Iron-chromium flow batteries(ICRFBs)have emerged as an ideal large-scale energy storage device with broad application prospects in recent years.Enhancement of the Cr^(3+)/Cr^(2+)redox reaction activity and inhibition ...Iron-chromium flow batteries(ICRFBs)have emerged as an ideal large-scale energy storage device with broad application prospects in recent years.Enhancement of the Cr^(3+)/Cr^(2+)redox reaction activity and inhibition of the hydrogen evolution side reaction(HER)are essential for the development of ICRFBs and require a novel catalyst design.However,elucidating the underlying mechanisms for modulating catalyst behaviors remains an unresolved challenge.Here,we show a novel precisely controlled preparation of a novel thermal-treated carbon cloth electrode with a uniform deposit of low-cost indium catalyst particles.The density functional theory analysis reveals the In catalyst has a significant adsorption effect on the reactants and improves the redox reaction activity of Cr^(3+)/Cr^(2+).Moreover,H+is more easily absorbed on the surface of the catalyst with a high migration energy barrier,thereby inhibiting the occurrence of HER.The assembled ICRFBs have an average energy efficiency of 83.91%at 140 mA cm^(-2),and this method minimizes the electrodeposition process and cleans the last obstacle for industry long cycle operation requirements.The ICRFBs exhibit exceptional long-term stability with an energy efficiency decay rate of 0.011%per cycle at 1000 cycles,the lowest ICRFBs reported so far.Therefore,this study provides a promising strategy for developing ICRFBs with low costs and long cycle life.展开更多
To satisfy the demands of modern society for high-energy–density sulfide-based all-solid-state lithium batteries(ASSLBs),Ni-rich cathode materials have gained much attention for their high capacity and energy density...To satisfy the demands of modern society for high-energy–density sulfide-based all-solid-state lithium batteries(ASSLBs),Ni-rich cathode materials have gained much attention for their high capacity and energy density.However,their practical deployment is hindered by accelerated interface degradation and capacity decay originating from surface oxygen release and lattice oxygen activation during prolonged cycling.In this study,Ti_(x)NbB_((1−x))C_(2)was successfully coated on the surface of LiNi_(0.94)Co_(0.05)Mn_(0.01)O_(2).Density functional theory(DFT)calculations first elucidate a“point-to-point”anchoring mechanism where each surface oxygen atom coordinates with single species(Ti/Nb/B)offered by Ti_(x)NbB_((1−x))C_(2),which forms robust O–M bonds and sustain a stable interface structure.The electron energy loss spectroscopy(EELS)reveals the segregation of Ti/Nb toward subsurface layers during cycling,creating an optimized lattice oxygen coordination environment and suppressing oxygen activation.The dual oxygen stabilization mechanism dramatically improves the reversibility of phase transition and the structural stability of the Ni-rich cathode materials.Moreover,Ti_(x)NbB_((1−x))C_(2)as the protective layer decreases mechanical strain and suppresses the parasitic reactions.Consequently,the engineered cathode delivers 91%capacity retention after 1000 cycles at 0.3 C,suggesting excellent cycling stability.The research delivers a new design philosophy for the coating layer that can stabilize surface oxygen.Furthermore,the atomistic understanding of the structure–property relationship of the Ni-rich cathode materials provides valuable guidance for the future design of new cathode materials with superior structural stability in ASSLBs.展开更多
Hexagonal MnMX-based(M=Co or Ni,X=Si or Ge)alloys exhibit giant reversible barocaloric effects.However,giant volume expansion would result in the as-cast MnMX ingots fragmenting into powders,and inevitably bring the d...Hexagonal MnMX-based(M=Co or Ni,X=Si or Ge)alloys exhibit giant reversible barocaloric effects.However,giant volume expansion would result in the as-cast MnMX ingots fragmenting into powders,and inevitably bring the deterioration of mechanical properties and formability.Grain fragmentation can bring degradation of structural transformation entropy change during cyclic application and removal of pressure.In this paper,giant reversible barocaloric effects with high thermal cycle stability can be achieved in the epoxy bonded(MnCoGe)0.96(CuCoSn)0.04 composite.Giant reversible isothermal entropy change of 43.0 J·kg^(−1)·K^(−1) and adiabatic temperature change from barocaloric effects(ΔT_(BCE))of 15.6 K can be obtained within a wide temperature span of 30 K at 360 MPa,which is mainly attributed to the integration of the change in the transition temperature driven by pressure of−101 K·GPa^(−1) and suitable thermal hysteresis of 11.1 K.Further,the variation of reversibleΔ_(TBCE) against the applied hydrostatic pressure reaches up to 43 K·GPa^(−1),which is at the highest level among the other reported giant barocaloric compounds.More importantly,after 60 thermal cycles,the composite does not break and the calorimetric curves coincide well,demonstrating good thermal cycle stability.展开更多
In order to improve the cycle stability of La-Mg-Ni-Co type alloy electrode, rapid quenching technology was employed. The effects of rapid quenching on the microstructure and cycle stability of the alloy were investig...In order to improve the cycle stability of La-Mg-Ni-Co type alloy electrode, rapid quenching technology was employed. The effects of rapid quenching on the microstructure and cycle stability of the alloy were investigated. The obtained results show that the La2Mg(Ni0.85Co0.15)9M0.1 (M=B, Cr) alloy electrodes are composed of (La, Mg)Ni3 phase, LaNi5 phase and a small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast MB alloy, and the Ni2B phase in the alloy nearly disappears after rapid quenching. Rapid quenching technology can slightly improve the cycling life of the alloy. When the quenching rate increases from 0 m·s-1 (As-cast is defined as quenching rate of 0 m·s-1) to 30 m·s-1, the cycle lives of the MB, MCr alloys enhance from 86 and 87 cycles to 106 and 119 cycles, respectively. On the other hand, the average capacity decay rates of the MB, MCr alloys decrease from 1.7172 and 1.7178 mAh·g-1·cycle-1 to 1.5751 and 1.3060 mAh·g-1·cycle-1 after 86 charge-discharges cycling, respectively.展开更多
High-capacity Ni-rich layered cathodes LiNi_(x)CoyMn_(1-x-y)O_(2)(NCM)have been widely recognized as highly promising candidates for lithium-ion batteries(LIBs).However,NCM cathodes are suffered from sluggish Li-ion k...High-capacity Ni-rich layered cathodes LiNi_(x)CoyMn_(1-x-y)O_(2)(NCM)have been widely recognized as highly promising candidates for lithium-ion batteries(LIBs).However,NCM cathodes are suffered from sluggish Li-ion kinetics and fast capacity decay.Herein,the Nb/Ti co-doping strategy has been proposed by formation energy analysis to enhance the mechanical and chemical integrities of NCM cathode.Nb/Ti co-doping facilitates Li-ion transport of NCM cathode for boosting the rate ability.Furthermore,the structure stability is prominently improved for the stronger Nb–O and Ti–O bonds,resulting from the suppressed sharp contraction of c axis,inhibited microcracks formation,and alleviated electrolyte corrosion.Inspired by the synergistic effect of Nb/Ti co-doping,the modified NCM exhibits superior comprehensive electrochemical performances.The Nb/Ti co-doping NCM exhibits an increased discharge capacity of 144.3 m Ah/g at10 C and an outstanding capacity retention remained 92.7%after 300 cycles at 1 C.This work offers a promising approach to developing high-performance cathode materials.展开更多
Rechargeable aqueous Zn-MoO_(x)batteries are promising energy storage devices with high theoretical specific capacity and low cost.However,MoO_(3)cathodes suffer drastic capacity decay during the initial discharging/c...Rechargeable aqueous Zn-MoO_(x)batteries are promising energy storage devices with high theoretical specific capacity and low cost.However,MoO_(3)cathodes suffer drastic capacity decay during the initial discharging/charging process in conventional electrolytes,resulting in a short cycle life and challenging the development of Zn-MoO_(x)batteries.Here we comprehensively investigate the dissolution mechanism of MoO_(3)cathodes and innovatively introduce a polymer to inhibit the irreversible processes.Our findings reveal that this capacity decay originates from the irreversible Zn^(2+)/H^(+)co-intercalation/extraction process in aqueous electrolytes.Even worse,during Zn^(2+)intercalation,the formed Zn_(x)MoO_(3-x)intermediate phase with lower valence states(Mo^(5+)/Mo^(4+))experiences severe dissolution in aqueous environments.To address these challenges,we developed a first instance of coating a polyaniline(PANI)shell around the MoO_(3)nanorod effectively inhibiting these irreversible processes and protecting structural integrity during long-term cycling.Detailed structural analysis and theoretical calculations indicate that=N-groups in PANI@MoO_(3-x)simultaneously weaken H+adsorption and enhance Zn^(2+)adsorption,which endowed the PANI@MoO_(3-x)cathode with reversible Zn^(2+)/H^(+)intercalation/extraction.Consequently,the obtained PANI@MoO_(3-x)cathode delivers an excellent discharge capacity of 316.86 mA h g^(-1)at 0.1 A g^(-1)and prolonged cycling stability of 75.49%capacity retention after 1000 cycles at 5 A g^(-1).This work addresses the critical issues associated with MoO_(3)cathodes and significantly advances the understanding of competitive multi-ion energy storage mechanisms in aqueous Zn-MoO_(3)batteries.展开更多
In the original publication,incorrect version of Corresponding authors has been published.You-Yuan Huang and Bo Wang should be corresponding authors.The corrected Correspondingg authors are provided in this correction.
Aqueous sodium-ion batteries(ASIBs) offer significant advantages for energy storage on a large scale,attributed to their economical cost,secure operatio n,and eco-friend ly natu re.Among the leading cathode materials ...Aqueous sodium-ion batteries(ASIBs) offer significant advantages for energy storage on a large scale,attributed to their economical cost,secure operatio n,and eco-friend ly natu re.Among the leading cathode materials for ASIBs,Na_(3)V_(2)(PO_(4))_(3)(NVP) exhibits excellent structural stability and a high Na+diffusion coefficient,making it a promising option.However,the high solubility of vanadium-based materials in aqueous electrolytes engenders suboptimal cycling stability for Na_(3)V_(2)(PO_(4))_(3),constraining its application in ASIBs.Herein,the Cr-substituted Na_(3)V_(1.3)Cr_(0.7)(PO_(4))3@C(NV_(1.3)Cr_(0.7)P) cathode material was synthesized via a simple sol-gel method.It is found that Cr substitution reduces the cell parameters of NV_(1.3)Cr_(0.7)P,effectively reinforcing the crystal structure.Furthermore,NV_(1.3)Cr_(0.7)P alters the Na^(+)insertion/extraction mechanism,transforming the typical two-phase reaction between Na_(1)V_(2)(PO_(4))_(3)and Na_(3)V_(2)(PO_(4))3into continuous solid-solution reactions with stable intermediates.The Cr substitution diminishes the sodium-ion diffusion energy barrier in NV_(1.3)Cr_(0.7)P,leading to smoother Na+insertion and extraction processes.Consequently,NV_(1.3)Cr_(0.7)P exhibits impressive cycling stability,retaining 74.8% of its capacity after 5,000 cycles at a current density of 5 A g^(-1),along with an outstanding rate performance of 79,2% at 10 A g^(-1).This work elucidates the stable Na^(+)insertion/extraction processes in Cr-substituted NV_(1.3)Cr_(0.7)P,offering insights into the application of vanadium-based materials in aqueous sodium-ion batteries.展开更多
Exploring cathode materials that combine excellent cycling stability and high energy density poses a challenge to aqueous Zn-ion hybrid supercapacitors(ZHSCs).Herein,polyaniline(PANI)coated boron-carbon-nitrogen(BCN)n...Exploring cathode materials that combine excellent cycling stability and high energy density poses a challenge to aqueous Zn-ion hybrid supercapacitors(ZHSCs).Herein,polyaniline(PANI)coated boron-carbon-nitrogen(BCN)nanoarray on carbon cloth surface is prepared as advanced cathode materials via simple high-temperature calcination and electrochemical deposition methods.Because of the excellent specific capacity and conductivity of PANI,the CC@BCN@PANI core-shell nanoarrays cathode shows an excellent ion storage capability.Moreover,the 3D nanoarray structure can provide enough space for the volume expansion and contraction of PANI in the charging/discharging cycles,which effectively avoids the collapse of the microstructure and greatly improves the electrochemical stability of PANI.Therefore,the CC@BCN@PANI-based ZHSCs exhibit superior electrochemical performances showing a specific capacity of 145.8 mAh/g,a high energy density of 116.78 Wh/kg,an excellent power density of 12 kW/kg,and a capacity retention rate of 86.2%after 8000 charge/discharge cycles at a current density of 2 A/g.In addition,the flexible ZHSCs(FZHSCs)also show a capacity retention rate of 87.7%at the current density of 2 A/g after 450 cycles.展开更多
The severe volumetric expansion and poor conductivity of silicon when used as anode in lithium-ion batteries present challenges in maintaining the stability of electrochemical performance.Herein,the binding between si...The severe volumetric expansion and poor conductivity of silicon when used as anode in lithium-ion batteries present challenges in maintaining the stability of electrochemical performance.Herein,the binding between silicon nanoparticles and carbon nanotubes(CNTs)is achieved by the utilization of sodium alginate(S A),which is then strengthened by the coordination between Ca^(2+)and the carboxyl group(-COO^(-))of SA,resulting in a stable conductive network with ionic transport pathway.The consolidated binding relationship enables silicon-based anode material to possess high mechanical strength and strong deformation resistance,preventing the separation of silicon from CNTs network.Consequently,this silicon-based anode material demonstrates a discharge specific capacity of811 mAh·g^(-1)after 100 cycles at a current density of 1 A·g^(-1),and exhibits high rate performance,with a discharge specific capacity of 1612 mAh·g^(-1)at 2 A·g^(-1).展开更多
The pursuit of safer and high-performance lithium-ion batteries(LIBs)has triggered extensive research activities on solid-state batteries,while challenges related to the unstable electrode-electrolyte interface hinder...The pursuit of safer and high-performance lithium-ion batteries(LIBs)has triggered extensive research activities on solid-state batteries,while challenges related to the unstable electrode-electrolyte interface hinder their practical implementation.Polymer has been used extensively to improve the cathode-electrolyte interface in garnet-based all-solid-state LIBs(ASSLBs),while it introduces new concerns about thermal stability.In this study,we propose the incorporation of a multi-functional flame-retardant triphenyl phos-phate additive into poly(ethylene oxide),acting as a thin buffer layer between LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode and garnet electro-lyte.Through electrochemical stability tests,cycling performance evaluations,interfacial thermal stability analysis and flammability tests,improved thermal stability(capacity retention of 98.5%after 100 cycles at 60℃,and 89.6%after 50 cycles at 80℃)and safety characteristics(safe and stable cycling up to 100℃)are demonstrated.Based on various materials characterizations,the mechanism for the improved thermal stability of the interface is proposed.The results highlight the potential of multi-functional flame-retardant additives to address the challenges associated with the electrode-electrolyte interface in ASSLBs at high temperature.Efficient thermal modification in ASSLBs operating at elevated temperatures is also essential for enabling large-scale energy storage with safety being the primary concern.展开更多
All-solid-state lithium-sulfur batteries(ASSLSBs) have become one of the most potential candidates for the next-generation high-energy systems due to their intrinsic safety and high theoretical energy density.However,...All-solid-state lithium-sulfur batteries(ASSLSBs) have become one of the most potential candidates for the next-generation high-energy systems due to their intrinsic safety and high theoretical energy density.However, PEO-based ASSLSBs face the dilemma of insufficient Coulombic efficiency and long-term stability caused by the coupling problems of dendrite growth of anode and polysulfide shuttle of cathode. In this work, 1,3,5-trioxane(TOX) is used as a functional additive to design a PEO-based composite solidstate electrolyte(denoted as TOX-CSE), which realizes the stable long-term cycle of an ASSLSB. The results show that TOX can in-situ decompose on the anode to form a composite solid electrolyte interphase(SEI) layer with rich-organic component. It yields a high average modulus of 5.0 GPa, greatly improving the mechanical stability of the SEI layer and thus inhibiting the growth of dendrites. Also,the robust SEI layer can act as a barrier to block the side reaction between polysulfides and lithium metal.As a result, a Li-Li symmetric cell assembled with a TOX-CSE exhibits prolonged cycling stability over 2000 h at 0.2 m A cm^(-2). The ASSLSB also shows a stable cycling performance of 500 cycles at 0.5 C.This work reveals the structure–activity relationship between the mechanical property of interface layer and the battery's cycling stability.展开更多
Elevating the operating voltage is an effective approach to improve the reversible capacity of ultra-high nickel layered oxide cathode LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x≥0.8)and solve the"range anxiety"confusi...Elevating the operating voltage is an effective approach to improve the reversible capacity of ultra-high nickel layered oxide cathode LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x≥0.8)and solve the"range anxiety"confusion of electric vehicles.However,the undesirable surface reconstruction induced by the high cut-off voltage has a fatal impact on the thermodynamic stability of the material,inevitably leading to fast capacity degradation.Herein,a mechanical fusion aided by alcohol is suggested to create a stable olivine structure for the single-crystal(SC)ultrahigh-nickel cathode LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2).The addition of nanoparticles effectively bridges the void of SC-NCM,builds an ideal particle grading,and significantly raises the cost efficiency,as well as promotes the cycling stability and safety of the full cell.Remarkably,the layered/olivine mixture forms a perfect shield by lowering the surface area between the NCM cathode and electrolyte,hence mitigating side reactions and contributing to an incredibly thin and stable cathode/electrolyte interface.Furthermore,the thermodynamic stability of highly delithiated NCM is improved,as both the particle cracks and structural degradation are simultaneously postponed.Consequently,the maximum temperature of the single-crystal LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)@LiFePO_(4)‖graphite pouch full cell is dramatically reduced from 599.4 to 351.4℃,and the full cell achieves 88.2%capacity retention after 800 cycles,demonstrating excellent thermal stability and cycling stability.This facile strategy provides a feasible technical reference for further exploiting the ultrahigh-capacity,highsafety,and long-life Ni-rich cathode for commercial application of lithium-ion batteries(LIBs).展开更多
Li-air batteries have attracted widespread attention due to their high theoretical energy density.However,safety and environmental challenges are significant in Li-air batteries based on organic liquid electrolytes,as...Li-air batteries have attracted widespread attention due to their high theoretical energy density.However,safety and environmental challenges are significant in Li-air batteries based on organic liquid electrolytes,as they are exposed to air.In this study,we synthesized a composite electrolyte membrane filled with garnet material using a casting method and successfully applied it to Li-air batteries.The polymer electrolyte composed of poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)filled with garnet LLZTO as an active filler(15-PHL CPE),which exhibited excellent flexibility,wide electrochemical window,high ion conductivity and good thermal stability.Furthermore,symmetric Li‖15-PHL CPE‖Li cells stably operate over 3500h at 0.1 mA cm^(-2)and 25℃.The assembled 15-PHL CPE-based Li-air battery reaches a stable cycling performance of 97 cycles at 200 mA g^(-1)with a well-maintained potential gap of1.93 V,which demonstrates promising application in Li-air batteries.展开更多
Lithium-sulfur(Li-S)batteries with high energy density suffer from the soluble lithium polysulfide species,Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commo...Lithium-sulfur(Li-S)batteries with high energy density suffer from the soluble lithium polysulfide species,Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commonly have limited catalytic abilities to improve battery performance.Herein,based on the Hume-Rothery rule and solvothermal method,the high-entropy sulfide NiCoCuTiVS_(x)derived from Co_(9)S_(8)was designed and synthesized,to realize the combination of small local strain and excellent catalytic performance.With all five metal elements(Ni,Co,Cu,Ti,and V)capable of chemical interactions with soluble polysulfides,NiCoCuTiVS_(x)exhibited strong chemical confinement of polysulfides and promoted fast kinetics for polysulfides conversion.Consequently,the S/NiCoCuTiVS_(x)cathode can maintain a high discharge capacity of 968.9 mA h g^(-1)after 200 cycles at 0.5 C and its capacity retention is 1.3 times higher than that of S/Co_(9)S_(8).The improved cycle stability can be attributed to the synergistic effect originating from the multiple metal elements,coupled with the reduced nucleation and activation barriers of Li_(2)S.The present work opens a path to explore novel electrocatalyst materials based on high entropy materials for the achievement of advanced Li-S batteries.展开更多
Manganese dioxide(MnO_(2))electrode material possesses the advantages of high energy density,structural diversity and high modification potential.This allows it become one of the important cathodes for aqueous zinc io...Manganese dioxide(MnO_(2))electrode material possesses the advantages of high energy density,structural diversity and high modification potential.This allows it become one of the important cathodes for aqueous zinc ion battery.However,the applications are limited by the poor electrical conductivity,narrow layer spacing and the ease of dissolution.Herein,we prepare MnO_(2)-PVP@0.03GO composites by the co-modification of polyvinylpyrrolidone(PVP)pre-insertion layer and graphene oxide(GO)self-assembly layer.The Zn//MnO_(2)-PVP@0.03GO cells deliver a discharge specific capacity of 442 mAh/g at a current density of 0.2 A/g.It also maintains 100%capacity for 1000 times cycling at 1 A/g.The assembled soft package batteries demonstrate superior flexibility and adaptability under different bending conditions.展开更多
Ni-rich layered oxides are considered promising cathodes for advanced lithium-ion batteries(LIBs)in the future,owing to their high capacity and low cost.However,the issues on structural and interfacial stability of Ni...Ni-rich layered oxides are considered promising cathodes for advanced lithium-ion batteries(LIBs)in the future,owing to their high capacity and low cost.However,the issues on structural and interfacial stability of Ni-rich cathodes still pose substantial obstacles in the practical application of advanced LIBs.Here,we employ a one-step method to synthesize a B-doped and La_(4)NiLiO_(8)-coated LiNi_(0.82)5Co_(0.115)Mn_(0.06)O_(2)(BL-1)cathode with reliable structure and interface,for the first time.The La_(4)NiLiO_(8)coating layer can prevent cathodes from electrolyte assault and facilitate Li+diffusion kinetics.Moreover,B-doping can effectively restrain the pernicious H_(2)-H_(3) phase transition and adjust the orientation of primary particles to a radial alignment,which is obstructive to the arise of microcracks induced by the change of anisotropic volume.Specifically,when tested in pouch cells,the BL-1 cathode exhibits outstanding capacity retention of 93.49%after 500 cycles at 1 C.This dual-modification strategy dramatically enhances the stability of the structure and interface for Ni-rich cathode materials,consequently accelerating the commercialization process of high-energy–density LIBs.展开更多
Aiming at the improvement of the cyclic stability of La-Mg-Ni system （PuNi3-type） hydrogen storage alloy, Ni in the alloy was partly substituted by Fe. The electrode alloys of La0.7Mg0.3Co0.45Ni255-xFex （x=0, 0.1, ...Aiming at the improvement of the cyclic stability of La-Mg-Ni system （PuNi3-type） hydrogen storage alloy, Ni in the alloy was partly substituted by Fe. The electrode alloys of La0.7Mg0.3Co0.45Ni255-xFex （x=0, 0.1, 0.2, 0.3, 0.4） were prepared by casting and rapid quenching. The influence of the quenching on cyclic stability as well as structure of the alloys was investigated in detail. The results of electrochemical measurement indicated that rapid quenching significantly improved cyclic stability. When the quenching rate rose from 0 （As-cast was defined as a quenching rate of 0 m/s） to 30 m/s, the cyclic life of Fe-free alloy （x=-0） increased from 81 to 105 cycles, and for alloy containing Fe（x=0.4）, it grew from 106 to 166 cycles at a current density of 600 mA/g. The results obtained by XRD, TEM and SEM revealed that the as-cast and quenched alloys had multiphase structures, including two major phases （La, Mg）Ni3 and LaNi5 as well as an imptLrity phase LaNi2. Rapid quenching helped the formation of an amorphous-like structure in Fe containing alloys.展开更多
A series of layered LiNi0.8?xCo0.1Mn0.1LaxO2(x=0,0.01,0.03)cathode materials were synthesized by combining co-precipitation and high temperature solid state reaction to investigate the effect of La-doping on LiNi0.8Co...A series of layered LiNi0.8?xCo0.1Mn0.1LaxO2(x=0,0.01,0.03)cathode materials were synthesized by combining co-precipitation and high temperature solid state reaction to investigate the effect of La-doping on LiNi0.8Co0.1Mn0.1O2.A new phase La2Li0.5Co0.5O4was observed by XRD,and the content of the new phase could be determined by Retiveld refinement and calculation.The cycle stability of the material is obviously increased from74.3%to95.2%after La-doping,while the initial capacity exhibits a decline trend from202mA·h/g to192mA·h/g.The enhanced cycle stability comes from both of the decrease of impurity and the protection of newly formed La2Li0.5Co0.5O4,which prevents the electrolytic corrosion to the active material.The CV measurement confirms that La-doped material exhibits better reversibility compared with the pristine material.展开更多
Cycle stability and thermal safety are critical to the commercialization of nickel-rich layered materials,yet whether there is a potential correlation between these two factors is still controversial. Herein, the rela...Cycle stability and thermal safety are critical to the commercialization of nickel-rich layered materials,yet whether there is a potential correlation between these two factors is still controversial. Herein, the relationship between the cycle stability and thermal stability of nickel-rich cathode materials have been systematically studied through five different calcination temperatures of Li[NiCoMn]O(NCM83) cathode materials. The research results confirm that the cycle stability and thermal safety of nickel-rich cathode materials do not necessarily show a positive correlation. Actually, with the calcination temperature elevated, the thermal stability of the NCM83 is enhanced, while the cycle stability is degraded. This opposite correlation is not commonly reported in previous literatures. In this work, systematical characterizations demonstrate that under the experimental conditions, the capacity retention of NCM83 is mainly determined by the Li/Ni cation disorder and H2-H3 irreversible phase transition,which is optimal at lower calcination temperature. Meanwhile, the thermal stability is mainly impacted by thermal expansion characteristics and interfacial stability of cathode material, and it is dramatically improved by the mechanical strength of the secondary particles reinforced at high calcinated temperature. This study provides some new insights on understanding and designing of the high-energy cathode materials with long cycle-life and superior safety.展开更多
基金support from the National Natural Science Foundation of China(No.22308378,22308380,22393963)the Science Foundation of China University of Petroleum,Beijing(No.2462023XKBH005,ZX20230078).
文摘Iron-chromium flow batteries(ICRFBs)have emerged as an ideal large-scale energy storage device with broad application prospects in recent years.Enhancement of the Cr^(3+)/Cr^(2+)redox reaction activity and inhibition of the hydrogen evolution side reaction(HER)are essential for the development of ICRFBs and require a novel catalyst design.However,elucidating the underlying mechanisms for modulating catalyst behaviors remains an unresolved challenge.Here,we show a novel precisely controlled preparation of a novel thermal-treated carbon cloth electrode with a uniform deposit of low-cost indium catalyst particles.The density functional theory analysis reveals the In catalyst has a significant adsorption effect on the reactants and improves the redox reaction activity of Cr^(3+)/Cr^(2+).Moreover,H+is more easily absorbed on the surface of the catalyst with a high migration energy barrier,thereby inhibiting the occurrence of HER.The assembled ICRFBs have an average energy efficiency of 83.91%at 140 mA cm^(-2),and this method minimizes the electrodeposition process and cleans the last obstacle for industry long cycle operation requirements.The ICRFBs exhibit exceptional long-term stability with an energy efficiency decay rate of 0.011%per cycle at 1000 cycles,the lowest ICRFBs reported so far.Therefore,this study provides a promising strategy for developing ICRFBs with low costs and long cycle life.
基金supported by the National Natural Science Foundation of China(21203008,21975025,12274025,22372008,and 22179007)Hainan Province Science and Technology Special Fund(ZDYF2021SHFZ232 and ZDYF2023GXJS022)Hainan Province Postdoctoral Science Foundation(300333)。
文摘To satisfy the demands of modern society for high-energy–density sulfide-based all-solid-state lithium batteries(ASSLBs),Ni-rich cathode materials have gained much attention for their high capacity and energy density.However,their practical deployment is hindered by accelerated interface degradation and capacity decay originating from surface oxygen release and lattice oxygen activation during prolonged cycling.In this study,Ti_(x)NbB_((1−x))C_(2)was successfully coated on the surface of LiNi_(0.94)Co_(0.05)Mn_(0.01)O_(2).Density functional theory(DFT)calculations first elucidate a“point-to-point”anchoring mechanism where each surface oxygen atom coordinates with single species(Ti/Nb/B)offered by Ti_(x)NbB_((1−x))C_(2),which forms robust O–M bonds and sustain a stable interface structure.The electron energy loss spectroscopy(EELS)reveals the segregation of Ti/Nb toward subsurface layers during cycling,creating an optimized lattice oxygen coordination environment and suppressing oxygen activation.The dual oxygen stabilization mechanism dramatically improves the reversibility of phase transition and the structural stability of the Ni-rich cathode materials.Moreover,Ti_(x)NbB_((1−x))C_(2)as the protective layer decreases mechanical strain and suppresses the parasitic reactions.Consequently,the engineered cathode delivers 91%capacity retention after 1000 cycles at 0.3 C,suggesting excellent cycling stability.The research delivers a new design philosophy for the coating layer that can stabilize surface oxygen.Furthermore,the atomistic understanding of the structure–property relationship of the Ni-rich cathode materials provides valuable guidance for the future design of new cathode materials with superior structural stability in ASSLBs.
基金financially supported by the National Natural Science Foundation of China(Nos.52301248,52271166,52071071,and 52275567)the Foundational Research Project of Shanxi Province,China(Nos.202203021222201 and 202203021212304)+1 种基金PhD Research Startup Foundation of Taiyuan University of Science and Technology(No.20222057)PhD Research Startup Foundation of Shanxi Province,China(No.20232051)。
文摘Hexagonal MnMX-based(M=Co or Ni,X=Si or Ge)alloys exhibit giant reversible barocaloric effects.However,giant volume expansion would result in the as-cast MnMX ingots fragmenting into powders,and inevitably bring the deterioration of mechanical properties and formability.Grain fragmentation can bring degradation of structural transformation entropy change during cyclic application and removal of pressure.In this paper,giant reversible barocaloric effects with high thermal cycle stability can be achieved in the epoxy bonded(MnCoGe)0.96(CuCoSn)0.04 composite.Giant reversible isothermal entropy change of 43.0 J·kg^(−1)·K^(−1) and adiabatic temperature change from barocaloric effects(ΔT_(BCE))of 15.6 K can be obtained within a wide temperature span of 30 K at 360 MPa,which is mainly attributed to the integration of the change in the transition temperature driven by pressure of−101 K·GPa^(−1) and suitable thermal hysteresis of 11.1 K.Further,the variation of reversibleΔ_(TBCE) against the applied hydrostatic pressure reaches up to 43 K·GPa^(−1),which is at the highest level among the other reported giant barocaloric compounds.More importantly,after 60 thermal cycles,the composite does not break and the calorimetric curves coincide well,demonstrating good thermal cycle stability.
基金This work was financially supported by National Natural Science Foundations of China (No.50131040)Key Technologies R & D Program of Inner Mongolia (No.20050205)College Scientific Research Project of Inner Mongolia (No.NJ05064).
文摘In order to improve the cycle stability of La-Mg-Ni-Co type alloy electrode, rapid quenching technology was employed. The effects of rapid quenching on the microstructure and cycle stability of the alloy were investigated. The obtained results show that the La2Mg(Ni0.85Co0.15)9M0.1 (M=B, Cr) alloy electrodes are composed of (La, Mg)Ni3 phase, LaNi5 phase and a small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast MB alloy, and the Ni2B phase in the alloy nearly disappears after rapid quenching. Rapid quenching technology can slightly improve the cycling life of the alloy. When the quenching rate increases from 0 m·s-1 (As-cast is defined as quenching rate of 0 m·s-1) to 30 m·s-1, the cycle lives of the MB, MCr alloys enhance from 86 and 87 cycles to 106 and 119 cycles, respectively. On the other hand, the average capacity decay rates of the MB, MCr alloys decrease from 1.7172 and 1.7178 mAh·g-1·cycle-1 to 1.5751 and 1.3060 mAh·g-1·cycle-1 after 86 charge-discharges cycling, respectively.
基金supported by the National Natural Science Foundation of China(Nos.52374299,52304320 and 52204306)Outstanding Youth Foundation of Hunan Province(No.2023JJ10044)+1 种基金Key Project of Hunan Provincial Department of Education(No.22A0211)Natural Science Foundation of Hunan Province(No.2023JJ40014)。
文摘High-capacity Ni-rich layered cathodes LiNi_(x)CoyMn_(1-x-y)O_(2)(NCM)have been widely recognized as highly promising candidates for lithium-ion batteries(LIBs).However,NCM cathodes are suffered from sluggish Li-ion kinetics and fast capacity decay.Herein,the Nb/Ti co-doping strategy has been proposed by formation energy analysis to enhance the mechanical and chemical integrities of NCM cathode.Nb/Ti co-doping facilitates Li-ion transport of NCM cathode for boosting the rate ability.Furthermore,the structure stability is prominently improved for the stronger Nb–O and Ti–O bonds,resulting from the suppressed sharp contraction of c axis,inhibited microcracks formation,and alleviated electrolyte corrosion.Inspired by the synergistic effect of Nb/Ti co-doping,the modified NCM exhibits superior comprehensive electrochemical performances.The Nb/Ti co-doping NCM exhibits an increased discharge capacity of 144.3 m Ah/g at10 C and an outstanding capacity retention remained 92.7%after 300 cycles at 1 C.This work offers a promising approach to developing high-performance cathode materials.
基金supported by National Natural Science Foundation of China(22209064,52071171,and 52202248)the Fundamental Research Funds for Public Universities in Liaoning(LJKLJ202434)+6 种基金the Australian Research Council(ARC)through Future Fellowship(FT210100298)Discovery Project(DP220100603)Linkage Project(LP210200504,LP220100088,LP230200897)Industrial Transformation Research Hub(IH240100009)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077)the Australian Renewable Energy Agency(ARENA)as part of ARENA’s Transformative Research Accelerating Commercialisation Program(TM021)European Commission’s Australia-Spain Network for Innovation and Research Excellence(AuSpire)。
文摘Rechargeable aqueous Zn-MoO_(x)batteries are promising energy storage devices with high theoretical specific capacity and low cost.However,MoO_(3)cathodes suffer drastic capacity decay during the initial discharging/charging process in conventional electrolytes,resulting in a short cycle life and challenging the development of Zn-MoO_(x)batteries.Here we comprehensively investigate the dissolution mechanism of MoO_(3)cathodes and innovatively introduce a polymer to inhibit the irreversible processes.Our findings reveal that this capacity decay originates from the irreversible Zn^(2+)/H^(+)co-intercalation/extraction process in aqueous electrolytes.Even worse,during Zn^(2+)intercalation,the formed Zn_(x)MoO_(3-x)intermediate phase with lower valence states(Mo^(5+)/Mo^(4+))experiences severe dissolution in aqueous environments.To address these challenges,we developed a first instance of coating a polyaniline(PANI)shell around the MoO_(3)nanorod effectively inhibiting these irreversible processes and protecting structural integrity during long-term cycling.Detailed structural analysis and theoretical calculations indicate that=N-groups in PANI@MoO_(3-x)simultaneously weaken H+adsorption and enhance Zn^(2+)adsorption,which endowed the PANI@MoO_(3-x)cathode with reversible Zn^(2+)/H^(+)intercalation/extraction.Consequently,the obtained PANI@MoO_(3-x)cathode delivers an excellent discharge capacity of 316.86 mA h g^(-1)at 0.1 A g^(-1)and prolonged cycling stability of 75.49%capacity retention after 1000 cycles at 5 A g^(-1).This work addresses the critical issues associated with MoO_(3)cathodes and significantly advances the understanding of competitive multi-ion energy storage mechanisms in aqueous Zn-MoO_(3)batteries.
文摘In the original publication,incorrect version of Corresponding authors has been published.You-Yuan Huang and Bo Wang should be corresponding authors.The corrected Correspondingg authors are provided in this correction.
基金financially supported by the Scientific and Technological Plan Project of Guizhou Province ([2024]054)Additional support came from the Industry and Education Combination Innovation Platform of Intelligent Manufacturing and Graduate Joint Training Base at Guizhou University (2020-520000-83-01324061)the Guizhou Engineering Research Center for Smart Services (2203-520102-04-04-298868)。
文摘Aqueous sodium-ion batteries(ASIBs) offer significant advantages for energy storage on a large scale,attributed to their economical cost,secure operatio n,and eco-friend ly natu re.Among the leading cathode materials for ASIBs,Na_(3)V_(2)(PO_(4))_(3)(NVP) exhibits excellent structural stability and a high Na+diffusion coefficient,making it a promising option.However,the high solubility of vanadium-based materials in aqueous electrolytes engenders suboptimal cycling stability for Na_(3)V_(2)(PO_(4))_(3),constraining its application in ASIBs.Herein,the Cr-substituted Na_(3)V_(1.3)Cr_(0.7)(PO_(4))3@C(NV_(1.3)Cr_(0.7)P) cathode material was synthesized via a simple sol-gel method.It is found that Cr substitution reduces the cell parameters of NV_(1.3)Cr_(0.7)P,effectively reinforcing the crystal structure.Furthermore,NV_(1.3)Cr_(0.7)P alters the Na^(+)insertion/extraction mechanism,transforming the typical two-phase reaction between Na_(1)V_(2)(PO_(4))_(3)and Na_(3)V_(2)(PO_(4))3into continuous solid-solution reactions with stable intermediates.The Cr substitution diminishes the sodium-ion diffusion energy barrier in NV_(1.3)Cr_(0.7)P,leading to smoother Na+insertion and extraction processes.Consequently,NV_(1.3)Cr_(0.7)P exhibits impressive cycling stability,retaining 74.8% of its capacity after 5,000 cycles at a current density of 5 A g^(-1),along with an outstanding rate performance of 79,2% at 10 A g^(-1).This work elucidates the stable Na^(+)insertion/extraction processes in Cr-substituted NV_(1.3)Cr_(0.7)P,offering insights into the application of vanadium-based materials in aqueous sodium-ion batteries.
基金supported by the Natural Science Foundation of Jiangxi Province(Grant Nos.20224BAB214006,20224BAB214029,and 20212ACB203004)the Planning Project of Jiangxi Provincial Technological Innovation Guidance(Grant No.20202BDH80003)the Youth Foundation of Jiangxi Provincial Department of Education(Grant Nos.GJJ210857 and GJJ210856).
文摘Exploring cathode materials that combine excellent cycling stability and high energy density poses a challenge to aqueous Zn-ion hybrid supercapacitors(ZHSCs).Herein,polyaniline(PANI)coated boron-carbon-nitrogen(BCN)nanoarray on carbon cloth surface is prepared as advanced cathode materials via simple high-temperature calcination and electrochemical deposition methods.Because of the excellent specific capacity and conductivity of PANI,the CC@BCN@PANI core-shell nanoarrays cathode shows an excellent ion storage capability.Moreover,the 3D nanoarray structure can provide enough space for the volume expansion and contraction of PANI in the charging/discharging cycles,which effectively avoids the collapse of the microstructure and greatly improves the electrochemical stability of PANI.Therefore,the CC@BCN@PANI-based ZHSCs exhibit superior electrochemical performances showing a specific capacity of 145.8 mAh/g,a high energy density of 116.78 Wh/kg,an excellent power density of 12 kW/kg,and a capacity retention rate of 86.2%after 8000 charge/discharge cycles at a current density of 2 A/g.In addition,the flexible ZHSCs(FZHSCs)also show a capacity retention rate of 87.7%at the current density of 2 A/g after 450 cycles.
基金financially supported by Ningbo S&T Innovation 2025 Major Special Program(No.2022Z022)the National Natural Science Foundation of China(No.22309195)Ningbo Natural Science Foundation(No.2023J348)。
文摘The severe volumetric expansion and poor conductivity of silicon when used as anode in lithium-ion batteries present challenges in maintaining the stability of electrochemical performance.Herein,the binding between silicon nanoparticles and carbon nanotubes(CNTs)is achieved by the utilization of sodium alginate(S A),which is then strengthened by the coordination between Ca^(2+)and the carboxyl group(-COO^(-))of SA,resulting in a stable conductive network with ionic transport pathway.The consolidated binding relationship enables silicon-based anode material to possess high mechanical strength and strong deformation resistance,preventing the separation of silicon from CNTs network.Consequently,this silicon-based anode material demonstrates a discharge specific capacity of811 mAh·g^(-1)after 100 cycles at a current density of 1 A·g^(-1),and exhibits high rate performance,with a discharge specific capacity of 1612 mAh·g^(-1)at 2 A·g^(-1).
基金This work was supported by the Australian Research Council via Discovery Projects(Nos.DP200103315,DP200103332 and DP230100685)Linkage Projects(No.LP220200920).The authors acknowledge the Microscopy and Microanalysis Facility—John de Laeter Centre,Curtin University for the scientific and technical assistance of material characterizations.L.Zhao and C.Cao would like to acknowledge the PhD scholarship supported by BLACKSTONE Minerals Ltd.
文摘The pursuit of safer and high-performance lithium-ion batteries(LIBs)has triggered extensive research activities on solid-state batteries,while challenges related to the unstable electrode-electrolyte interface hinder their practical implementation.Polymer has been used extensively to improve the cathode-electrolyte interface in garnet-based all-solid-state LIBs(ASSLBs),while it introduces new concerns about thermal stability.In this study,we propose the incorporation of a multi-functional flame-retardant triphenyl phos-phate additive into poly(ethylene oxide),acting as a thin buffer layer between LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode and garnet electro-lyte.Through electrochemical stability tests,cycling performance evaluations,interfacial thermal stability analysis and flammability tests,improved thermal stability(capacity retention of 98.5%after 100 cycles at 60℃,and 89.6%after 50 cycles at 80℃)and safety characteristics(safe and stable cycling up to 100℃)are demonstrated.Based on various materials characterizations,the mechanism for the improved thermal stability of the interface is proposed.The results highlight the potential of multi-functional flame-retardant additives to address the challenges associated with the electrode-electrolyte interface in ASSLBs at high temperature.Efficient thermal modification in ASSLBs operating at elevated temperatures is also essential for enabling large-scale energy storage with safety being the primary concern.
基金National Natural Science Foundation of China (Grant Nos. 22178125 and 21875071)。
文摘All-solid-state lithium-sulfur batteries(ASSLSBs) have become one of the most potential candidates for the next-generation high-energy systems due to their intrinsic safety and high theoretical energy density.However, PEO-based ASSLSBs face the dilemma of insufficient Coulombic efficiency and long-term stability caused by the coupling problems of dendrite growth of anode and polysulfide shuttle of cathode. In this work, 1,3,5-trioxane(TOX) is used as a functional additive to design a PEO-based composite solidstate electrolyte(denoted as TOX-CSE), which realizes the stable long-term cycle of an ASSLSB. The results show that TOX can in-situ decompose on the anode to form a composite solid electrolyte interphase(SEI) layer with rich-organic component. It yields a high average modulus of 5.0 GPa, greatly improving the mechanical stability of the SEI layer and thus inhibiting the growth of dendrites. Also,the robust SEI layer can act as a barrier to block the side reaction between polysulfides and lithium metal.As a result, a Li-Li symmetric cell assembled with a TOX-CSE exhibits prolonged cycling stability over 2000 h at 0.2 m A cm^(-2). The ASSLSB also shows a stable cycling performance of 500 cycles at 0.5 C.This work reveals the structure–activity relationship between the mechanical property of interface layer and the battery's cycling stability.
基金the support from the Natural Science Foundation of Hunan Province,China(2024JJ7301)the science and technology innovation Program of Hunan Province(2024JK2097)+5 种基金the Project of the Scientific Research Fund of Hunan Provincial Education Department(No.22C0383)Changde Scientific and Technological Innovation Plan(CDKJJ20220517)Start-up Foundation for Doctors of Hunan University of Arts and Science(No.22BSQD22,21BSQD14 and 21BSQD15)Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Provincepartially supported by the Research Grants Council of the Hong Kong Special Administrative Region,China(PolyU152178/20E)the Innovation and Technology Commission of Hong Kong(MHP/080/22)。
文摘Elevating the operating voltage is an effective approach to improve the reversible capacity of ultra-high nickel layered oxide cathode LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x≥0.8)and solve the"range anxiety"confusion of electric vehicles.However,the undesirable surface reconstruction induced by the high cut-off voltage has a fatal impact on the thermodynamic stability of the material,inevitably leading to fast capacity degradation.Herein,a mechanical fusion aided by alcohol is suggested to create a stable olivine structure for the single-crystal(SC)ultrahigh-nickel cathode LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2).The addition of nanoparticles effectively bridges the void of SC-NCM,builds an ideal particle grading,and significantly raises the cost efficiency,as well as promotes the cycling stability and safety of the full cell.Remarkably,the layered/olivine mixture forms a perfect shield by lowering the surface area between the NCM cathode and electrolyte,hence mitigating side reactions and contributing to an incredibly thin and stable cathode/electrolyte interface.Furthermore,the thermodynamic stability of highly delithiated NCM is improved,as both the particle cracks and structural degradation are simultaneously postponed.Consequently,the maximum temperature of the single-crystal LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)@LiFePO_(4)‖graphite pouch full cell is dramatically reduced from 599.4 to 351.4℃,and the full cell achieves 88.2%capacity retention after 800 cycles,demonstrating excellent thermal stability and cycling stability.This facile strategy provides a feasible technical reference for further exploiting the ultrahigh-capacity,highsafety,and long-life Ni-rich cathode for commercial application of lithium-ion batteries(LIBs).
基金supported by the National Natural Science Foundation of China(U2330124,22411560292,U20A2072,52072352,21875226)the Foundation for the Youth S&T Innovation Team of Sichuan Province(2020JDTD0035)Sichuan Science and Technology Program(2023ZYD0026)。
文摘Li-air batteries have attracted widespread attention due to their high theoretical energy density.However,safety and environmental challenges are significant in Li-air batteries based on organic liquid electrolytes,as they are exposed to air.In this study,we synthesized a composite electrolyte membrane filled with garnet material using a casting method and successfully applied it to Li-air batteries.The polymer electrolyte composed of poly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)filled with garnet LLZTO as an active filler(15-PHL CPE),which exhibited excellent flexibility,wide electrochemical window,high ion conductivity and good thermal stability.Furthermore,symmetric Li‖15-PHL CPE‖Li cells stably operate over 3500h at 0.1 mA cm^(-2)and 25℃.The assembled 15-PHL CPE-based Li-air battery reaches a stable cycling performance of 97 cycles at 200 mA g^(-1)with a well-maintained potential gap of1.93 V,which demonstrates promising application in Li-air batteries.
基金financially supported by the National Natural Science Foundation of China(U22A20113,52261135543)。
文摘Lithium-sulfur(Li-S)batteries with high energy density suffer from the soluble lithium polysulfide species,Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commonly have limited catalytic abilities to improve battery performance.Herein,based on the Hume-Rothery rule and solvothermal method,the high-entropy sulfide NiCoCuTiVS_(x)derived from Co_(9)S_(8)was designed and synthesized,to realize the combination of small local strain and excellent catalytic performance.With all five metal elements(Ni,Co,Cu,Ti,and V)capable of chemical interactions with soluble polysulfides,NiCoCuTiVS_(x)exhibited strong chemical confinement of polysulfides and promoted fast kinetics for polysulfides conversion.Consequently,the S/NiCoCuTiVS_(x)cathode can maintain a high discharge capacity of 968.9 mA h g^(-1)after 200 cycles at 0.5 C and its capacity retention is 1.3 times higher than that of S/Co_(9)S_(8).The improved cycle stability can be attributed to the synergistic effect originating from the multiple metal elements,coupled with the reduced nucleation and activation barriers of Li_(2)S.The present work opens a path to explore novel electrocatalyst materials based on high entropy materials for the achievement of advanced Li-S batteries.
基金supported by National Natural Science Foundation of China(No.52172218).
文摘Manganese dioxide(MnO_(2))electrode material possesses the advantages of high energy density,structural diversity and high modification potential.This allows it become one of the important cathodes for aqueous zinc ion battery.However,the applications are limited by the poor electrical conductivity,narrow layer spacing and the ease of dissolution.Herein,we prepare MnO_(2)-PVP@0.03GO composites by the co-modification of polyvinylpyrrolidone(PVP)pre-insertion layer and graphene oxide(GO)self-assembly layer.The Zn//MnO_(2)-PVP@0.03GO cells deliver a discharge specific capacity of 442 mAh/g at a current density of 0.2 A/g.It also maintains 100%capacity for 1000 times cycling at 1 A/g.The assembled soft package batteries demonstrate superior flexibility and adaptability under different bending conditions.
基金financially supported by the National Natural Science Foundation of China(51774051,52072323,52122211)the Science and Technology Planning Project of Hunan Province(2019RS2034)+1 种基金the Hunan High-tech Industry Science and Technology Innovation Leading Plan(2020GK2072)the Changsha City Fund for Distinguished and Innovative Young Scholars(KQ1707014)。
文摘Ni-rich layered oxides are considered promising cathodes for advanced lithium-ion batteries(LIBs)in the future,owing to their high capacity and low cost.However,the issues on structural and interfacial stability of Ni-rich cathodes still pose substantial obstacles in the practical application of advanced LIBs.Here,we employ a one-step method to synthesize a B-doped and La_(4)NiLiO_(8)-coated LiNi_(0.82)5Co_(0.115)Mn_(0.06)O_(2)(BL-1)cathode with reliable structure and interface,for the first time.The La_(4)NiLiO_(8)coating layer can prevent cathodes from electrolyte assault and facilitate Li+diffusion kinetics.Moreover,B-doping can effectively restrain the pernicious H_(2)-H_(3) phase transition and adjust the orientation of primary particles to a radial alignment,which is obstructive to the arise of microcracks induced by the change of anisotropic volume.Specifically,when tested in pouch cells,the BL-1 cathode exhibits outstanding capacity retention of 93.49%after 500 cycles at 1 C.This dual-modification strategy dramatically enhances the stability of the structure and interface for Ni-rich cathode materials,consequently accelerating the commercialization process of high-energy–density LIBs.
基金863 Program (2006AA05Z132)the National Natural Science Foundation of China (50642033)+1 种基金Natural Science Founda-tion of Inner Mongolia, China (200711020703)Science and Technology Planned Project of Inner Mongolia, China (20050205)
文摘Aiming at the improvement of the cyclic stability of La-Mg-Ni system （PuNi3-type） hydrogen storage alloy, Ni in the alloy was partly substituted by Fe. The electrode alloys of La0.7Mg0.3Co0.45Ni255-xFex （x=0, 0.1, 0.2, 0.3, 0.4） were prepared by casting and rapid quenching. The influence of the quenching on cyclic stability as well as structure of the alloys was investigated in detail. The results of electrochemical measurement indicated that rapid quenching significantly improved cyclic stability. When the quenching rate rose from 0 （As-cast was defined as a quenching rate of 0 m/s） to 30 m/s, the cyclic life of Fe-free alloy （x=-0） increased from 81 to 105 cycles, and for alloy containing Fe（x=0.4）, it grew from 106 to 166 cycles at a current density of 600 mA/g. The results obtained by XRD, TEM and SEM revealed that the as-cast and quenched alloys had multiphase structures, including two major phases （La, Mg）Ni3 and LaNi5 as well as an imptLrity phase LaNi2. Rapid quenching helped the formation of an amorphous-like structure in Fe containing alloys.
基金Project(2014CB643406)supported by the National Basic Research Program of China
文摘A series of layered LiNi0.8?xCo0.1Mn0.1LaxO2(x=0,0.01,0.03)cathode materials were synthesized by combining co-precipitation and high temperature solid state reaction to investigate the effect of La-doping on LiNi0.8Co0.1Mn0.1O2.A new phase La2Li0.5Co0.5O4was observed by XRD,and the content of the new phase could be determined by Retiveld refinement and calculation.The cycle stability of the material is obviously increased from74.3%to95.2%after La-doping,while the initial capacity exhibits a decline trend from202mA·h/g to192mA·h/g.The enhanced cycle stability comes from both of the decrease of impurity and the protection of newly formed La2Li0.5Co0.5O4,which prevents the electrolytic corrosion to the active material.The CV measurement confirms that La-doped material exhibits better reversibility compared with the pristine material.
基金financially supported by the China Postdoctoral Science Foundation(2021M700396)the National Natural Science Foundation of China(52102206)the National Research Foundation of Republic of Korea(2021K2A9A2A06044652)。
文摘Cycle stability and thermal safety are critical to the commercialization of nickel-rich layered materials,yet whether there is a potential correlation between these two factors is still controversial. Herein, the relationship between the cycle stability and thermal stability of nickel-rich cathode materials have been systematically studied through five different calcination temperatures of Li[NiCoMn]O(NCM83) cathode materials. The research results confirm that the cycle stability and thermal safety of nickel-rich cathode materials do not necessarily show a positive correlation. Actually, with the calcination temperature elevated, the thermal stability of the NCM83 is enhanced, while the cycle stability is degraded. This opposite correlation is not commonly reported in previous literatures. In this work, systematical characterizations demonstrate that under the experimental conditions, the capacity retention of NCM83 is mainly determined by the Li/Ni cation disorder and H2-H3 irreversible phase transition,which is optimal at lower calcination temperature. Meanwhile, the thermal stability is mainly impacted by thermal expansion characteristics and interfacial stability of cathode material, and it is dramatically improved by the mechanical strength of the secondary particles reinforced at high calcinated temperature. This study provides some new insights on understanding and designing of the high-energy cathode materials with long cycle-life and superior safety.
