic Al anode. Thus, this work represents a significant step forward for practical safe, low-cost and high working voltage dual-ion batteries,showing attractive potential for future energy storage application.
基金Financial support from National Key R&D Program of China(Grant No.2018YFB0104400)the National Natural Science Foundation of China(Grant Nos.11672341,11572002 and 51874019)+2 种基金Innovative Research Groups of the National Natural Science Foundation of China(Grant No.11521202)National Materials Genome Project(Grant No.2016YFB0700600)Beijing Natural Science Foundation(Grant Nos.16L00001 and 2182065).
文摘For addressing the critical problems in current collectors in the aluminium batteries,a variety of carbonbased current collectors,including carbon fiber textiles and three-dimensional(3D)biomass-derivative carbon(BDC)networks,are employed for serving as lightweight non-metal current collectors.The results indicate that all the carbon-based current collectors have electrochemical stability in the acidic electrolyte environments.In the assembled aluminium batteries with all-carbon positive electrodes,thermal annealing process on the carbon-based current collectors has substantially promoted the entire electrochemical energy storage performance.Additionally,both the structure configuration and chemical components of the current collectors have also great impact on the rate capability and cycling stability,implying that the 3D BDC networks are more favorable to offer promoted energy storage capability.Implication of the results from suggests that the carbon-based current collectors and all-carbon positive electrodes are able to deliver more advantages in energy storage behaviors in comparison with the traditional positive electrodes with metal Mo current collectors.Such novel strategy promises a new route for fabricating highperformance positive electrodes for stable advanced aluminium batteries.
基金supported by the Beijing Nova Program (No. Z211100002121082)the National Natural Science Foundation of China (Nos. 51725401 and 51874019)
文摘Potassium-ion batteries(PIBs),also known as“novel post-lithium-ion batteries,”have promising energy storage and utilization prospects due to their abundant and inexpensive raw materials.Appropriate anode materials are critical for realizing high-performance PIBs because they are an important component determining the energy and power densities.Two-dimensional(2D)layered anode materials with increased interlayer distances,specific surface areas,and more active sites are promising candidates for PIBs,which have a high reversible capacity in the energetic pathway.In this review,we briefly summarize K+storage behaviors in 2D layered carbon,transition metal chalcogenides,and MXene materials and provide some suggestions on how to select and optimize appropriate 2D anode materials to achieve ideal electrochemical performance.
基金supported by the National Key R&D Program of China(Grant No.2021YFB2401900)the National Natural Science Foundation of China(Grant Nos.11672341,11572002,52074036)+1 种基金the Technology Innovation Program of Beijing Institute of Technology(Grant No.2019CX01021)the BIT Teli Young Fellow。
文摘Internal gases caused by side reactions are crucial signals for evaluating health and safety states of Li-ion batteries(LIBs)while it is still a great challenge to timely realize accurate monitoring.To address the issues of implanting various gas sensors into commercial batteries,here a novel method is developed to fast operando monitoring gas evolution via equipping non-dispersive infrared multi-gases sensors into a sealed tank,where real commercial batteries with one open end could be settled for operating.The generated CO_(2)concentration is strongly linked with both voltage and temperature,while the concentrations of CH_(4) and C_(2)H_(4) are solely dependent on temperature.As a typical trace gas,evolution behaviors of CO_(2)have been related to 0_(2) generation from LiNi_(o.5)Mn_(0.3)CoO_(2)0_(2) positive electrode,implying stable CO_(2)release below a critical voltage of 4.5 V.By tracking CO_(2)concentration,an increased amount of Li_(2)CO_(3) was monitored on the surface of graphite negative electrode during discharge process at dfferent temperatures and cutoff voltages,which contributes to the component variation of solid electrolyte interfaces.Such operando techniques promise a plaform for well understanding the interaction of side reactions linked with gas evolution between positive and negative electrodes in commercial LIBs.
基金supported by the National Natural Science Foundation of China(No.51725401 and 51874019)the Fundamental Research Funds for the Central Universities(FRF-TP-17-002C2)。
文摘Aluminum batteries are attractive in electrochemical energy storage due to high energy density and lowcost aluminum,while the energy density is limited for the lack of favorable positive electrode materials to match aluminum negative electrodes.Tellurium positive electrode is intrinsically electrically conductive among chalcogen and holds high theoretical specific capacity(1260.27 mAh g^(-1)) and discharge voltage plateau(~1,5 V).However,the chemical and electrochemical dissolution of Te active materials results in the low material utilization and poor cycling stability.To enhance the electrochemical performance,herein a nitrogen doped porous carbon(N-PC) is derived from zeolite imidazolate framework(ZIF-67)as an effective tellurium host to suppress the undesired shuttle effect.In order to inhibit the volume expansion of N-PC during the charge/discharge process,the reduced graphene oxide(rGO) nanosheets are introduced to form a stable host materials(N-PC-rGO) for stabilizing Te.The physical encapsulation and chemical confinement to soluble tellurium species are achieved.N-PC-rGO-Te positive electrode exhibits an improved initial specific capacity and long-term cycling performance at a current density of 500 mA g^(-1)(initial specific capacity:935.5 mAh g^(-1);after 150 cycles:467.5 mAh g^(-1)), highlighting a promising design strategy for inhibiting chemical and electrochemical dissolution of Te.
基金supported by the National Natural Science Foundation of China (51804221, 51474200, 91845113)Project funded by China Postdoctoral Science Foundation (2018M642906)the Fundamental Research Funds for the Central Universities (FRF-TP18-010B1)
文摘Carbon contamination and the formation of low-valence oxides limit the preparation of refractory metals by molten salt electrolysis.In this paper,a liquid Zn cathode is adopted for the electrochemical reduction of soluble K2CrO4 to metallic Cr in CaCl2-KCl molten salt.It is found that CrO4^2-can be directly electrochemically reduced to Cr via a six-electron-transfer step and low-valence Cr oxides is hardly produced.The reduction rate is obviously increased from 16.7 mgCrh^-1cm^-2 on the solid Mo cathode to58.7 mgCrh-1cm-2on liquid Zn cathode.The electrodeposited Cr is distributed in liquid Zn cathode.Carbon contamination is effectively avoided due to the negligible solubility of carbon in the liquid Zn cathode.Furthermore,Cr can be effectively separated and enriched to the bottom of liquid Zn under supergravity field,realizing the efficient acquisition of metallic Cr and recycling of liquid Zn.The method herein provides a promising route for the preparation of refractory metals with high-purity by molten salt electrolysis.
基金Financial support from 973 Project (2015CB932500)the National Natural Science Foundation of China (11672341,111572002,51302011)+2 种基金Innovative Research Groups of the National Natural Science Foundation of China (11521202)National Materials Genome Project (2016YFB0700600)Beijing Natural Science Foundation (16L00001,2182065) is gratefully acknowledged
文摘Graphite has been currently considered as a promising cathode material in dual ion batteries(DIBs)due to its unique features of sp2 hybridized carbon and stacked two-dimensional layered structures.However,unexpected volume/thickness changes in the graphite cathodes,induced by the intercalation/deintercalation of anions with large molecular size have been known to be a critical problem in designing DIB cells.To understand the volume/thickness changes in the DIB electrodes,in operando optical observing apparatus has been employed to observe the cross-section view of a graphite-based cathode upon cycles in the present work.The observation suggests that the cathode initially presented a huge irreversible thickness change(60%),and such thickness variation was prone to reduce and remain <20% in the following cycles.The results from both in operando observation and electrochemical characterizations collectively indicate that the greater thickness variation at initial cycle should be attributed to both anion intercalation into graphite-based cathodes and irreversible decomposition of chemical components in the DIB system.The method here highlights a universal route for fundamentally understanding the electrodes of huge volume variation.
基金financially supported by the National Science Foundation of China for Distinguished Young Scholars(No.51725401)the Fundamental Research Funds for the Central Universities(No.FRF-TP-18-003C2)China Postdoctoral Science Foundation(No.2018M641193)。
文摘Normal titanium oxycarbide exhibits an excellent electrical conductivity and a high carrier concentration of approximately 10^(21) cm^(-3);however,the low Seebeck coefficient limits the thermoelectric application.In this study,first-principle calculations demonstrate that the metal vacancy of titanium oxycarbide weakens the density of state passing through the valence band at the Fermi level,impairing the carrier concentration and enhancing carrier mobility.Thermodynamic analysis justifies the formation of titanium oxycarbide with metal vacancy through solid-state reaction.Transmission electron microscopic images demonstrate the segregation of metal vacancy based on the observation of the defect-rich and single-crystal face-centered cubic regions.Metal vacancy triggers the formation of vacancy-rich and single-crystal face-centered cubic regions.The aggregation of metal vacancy leads to the formation of the vacancy-rich region and other regions with a semi-coherent interface,suppressing the carrier concentration from 1.71×10^(21) to 4.5×10^(20) cm^(-3) and resulting in the Seebeck coefficient from -11μV/K of TiC_(0.5)O_(0.5) to -64μV/K at 1073 K.Meanwhile,vacancies accelerate electron migration from 1.65 to 4.22 cm^(-2)·V^(-1)·s^(-1),maintaining high conductivity.The figure of merit(ZT)increases more than five orders of magnitude via the introduction of metal vacancy,with the maximum figure of 2.11×10^(-2) at 1073 K.These results indicate the potential thermoelectric application of metal-oxycarbide materials through vacancy engineering.
基金supported by National Natural Science Foundation of China(No.52074036)Technology Innovation Program of Beijing Institute of Technology(No.2019CX01021)BIT Teli Young Fellow。
文摘With the advent of flexible/wearable electronic devices,flexible lithium-ion batteries(LIBs)have attracted significant attention as optimal power source candidates.Flexible LIBs with good flexibility,mechanical stability,and high energy density are still an enormous challenge.In recent years,many complex and diverse design methods for flexible LIBs have been reported.The design and evaluation of ideal flexible LIBs must take into consideration both mechanical and electrochemical factors.In this review,the recent progress and challenges of flexible LIBs are reviewed from a mechano-electrochemical perspective.The recent progress in flexible LIB design is addressed concerning flexible material and configuration design.The mechanical and electrochemical evaluations of flexible LIBs are also summarized.Furthermore,mechano-electrochemical perspectives for the future direction of flexible LIBs are also discussed.Finally,the relationship between mechanical loading and the electrode process is analyzed from a mechano-electrochemical perspective.The evaluation of flexible LIBs should be based on mechano-electrochemical processes.Reviews and perspectives are of great significance to the design and practicality of flexible LIBs,which is contributed to bridging the gap between laboratory exploration and practical applications.
基金supported by the National Natural Science Foundation of China(12002183)。
文摘Structural deformation and dendrite formation, which would impact the electrochemical processes of rechargeable metal batteries, are usually observed in the high-energy density metal electrodes. Herein,we design an in-situ optical mechano-electrochemical system to study Al deposition on the Al electrode in non-aqueous Al batteries under non-uniform strain. Inhomogeneous distribution of applied strain is realized by creating an oval hole in the Al electrode. The results of the in-situ experiments suggest that the dense Al deposition, which is related to the evolution of surface morphology and increasing reactive sites, is achieved in the regions of stress concentration. The evolution of surface morphology is monitored by the in-situ tension experiments using scanning electron microscope and atomic force microscope.Besides, a qualitative mathematical model is employed to analyze the changes of the local reaction rate owing to the changed surface morphology and the cracks of oxide film under tensile stress. The results are useful to understand the Al deposition when the mechanical force is applied to the metal electrode.
基金supported by the National Natural Science Foundation of China (51874020 and 52004022)the Fundamental Research Funds for the Central Universities (FRF-IP-19-001)。
文摘Metal sulfides with high theoretical capacities are expected as promising cathode materials of Al batteries(AIBs). However, powdery active materials are mainly synthesized and loaded on current collector by insulating binder without capacity. Meanwhile, S as inert element in metal sulfides can not usually provide capacity. So, powdery metal sulfides only exhibit limiting practical capacity and poor cycling stability due to weak conductivity and low mass utilization. Herein, the novel self-supporting and dual-active Co-S nanosheets on carbon cloth (i.e. Co-S/CC) with hierarchically porous structure are constructed as cathode of AIBs. Co-S nanosheets are derived from ZIF-67 nanosheets on CC by a facile ligand replacement reaction. As a result, the binder-free Co-S/CC cathode with good conductivity delivers excellent initial discharge capacity of 383.4 m Ah g^(-1)(0.211 m Ah cm^(-2)) at current density of 200 m A g^(-1)and maintain reversible capacity of 156.9 m Ah g^(-1)(0.086 m Ah cm^(-2)) with Coulombic efficiency of 95.8% after 500 cycles,which are much higher than those of the traditional slurry-coating cathodes. Both Co and S as active elements in Co-S/CC contribute to capacity, which leads to a high mass utilization. This work provides a significant strategy for the construction of self-supporting metallic cathode for advanced high-energy density Al battery.
基金financially supported by the National Natural Science Foundation of China(No.51874019)。
文摘Metal aluminum batteries(MABs)are considered potential large-scale energy storage devices because of their high energy density,resource abundance,low cost,safety,and environmental friendliness.Given their high electrical conductivity,high theoretical specific capacity,and high discharge potential,Te is considered a potential positive electrode material for MABs.Nonetheless,the critical issues induced by the chemical and electrochemical dissolution of tellurium and subsequent chemical precipitation on bare Al negative electrodes result in poor cycle stability and low discharge capacity of Al-Te batteries.Here an efficient TiB_(2)-based modified layer has been proposed to address bare Al electrodes(Al/TB).Consequently,the low-voltage hysteresis and long cycle life of the Al/TB negative electrode have been achieved.In addition,the electrochemical performance of the Al-Te battery based on the Al/TB negative electrode is dramatically improved.Furthermore,the modified separator technology is introduced to match with the as-designed Al/TB negative electrode.Therefore,the record-setting long-term cycle stability of up to 500 cycles has been achieved in the Al-Te battery.The facile strategy also opens a potential route for other high-energy density battery systems,such as Al-S and Al-Se batteries.
基金National Natural Science Foundation of China,Grant/Award Number:51874019Fundamental Research Funds for the Central Universities,Grant/Award Number:FRF-TP-19-079A1State Scholarship Fund。
文摘Aluminum-selenium(Al-Se)batteries have been considered as one of the most promising energy storage systems owing to their high capacity,energy density,and cost effectiveness,but Se falls challenges in addressing the shuttle effect of soluble intermediate product and sluggish reaction kinetics in the solid-solid conversion process during cycling.Herein,we propose an unprecedented design concept for fabricating uniform Se/C hollow microspheres with controllable morphologies through low-temperature electro-deoxidation in neutral NaCl-AlCl3 molten salt system.Such Se/C hollow microspheres are demonstrated to hold a favorable hollow structure for hosting Se,which can not only suppress the dissolution of soluble intermediate products into the electrolyte,thereby maintaining the structural integrity and maximizing Se utilization of the active material,but also promote the electrical/ionic conductivity,thus facilitating the rapid reaction kinetics during cycling.Accordingly,the as-prepared Se/C hollow microspheres exhibit a high reversible capacity of 720.1 mAh g^(−1)at 500 mA g^(−1).Even at the high current density of 1000 mA g^(−1),Se/C delivers a high discharge capacity of 564.0 mAh g^(−1),long-term stability over 1100 cycles and high Coulombic efficiency of 98.6%.This present work provides valuable insights into short-process recovery of advanced Se-containingmaterials and value-added utilization for energy storage.
基金This work has been supported by National Natural Science Foundation of China(51725401).
文摘Despite its existence for more than 80 years,the titanium industry is still challenged by massive carbon emissions,high production costs,and large resource waste.More than one hundred million tons of Ti-bearing blast furnace slag(TB-slag)has been discarded in China because of the difficulty of reutilization,which requires efficient titanium extraction and recovery technologies.This paper describes a low-cost,carbon-emission-free method for Ti extraction and oxygen evolution via molten oxide electrolysis(MOE)vacuum distillation.After a comprehensive analysis of the binding energies and activities of liquid metals,the highlights of our study are as follows.1)Sb has the best preferential deposition of Ti among a series of high-Ti-affinitive liquid metal cathodes(Cu,Ni,Pb,Sn,and Sb).2)The Ir anode was first used in TB-slag with IrO_(2) formed on its surface to protect it from further corrosion.3)An alloy containing Ti and Ca can be obtained by MOE,and Ti and Ca metals can be refined by further vacuum distillation.4)A closed loop is formed in the overall process owing to the recyclable Sb cathode and continuous feeding of TB-slag into the electrolyte.This simple,low-cost,and environmentally friendly method can realize the efficient utilization of Ti resources and achieve carbon neutrality.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.51725401 and 51874019)the Fundamental Research Funds for the Central Universities(No.FRF-TP-17-002C2)。
文摘Aluminum-sulfur(Al-S)batteries are regarded as a desirable candidate for large-scale energy storage be-cause of their high energy density and abundant natural resources of electrode materials.To address the critical issues of low discharge voltage and rapid capacity decay in Al-S batteries,here an electrocatalyst-assisted gel-polymer electrolyte(GPE)-based Al-S battery is fabricated using platinum nanoparticles deco-rated platinum/nitrogen co-doped graphene(PtNG)as sulfur host for positive electrode and metal-organic frameworks(MOF)filled GPE(MOF@GPE)as solid electrolyte.Pt-based active sites derived from Pt nan-oclusters’surface and atomically dispersed Pt-N_(2) chemical bonds in PtNG can catalyze the decomposition of sulfur and polysulfides in the electrochemical process,greatly accelerating the sulfur redox kinetics.Furthermore,the MOF fillers in MOF@GPE electrolyte significantly inhibit the shuttle effect of polysul-fides,efficiently improving the utilization of sulfur.Consequently,the established Al-S battery delivers a specific capacity of 1009 mAh g^(−1) with a discharge plateau of∼0.95 V,along with a capacity retention of 65% after 300 cycles,revealing ultrahigh energy density and long cycle life.Such a strategy of combin-ing electrocatalyst and MOF-based gel electrolyte affords a fresh plateau for promoting the rechargeable ability of Al-S batteries,advancing remarkable routes for achieving efficient and stable energy storage devices.
基金supported by the National Natural Science Foundation of China(No.52374350)China Postdoctoral Science Foundation(Nos.2020M680347 and 2021T140051)the Fundamental Research Funds for the Central Universities(No.FRF-TP-20-045A1)。
文摘Incorporating a selenium(Se)positive electrode into aluminum(Al)-ion batteries is an effective strategy for improving the overall battery performance.However,the cycling stability of Se positive electrodes has challenges due to the dissolution of intermediate reaction products.In this work,we aim to harness the advantages of Se while reducing its limitations by preparing a core-shell mesoporous carbon hollow sphere with a titanium nitride(C@TiN)host to load 63.9wt%Se as the positive electrode material for Al-Se batteries.Using the physical and chemical confinement offered by the hollow mesoporous carbon and TiN,the obtained core-shell mesoporous carbon hollow spheres coated with Se(Se@C@TiN)display superior utilization of the active material and remarkable cycling stability.As a result,Al-Se batteries equipped with the as-prepared Se@C@TiN composite positive electrodes show an initial discharge specific capacity of 377 mAh·g^(-1)at a current density of 1000 mA·g^(-1)while maintaining a discharge specific capacity of 86.0 mAh·g^(-1)over 200 cycles.This improved cycling performance is ascribed to the high electrical conductivity of the core-shell mesoporous carbon hollow spheres and the unique three-dimensional hierarchical architecture of Se@C@TiN.