Aqueous zinc(Zn)batteries with Zn metal anodes are promising clean energy storage devices with intrinsic safety and low cost.However,Zn dendrite growth severely restricts the use of Zn anodes.To effectively suppress Z...Aqueous zinc(Zn)batteries with Zn metal anodes are promising clean energy storage devices with intrinsic safety and low cost.However,Zn dendrite growth severely restricts the use of Zn anodes.To effectively suppress Zn dendrite growth,we propose a bilayer separator consisting of commercial butter paper and glassfiber membrane.The dense cellulose-based butter paper(BP)with low zincophilicity and high mechanical properties prevents the pore-filling behavior of deposited Zn and related separator piercing,effectively suppressing the Zn dendrite growth.As a result,the bilayer separators endow the ZnjjZn symmetrical batteries with a superlong cycling life of Zn anodes(over 5000 h)at 0.5 mA cm^(-2) and the full batteries enhanced capacity retention,demonstrating the advancement of the bilayer separator to afford excellent cyclability of aqueous metal batteries.展开更多
The island-based energy storage is of urgent need for the grid construction combined with renewable energy for offshore operation.The direct use of seawater as a substitute of deionized water shows its great promise f...The island-based energy storage is of urgent need for the grid construction combined with renewable energy for offshore operation.The direct use of seawater as a substitute of deionized water shows its great promise for aqueous zinc-ion batteries in such a specific situation.However,the metal corrosion,dendrite growth,and hydrogen evolution stand out in the harsh seawater environment.To address these challenges,we proposed a corrosion inhibitor that was effective in the field of metal anti-corrosion,2-phosphonobutane-1,2,4-tricarboxylic acid(PBTCA),to inhibit anode corrosion caused by Cl-and active H_(2)O molecules by forming a stable solid electrolyte interphase(SEI)film in the seawater-based electrolyte.Besides,PBTCA can chelate with other cations present in seawater,such as Ca^(2+)and Mg^(2+),thereby preventing the aggregation and precipitation of sparingly soluble species.Under a current density of5 mA cm^(-2),the seawater-based zinc-ion battery exhibited an exceptional cycle life exceeding 2000 h and maintained a Coulombic efficiency of over 99.6%after 2000 cycles.Additionally,the performance of the Zn||ZVO full battery was significantly enhanced with the addition of PBTCA.This study provides a simple,low-cost,and efficient approach for making the seawater-based zinc-ion batteries useable.展开更多
Carbon materials are considered to be one of the most promising anode materials for sodium-ion batteries(SIBs),but the well-ordered graphitic structure limits the intercalation of sodium ions.Besides,the sluggish inte...Carbon materials are considered to be one of the most promising anode materials for sodium-ion batteries(SIBs),but the well-ordered graphitic structure limits the intercalation of sodium ions.Besides,the sluggish intercalation kinetics of sodium ions impedes the rate performance.Thus,the precise structure control of carbon materials is important to improve the battery performance.Herein,a 3D porous hard-soft composite carbon(3DHSC)was prepared using the NaCl as the template and phenolic resin and pitch as carbon precursors.The NaCl template restrains the growth of the graphite crystallite during the carbonization process,resulting in small graphitic domains with expanded interlayer spacing which is favorable for the sodium storage.Moreover,the Na Cl templates help to create abundant mesopores and macropores for fast sodium ion diffusion.The porous structure and the graphite crystalline structure can be precisely controlled by simply adjusting the mass ratio of Na Cl,and thus,the suitable structure can be prepared to reach high capacity and rate performance while keeping a relatively high Coulombic efficiency.Typically,a high reversible capacity(215 mA h g^(-1)at 0.05 A g^(-1)),an excellent rate capability(97 mA h g^(-1)at 5 A g^(-1)),and a high initial Coulombic efficiency(60%)are achieved.展开更多
Pore structure of hard carbon has a fundamental influence on the electrochemical properties in sodium-ion batteries(SIBs).Ultra-micropores(<0.5 nm)of hard carbon can function as ionic sieves to reduce the diffusion...Pore structure of hard carbon has a fundamental influence on the electrochemical properties in sodium-ion batteries(SIBs).Ultra-micropores(<0.5 nm)of hard carbon can function as ionic sieves to reduce the diffusion of slovated Na+but allow the entrance of naked Na^(+) into the pores,which can reduce the interficial contact between the electrolyte and the inner pores without sacrificing the fast diffusion kinetics.Herein,a molten diffusion-carbonization method is proposed to transform the micropores(>1 nm)inside carbon into ultra-micropores(<0.5 nm).Consequently,the designed carbon anode displays an enhanced capacity of 346 mAh g^(−1) at 30 mA g^(−1) with a high ICE value of~80.6%and most of the capacity(~90%)is below 1 V.Moreover,the high-loading electrode(~19 mg cm^(−2))exhibits a good temperature endurance with a high areal capacity of 6.14 mAh cm^(−2) at 25℃ and 5.32 mAh cm^(−2) at −20℃.Based on the in situ X-ray diffraction and ex situ solid-state nuclear magnetic resonance results,the designed ultra-micropores provide the extra Na+storage sites,which mainly contributes to the enhanced capacity.This proposed strategy shows a good potential for the development of high-performance SIBs.展开更多
Lithium-sulfur(Li-S)batteries are promising next-generation high energy density batteries but their practical application is hindered by several key problems,such as the intermediate polysulfide shuttling and the elec...Lithium-sulfur(Li-S)batteries are promising next-generation high energy density batteries but their practical application is hindered by several key problems,such as the intermediate polysulfide shuttling and the electrode degradation caused by the sulfur volume changes.Binder acts as one of the most essential components to build the electrodes of Li-S batteries,playing vital roles in improving the performance and maintaining the integrity of the cathode structure during cycling,especially those with high sulfur loadings.To date,tremendous efforts have been devoted to improving the properties of binders,in terms of the viscosity,elasticity,stability,toughness and conductivity,by optimizing the composition and structure of polymer binders.Moreover,the binder modification endows them strong polysulfide trapping ability to suppress the shuttling and decreases the swelling to maintain the porous structure of cathode.In this review,we summarize the recent progress on the binders for Li-S batteries and discuss the various routes,including the binder combination use,functionalization,in-situ polymerization and ion cross-linking,etc.,to enhance their performance in stabilizing the cathode,building the high sulfur loading electrode and improving the cyclic stability.At last,the design principles and the problems in further applications are also highlighted.展开更多
Noble nanometals are of significance in both scientific interest and technological applications,which are usually obtained by conventional wet-chemical synthesis.Organic surfactants are always used in the synthesis to...Noble nanometals are of significance in both scientific interest and technological applications,which are usually obtained by conventional wet-chemical synthesis.Organic surfactants are always used in the synthesis to prevent unexpected overgrowth and aggregation of noble nanometals.However,the surfactants are hard to remove and may interfere with plasmonic and catalytic studies,remaining surfactant-free synthesis of noble nanometals a challenge.Herein,we report an approach to epitaxial growth of sizecontrolled noble nanometals on MXenes.As piloted by density functional theory calculations,along with work function experimental determination,kinetic and spectroscopic studies,epitaxial growth of noble nanometals is initiated via a mechanism that involves an in situ redox reaction.In the redox,MXenes as two-dimensional solid reductants whose work functions are compatible with the reduction potentials of noble metal cations,enable spontaneous donation of electrons from the MXenes to noble metal cations and reduce the cations into nanoscale metallic metals on the outmost surface of MXenes.Neither surfactants nor external reductants are used during the whole synthesis process,which addresses a long-standing interference issue of surfactant and external reductant in the conventional wet-chemical synthesis.Moreover,the MXenes induced noble nanometals are size-controlled.Impressively,noble nanometals firmly anchored on MXenes exhibit excellent performance towards surface enhanced Raman scattering.Our developed strategy will promote the nanostructure-controlled synthesis of noble nanometals,offering new opportunities to further improve advanced functional properties towards practical applications.展开更多
Fiber supercapacitor(FSC)is a promising power source for wearable/stretchable electronics and high capacitive performance of FSCs is highly desirable for practice flexible applications.Here,we report a composite of ma...Fiber supercapacitor(FSC)is a promising power source for wearable/stretchable electronics and high capacitive performance of FSCs is highly desirable for practice flexible applications.Here,we report a composite of manganese dioxide(Mn O_2)and activated carbon fibers(ACFs)with high MnO_2mass loading and microporous structure(abbreviated as Mn O_2@ACF),which is used as a fiber electrode to produce a FSC with a high capacitive performance and a good flexibility.The MnO_2@ACF composite electrode in FSCs delivers an ultrahigh specific capacitance of 410 mF/cm^2at 0.1 mA/cm^2,corresponding to a high energy density of 36μWh/cm^2and high power density of 726μW/cm^2.Such high capacitive performance and simple fabrication method indicates that the Mn O_2@ACF composite is a very promising electrode material for flexible fiber supercapacitors.展开更多
Coating polymer on the surface is an effective way to realize functional modification of the materials for diverse applications,which has been proved to enhance the stability of metal anodes in batteries.However,given...Coating polymer on the surface is an effective way to realize functional modification of the materials for diverse applications,which has been proved to enhance the stability of metal anodes in batteries.However,given the limited operability of coating from polymer dispersions,it is imperative to develop simple aqueous-based strategies from monomers for versatile polymer coating.Herein,a Ti_(3)C_(2)Tx MXene-assisted approach is proposed to construct polymer coating on zinc metal surfaces directly from the aqueous solution of monomers in an ice bath.By combining a doctor-blading method with spontaneous polymerization of monomers on the substrates at room temperature,a uniform,adhesive,and versatile coating layer assisted by a small amount of MXene is produced in one step.Additionally,MXene nanosheets serve as nanofillers to further enhance the mechanical strength and ionic conductivity of the polymer coating.Benefiting from good film formation and improved interfacial contact,the coated zinc anode exhibits a long cycling lifespan of over 1900 h.The assembled full cells show excellent cycling stability with a high capacity retention of 85.0%at 16 A g^(-1)over 2600 cycles.This work provides a simple and efficient way to produce polymer coatings directly from monomers,which may give new insights into design multifunctional polymer coatings for various applications.展开更多
Excess greenhouse gas emissions,primarily carbon dioxide(CO_(2)),have caused major environmental concerns worldwide.The electroreduction of CO_(2)into valuable chemicals using renewable energy is an ecofriendly approa...Excess greenhouse gas emissions,primarily carbon dioxide(CO_(2)),have caused major environmental concerns worldwide.The electroreduction of CO_(2)into valuable chemicals using renewable energy is an ecofriendly approach to achieve carbon neutrality.In this regard,copper(Cu)has attracted considerable attention as the only known metallic catalyst available for converting CO_(2)to high-value multicarbon(C_(2+))products.The production of C_(2+)involves complicated C-C coupling steps and thus imposes high demands on intermediate regulation.In this review,we discuss multiple strategies for modulating intermediates to facilitate C_(2+)formation on Cu-based catalysts.Furthermore,several sophisticated in situ characterization techniques are outlined for elucidating the mechanism of C-C coupling.Lastly,the challenges and future directions of CO_(2)electroreduction to C_(2+)are envisioned.展开更多
Lithium sulfur batteries are one of the most promising alternative electrochemical systems,but their practical applications are largely hindered by the serious shuttling problems and sluggish redox kinetics.Here,the c...Lithium sulfur batteries are one of the most promising alternative electrochemical systems,but their practical applications are largely hindered by the serious shuttling problems and sluggish redox kinetics.Here,the conductive and polar niobium nitride(NbN)is in-situ introduced onto graphene with ultrasmall size and high dispersion,and their composite is used to construct an efficient lithium polysulfide blocking layer.The graphene helps to construct highly conductive pathways,and niobium nitride serves as the sulfiphilic sites to chemically adsorb the migrating lithium polysulfides and catalyze their redox conversion.Hence,the cells with the Nb N/G interlayers exhibit a long cycle life with a lower capacity decay of 0.096%/cycle at 1 C for 300 cycles and high rate capability of 937 m Ah g^-1 at 2 C.Further coupling with a sulfur/carbon nanofiber electrode,the cell with an ultra-high sulfur loading of 10.8 mg cm^-2 delivers an areal capacity of 12.5 m Ah cm^-2 at 0.1 C.展开更多
The structures of electrode meso-macropore and the solvent polarity are the crucial factors dominating the performance of the electric double layer capacitors(EDLCs),but their impacts are usually tangled and difficult...The structures of electrode meso-macropore and the solvent polarity are the crucial factors dominating the performance of the electric double layer capacitors(EDLCs),but their impacts are usually tangled and difficult to decouple and quantitate.Here the effects of electrode meso-macropore structure and solvent polarity on the specific capacitance of an EDLC are quantitatively investigated using a steady-state continuum model.The simulation results indicate the specific capacitances are significantly affected by the meso-macropore surface structure.The specific capacitances significantly decrease for both convex surface structures but obviously increase for both concave surface structures,with the increase of curvature radius from 1 to 20 nm.As for solvents,the polar solvent with high saturated dielectric permittivity improves the capacitance performance.Moreover,the electrode meso-macropore structure is of more concern compared with solvent polarity when aiming at enhancing the specific capacitance.These results provide fundamentals for the rational design of porous electrodes and polar electrolytes for EDLCs.展开更多
Lithium-Sulfur (Li-S) batteries with high theoretical energy density are promising energy storage systems in the next decades, while the lithium polysulfides (LiPSs) shuttling caused by the sluggish sulfur redox react...Lithium-Sulfur (Li-S) batteries with high theoretical energy density are promising energy storage systems in the next decades, while the lithium polysulfides (LiPSs) shuttling caused by the sluggish sulfur redox reaction severely lowers the practical performance. The use of interlayer between the cathode and separator has been widely investigated to physically or chemically block the LiPSs, while the introduction of catalytic materials is a more effective strategy to accelerate the conversion of LiPSs. MXene with rich surface chemistry has shown its potential for facilitating the catalytic conversion, however, the aggregation of MXene sheets usually leads to the loss of the catalytic active sites. Herein, we report a diatomite/MXene (DE/MX) hybrid material as the bifunctional interlayer for improving the adsorption/conversion of LiPSs in Li-S batteries. The diatomite with porous structure and rich silica-hydroxyl functional groups could trap LiPSs effectively, while prevent the aggregation of MXene. The DE/MX based interlayer showed bifunctions of enhancing the chemical adsorption and promoting the conversion of LiPSs. The Li-S batteries with the DE/MX interlayer delivered an improved cycling stability with a low capacity decay of 0.059% per cycle over 1000 cycles at 1.0 C. Moreover, stable 200 cycles can be realized with a high sulfur loading electrode up to 6.0 mg cm^(−2). This work provides an effective strategy to construct bifunctional interlayers for hindering the shuttling of LiPSs and boosting the practical application of Li-S batteries.展开更多
A dual functional CNTs@graphene/CNTs cathode for Li–Se battery was constructed by a CNTs@graphene network and a CNTs interlayer. CNTs were first integrated with graphene to form a three-dimensional（3D） framework an...A dual functional CNTs@graphene/CNTs cathode for Li–Se battery was constructed by a CNTs@graphene network and a CNTs interlayer. CNTs were first integrated with graphene to form a three-dimensional（3D） framework and work together as a conductive matrix for Se confinement. The optimized composite cathode delivers a high initial capacity of 575 mAh·g^-1 at 0.5 A·g^-1 and good rate capacity with a retained capacity of 479 mAh·g^-1 at 2.0 A·g^-1（73% of the capacity at 0.2 A·g^-1）. CNTs were further served as an interlayer to confine the diffusion of polyselenides by constructing a thin CNTs layer outside the CNTs@graphene network. An improved initial capacity of 616 mAh·g^-1 at 0.5 A·g^-1 is achieved with a retained capacity of 538 mAh·g^-1 after 80 cycles, indicating the effective dual function of CNTs in this novel cathode construction and great application potential for Li–Se battery.展开更多
Carbon materials are key components in energy storage and conversion devices and most directly impact device performance.The need for advanced carbon materials has become more pressing with the increasing demand for h...Carbon materials are key components in energy storage and conversion devices and most directly impact device performance.The need for advanced carbon materials has become more pressing with the increasing demand for high-performance energy conversion and storage facilities.Nonetheless,realizing significant performance improvements across devices remains challenging because of the difficulties in controlling irreg-ularly organized microstructures and the specific carbon structures concerned.With the aim of realizing devis-able structures,adjustable functions,and performance breakthroughs,this review proposes the concept of superstructured carbons.In fact,superstructured carbons are a category of carbon-based materials charac-terized by precisely built pores,networks,and interfaces.This unique category meets the particular func-tional demands of high-performance devices and exceeds the rigid structure of traditional carbons.In the context of these superstructured carbons,we present methods for realizing both custom-built structures and target-oriented functionalities.For specific energy-related reactions,we emphasize the targeted property-structure relationships in these well-defined superstructured carbons.Finally,future developments and practi-cability challenges of superstructured carbons are also proposed.展开更多
Solid-state batteries(SSBs)have been considered the most promising technology because of their superior energy density and safety.Among all the solid-state electrolytes(SEs),Li_(7) La_(3) Zr_(2) O_(12)(LLZO)with high ...Solid-state batteries(SSBs)have been considered the most promising technology because of their superior energy density and safety.Among all the solid-state electrolytes(SEs),Li_(7) La_(3) Zr_(2) O_(12)(LLZO)with high ionic conductivity(3×10^(−4) S/cm)has been widely investigated.However,its large-scale production in ambient air faces a challenge.After air exposure,the generated Li_(2)CO_(3) layer deteriorates the ionic conductivity and interfacial wettability,thus greatly compromising the electrochemical performance of SSBs.Many works aim to eliminate this layer to recover the pristine LLZO surface.Unfor-tunately,few articles have emphasized the merits of Li_(2)CO_(3).In this review,we focus on the two-sidedness of Li_(2)CO_(3).We discuss the various characteristics of Li_(2)CO_(3) that can be used and recapitulate the strategies that utilize Li_(2)CO_(3).Insulating Li_(2)CO_(3) is no longer an obstacle but an opportunity for realizing intimate interfacial contact,high air stability,and outstand-ing electrochemical performance.This review aims to off er insightful guidelines for treating air-induced Li_(2)CO_(3) and lead to developing the enhanced air stability and electrochemical performance of LLZO.展开更多
Elucidating the fundamental mechanisms underlying Cu reconstruction is paramount for the rational design of catalysts that meet the stringent activity,selectivity,and durability requirements for industrial-scale CO_(2...Elucidating the fundamental mechanisms underlying Cu reconstruction is paramount for the rational design of catalysts that meet the stringent activity,selectivity,and durability requirements for industrial-scale CO_(2)/CO electroreduction(CO_(2)RR/CORR).While both dissolution-redeposition and atomic migration pathways have been proposed,the operational conditions dictating their relative dominance remain poorly understood.Through quasi in situ Cu^(+)detection and in situ atomic force microscopy(AFM),we reveal a striking mechanistic dichotomy:Cu reconstruction during CO_(2)RR occurs strictly in the presence of Cu^(+),whereas CORR-induced reconstruction proceeds independently of Cu^(+)species.These findings suggest that Cu reconstruction in CO_(2)RR follows a dissolution-redeposition mechanism induced by oxidative radicals,while atomic migration emerges as the dominant pathway in CORR.Density functional theory calculations further demonstrate that adsorbed*CO intermediates reduce Cu-Cu bond strength,creating metastable surface configurations that promote Cu atomic migration.These insights provide a foundation for leveraging reconstruction to design high-performance Cu-based catalysts.展开更多
Electrocatalytic nitrate reduction reaction is considered as a promising and sustainable method for ammonia synthesis.However,the selectivity and yield rate of ammonia are limited by the competitive hydrogen evolution...Electrocatalytic nitrate reduction reaction is considered as a promising and sustainable method for ammonia synthesis.However,the selectivity and yield rate of ammonia are limited by the competitive hydrogen evolution reaction and the complex eight-electron transfer process.Herein,we developed a(FeCoNiCu)Ox/CeO_(2)polymetallic oxide electrocatalyst for effective nitrate reduction to ammonia.The synergistic effects among the multiple elements in the electrocatalyst were clearly elucidated by comprehensive experiments.Specifically,Cu acted as the active site for reducing nitrate to nitrite,and Co facilitated the subsequent reduction of nitrite to ammonia,while Fe and Ni promoted water dissociation to provide protons.Furthermore,the incorporation of CeO_(2)increased the active surface area of(FeCoNiCu)Ox,resulting in an improved ammonia yield rate to meet industrial demands.Consequently,the(FeCoNiCu)Ox/CeO_(2)electrocatalyst achieved an ammonia current density of 382 mA cm^(-2)and a high ammonia yield rate of 30.3 mg h^(-1)cm^(-2)with a long-term stability.This work offers valuable insights for the future design of highly efficient multi-element electrocatalysts.展开更多
Metal sulfide(MS)have good conductivity,strong adsorption ability,and excellent catalytic activity for the conversion of sulfur species,and thus,show great promise as the catalysts in LieS batteries.However,the relati...Metal sulfide(MS)have good conductivity,strong adsorption ability,and excellent catalytic activity for the conversion of sulfur species,and thus,show great promise as the catalysts in LieS batteries.However,the relationship between their properties and electrochemical performance is still unclear.Thus,further in-depth discussions are required to improve their design in Li-S batteries.This review systematically summarizes the basic structural and electrochemical properties of MSs and highlights the advantages that guarantee them as high-performance catalysts in Li-S batteries.Then,various modification strategies for MSs to enhance the catalytic activity,efficiency,and stability are also reviewed.At last,future opportunities for MS catalysts in Li-S batteries are proposed.展开更多
Lithium metal is considered to be the most promising anode material for the next-generation rechargeable batteries. However, the uniform and dendrite-free deposition of Li metal anode is hard to achieve, hindering its...Lithium metal is considered to be the most promising anode material for the next-generation rechargeable batteries. However, the uniform and dendrite-free deposition of Li metal anode is hard to achieve, hindering its practical applications. Herein, a lightweight, free-standing and nitrogen-doped carbon nanofiber-based 3D structured conductive matrix(NCNF), which is characterized by a robust and interconnected 3D network with high doping level of 9.5 at%, is prepared by electrospinning as the current collector for Li metal anode. Uniform Li nucleation with reduced polarization and dendrite-free Li deposition are achieved because the NCNF with high nitrogen-doping level and high conductivity provide abundant and homogenous metallic Li nucleation and deposition sites. Excellent cycling stability with high coulombic efficiency are realized. The Li plated NCNF was paired with LiFePO4 to assemble the full battery, also showing high cyclic stability.展开更多
基金supported by grants from the National Key Research and Development Program of China(No.2021YFF0500600)the Haihe Laboratory of Sustainable Chemical Transformations,and the Fundamental Research Funds for the Central Universities.We appreciate Neware Technology Co.,Ltd for their battery test systems in the TJU Nanoyang-Neware Joint Laboratory for Energy Innovation.
文摘Aqueous zinc(Zn)batteries with Zn metal anodes are promising clean energy storage devices with intrinsic safety and low cost.However,Zn dendrite growth severely restricts the use of Zn anodes.To effectively suppress Zn dendrite growth,we propose a bilayer separator consisting of commercial butter paper and glassfiber membrane.The dense cellulose-based butter paper(BP)with low zincophilicity and high mechanical properties prevents the pore-filling behavior of deposited Zn and related separator piercing,effectively suppressing the Zn dendrite growth.As a result,the bilayer separators endow the ZnjjZn symmetrical batteries with a superlong cycling life of Zn anodes(over 5000 h)at 0.5 mA cm^(-2) and the full batteries enhanced capacity retention,demonstrating the advancement of the bilayer separator to afford excellent cyclability of aqueous metal batteries.
基金the National Key Research and Development Program of China (Nos.2022YFB2404500 and 2021YFF0500600)the National Natural Science Foundation of China (Nos.52172223,52272230,52302300)the China Postdoctoral Science Foundation (No.2022M722361)。
文摘The island-based energy storage is of urgent need for the grid construction combined with renewable energy for offshore operation.The direct use of seawater as a substitute of deionized water shows its great promise for aqueous zinc-ion batteries in such a specific situation.However,the metal corrosion,dendrite growth,and hydrogen evolution stand out in the harsh seawater environment.To address these challenges,we proposed a corrosion inhibitor that was effective in the field of metal anti-corrosion,2-phosphonobutane-1,2,4-tricarboxylic acid(PBTCA),to inhibit anode corrosion caused by Cl-and active H_(2)O molecules by forming a stable solid electrolyte interphase(SEI)film in the seawater-based electrolyte.Besides,PBTCA can chelate with other cations present in seawater,such as Ca^(2+)and Mg^(2+),thereby preventing the aggregation and precipitation of sparingly soluble species.Under a current density of5 mA cm^(-2),the seawater-based zinc-ion battery exhibited an exceptional cycle life exceeding 2000 h and maintained a Coulombic efficiency of over 99.6%after 2000 cycles.Additionally,the performance of the Zn||ZVO full battery was significantly enhanced with the addition of PBTCA.This study provides a simple,low-cost,and efficient approach for making the seawater-based zinc-ion batteries useable.
基金supported by the Guangdong Natural Science Funds for Distinguished Young Scholar (2017B030306006)the National Natural Science Foundation of China (Nos. 51772164, U1601206 and U1710256)+2 种基金the National Key Basic Research Program of China (2014CB932400)the Shenzhen Technical Plan Project (Nos. KQJSCX20160226191136, JCYJ20150529164918734 and JCYJ20170412171630020)the Shenzhen Environmental Science and New Energy Technology Engineering Laboratory (No. SDRC [2016]172)
文摘Carbon materials are considered to be one of the most promising anode materials for sodium-ion batteries(SIBs),but the well-ordered graphitic structure limits the intercalation of sodium ions.Besides,the sluggish intercalation kinetics of sodium ions impedes the rate performance.Thus,the precise structure control of carbon materials is important to improve the battery performance.Herein,a 3D porous hard-soft composite carbon(3DHSC)was prepared using the NaCl as the template and phenolic resin and pitch as carbon precursors.The NaCl template restrains the growth of the graphite crystallite during the carbonization process,resulting in small graphitic domains with expanded interlayer spacing which is favorable for the sodium storage.Moreover,the Na Cl templates help to create abundant mesopores and macropores for fast sodium ion diffusion.The porous structure and the graphite crystalline structure can be precisely controlled by simply adjusting the mass ratio of Na Cl,and thus,the suitable structure can be prepared to reach high capacity and rate performance while keeping a relatively high Coulombic efficiency.Typically,a high reversible capacity(215 mA h g^(-1)at 0.05 A g^(-1)),an excellent rate capability(97 mA h g^(-1)at 5 A g^(-1)),and a high initial Coulombic efficiency(60%)are achieved.
基金Singapore MOE Tier Ⅱ grant R143-000-A29-112the National Research Foundation under the Grant of NRF2017NRF-NSFC001-007.
文摘Pore structure of hard carbon has a fundamental influence on the electrochemical properties in sodium-ion batteries(SIBs).Ultra-micropores(<0.5 nm)of hard carbon can function as ionic sieves to reduce the diffusion of slovated Na+but allow the entrance of naked Na^(+) into the pores,which can reduce the interficial contact between the electrolyte and the inner pores without sacrificing the fast diffusion kinetics.Herein,a molten diffusion-carbonization method is proposed to transform the micropores(>1 nm)inside carbon into ultra-micropores(<0.5 nm).Consequently,the designed carbon anode displays an enhanced capacity of 346 mAh g^(−1) at 30 mA g^(−1) with a high ICE value of~80.6%and most of the capacity(~90%)is below 1 V.Moreover,the high-loading electrode(~19 mg cm^(−2))exhibits a good temperature endurance with a high areal capacity of 6.14 mAh cm^(−2) at 25℃ and 5.32 mAh cm^(−2) at −20℃.Based on the in situ X-ray diffraction and ex situ solid-state nuclear magnetic resonance results,the designed ultra-micropores provide the extra Na+storage sites,which mainly contributes to the enhanced capacity.This proposed strategy shows a good potential for the development of high-performance SIBs.
基金supported by the National Natural Science Foundation of China(Nos.51772164 and U1601206)the Guangdong Natural Science Funds for Distinguished Young Scholars(2017B030306006)+2 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01N111)the Guangdong Special Support Program(2017TQ04C664)the Shenzhen Basic Research Project(Grant Nos.JCYJ20170412171359175)
文摘Lithium-sulfur(Li-S)batteries are promising next-generation high energy density batteries but their practical application is hindered by several key problems,such as the intermediate polysulfide shuttling and the electrode degradation caused by the sulfur volume changes.Binder acts as one of the most essential components to build the electrodes of Li-S batteries,playing vital roles in improving the performance and maintaining the integrity of the cathode structure during cycling,especially those with high sulfur loadings.To date,tremendous efforts have been devoted to improving the properties of binders,in terms of the viscosity,elasticity,stability,toughness and conductivity,by optimizing the composition and structure of polymer binders.Moreover,the binder modification endows them strong polysulfide trapping ability to suppress the shuttling and decreases the swelling to maintain the porous structure of cathode.In this review,we summarize the recent progress on the binders for Li-S batteries and discuss the various routes,including the binder combination use,functionalization,in-situ polymerization and ion cross-linking,etc.,to enhance their performance in stabilizing the cathode,building the high sulfur loading electrode and improving the cyclic stability.At last,the design principles and the problems in further applications are also highlighted.
基金supported by the National Natural Science Foundation of China(No.51972310)the Shenyang National Laboratory for Materials Science,Institute of Metal Research,Chinese Academy of Sciences(CAS)+1 种基金the Youth Innovation Promotion Association,CAS(No.2011152)the Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund(the second phase)(No.U1501501).
文摘Noble nanometals are of significance in both scientific interest and technological applications,which are usually obtained by conventional wet-chemical synthesis.Organic surfactants are always used in the synthesis to prevent unexpected overgrowth and aggregation of noble nanometals.However,the surfactants are hard to remove and may interfere with plasmonic and catalytic studies,remaining surfactant-free synthesis of noble nanometals a challenge.Herein,we report an approach to epitaxial growth of sizecontrolled noble nanometals on MXenes.As piloted by density functional theory calculations,along with work function experimental determination,kinetic and spectroscopic studies,epitaxial growth of noble nanometals is initiated via a mechanism that involves an in situ redox reaction.In the redox,MXenes as two-dimensional solid reductants whose work functions are compatible with the reduction potentials of noble metal cations,enable spontaneous donation of electrons from the MXenes to noble metal cations and reduce the cations into nanoscale metallic metals on the outmost surface of MXenes.Neither surfactants nor external reductants are used during the whole synthesis process,which addresses a long-standing interference issue of surfactant and external reductant in the conventional wet-chemical synthesis.Moreover,the MXenes induced noble nanometals are size-controlled.Impressively,noble nanometals firmly anchored on MXenes exhibit excellent performance towards surface enhanced Raman scattering.Our developed strategy will promote the nanostructure-controlled synthesis of noble nanometals,offering new opportunities to further improve advanced functional properties towards practical applications.
基金supported by the National Natural Science Foundation of China (No. 51702229, and No. 51525204)the National Key Basic Research Program of China (2014CB932400)
文摘Fiber supercapacitor(FSC)is a promising power source for wearable/stretchable electronics and high capacitive performance of FSCs is highly desirable for practice flexible applications.Here,we report a composite of manganese dioxide(Mn O_2)and activated carbon fibers(ACFs)with high MnO_2mass loading and microporous structure(abbreviated as Mn O_2@ACF),which is used as a fiber electrode to produce a FSC with a high capacitive performance and a good flexibility.The MnO_2@ACF composite electrode in FSCs delivers an ultrahigh specific capacitance of 410 mF/cm^2at 0.1 mA/cm^2,corresponding to a high energy density of 36μWh/cm^2and high power density of 726μW/cm^2.Such high capacitive performance and simple fabrication method indicates that the Mn O_2@ACF composite is a very promising electrode material for flexible fiber supercapacitors.
基金the support from the National Natural Science Foundation of China(51972228 and 22109116)the TJU Nanoyang-Neware Joint Laboratory for Energy Innovation。
文摘Coating polymer on the surface is an effective way to realize functional modification of the materials for diverse applications,which has been proved to enhance the stability of metal anodes in batteries.However,given the limited operability of coating from polymer dispersions,it is imperative to develop simple aqueous-based strategies from monomers for versatile polymer coating.Herein,a Ti_(3)C_(2)Tx MXene-assisted approach is proposed to construct polymer coating on zinc metal surfaces directly from the aqueous solution of monomers in an ice bath.By combining a doctor-blading method with spontaneous polymerization of monomers on the substrates at room temperature,a uniform,adhesive,and versatile coating layer assisted by a small amount of MXene is produced in one step.Additionally,MXene nanosheets serve as nanofillers to further enhance the mechanical strength and ionic conductivity of the polymer coating.Benefiting from good film formation and improved interfacial contact,the coated zinc anode exhibits a long cycling lifespan of over 1900 h.The assembled full cells show excellent cycling stability with a high capacity retention of 85.0%at 16 A g^(-1)over 2600 cycles.This work provides a simple and efficient way to produce polymer coatings directly from monomers,which may give new insights into design multifunctional polymer coatings for various applications.
基金support of the National Natural Science Foundation of China(Nos.51972223,51932005 and 22109116)the Natural Science Foundation of Tianjin(No.20JCYBJC01550)+1 种基金the Fundamental Research Funds for the Cen-tral Universitiesthe Haihe Laboratory of Sustainable Chemical Transformations.
文摘Excess greenhouse gas emissions,primarily carbon dioxide(CO_(2)),have caused major environmental concerns worldwide.The electroreduction of CO_(2)into valuable chemicals using renewable energy is an ecofriendly approach to achieve carbon neutrality.In this regard,copper(Cu)has attracted considerable attention as the only known metallic catalyst available for converting CO_(2)to high-value multicarbon(C_(2+))products.The production of C_(2+)involves complicated C-C coupling steps and thus imposes high demands on intermediate regulation.In this review,we discuss multiple strategies for modulating intermediates to facilitate C_(2+)formation on Cu-based catalysts.Furthermore,several sophisticated in situ characterization techniques are outlined for elucidating the mechanism of C-C coupling.Lastly,the challenges and future directions of CO_(2)electroreduction to C_(2+)are envisioned.
基金financial support from the National Key R&D Program of China(2016YFB0100100 and 2016YFA0200100)the National Natural Science Foundation of China(Nos.51972313,51525206 and 51521091)+1 种基金the Strategic Priority Research Program of Chinese Academy of Science(XDA22010602)China Petrochemical Cooperation(No.218025)。
文摘Lithium sulfur batteries are one of the most promising alternative electrochemical systems,but their practical applications are largely hindered by the serious shuttling problems and sluggish redox kinetics.Here,the conductive and polar niobium nitride(NbN)is in-situ introduced onto graphene with ultrasmall size and high dispersion,and their composite is used to construct an efficient lithium polysulfide blocking layer.The graphene helps to construct highly conductive pathways,and niobium nitride serves as the sulfiphilic sites to chemically adsorb the migrating lithium polysulfides and catalyze their redox conversion.Hence,the cells with the Nb N/G interlayers exhibit a long cycle life with a lower capacity decay of 0.096%/cycle at 1 C for 300 cycles and high rate capability of 937 m Ah g^-1 at 2 C.Further coupling with a sulfur/carbon nanofiber electrode,the cell with an ultra-high sulfur loading of 10.8 mg cm^-2 delivers an areal capacity of 12.5 m Ah cm^-2 at 0.1 C.
基金financially supported by the National Basic Research Program of China(2014CB239702)the National Natural Science Foundation of China(21676082,22008067)the China Postdoctoral Science Foundation(2020M681202,2021T140204)。
文摘The structures of electrode meso-macropore and the solvent polarity are the crucial factors dominating the performance of the electric double layer capacitors(EDLCs),but their impacts are usually tangled and difficult to decouple and quantitate.Here the effects of electrode meso-macropore structure and solvent polarity on the specific capacitance of an EDLC are quantitatively investigated using a steady-state continuum model.The simulation results indicate the specific capacitances are significantly affected by the meso-macropore surface structure.The specific capacitances significantly decrease for both convex surface structures but obviously increase for both concave surface structures,with the increase of curvature radius from 1 to 20 nm.As for solvents,the polar solvent with high saturated dielectric permittivity improves the capacitance performance.Moreover,the electrode meso-macropore structure is of more concern compared with solvent polarity when aiming at enhancing the specific capacitance.These results provide fundamentals for the rational design of porous electrodes and polar electrolytes for EDLCs.
基金The authors appreciate support from the National Key Research and Development Program of China(No.2018YFE0124500)the Young Elite Scientists Sponsorship Program by Tianjin(TJSQNTJ-2020-11)the National Natural Science Foundation of China(Nos.51932005,U1710109).
文摘Lithium-Sulfur (Li-S) batteries with high theoretical energy density are promising energy storage systems in the next decades, while the lithium polysulfides (LiPSs) shuttling caused by the sluggish sulfur redox reaction severely lowers the practical performance. The use of interlayer between the cathode and separator has been widely investigated to physically or chemically block the LiPSs, while the introduction of catalytic materials is a more effective strategy to accelerate the conversion of LiPSs. MXene with rich surface chemistry has shown its potential for facilitating the catalytic conversion, however, the aggregation of MXene sheets usually leads to the loss of the catalytic active sites. Herein, we report a diatomite/MXene (DE/MX) hybrid material as the bifunctional interlayer for improving the adsorption/conversion of LiPSs in Li-S batteries. The diatomite with porous structure and rich silica-hydroxyl functional groups could trap LiPSs effectively, while prevent the aggregation of MXene. The DE/MX based interlayer showed bifunctions of enhancing the chemical adsorption and promoting the conversion of LiPSs. The Li-S batteries with the DE/MX interlayer delivered an improved cycling stability with a low capacity decay of 0.059% per cycle over 1000 cycles at 1.0 C. Moreover, stable 200 cycles can be realized with a high sulfur loading electrode up to 6.0 mg cm^(−2). This work provides an effective strategy to construct bifunctional interlayers for hindering the shuttling of LiPSs and boosting the practical application of Li-S batteries.
基金financially supported by the National Basic Research Program of China(No.2014CB932400)the National Science Foundation of China(Nos.21406161 and 51602220)
文摘A dual functional CNTs@graphene/CNTs cathode for Li–Se battery was constructed by a CNTs@graphene network and a CNTs interlayer. CNTs were first integrated with graphene to form a three-dimensional（3D） framework and work together as a conductive matrix for Se confinement. The optimized composite cathode delivers a high initial capacity of 575 mAh·g^-1 at 0.5 A·g^-1 and good rate capacity with a retained capacity of 479 mAh·g^-1 at 2.0 A·g^-1（73% of the capacity at 0.2 A·g^-1）. CNTs were further served as an interlayer to confine the diffusion of polyselenides by constructing a thin CNTs layer outside the CNTs@graphene network. An improved initial capacity of 616 mAh·g^-1 at 0.5 A·g^-1 is achieved with a retained capacity of 538 mAh·g^-1 after 80 cycles, indicating the effective dual function of CNTs in this novel cathode construction and great application potential for Li–Se battery.
基金supported by the National Basic Research Program of China(2014CB932400)the National Natural Science Foundation of China(Nos.51932005,52022041 and 52172040)Taishan Scholar Project of Shandong Province(No.tsqnz20221118).
文摘Carbon materials are key components in energy storage and conversion devices and most directly impact device performance.The need for advanced carbon materials has become more pressing with the increasing demand for high-performance energy conversion and storage facilities.Nonetheless,realizing significant performance improvements across devices remains challenging because of the difficulties in controlling irreg-ularly organized microstructures and the specific carbon structures concerned.With the aim of realizing devis-able structures,adjustable functions,and performance breakthroughs,this review proposes the concept of superstructured carbons.In fact,superstructured carbons are a category of carbon-based materials charac-terized by precisely built pores,networks,and interfaces.This unique category meets the particular func-tional demands of high-performance devices and exceeds the rigid structure of traditional carbons.In the context of these superstructured carbons,we present methods for realizing both custom-built structures and target-oriented functionalities.For specific energy-related reactions,we emphasize the targeted property-structure relationships in these well-defined superstructured carbons.Finally,future developments and practi-cability challenges of superstructured carbons are also proposed.
基金the support from the National Natural Science Foundation of China (Nos.U2001220 and 51902223)the Haihe Laboratory of Sustainable Chemical Transformations+2 种基金the Fundamental Research Funds for the Central Universitiesthe National Key Research and Development Program of China (Nos.2021YFF0500600 and 2019YFE0118800)the Natural Science Foundation of Tianjin (No.20JCYBJC00850)
文摘Solid-state batteries(SSBs)have been considered the most promising technology because of their superior energy density and safety.Among all the solid-state electrolytes(SEs),Li_(7) La_(3) Zr_(2) O_(12)(LLZO)with high ionic conductivity(3×10^(−4) S/cm)has been widely investigated.However,its large-scale production in ambient air faces a challenge.After air exposure,the generated Li_(2)CO_(3) layer deteriorates the ionic conductivity and interfacial wettability,thus greatly compromising the electrochemical performance of SSBs.Many works aim to eliminate this layer to recover the pristine LLZO surface.Unfor-tunately,few articles have emphasized the merits of Li_(2)CO_(3).In this review,we focus on the two-sidedness of Li_(2)CO_(3).We discuss the various characteristics of Li_(2)CO_(3) that can be used and recapitulate the strategies that utilize Li_(2)CO_(3).Insulating Li_(2)CO_(3) is no longer an obstacle but an opportunity for realizing intimate interfacial contact,high air stability,and outstand-ing electrochemical performance.This review aims to off er insightful guidelines for treating air-induced Li_(2)CO_(3) and lead to developing the enhanced air stability and electrochemical performance of LLZO.
基金supported by the National Natural Science Foundation of China(52471235 and 51972223)the National Industry-Education Platform for Energy Storage(Tianjin University)the Fundamental Research Funds for the Central Universities,and the Haihe Laboratory of Sustainable Chemical.
文摘Elucidating the fundamental mechanisms underlying Cu reconstruction is paramount for the rational design of catalysts that meet the stringent activity,selectivity,and durability requirements for industrial-scale CO_(2)/CO electroreduction(CO_(2)RR/CORR).While both dissolution-redeposition and atomic migration pathways have been proposed,the operational conditions dictating their relative dominance remain poorly understood.Through quasi in situ Cu^(+)detection and in situ atomic force microscopy(AFM),we reveal a striking mechanistic dichotomy:Cu reconstruction during CO_(2)RR occurs strictly in the presence of Cu^(+),whereas CORR-induced reconstruction proceeds independently of Cu^(+)species.These findings suggest that Cu reconstruction in CO_(2)RR follows a dissolution-redeposition mechanism induced by oxidative radicals,while atomic migration emerges as the dominant pathway in CORR.Density functional theory calculations further demonstrate that adsorbed*CO intermediates reduce Cu-Cu bond strength,creating metastable surface configurations that promote Cu atomic migration.These insights provide a foundation for leveraging reconstruction to design high-performance Cu-based catalysts.
基金supported by the National Natural Science Foundation of China(51972223,52202279)the Natural Science Foundation of Tianjin(20JCYBJC01550)+2 种基金the National Industry-Education Integration Platform of Energy Storagethe Fundamental Research Funds for the Central Universitiesthe Haihe Laboratory of Sustainable Chemical Transformations。
文摘Electrocatalytic nitrate reduction reaction is considered as a promising and sustainable method for ammonia synthesis.However,the selectivity and yield rate of ammonia are limited by the competitive hydrogen evolution reaction and the complex eight-electron transfer process.Herein,we developed a(FeCoNiCu)Ox/CeO_(2)polymetallic oxide electrocatalyst for effective nitrate reduction to ammonia.The synergistic effects among the multiple elements in the electrocatalyst were clearly elucidated by comprehensive experiments.Specifically,Cu acted as the active site for reducing nitrate to nitrite,and Co facilitated the subsequent reduction of nitrite to ammonia,while Fe and Ni promoted water dissociation to provide protons.Furthermore,the incorporation of CeO_(2)increased the active surface area of(FeCoNiCu)Ox,resulting in an improved ammonia yield rate to meet industrial demands.Consequently,the(FeCoNiCu)Ox/CeO_(2)electrocatalyst achieved an ammonia current density of 382 mA cm^(-2)and a high ammonia yield rate of 30.3 mg h^(-1)cm^(-2)with a long-term stability.This work offers valuable insights for the future design of highly efficient multi-element electrocatalysts.
基金the support from the National Key R&D Program of China(No.2021YFF0500600)National Natural Science Foundation of China(No.51932005 and 52022041)+3 种基金Guangdong Basic and Applied Basic Research Foundation(2021B1515120079)All-Solid-State Lithium Battery Electrolyte Engineering Research Centre(XMHT20200203006)Shenzhen Science and Technology Program(No.JCYJ20220818101008018)Haihe Laboratory of Sustainable Chemical Transformations and the Fundamental Research Funds for the Central Universities.
文摘Metal sulfide(MS)have good conductivity,strong adsorption ability,and excellent catalytic activity for the conversion of sulfur species,and thus,show great promise as the catalysts in LieS batteries.However,the relationship between their properties and electrochemical performance is still unclear.Thus,further in-depth discussions are required to improve their design in Li-S batteries.This review systematically summarizes the basic structural and electrochemical properties of MSs and highlights the advantages that guarantee them as high-performance catalysts in Li-S batteries.Then,various modification strategies for MSs to enhance the catalytic activity,efficiency,and stability are also reviewed.At last,future opportunities for MS catalysts in Li-S batteries are proposed.
基金the financial support from the Guangdong Natural Science Funds for Distinguished Young Scholar (2017B030306006) the National Natural Science Foundation of China (51772164, U1601206 and U1710256)+1 种基金 the National Key Basic Research Program of China (2014CB932400)Shenzhen Technical Plan Project (JCYJ20150529164918734 and JCYJ20170412171359175)
文摘Lithium metal is considered to be the most promising anode material for the next-generation rechargeable batteries. However, the uniform and dendrite-free deposition of Li metal anode is hard to achieve, hindering its practical applications. Herein, a lightweight, free-standing and nitrogen-doped carbon nanofiber-based 3D structured conductive matrix(NCNF), which is characterized by a robust and interconnected 3D network with high doping level of 9.5 at%, is prepared by electrospinning as the current collector for Li metal anode. Uniform Li nucleation with reduced polarization and dendrite-free Li deposition are achieved because the NCNF with high nitrogen-doping level and high conductivity provide abundant and homogenous metallic Li nucleation and deposition sites. Excellent cycling stability with high coulombic efficiency are realized. The Li plated NCNF was paired with LiFePO4 to assemble the full battery, also showing high cyclic stability.
