FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium stor...FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.展开更多
The discovery of novel materials with compelling properties is more accessible with the help of advanced computational algorithms.Recent experimental synthesis of the biphenylene network(C_(6))motivated us to discover...The discovery of novel materials with compelling properties is more accessible with the help of advanced computational algorithms.Recent experimental synthesis of the biphenylene network(C_(6))motivated us to discover new BN-doped biphenylene networks(C_(4)BN,C_(2)B_(2)N_(2),and B_(4)N_(4))and their applications in Li(K)-ion batteries using an evolutionary algorithm and the first-principles calculations.The thermodynamic,thermal,and mechanical stability calculations and decomposition energy suggest the experimental synthesis of predicted biphenylene networks.Adding BN in the biphenylene networks shows a transition from metal to semimetal to semiconductor.The BN biphenylene network shows an HSE06 band gap of 3.06 eV,smaller than h-BN.The C_(4)BN and C_(2)B_(2)N_(2)biphenylene networks offer Li(K)adsorption energy of-0.56 eV(-0.81 eV)and-0.14 eV(-0.28 eV),respectively,with a low diffusion barrier of 178 meV(58 meV)and 251 meV(79 meV),and a large diffusion constant of 8.50×10^(-5)cm^(2)=s(8.78×10^(-3)cm^(2)=s)and 5.33×10^(-6)cm^(2)=s(4.12×10^(-3)cm^(2)=s),respectively.The calculated Li(K)theoretical capacity of C_(4)BN and C_(2)B_(2)N_(2)biphenylene networks is 940.21 mA h g^(-1)(899.01 mA h g^(-1))and 768.08 mA h g^(-1)(808.47 mA h g^(-1)),with a low open circuit voltage of 0.34 V(0.23 V),and 0.17 V(0.13 V),resulting in very high energy density of 2576.18 mW h g^(-1)(2445.31 mW h g^(-1))and 2181.35 mW h g^(-1)(2263.72 mW h g^(-1)),respectively.Only a slight volume change of 1.6%confirms the robustness of BN-doped carbon-based biphenylene networks.Our findings present novel 2D BN-doped biphenylene networks and a pathway toward their applications in metal-ion batteries.展开更多
The distinguishing feature of Fe_(3)GeTe_(2)lies in its robu st in-plane chemical bonds within layers,which are interconnected by the weak van der Waals forces between adjacent layers,offering a stable framework chara...The distinguishing feature of Fe_(3)GeTe_(2)lies in its robu st in-plane chemical bonds within layers,which are interconnected by the weak van der Waals forces between adjacent layers,offering a stable framework characterized by enhanced interlayer spacing,thereby facilitating the migration of large-sized alkali metal ions.However,to date,there have been no reported studies on the ion storage performance of Fe_(3)GeTe_(2).In this study,Fe_(3)GeTe_(2)is synthesized via the chemical vapor transport method to assess its sodium/potassium storage capabilities.Fe_(3)GeTe_(2)is characterized by its impressive conductivity,a distinctive layered architecture,and a notably wide interlayer spacing,all of these attributes collectively contributing to its superior ion storage proficiency in both sodium-ion batteries(SIBs)and potassiumion batteries(PIBs).Specifically,it demonstrates exceptional electrochemical performance,maintaining a capacity of 291.8 mA h g^(-1)at 5 A g^(-1)in SIBs and 125.0 mA h g^(-1)over 6000 cycles at 3 A g^(-1)in PIBs.A series of in/ex situ characterizations uncover the reaction mechanism of Fe_(3)GeTe_(2)in the both systems,involving a combined process of intercalation,conversion,and alloying.Theoretical calculations provide further insights into the high ion adsorption affinity and diffusion kinetics of Fe_(3)GeTe_(2)in these systems.Analytical findings reveal its superior electrochemical performance in SIBs compared to PIBs,owing to higher diffusion kinetics and reactivity.This research establishes both experimental evidence and theoretical underpinnings for the utilization of Fe_(3)GeTe_(2)in SIBs and PIBs,opening up a new avenue for the utilization of germanium-based ternary materials in the field of energy storage.展开更多
Tin dioxide(SnO_(2))with a high theoretical specific capacity of 1494 mAh g^(-1)is a promising candidate anode material for lithium storage.However,the shortcomings of serious volume expansion and low conductivity lim...Tin dioxide(SnO_(2))with a high theoretical specific capacity of 1494 mAh g^(-1)is a promising candidate anode material for lithium storage.However,the shortcomings of serious volume expansion and low conductivity limit its wide application.Herein,coaxial nano-multilayered C/SnO_(2)/TiO_(2)composites were fabricated via layerby-layer self-assembly of TiO_(2)and SnO_(2)-gel layers on the natural cellulose filter paper,followed by thermal treatment under a nitrogen atmosphere.Through engineering design of the assembly process,the optimal C/SinO_(2)/TiO_(2)composite features five alternating SnO_(2)and TiO_(2)nanolayers,with TiO_(2)as the outside shell(denoted as C/TSTST).This unique structure endows the C/TSTST with excellent structural stability and electrochemical kinetics,making it a high-performance anode for lithium-ion batteries(LIBs).The C/TSTST composite delivers a high reversible capacity of 676 mAh g^(-1)at 0.1 A g^(-1)after 200 cycles and retains a capacity of 504 mAh g^(-1)at 1.0 A g^(-1),which can be recovered to 781 mAh g^(-1)at 0.1 A g^(-1)The significantly enhanced electrochemical performance is attributed to the hierarchical hybrid structure,where the carbon core combined with coaxial TiO_(2)nanolayers serves as a structural scaffold,ameliorating volume change of SnO_(2)while creating abundant interfacial defects for enhanced lithium storage and rapid charge transport.These findings are further demonstrated by the density functional theory(DFT)calculations.This work provides an efficient strategy for designing coaxial nano-multilayered transition metal oxide-related electrode materials,offering new insights into high-performance LIBs anodes.展开更多
Transition metal selenides are considered promising electrochemical energy storage materials due to their excellent rate properties and high capacity based on multi-step conversion reactions.However,its practical appl...Transition metal selenides are considered promising electrochemical energy storage materials due to their excellent rate properties and high capacity based on multi-step conversion reactions.However,its practical applications are hampered by poor conductivity and large volume variation for Na^(+)storage,which resulting fast capacity decay.Herein,a facile metal-organic framework(MOF)derived method is explored to embed Cu_(2-x)Se@C particles into a carbon nanobelts matrix.Such carbon encapsulated nanobelts'structural moderate integral electronic conductivity and maintained the structure from collapsing during Na^(+)insertion/extraction.Furthermore,the porous structure of these nanobelts endows enough void space to mitigate volume stress and provide more diffusion channels for Na^(+)/electrons transporting.Due to the unique structure,these Cu_(2-x)Se@C nanobelts achieved ultra-stable cycling performance(170.7 m Ah/g at1.0 A/g after 1000 cycles)and superior rate capability(94.6 m Ah/g at 8 A/g)for sodium-ion batteries.The kinetic analysis reveals that these Cu_(2-x)Se@C nanobelts with considerable pesoudecapactive contribution benefit the rapid sodiation/desodiation.This rational design strategy broadens an avenue for the development of metal selenide materials for energy storage devices.展开更多
Aqueous zinc-ion batteries(ZIBs)are promising candidates for next-generation energy storage,but the problems related to Zn dendrites and side reactions severely hinder their practical applications.Herein,a self-recogn...Aqueous zinc-ion batteries(ZIBs)are promising candidates for next-generation energy storage,but the problems related to Zn dendrites and side reactions severely hinder their practical applications.Herein,a self-recognition separator based on a Bi-based metal-organic framework(GF@CAU-17)is developed for ion management to achieve highly reversible Zn anodes.The GF@CAU-17 has self-recognition behavior to customize selective Zn^(2+)channels,effectively repelling SO_(4)^(2-)and H_(2)O,but facilitating Zn^(2+)conduction.The inherent properties of CAU-17 result in the repulsion of SO_(4)^(2-)ions while disrupting the hydrogen bond network among free H_(2)O molecules,restraining side reactions and by-products.Simultaneously,the zincophilic characteristic of CAU-17 expedites the desolvation of[Zn(H_(2)O)6]^(2+),leading to a self-expedited Zn^(2+)ion pumping effect that dynamically produces a steady and homogeneous Zn^(2+)ion flux,and thereby alleviates concentration polarization.Consequently,a symmetric cell based on the GF@CAU-17 separator can achieve a long lifespan of 4450 h.Moreover,the constructed Zn//GF@CAU-17//MnO_(2)cell delivers a high specific capacity of 221.8 mAh g^(-1)and 88.0%capacity retention after 2000 cycles.展开更多
SnO_(2)-based anodes for lithium-ion batteries(LIBs)experience volume expansion,leading to rapid capacity decay and low conductivity.To address this problem,a composite consists of C/SnO_(2) with a core-shell structur...SnO_(2)-based anodes for lithium-ion batteries(LIBs)experience volume expansion,leading to rapid capacity decay and low conductivity.To address this problem,a composite consists of C/SnO_(2) with a core-shell structure and a carbonized nitrogen-doped Co-metal organic framework(Co-MOF)(NC)supported on carbon cloth(CC)was designed and prepared,which was denoted as C/SnO_(2)@NC@CC.C/SnO_(2)@NC@CC could be used directly as a flexible anode for LIBs.The combination of core-shell structure centered on carbon spheres,carbonized nitrogen-doped Co-MOF,and CC not only restricts the volume expansion but also functions as conductive networks to improve the electrical conductivity.C/SnO_(2)@NC@CC exhibits excellent electrochemical performance with charge and discharge specific capacities of 2066.0 and 2077.1 mAh/g,respectively,after 120 cycles at a current density of 0.5 A/g.展开更多
This work is devoted to the development of a low cost dimensionally stable anode with high oxygen evolution catalytic activity for practical applications.For this purpose,a Ti/SnO_(x)/MnO_(2) anode was fabricated thro...This work is devoted to the development of a low cost dimensionally stable anode with high oxygen evolution catalytic activity for practical applications.For this purpose,a Ti/SnO_(x)/MnO_(2) anode was fabricated through an innovative strategy involving Sn electrodeposition,oxidation,and MnO_(2)-layer preparation.The structure of the anode was characterized,and the oxygen evolution performance was evaluated in a H_(2)SO_(4) solution.The results show that compared with the Ti/SnO_(2)/MnO_(2) anode prepared by the conventional brushing-annealing process,the Ti/SnO_(x)/MnO_(2) anode fabricated through the innovative procedure exhibits a lower oxygen evolution potential and a nearly 40%longer accelerated lifespan.The superior oxygen evolution performance of the Ti/SnO_(x)/MnO_(2) anode is attributed to the distinctive SnO_(x) intermediate layer fabricated through Sn electrodeposition followed by oxidation,which indicates the great potential of the anode as a dimensionally stable anode for metal electrowinning and hydrogen production by electrolysis,etc.展开更多
Conversion-type anode materials are highly desirable for Na-ion batteries(NIBs)due to their high theoretical capacity.Nevertheless,the active materials undergo severe expansion and pulverization during the sodiation,r...Conversion-type anode materials are highly desirable for Na-ion batteries(NIBs)due to their high theoretical capacity.Nevertheless,the active materials undergo severe expansion and pulverization during the sodiation,resulting in inferior cycling stability.Herein,a self-supporting three-dimensional(3D)graphene sponge decorated with Fe_(2)O_(3)nanocubes(rGO@Fe_(2)O_(3))is constructed.Specifically,the 3D graphene sponge with resilience and high porosity benefits to accommodate the volume expansion of the Fe_(2)O_(3)nanocubes and facilitates the rapid electrons/ions transport,enabling spatial confinement to achieve outstanding results.Besides,the free-standing rGO@Fe_(2)O_(3)can be directly used as an electrode without additional binders and conductive additives,which helps to obtain a higher energy density.Based on the total mass of the rGO@Fe_(2)O_(3)material,the rGO@Fe_(2)O_(3)anode presents a specific capacity of 859 mAh/g at 0.1 A/g.It also delivers an impressive cycling performance(327 mAh/g after 2000 cycles at 1 A/g)and a superior rate capacity(162mAh/g at 20 A/g).The coin-type Na_(3)V_(2)(PO_(4))_(3)@C//rGO@Fe_(2)O_(3)NIB exhibits an energy density of 265.3Wh/kg.This unique 3D ionic/electronic conductive network may provide new strategies to design advanced conversion-type anode materials for high-performance NIBs.展开更多
In sulfide-based all-solid-state lithium batteries(ASLBs),the development of high-capacity anode materials with stable interfaces to sulfide solid-state electrolytes(SSEs)is critical.Here,In_(2)O_(3)is explored as an ...In sulfide-based all-solid-state lithium batteries(ASLBs),the development of high-capacity anode materials with stable interfaces to sulfide solid-state electrolytes(SSEs)is critical.Here,In_(2)O_(3)is explored as an anode material for ASLBs for the first time,demonstrating exceptional interfacial stability and electrochemical performance.The In_(2)O_(3)anode,with a substantial mass loading of 7.64 mg cm^(-2),sustains a charge-specific capacity of528.0 mAh g^(-1)(4.03 mAh cm^(-2))at a current density of0.76 mA cm^(-2)over 500 cycles,with a capacity retention of 81.2%.Additionally,it exhibits remarkable long-term cycling stability(2900 cycles)under a high current density of 3.82 mA cm^(-2),with an exceptionally low decay rate of0.016%per cycle.The charge-discharge mechanism of the In_(2)O_(3)anode is elucidated in detail,revealing that the electrochemical evolution of In_(2)O_(3)in ASLBs involves notonly the alloying/dealloying process of indium(In)but also a conversion reaction between In and Li_(2)O.Notably,as cycling progresses,the conversion reaction of In and Li_(2)O diminishes,with the reversible alloy ing/dealloy ing process becoming predominant.This work offers valuable insights for advancing oxide anode materials in sulfide-based ASLBs.展开更多
Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the ...Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn^(2+)-solvation and deposition behavior demand comprehensive investigation.Organic molecules endowed with special functional groups (such as hydroxyl,carboxyl,etc.) have the potential to significantly optimize the solvation structure of Zn^(2+)and regulate the interfacial electric double layer (EDL).By increasing nucleation overpotential and decreasing interfacial free energy,these functional groups facilitate a lower critical nucleation radius,thereby forming an asymptotic nucleation model to promote uniform Zn deposition.Herein,this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure.The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques,indicating that the H-Zn anode exhibits dendrite-free growth,no by-products,and weak hydrogen evolution,in sharp contrast to the bare Zn.Consequently,the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h.Moreover,the H-Zn//NH_(4)V_(4)O^(10)(NVO) full battery showcases exceptional cycle stability,retaining 95.04%capacity retention after 400 cycles at a large current density of 5 A g^(-1).This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.展开更多
The sluggish electrochemical catalytic activity of the graphite felt electrodes for anode reaction is still a barrier for achieving high-performance vanadium redox flow battery(VRFB).It is significant to leverage the ...The sluggish electrochemical catalytic activity of the graphite felt electrodes for anode reaction is still a barrier for achieving high-performance vanadium redox flow battery(VRFB).It is significant to leverage the exceptional conductivity,excellent electrocatalytic activity,and structural tunability of MXene to address this issue.Herein,this work introduces nitrogen atoms to modulate the carbon layer structure of Ti_(3)C_(2)T_(x)MXene,inducing a reconfiguration of the local electronic structure,which enhances the anode interface activity and thereby improves the performance of VRFB.Ti_(3)C_(2)T_(x)exhibits high conductivity,excellent hydrophilicity,and a large specific surface area,providing excellent interface characteristics for V^(3+)/V^(2+)redox reaction.Moreover,interlayer treatment to modulate the mesoporous structure of MXene further increases the reactive surface area.Importantly,doping nitrogen atoms at carbon layer induces lattice distortions in Ti_(3)C_(2)T_(x),which enhances the charge transfer processes of the V^(3+)/V^(2+)redox reaction.The catalysis mechanism is also validated through density functional theory.Furthermore,the modified graphite felt electrode,as the anode of VRFB,relieves a higher energy efficiency of 68%at 250 mA cm^(-2),while the pristine electrode cannot operate at this current density.In addition,at 150 mA cm^(-2),the modified battery maintains energy efficiency at 75%without degradation after 500 cycles.This study utilizes rational atomic-level engineering for effective structural modulation to significantly enhance the catalytic activity of electrode reaction,offering a unique perspective for developing high-performance MXene electrocatalysts of VRFB.展开更多
Al/α-PbO2/β-PbO2 composite electrodes doped with rare earth oxide （CeO2） were prepared by anodic oxidation method investigate the influence of nano-CeO2 dopants on the properties of Al/α-PbO2/β-PbO2-CeO2 electro...Al/α-PbO2/β-PbO2 composite electrodes doped with rare earth oxide （CeO2） were prepared by anodic oxidation method investigate the influence of nano-CeO2 dopants on the properties of Al/α-PbO2/β-PbO2-CeO2 electrodes and the impact of α-PbO2 as the intermediate layer. The results show that using α-PbO2 as the intermediate layer will benefit the crystallization of β-PbO2 and β-PbO2 is more suitable as the surface layer than α-PbO2. CeO2 dopants change the crystallite size and crystal structure, enhance the catalytic activity, and even change the deposition mechanism of PbO2. The doping of CeO2 in the PbO2 electrodes can enhance the electro-catalytic activity, which is helpful for oxygen evolution, and therefore reduce the cell voltage.展开更多
A comparative study on the corrosion resistance of 17Ni/（NiFe2O4-10NiO） cermet inert anode prepared in differentsintering atmospheres was conducted in Na3AlF6-Al2O3 melt. The results indicate that the corrosion rate...A comparative study on the corrosion resistance of 17Ni/（NiFe2O4-10NiO） cermet inert anode prepared in differentsintering atmospheres was conducted in Na3AlF6-Al2O3 melt. The results indicate that the corrosion rates of NiFe2O4-based cermetanodes prepared in the vacuum and the atmosphere with oxygen content of 2×10^-3 （volume fraction） are 6.46 and 2.71 cm/a,respectively. Though there is a transition layer with lots of holes or pores, a densified layer is formed on the surface of anode due tosome reactions producing aluminates. For the anode prepared in the atmosphere with oxygen content of 2×10^-3, the thickness of thedensification layer （about 50 μm） is thicker than that （about 30 μm） formed on the surface of anode prepared in the vacuum. Thecontents of NiO and Fe（II） in NiFe2xO4-y-z increase with the decrease of oxygen content in sintering atmosphere, which reduces thecorrosion resistance of the material.展开更多
NiFe2O4-10NiO-based cermet inert anodes for aluminium electrolysis were prepared and their properties were investigated in a lab-scale electrolysis cell. The results show that the inert anodes exhibit good performance...NiFe2O4-10NiO-based cermet inert anodes for aluminium electrolysis were prepared and their properties were investigated in a lab-scale electrolysis cell. The results show that the inert anodes exhibit good performance during electrolysis in molten salt cryolite at 960 °C, but according to the analyses of phase compositions and microstructures through XRD, SEM/EDX and metallographic analysis, the metal in the anodes is preferentially corroded and many pores are produced on the anode surface after electrolysis. The preferential dissolution of Fe in the NiFe2O4 phase may lead to the non-uniform corrosion of NiFe2O4 grains. Moreover, a dense protective layer of NiFe2O4-NiAl2O4-FeAl2O4 is formed on the anode surface, which originates from the reaction of Al2O3 dissolved in the electrolyte with NiO or FeO, the annexation of NiFe2O4-NiAl2O4-FeAl2O4 to NiO and volume expansion. Thus, the dense NiFe2O4-NiAl2O4-FeAl2O4 layer inhibits the metal loss and ceramic-phase corrosion on the surface of the cermet inert anodes.展开更多
A novel SnO2-based gas anode was developed for aluminum electrolysis in molten cryolite at 850 ＆#176;C to reduce energy consumption and decrease CO2 emissions. Hydrogen was introduced into the anode, participating in...A novel SnO2-based gas anode was developed for aluminum electrolysis in molten cryolite at 850 ＆#176;C to reduce energy consumption and decrease CO2 emissions. Hydrogen was introduced into the anode, participating in the anode reaction. Carbon and aluminum were used as the cathode and reference electrodes, respectively. Cyclic voltammetry was applied in the cell to investigate the electrochemical behavior of oxygen ion on platinum and SnO2-based materials. The potential for oxygen evolution on these electrode materials was determined. Then, galvanostatic electrolysis was performed on the gas anode, showing a significant depolarization effect （a decrease of ~0.8 V of the anode potential） after the introduction of hydrogen, compared with no gas introduction or the introduction of argon. The results indicate the involvement of hydrogen in the anode reaction （three-phase-boundary reaction including gas, electrolyte and electrode） and give the possibility for the utilization of reducing gas anodes for aluminum electrolysis.展开更多
基金supported by the National Natural Science Foundation of China(22179063,22479078,and 22409093)the Natural Science Foundation of Jiangsu Province of China(BK20240579)。
文摘FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.
基金the Khalifa University of Science and Technology through the internal grant RIG-2023-01.
文摘The discovery of novel materials with compelling properties is more accessible with the help of advanced computational algorithms.Recent experimental synthesis of the biphenylene network(C_(6))motivated us to discover new BN-doped biphenylene networks(C_(4)BN,C_(2)B_(2)N_(2),and B_(4)N_(4))and their applications in Li(K)-ion batteries using an evolutionary algorithm and the first-principles calculations.The thermodynamic,thermal,and mechanical stability calculations and decomposition energy suggest the experimental synthesis of predicted biphenylene networks.Adding BN in the biphenylene networks shows a transition from metal to semimetal to semiconductor.The BN biphenylene network shows an HSE06 band gap of 3.06 eV,smaller than h-BN.The C_(4)BN and C_(2)B_(2)N_(2)biphenylene networks offer Li(K)adsorption energy of-0.56 eV(-0.81 eV)and-0.14 eV(-0.28 eV),respectively,with a low diffusion barrier of 178 meV(58 meV)and 251 meV(79 meV),and a large diffusion constant of 8.50×10^(-5)cm^(2)=s(8.78×10^(-3)cm^(2)=s)and 5.33×10^(-6)cm^(2)=s(4.12×10^(-3)cm^(2)=s),respectively.The calculated Li(K)theoretical capacity of C_(4)BN and C_(2)B_(2)N_(2)biphenylene networks is 940.21 mA h g^(-1)(899.01 mA h g^(-1))and 768.08 mA h g^(-1)(808.47 mA h g^(-1)),with a low open circuit voltage of 0.34 V(0.23 V),and 0.17 V(0.13 V),resulting in very high energy density of 2576.18 mW h g^(-1)(2445.31 mW h g^(-1))and 2181.35 mW h g^(-1)(2263.72 mW h g^(-1)),respectively.Only a slight volume change of 1.6%confirms the robustness of BN-doped carbon-based biphenylene networks.Our findings present novel 2D BN-doped biphenylene networks and a pathway toward their applications in metal-ion batteries.
基金supported by the Natural Science Foundation of Henan Province(222300420083)the Opening Foundation of State Key Laboratory of Chemistry and Utilization of Carbonbased Energy Resource of Xinjiang University(KFKT2021004)supported by the National Supercomputing Center in Zhengzhou and the Shanxi Supercomputing Center。
文摘The distinguishing feature of Fe_(3)GeTe_(2)lies in its robu st in-plane chemical bonds within layers,which are interconnected by the weak van der Waals forces between adjacent layers,offering a stable framework characterized by enhanced interlayer spacing,thereby facilitating the migration of large-sized alkali metal ions.However,to date,there have been no reported studies on the ion storage performance of Fe_(3)GeTe_(2).In this study,Fe_(3)GeTe_(2)is synthesized via the chemical vapor transport method to assess its sodium/potassium storage capabilities.Fe_(3)GeTe_(2)is characterized by its impressive conductivity,a distinctive layered architecture,and a notably wide interlayer spacing,all of these attributes collectively contributing to its superior ion storage proficiency in both sodium-ion batteries(SIBs)and potassiumion batteries(PIBs).Specifically,it demonstrates exceptional electrochemical performance,maintaining a capacity of 291.8 mA h g^(-1)at 5 A g^(-1)in SIBs and 125.0 mA h g^(-1)over 6000 cycles at 3 A g^(-1)in PIBs.A series of in/ex situ characterizations uncover the reaction mechanism of Fe_(3)GeTe_(2)in the both systems,involving a combined process of intercalation,conversion,and alloying.Theoretical calculations provide further insights into the high ion adsorption affinity and diffusion kinetics of Fe_(3)GeTe_(2)in these systems.Analytical findings reveal its superior electrochemical performance in SIBs compared to PIBs,owing to higher diffusion kinetics and reactivity.This research establishes both experimental evidence and theoretical underpinnings for the utilization of Fe_(3)GeTe_(2)in SIBs and PIBs,opening up a new avenue for the utilization of germanium-based ternary materials in the field of energy storage.
基金financially supported by the National Natural Science Foundation of China(Nos.22302133 and 22405161)Central Guidance on Local Science and Technology Development Fund of Hebei Province,China(No.236Z4406G)+5 种基金the Natural Science Foundation of Hebei Education Department,China(No.BJ2025100)the Natural Science Foundation of Hebei Province,China(No.B2021210001)the Natural Science Foundation of Xinjiang Uygur Autonomous Region(No.2024D01A157)the Key R&D Plan of Karamay(No.2024zdyf0009)Karamay Innovation Environment Construction Plan(Innovative Talents)Project(No.2024hjcxrc0029)the Research Foundation of China University of Petroleum-Beijing at Karamay(No.XQZX20240023)
文摘Tin dioxide(SnO_(2))with a high theoretical specific capacity of 1494 mAh g^(-1)is a promising candidate anode material for lithium storage.However,the shortcomings of serious volume expansion and low conductivity limit its wide application.Herein,coaxial nano-multilayered C/SnO_(2)/TiO_(2)composites were fabricated via layerby-layer self-assembly of TiO_(2)and SnO_(2)-gel layers on the natural cellulose filter paper,followed by thermal treatment under a nitrogen atmosphere.Through engineering design of the assembly process,the optimal C/SinO_(2)/TiO_(2)composite features five alternating SnO_(2)and TiO_(2)nanolayers,with TiO_(2)as the outside shell(denoted as C/TSTST).This unique structure endows the C/TSTST with excellent structural stability and electrochemical kinetics,making it a high-performance anode for lithium-ion batteries(LIBs).The C/TSTST composite delivers a high reversible capacity of 676 mAh g^(-1)at 0.1 A g^(-1)after 200 cycles and retains a capacity of 504 mAh g^(-1)at 1.0 A g^(-1),which can be recovered to 781 mAh g^(-1)at 0.1 A g^(-1)The significantly enhanced electrochemical performance is attributed to the hierarchical hybrid structure,where the carbon core combined with coaxial TiO_(2)nanolayers serves as a structural scaffold,ameliorating volume change of SnO_(2)while creating abundant interfacial defects for enhanced lithium storage and rapid charge transport.These findings are further demonstrated by the density functional theory(DFT)calculations.This work provides an efficient strategy for designing coaxial nano-multilayered transition metal oxide-related electrode materials,offering new insights into high-performance LIBs anodes.
基金supported by the National Key Research and Development Program of China(No.2022YFB2502000)the National Natural Science Foundation of China(Nos.U21A2033251771076,52301266,42203047)+2 种基金R&D Program in Key Areas of Guangdong Province(No.2020B0101030005)Science and Technology Planning Project of Guangzhou(No.2024A04J9999)GDUT Large-Scale Instruments Open Foundation(No.ATC2022201)。
文摘Transition metal selenides are considered promising electrochemical energy storage materials due to their excellent rate properties and high capacity based on multi-step conversion reactions.However,its practical applications are hampered by poor conductivity and large volume variation for Na^(+)storage,which resulting fast capacity decay.Herein,a facile metal-organic framework(MOF)derived method is explored to embed Cu_(2-x)Se@C particles into a carbon nanobelts matrix.Such carbon encapsulated nanobelts'structural moderate integral electronic conductivity and maintained the structure from collapsing during Na^(+)insertion/extraction.Furthermore,the porous structure of these nanobelts endows enough void space to mitigate volume stress and provide more diffusion channels for Na^(+)/electrons transporting.Due to the unique structure,these Cu_(2-x)Se@C nanobelts achieved ultra-stable cycling performance(170.7 m Ah/g at1.0 A/g after 1000 cycles)and superior rate capability(94.6 m Ah/g at 8 A/g)for sodium-ion batteries.The kinetic analysis reveals that these Cu_(2-x)Se@C nanobelts with considerable pesoudecapactive contribution benefit the rapid sodiation/desodiation.This rational design strategy broadens an avenue for the development of metal selenide materials for energy storage devices.
基金supported by the National Natural Science Foundation of China(22272150)the Major Program of Zhejiang Provincial Natural Science Foundation of China(LD22B030002)+2 种基金the Zhejiang Provincial Ten Thousand Talent Program(2021R51009)the Zhejiang Provincial Natural Science of China(LZ23B030001)the Key Science and Technology Project of Jinhua City(2022-1-083,2023-1-093).
文摘Aqueous zinc-ion batteries(ZIBs)are promising candidates for next-generation energy storage,but the problems related to Zn dendrites and side reactions severely hinder their practical applications.Herein,a self-recognition separator based on a Bi-based metal-organic framework(GF@CAU-17)is developed for ion management to achieve highly reversible Zn anodes.The GF@CAU-17 has self-recognition behavior to customize selective Zn^(2+)channels,effectively repelling SO_(4)^(2-)and H_(2)O,but facilitating Zn^(2+)conduction.The inherent properties of CAU-17 result in the repulsion of SO_(4)^(2-)ions while disrupting the hydrogen bond network among free H_(2)O molecules,restraining side reactions and by-products.Simultaneously,the zincophilic characteristic of CAU-17 expedites the desolvation of[Zn(H_(2)O)6]^(2+),leading to a self-expedited Zn^(2+)ion pumping effect that dynamically produces a steady and homogeneous Zn^(2+)ion flux,and thereby alleviates concentration polarization.Consequently,a symmetric cell based on the GF@CAU-17 separator can achieve a long lifespan of 4450 h.Moreover,the constructed Zn//GF@CAU-17//MnO_(2)cell delivers a high specific capacity of 221.8 mAh g^(-1)and 88.0%capacity retention after 2000 cycles.
基金National Natural Science Foundation of China(No.61376017)。
文摘SnO_(2)-based anodes for lithium-ion batteries(LIBs)experience volume expansion,leading to rapid capacity decay and low conductivity.To address this problem,a composite consists of C/SnO_(2) with a core-shell structure and a carbonized nitrogen-doped Co-metal organic framework(Co-MOF)(NC)supported on carbon cloth(CC)was designed and prepared,which was denoted as C/SnO_(2)@NC@CC.C/SnO_(2)@NC@CC could be used directly as a flexible anode for LIBs.The combination of core-shell structure centered on carbon spheres,carbonized nitrogen-doped Co-MOF,and CC not only restricts the volume expansion but also functions as conductive networks to improve the electrical conductivity.C/SnO_(2)@NC@CC exhibits excellent electrochemical performance with charge and discharge specific capacities of 2066.0 and 2077.1 mAh/g,respectively,after 120 cycles at a current density of 0.5 A/g.
文摘This work is devoted to the development of a low cost dimensionally stable anode with high oxygen evolution catalytic activity for practical applications.For this purpose,a Ti/SnO_(x)/MnO_(2) anode was fabricated through an innovative strategy involving Sn electrodeposition,oxidation,and MnO_(2)-layer preparation.The structure of the anode was characterized,and the oxygen evolution performance was evaluated in a H_(2)SO_(4) solution.The results show that compared with the Ti/SnO_(2)/MnO_(2) anode prepared by the conventional brushing-annealing process,the Ti/SnO_(x)/MnO_(2) anode fabricated through the innovative procedure exhibits a lower oxygen evolution potential and a nearly 40%longer accelerated lifespan.The superior oxygen evolution performance of the Ti/SnO_(x)/MnO_(2) anode is attributed to the distinctive SnO_(x) intermediate layer fabricated through Sn electrodeposition followed by oxidation,which indicates the great potential of the anode as a dimensionally stable anode for metal electrowinning and hydrogen production by electrolysis,etc.
基金supported by National Natural Science Foundation of China(Nos.52307239,52102300,52207234)the Natural Science Foundation of Hubei Province(Nos.2022CFB1003,2021CFA025).
文摘Conversion-type anode materials are highly desirable for Na-ion batteries(NIBs)due to their high theoretical capacity.Nevertheless,the active materials undergo severe expansion and pulverization during the sodiation,resulting in inferior cycling stability.Herein,a self-supporting three-dimensional(3D)graphene sponge decorated with Fe_(2)O_(3)nanocubes(rGO@Fe_(2)O_(3))is constructed.Specifically,the 3D graphene sponge with resilience and high porosity benefits to accommodate the volume expansion of the Fe_(2)O_(3)nanocubes and facilitates the rapid electrons/ions transport,enabling spatial confinement to achieve outstanding results.Besides,the free-standing rGO@Fe_(2)O_(3)can be directly used as an electrode without additional binders and conductive additives,which helps to obtain a higher energy density.Based on the total mass of the rGO@Fe_(2)O_(3)material,the rGO@Fe_(2)O_(3)anode presents a specific capacity of 859 mAh/g at 0.1 A/g.It also delivers an impressive cycling performance(327 mAh/g after 2000 cycles at 1 A/g)and a superior rate capacity(162mAh/g at 20 A/g).The coin-type Na_(3)V_(2)(PO_(4))_(3)@C//rGO@Fe_(2)O_(3)NIB exhibits an energy density of 265.3Wh/kg.This unique 3D ionic/electronic conductive network may provide new strategies to design advanced conversion-type anode materials for high-performance NIBs.
基金financially supported by the National Natural Science Foundation of China(No.22301151)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(No.2022QN05024)+1 种基金the Science and Technology Projects of Inner Mongolia Autonomous Region(No.2024SKYPT0011)the Science and Technology Planning Project of Hohhot,China(No.2024-JieBangGuaShuai-Gao-4)
文摘In sulfide-based all-solid-state lithium batteries(ASLBs),the development of high-capacity anode materials with stable interfaces to sulfide solid-state electrolytes(SSEs)is critical.Here,In_(2)O_(3)is explored as an anode material for ASLBs for the first time,demonstrating exceptional interfacial stability and electrochemical performance.The In_(2)O_(3)anode,with a substantial mass loading of 7.64 mg cm^(-2),sustains a charge-specific capacity of528.0 mAh g^(-1)(4.03 mAh cm^(-2))at a current density of0.76 mA cm^(-2)over 500 cycles,with a capacity retention of 81.2%.Additionally,it exhibits remarkable long-term cycling stability(2900 cycles)under a high current density of 3.82 mA cm^(-2),with an exceptionally low decay rate of0.016%per cycle.The charge-discharge mechanism of the In_(2)O_(3)anode is elucidated in detail,revealing that the electrochemical evolution of In_(2)O_(3)in ASLBs involves notonly the alloying/dealloying process of indium(In)but also a conversion reaction between In and Li_(2)O.Notably,as cycling progresses,the conversion reaction of In and Li_(2)O diminishes,with the reversible alloy ing/dealloy ing process becoming predominant.This work offers valuable insights for advancing oxide anode materials in sulfide-based ASLBs.
基金National Natural Science Foundation of China (52301273, 52072411)Science and Technology Innovation Program of Hunan Province (2024RC3222)+3 种基金Key project of scientific research project of Hunan Provincial Department of Education (22A0479)China Postdoctoral Science Foundation (2024M753668)Central South University Innovation-Driven Research Programme (2023CXQD038)Hunan Provincial Postgraduate Research Innovation Programme(CX20240970)。
文摘Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn^(2+)-solvation and deposition behavior demand comprehensive investigation.Organic molecules endowed with special functional groups (such as hydroxyl,carboxyl,etc.) have the potential to significantly optimize the solvation structure of Zn^(2+)and regulate the interfacial electric double layer (EDL).By increasing nucleation overpotential and decreasing interfacial free energy,these functional groups facilitate a lower critical nucleation radius,thereby forming an asymptotic nucleation model to promote uniform Zn deposition.Herein,this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure.The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques,indicating that the H-Zn anode exhibits dendrite-free growth,no by-products,and weak hydrogen evolution,in sharp contrast to the bare Zn.Consequently,the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h.Moreover,the H-Zn//NH_(4)V_(4)O^(10)(NVO) full battery showcases exceptional cycle stability,retaining 95.04%capacity retention after 400 cycles at a large current density of 5 A g^(-1).This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.
基金financially supported by the National Natural Science Foundation of China(51872090,51772097)Hebei Natural Science Fund for Distinguished Young Scholar(E2019209433)+3 种基金Youth Talent Program of Hebei Provincial Education Department(BJ2018020)Natural Science Foundation of Hebei Province(E2020209151,E2024209029)National Key R&D Plan Project(2022YFB4200305)Research Projects of China National Petroleum Corporation(2024ZG50,2023DQ03-04)。
文摘The sluggish electrochemical catalytic activity of the graphite felt electrodes for anode reaction is still a barrier for achieving high-performance vanadium redox flow battery(VRFB).It is significant to leverage the exceptional conductivity,excellent electrocatalytic activity,and structural tunability of MXene to address this issue.Herein,this work introduces nitrogen atoms to modulate the carbon layer structure of Ti_(3)C_(2)T_(x)MXene,inducing a reconfiguration of the local electronic structure,which enhances the anode interface activity and thereby improves the performance of VRFB.Ti_(3)C_(2)T_(x)exhibits high conductivity,excellent hydrophilicity,and a large specific surface area,providing excellent interface characteristics for V^(3+)/V^(2+)redox reaction.Moreover,interlayer treatment to modulate the mesoporous structure of MXene further increases the reactive surface area.Importantly,doping nitrogen atoms at carbon layer induces lattice distortions in Ti_(3)C_(2)T_(x),which enhances the charge transfer processes of the V^(3+)/V^(2+)redox reaction.The catalysis mechanism is also validated through density functional theory.Furthermore,the modified graphite felt electrode,as the anode of VRFB,relieves a higher energy efficiency of 68%at 250 mA cm^(-2),while the pristine electrode cannot operate at this current density.In addition,at 150 mA cm^(-2),the modified battery maintains energy efficiency at 75%without degradation after 500 cycles.This study utilizes rational atomic-level engineering for effective structural modulation to significantly enhance the catalytic activity of electrode reaction,offering a unique perspective for developing high-performance MXene electrocatalysts of VRFB.
基金Project(50964008)supported by the National Natural Science Foundation of ChinaProject(2010287)supported by Analysis and Testing Foundation of Kunming University of Science and Technology,China
文摘Al/α-PbO2/β-PbO2 composite electrodes doped with rare earth oxide （CeO2） were prepared by anodic oxidation method investigate the influence of nano-CeO2 dopants on the properties of Al/α-PbO2/β-PbO2-CeO2 electrodes and the impact of α-PbO2 as the intermediate layer. The results show that using α-PbO2 as the intermediate layer will benefit the crystallization of β-PbO2 and β-PbO2 is more suitable as the surface layer than α-PbO2. CeO2 dopants change the crystallite size and crystal structure, enhance the catalytic activity, and even change the deposition mechanism of PbO2. The doping of CeO2 in the PbO2 electrodes can enhance the electro-catalytic activity, which is helpful for oxygen evolution, and therefore reduce the cell voltage.
基金Project(51474238)supported by the National Natural Science Foundation of China
文摘A comparative study on the corrosion resistance of 17Ni/（NiFe2O4-10NiO） cermet inert anode prepared in differentsintering atmospheres was conducted in Na3AlF6-Al2O3 melt. The results indicate that the corrosion rates of NiFe2O4-based cermetanodes prepared in the vacuum and the atmosphere with oxygen content of 2×10^-3 （volume fraction） are 6.46 and 2.71 cm/a,respectively. Though there is a transition layer with lots of holes or pores, a densified layer is formed on the surface of anode due tosome reactions producing aluminates. For the anode prepared in the atmosphere with oxygen content of 2×10^-3, the thickness of thedensification layer （about 50 μm） is thicker than that （about 30 μm） formed on the surface of anode prepared in the vacuum. Thecontents of NiO and Fe（II） in NiFe2xO4-y-z increase with the decrease of oxygen content in sintering atmosphere, which reduces thecorrosion resistance of the material.
基金Project (2012FJ6123) supported by the Project of Science and Technology of Hunan Province,ChinaProject supported by Post-Doctoral Foundation of Central South University,China+1 种基金Project (CL12100) supported the Undergraduate Innovative Training of Central South University,ChinaProject (2282013bkso13) supported by Free Exploration Plan of Central South University,China
文摘NiFe2O4-10NiO-based cermet inert anodes for aluminium electrolysis were prepared and their properties were investigated in a lab-scale electrolysis cell. The results show that the inert anodes exhibit good performance during electrolysis in molten salt cryolite at 960 °C, but according to the analyses of phase compositions and microstructures through XRD, SEM/EDX and metallographic analysis, the metal in the anodes is preferentially corroded and many pores are produced on the anode surface after electrolysis. The preferential dissolution of Fe in the NiFe2O4 phase may lead to the non-uniform corrosion of NiFe2O4 grains. Moreover, a dense protective layer of NiFe2O4-NiAl2O4-FeAl2O4 is formed on the anode surface, which originates from the reaction of Al2O3 dissolved in the electrolyte with NiO or FeO, the annexation of NiFe2O4-NiAl2O4-FeAl2O4 to NiO and volume expansion. Thus, the dense NiFe2O4-NiAl2O4-FeAl2O4 layer inhibits the metal loss and ceramic-phase corrosion on the surface of the cermet inert anodes.
基金Project(51404001)supported by the National Natural Science Foundation of ChinaProject([2014]1685)supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,Ministry of Education,China
文摘A novel SnO2-based gas anode was developed for aluminum electrolysis in molten cryolite at 850 ＆#176;C to reduce energy consumption and decrease CO2 emissions. Hydrogen was introduced into the anode, participating in the anode reaction. Carbon and aluminum were used as the cathode and reference electrodes, respectively. Cyclic voltammetry was applied in the cell to investigate the electrochemical behavior of oxygen ion on platinum and SnO2-based materials. The potential for oxygen evolution on these electrode materials was determined. Then, galvanostatic electrolysis was performed on the gas anode, showing a significant depolarization effect （a decrease of ~0.8 V of the anode potential） after the introduction of hydrogen, compared with no gas introduction or the introduction of argon. The results indicate the involvement of hydrogen in the anode reaction （three-phase-boundary reaction including gas, electrolyte and electrode） and give the possibility for the utilization of reducing gas anodes for aluminum electrolysis.
