Metal-nitrogen-carbon(M-N-C)single-atom catalysts exhibit desirable electrochemical catalytic properties.However,the replacement of N atoms by heteroatoms(B,P,S,etc.)has been regarded as a useful method for regulating...Metal-nitrogen-carbon(M-N-C)single-atom catalysts exhibit desirable electrochemical catalytic properties.However,the replacement of N atoms by heteroatoms(B,P,S,etc.)has been regarded as a useful method for regulating the coordination environment.The structure engineered M-N-C sites via doping heteroatoms play an important role to the adsorption and activation of the oxygen intermediate.Herein,we develop an efficient strategy to construct dual atomic site catalysts via the formation of a Co_(1)-PN and Ni1-PN planar configuration.The developed Co_(1)-PNC/Ni1-PNC catalyst exhibits excellent bifunctional electrocatalytic performance in alkaline solution.Both experimental and theoretical results demonstrated that the N/P coordinated Co/Ni sites moderately reduced the binding interaction of oxygen intermediates.The Co_(1)-PNC/Ni1-PNC endows a rechargeable Zn-air battery with excellent power density and cycling stability as an air-cathode,which is superior to that of the benchmark Pt/C+IrO_(2).This work paves an avenue for design of dual single-atomic sites and regulation of the atomic configuration on carbon-based materials to achieve high-performance electrocatalysts.展开更多
Solid electrolytes with desirable properties such as high ionic conductivity,wide electrochemical stable window,and suitable mechanical strength,and stable electrode-electrolyte interfaces on both cathode and anode si...Solid electrolytes with desirable properties such as high ionic conductivity,wide electrochemical stable window,and suitable mechanical strength,and stable electrode-electrolyte interfaces on both cathode and anode side are essential for high-voltage all-solid-state lithium batteries(ASSLBs)to achieve excellent cycle stability.In this work,a novel strategy of using LiF and LiNO_(3) as synergistic additives to boost the performance of PEO-PVDF/LLZTO-based composite solid electrolytes(CSEs)is developed,which also promotes the assembled high-voltage ASSLBs with dual-interfaces stability characteristic.Specifically,LiF as an inactive additive can increase the electrochemical stability of the CSE under high cut-off voltage,and improve the high-voltage compatibility between cathode and CSE,thus leading to a stable cathode/CSE interface.LiNO_(3) as an active additive can lead to an enhanced ionic conductivity of CSE due to the increased free-mobile Li+and ensure a stable CSE/Li interface by forming stable solid electrolyte interphase(SEI)on Li anode surface.Benefiting from the improved performance of CSE and stable dualinterfaces,the assembled NCM622/9[PEO_(15)-LiTFSI]-PVDF-15 LLZTO-2 LiF-3 LiNO_(3)/Li cell delivers a high rate capacity of 102.1 mAh g^(-1) at 1.0 C and a high capacity retention of 77.4%after 200 cycles at 0.5 C,which are much higher than those of the ASSLB assembled with additive-free CSE,with only 60.0 mAh g^(-1) and 52.0%,respectively.Furthermore,novel cycle test modes of resting for 5 h at different charge states after every 5 cycles are designed to investigate the high-voltage compatibility between cathode and CSE,and the results suggest that LiF additive can actually improve the high-voltage compatibility of cathode and CSE.All the obtained results confirm that the strategy of using synergistic additives in CSE is an effective way to achieve high-voltage ASSLBs with dual-interfaces stability.展开更多
Dual-ion battery(DIB) composed of graphite cathode and lithium anode is regarded as an advanced secondary battery because of the low cost, high working voltage and environmental friendliness. However,DIB operated at h...Dual-ion battery(DIB) composed of graphite cathode and lithium anode is regarded as an advanced secondary battery because of the low cost, high working voltage and environmental friendliness. However,DIB operated at high potential(usually ≥ 4.5 V versus Li+/Li) is confronted with severe challenges including electrolyte decomposition on cathode interface, and structural deterioration of graphite accompanying with anions de-/intercalation, hinder its cyclic life. To address those drawbacks and preserve the DIB virtues, a feasible and scalable surface modification is achieved for the commercial graphite cathode of mesocarbon microbead. In/ex-situ studies reveal that, such an interfacial engineering facilitates and reconstructs the formation of chemically stable cathode electrolyte interphase with better flexibility alleviating the decomposition of electrolyte, regulating the anions de-/intercalation behavior in graphite with the retainment of structural integrity and without exerting considerable influence on kinetics of anions diffusion. As a result, the modified mesocarbon microbead exhibits a much-extended cycle life with high capacity retention of 82.3% even after 1000 cycles. This study demonstrates that the interface modification of electrode and coating skeleton play important roles on DIB performance improvement, providing the feasible basis for practical application of DIB owing to the green and scalable coating procedures.展开更多
The key to realize long-life high energy density lithium batteries is to exploit functional electrolytes capable of stabilizing both high voltage cathode and lithium anode.The emergence of localized high-concentration...The key to realize long-life high energy density lithium batteries is to exploit functional electrolytes capable of stabilizing both high voltage cathode and lithium anode.The emergence of localized high-concentration electrolytes(LHCEs)shows great promise for ameliorating the above-mentioned interfacial issues.In this work,a lithium difluoro(oxalate)borate(LiDFOB)based nonflammable dual-anion LHCE is designed and prepared.Dissolving in the mixture of trimethyl phosphate(TMP)/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)),the continuously consumption of LiDFOB is suppressed by simply introducing lithium nitrate(LiNO_(3)).Meantime,as most of the TMP molecular are coordinated with Li^(+),the electrolyte does not show incompatibility issue between neither metal lithium nor graphite anode.Therefore,it demonstrates excellent capability in stabilizing the interface of Ni-rich cathode and regulating lithium deposition morphology.The Li||LiNi_(0.87)Co_(0.08)Mn_(0.05)O_(2)(NCM87)batteries exhibit high capacity retention of more than 90%after 200 cycles even under the high cutoff voltage of 4.5 V,1 C rate.This study offers a prospective method to develop safe electrolytes suitable for high voltage applications,thus providing higher energy densities.展开更多
An electrolyte destined for use in a dual-ion battery(DIB)must be stable at the inherently high potential required for anion intercalation in the graphite electrode,while also protecting the Al current collector from ...An electrolyte destined for use in a dual-ion battery(DIB)must be stable at the inherently high potential required for anion intercalation in the graphite electrode,while also protecting the Al current collector from anodic dissolution.A higher salt concentration is needed in the electrolyte,in comparison to typical battery electrolytes,to maximize energy density,while ensuring acceptable ionic conductivity and operational safety.In recent years,studies have demonstrated that highly concentrated organic electrolytes,ionic liquids,gel polymer electrolytes(GPEs),ionogels,and water-in-salt electrolytes can potentially be used in DIBs.GPEs can help reduce the use of solvents and thus lead to a substantial change in the Coulombic efficiency,energy density,and long-term cycle life of DIBs.Furthermore,GPEs are suited to manufacture compact DIB designs without separators by virtue of their mechanical strength and electrical performance.In this review,we highlight the latest advances in the application of different electrolytes in DIBs,with particular emphasis on GPEs.展开更多
The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previo...The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previous studies using Zn I_(2)additive,this work designs an aqueous Bi I_(3)-Zn battery with selfsupplied I^(-).Ex situ tests reveal the conversion of Bi I_(3)into Bi(discharge)and Bi OI(charge)at the 1st cycle and the dissolved I^(-)in electrolyte.The active I^(-)species enhances the specific capacity and discharge medium voltage of electrode as well as improves the generation of Zn dendrite and by-product.Furthermore,the porous hard carbon is introduced to enhance the electronic/ionic conductivity and adsorb iodine species,proven by experimental and theoretical studies.Accordingly,the well-designed Bi I_(3)-Zn battery delivers a high reversible capacity of 182 m A h g^(-1)at 0.2 A g^(-1),an excellent rate capability with 88 m A h g^(-1)at 10 A g^(-1),and an impressive cyclability with 63%capacity retention over 20 K cycles at 10 A g^(-1).An excellent electrochemical performance is obtained even at a high mass loading of 6 mg cm^(-2).Moreover,a flexible quasi-solid-state Bi I_(3)-Zn battery exhibits satisfactory battery performances.This work provides a new idea for designing high-performance aqueous battery with dual mechanisms.展开更多
The stable operation of solid-state lithium metal batteries at low temperatures is plagued by severe restrictions from inferior electrolyte-electrode interface compatibility and increased energy barrier for Li^(+)migr...The stable operation of solid-state lithium metal batteries at low temperatures is plagued by severe restrictions from inferior electrolyte-electrode interface compatibility and increased energy barrier for Li^(+)migration.Herein,we prepare a dual-salt poly(tetrahydrofuran)-based electrolyte consisting of lithium hexafluorophosphate and lithium difluoro(oxalato)borate(LiDFOB).The Li-salt anions(DFOB−)not only accelerate the ring-opening polymerization of tetrahydrofuran,but also promote the formation of highly ion-conductive and sustainable interphases on Li metal anodes without sacrificing the Li^(+)conductivity of electrolytes,which is favorable for Li^(+)transport kinetics at low temperatures.Applications of this polymer electrolyte in Li||LiFePO_(4)cells show 82.3%capacity retention over 1000 cycles at 30℃and endow stable discharge capacity at−30℃.Remarkably,the Li||LiFePO4 cells retain 52%of their room-temperature capacity at−20℃and 0.1 C.This rational design of dual-salt polymer-based electrolytes may provide a new perspective for the stable operation of quasi-solid-state batteries at low temperatures.展开更多
Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,featur...Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,features the merits of high operating voltage,small volume change and favorable specific energy density.However,it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity.Herein,we propose an ingenious strategy targeting superior SIBs through cross-linked NVPF with multi-dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes(NVPF@C@CNTs).This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network,thus leading to enhanced charge transfer kinetics and superior cycling stability.Benefited from this unique structure,significantly improved electrochemical properties are obtained,including high specific capacity(126.9 mAh g^(-1)at 1 C,1 C=128 mA g^(-1))and remarkably improved long-term cycling stability with 93.9%capacity retention after 1000 cycles at 20 C.The energy density of 286.8 Wh kg^(-1)can be reached for full cells with hard carbon as anode(NVPF@C@CNTs//HC).Additionally,the electrochemical performance of the full cell at high temperature is also investigated(95.3 mAh g^(-1)after 100 cycles at 1 C at 50℃).Such nanoscale dual-carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large-scale energy storages.展开更多
It is challenging for precise governing of electronic configuration of the individually-atomic catalysts toward optimal electrocatalysis,as d-band configuration of a metal center determines the adsorption behavior of ...It is challenging for precise governing of electronic configuration of the individually-atomic catalysts toward optimal electrocatalysis,as d-band configuration of a metal center determines the adsorption behavior of reactive species to the center in oxygen reduction reaction(ORR).The addition of Cu atom modifies the d-band center position of Fe central atom,thus strengthening the d-π*orbital interactions.Herein,FeCu-NC catalyst in the nitrogen-doped carbon(NC)support containing individual dual-metal CuN4/FeN4 sites was prepared by the surface confinement strategy of zeolitic imidazolate framework(ZIF),treated as a model catalyst.Experimentally and theoretically co-verified dual-metal CuN4/FeN4 sites highly dispersed in the NC support,enable transferring more electrons from FeN4 sites to*OH intermediates,thereby accelerating the desorption process of*OH species.Superior to those commercial Pt/C,Our FeCu-NC catalyst exhibited extraordinary ORR activity(with a E1/2 as high as 0.87 V)and cycling stability in 0.1 M KOH electrolyte,and thereof demonstrated excellent discharge performance in zinc-air batteries.Our construction of dual-atom catalysts(DACs)provides a strategy for atom-by-atom designing high-efficiency catalysts via orbital regulation.展开更多
Lithium-sulfur batteries are severely restricted by low electronic conductivity of sulfur and Li_(2)S,shuttle effect,and slow conversion reaction of lithium polysulfides(LiPSs).Herein,we report a facile and highyield ...Lithium-sulfur batteries are severely restricted by low electronic conductivity of sulfur and Li_(2)S,shuttle effect,and slow conversion reaction of lithium polysulfides(LiPSs).Herein,we report a facile and highyield strategy for synthesizing dual-core single-atom catalyst(ZnCoN_(4)O_(2)/CN)with atomically dispersed nitrogen/oxygen-coordinated Zn-Co sites on carbon nanosheets.Based on density functional theory(DFT)calculations and LiPSs conversion catalytic ability,ZnCoN_(4)O_(2)/CN provides dual-atom sites of Zn and Co,which could facilitate Li^(+)transport and Li_(2)S diffusion,and catalyze LiPSs conversion more effectively than homonuclear bimetallic single-atom catalysts or their simple mixture and previously reported singleatom catalysts.Li-S cell with ZnCoN_(4)O_(2)/CN modified separator showed excellent rate performance(789.4 mA h g^(-1)at 5 C)and stable long cycle performance(0.05%capacity decay rate at 6C with 1000cycles,outperforming currently reported single atomic catalysts for LiPSs conversion.This work highlights the important role of metal active centers and provides a strategy for producing multifunctional dual-core single atom catalysts for high-performance Li-S cells.展开更多
Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIB...Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIBs featuring with high kinetics and long durability. Herein, we report the design and fabrication of N-doped carbon film-modified niobium sulfur–selenium(NbSSe/NC) nanosheets architecture, which holds favorable merits for Na^(+) storage of enlarged interlayer space, improved electrical conductivity, as well as enhanced reaction reversibility, endowing it with high capacity, high-rate capability and high cycling stability. The combined electrochemical studies with density functional theory calculation reveal that the enriched defects in such nanosheets architecture can benefit for facilitating charge transfer and Na+ adsorption to speed the electrochemical kinetics. The NbSSe/NC composites are studied as the anode of a full SDIBs by pairing the expanded graphite as cathode, which shows an impressively cyclic durability with negligible capacity attenuation over 1000 cycles at 0.5 A g^(-1), as well as an outstanding energy density of 230.6 Wh kg^(-1) based on the total mass of anode and cathode.展开更多
The electronic and functional synergies between the twin metal centers make dual single-atom catalysts(DACs) attractive for oxygen electrocatalysis. The catalytic activities of DACs are largely decided by their surrou...The electronic and functional synergies between the twin metal centers make dual single-atom catalysts(DACs) attractive for oxygen electrocatalysis. The catalytic activities of DACs are largely decided by their surrounding micro-environment and supporting substrates. Modulating the micro-environment as well as engineering the efficient support is challenging tasks. Moreover, both are critical to optimizing the performance of DACs. Herein, a novel bio-cooperative strategy is developed to synthesize Fe Ni-DAC wherein Fe-Ni dual-atom sites are embedded in the N, P codoped tyre shaped carbon matrix. The configuration matching of Fe-Ni dual centers together with the local electronic engineering of N, P heteroatoms synergistically boost the catalytic activity on the oxygen reaction. Furthermore, the central-hollow highlyporous carbon matrix not only gives rise to a large amount of active sites, but also facilitates fast kinetics.Taking advantage of both the DAC and the substrate, the Fe Ni-NPC hollow tyre(HT) catalyst scores high in both oxygen reduction and evolution reactions, which exhibits the narrow potential difference and excellent durability. The aqueous Zn-air full battery(ZAB) integrating the Fe Ni-NPC HT air cathode has a high power density and a good stability over long-term cycling. Moreover, the flexible solid-state ZAB assembled with the polymer electrolyte obtains the high reliability over a wide range of temperatures or under diverse outside deformations. Therefore, this work offers a new green approach to prepare highly efficient DACs with built-in modulated micro-environment and tailor-made substrates. Moreover,it also paves a new way to develop highly-pliable power source for flexible electronics.展开更多
Lithium-metal batteries(LMBs)based on high-voltage cathodes would deliver high specific energy density to meet the demand of future energy storage.However,developing liquid electrolytes with wide electrochemical windo...Lithium-metal batteries(LMBs)based on high-voltage cathodes would deliver high specific energy density to meet the demand of future energy storage.However,developing liquid electrolytes with wide electrochemical window for high-energy LMBs is intrinsically challenging.Herein,we demonstrate metal-organic framework-functionalized separators(PE@MOF)with solvent sieving capability that implement dual electrolyte for LMBs.The capability of PE@MOF separator to block the diffusion of liquid electrolytes has been investigated.The PE@MOF separator notably suppresses solvents shuttling,enabling the independent optimization of cathode-electrolyte and anode-electrolyte interfaces.By adapting commercial carbonate and ether electrolytes on cathode and anode sides,respectively,robust cathode-electrolyte interphase(CEI)and solid electrolyte interface(SEI)have been built on both electrodes.The lifespan of LiCoO_(2)(LCO)|Li full cell has been notably extended when using dual electrolyte and the solvent-sieving PE@MOF separator.This work demonstrates a new strategy to separately optimize the local environments at electrodes and to develop high-energy LMBs using low-cost and commercially available electrolytes.展开更多
Vanadium flow battery(VFB)is one of the most promising energy storage technologies because of its superior safety,reliability and cycle life,but the poor electrochemical performance at high cur-rent density limits its...Vanadium flow battery(VFB)is one of the most promising energy storage technologies because of its superior safety,reliability and cycle life,but the poor electrochemical performance at high cur-rent density limits its commercial application.Herein,an advanced design of the dual-gradient carbon nanofibers/graphite felt(DG-CNFs/GF)composite electrode is firstly proposed for the next-generation VFB with high power density.Specifically,there is a macro gradient distribution of CNFs along the thickness direction of the electrode,meanwhile a micro gradient distribution of CNFs is also existed along the ra-dial direction of a single fiber,and both the macro and micro gradient structure are verified through the physicochemical characterizations.In addition,the DG-CNFs/GF with a dual-gradient structure exhibits an excellent electrocatalytic activity and a fast mass transfer characteristic.It is worth noting that the energy conversion efficiencies,cycling stability in addition to power density of VFB with DG-CNFs/GF are much better than those with commercial GF,which make the dual-gradient DG-CNFs/GF to be a promis-ing alternative.Most importantly,the accomplishment of this work will provide a promising development direction of the highly efficient electrode for the next-generation VFB with high power density.展开更多
Electrode materials which can reversibly react with anions are of interest for aqueous dual-ion batteries.Herein,we propose a novel anion electrode,Cu3(PO4)2,for constructing an aqueous dual-ion cell.The Cu3(PO4)2 ele...Electrode materials which can reversibly react with anions are of interest for aqueous dual-ion batteries.Herein,we propose a novel anion electrode,Cu3(PO4)2,for constructing an aqueous dual-ion cell.The Cu3(PO4)2 electrode can operate in a quasi-neutral condition and deliver a reversible capacity of 115.6 mAh g^−1 with a well-defined plateau at−0.17 V versus Ag/AgCl.Its reaction mechanism shows that Cu3(PO4)2 decomposes into Cu2O and subsequently is converted into Cu during the initial discharge process.In the following charge process,Cu is oxidized into Cu2O.It suggests Cu3(PO4)2 reacts with OH−ions instead of PO43−ions after the initial discharge process and its potential thereby depends upon the OH−ions concentration in electrolyte.Additionally,an aqueous dual-ion cell is built by using pretreated Cu3(PO4)2 and Na0.44MnO2 as anode and cathode,respectively.During cycling,OH−ions and Na^+ions in electrolyte can be stored and released.Such a cell can provide a discharge capacity of 52.6 mAh g^−1 with plateaus at 0.70 and 0.45 V,exhibiting the potential of application.This work presents an available aqueous dual-ion cell and provides new insights into renewable energy storage and adjustment of the OH−ions concentration in aqueous buffer solution.展开更多
While aqueous Zn-Na hybrid batteries have garnered widespread attention because of their low cost and high safety,it is still challenging to achieve long cycle-life and stable discharge-voltage due to sluggish reactio...While aqueous Zn-Na hybrid batteries have garnered widespread attention because of their low cost and high safety,it is still challenging to achieve long cycle-life and stable discharge-voltage due to sluggish reaction kinetics,zinc dendrite formation,and side reactions.Herein,we design a Zn^(2+)/Na^(+) dual-salt battery,in which sodiation of the NVP cathode favors zinc intercalation under an energy threshold,leading to decoupled redox reactions on the cathode and anode.Systematic investigations of the electrolyte effects show that the ion intercalation mechanism and the kinetics in the mixture of triflate-and acetate-based electrolytes are superior to those in the common acetate-only electrolytes.As a result,we have achieved fast discharging capability,suppressed zinc dendrites,a stable discharge voltage at 1.45 V with small polarization,and nearly 100%Coulombic efficiency in the dual-salt mixture electrolyte with optimized concentration of 1 M Zn(OAc)_(2)+1 M NaCF_(3)SO_(3).This work demonstrates the importance of electrolyte regulation in aqueous dual-salt hybrid batteries for the energy storage.展开更多
Graphite as a positive electrode material of dual ion batteries(DIBs)has attracted tremendous attentions for its advantages including low lost,high working voltage and high energy density.However,very few literatures ...Graphite as a positive electrode material of dual ion batteries(DIBs)has attracted tremendous attentions for its advantages including low lost,high working voltage and high energy density.However,very few literatures regarding to the real-time observation of anion intercalation behavior and surface evolution of graphite in DIBs have been reported.Herein,we use in situ atomic force microscope(AFM)to directly observe the intercalation/de-intercalation processes of PF6^-in graphite in real time.First,by measuring the change in the distance between graphene layers during intercalation,we found that PF6^-intercalates in one of every three graphite layers and the intercalation speed is measured to be 2μm-min^-1.Second,graphite will wrinke and suffer structural damnages at high voltages,along with severe electrolyte decomposition on the surface.These findings provide useful information for further optimizing the capacity and the stability of graphite anode in DIBs.展开更多
基金This work was supported by the National Natural Science Foundation of China(Nos.21971135,21925202,21872076,and 21590792)the National Key R&D Program of China(Nos.2017YFA0700101 and 2016YFA0202801)Beijing Natural Science Foundation(No.JQ18007).
文摘Metal-nitrogen-carbon(M-N-C)single-atom catalysts exhibit desirable electrochemical catalytic properties.However,the replacement of N atoms by heteroatoms(B,P,S,etc.)has been regarded as a useful method for regulating the coordination environment.The structure engineered M-N-C sites via doping heteroatoms play an important role to the adsorption and activation of the oxygen intermediate.Herein,we develop an efficient strategy to construct dual atomic site catalysts via the formation of a Co_(1)-PN and Ni1-PN planar configuration.The developed Co_(1)-PNC/Ni1-PNC catalyst exhibits excellent bifunctional electrocatalytic performance in alkaline solution.Both experimental and theoretical results demonstrated that the N/P coordinated Co/Ni sites moderately reduced the binding interaction of oxygen intermediates.The Co_(1)-PNC/Ni1-PNC endows a rechargeable Zn-air battery with excellent power density and cycling stability as an air-cathode,which is superior to that of the benchmark Pt/C+IrO_(2).This work paves an avenue for design of dual single-atomic sites and regulation of the atomic configuration on carbon-based materials to achieve high-performance electrocatalysts.
基金supported by the National Natural Science Foundation of China(Grant No.21875071)the Guangzhou Scientific and Technological Planning Project(Grant No.201704030061)the Guangdong Key R&D Program of China(Grant No.2019B090908001)。
文摘Solid electrolytes with desirable properties such as high ionic conductivity,wide electrochemical stable window,and suitable mechanical strength,and stable electrode-electrolyte interfaces on both cathode and anode side are essential for high-voltage all-solid-state lithium batteries(ASSLBs)to achieve excellent cycle stability.In this work,a novel strategy of using LiF and LiNO_(3) as synergistic additives to boost the performance of PEO-PVDF/LLZTO-based composite solid electrolytes(CSEs)is developed,which also promotes the assembled high-voltage ASSLBs with dual-interfaces stability characteristic.Specifically,LiF as an inactive additive can increase the electrochemical stability of the CSE under high cut-off voltage,and improve the high-voltage compatibility between cathode and CSE,thus leading to a stable cathode/CSE interface.LiNO_(3) as an active additive can lead to an enhanced ionic conductivity of CSE due to the increased free-mobile Li+and ensure a stable CSE/Li interface by forming stable solid electrolyte interphase(SEI)on Li anode surface.Benefiting from the improved performance of CSE and stable dualinterfaces,the assembled NCM622/9[PEO_(15)-LiTFSI]-PVDF-15 LLZTO-2 LiF-3 LiNO_(3)/Li cell delivers a high rate capacity of 102.1 mAh g^(-1) at 1.0 C and a high capacity retention of 77.4%after 200 cycles at 0.5 C,which are much higher than those of the ASSLB assembled with additive-free CSE,with only 60.0 mAh g^(-1) and 52.0%,respectively.Furthermore,novel cycle test modes of resting for 5 h at different charge states after every 5 cycles are designed to investigate the high-voltage compatibility between cathode and CSE,and the results suggest that LiF additive can actually improve the high-voltage compatibility of cathode and CSE.All the obtained results confirm that the strategy of using synergistic additives in CSE is an effective way to achieve high-voltage ASSLBs with dual-interfaces stability.
基金the financial support from the National Natural Science Foundation of China(91963118)the Fundamental Research Funds for the Central Universities(2412019ZD010)。
文摘Dual-ion battery(DIB) composed of graphite cathode and lithium anode is regarded as an advanced secondary battery because of the low cost, high working voltage and environmental friendliness. However,DIB operated at high potential(usually ≥ 4.5 V versus Li+/Li) is confronted with severe challenges including electrolyte decomposition on cathode interface, and structural deterioration of graphite accompanying with anions de-/intercalation, hinder its cyclic life. To address those drawbacks and preserve the DIB virtues, a feasible and scalable surface modification is achieved for the commercial graphite cathode of mesocarbon microbead. In/ex-situ studies reveal that, such an interfacial engineering facilitates and reconstructs the formation of chemically stable cathode electrolyte interphase with better flexibility alleviating the decomposition of electrolyte, regulating the anions de-/intercalation behavior in graphite with the retainment of structural integrity and without exerting considerable influence on kinetics of anions diffusion. As a result, the modified mesocarbon microbead exhibits a much-extended cycle life with high capacity retention of 82.3% even after 1000 cycles. This study demonstrates that the interface modification of electrode and coating skeleton play important roles on DIB performance improvement, providing the feasible basis for practical application of DIB owing to the green and scalable coating procedures.
基金financially supported by National Key Research and Development Program of China(No.2019YFA0705603)National Natural Science Foundation of China(No.22078341,No.21808228 and No.21776290)+1 种基金Science Fund for Creative Research Groups of the National Natural Science Foundation of China(No.21921005)S&T Program of Hebei(No.B2020103028).
文摘The key to realize long-life high energy density lithium batteries is to exploit functional electrolytes capable of stabilizing both high voltage cathode and lithium anode.The emergence of localized high-concentration electrolytes(LHCEs)shows great promise for ameliorating the above-mentioned interfacial issues.In this work,a lithium difluoro(oxalate)borate(LiDFOB)based nonflammable dual-anion LHCE is designed and prepared.Dissolving in the mixture of trimethyl phosphate(TMP)/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)),the continuously consumption of LiDFOB is suppressed by simply introducing lithium nitrate(LiNO_(3)).Meantime,as most of the TMP molecular are coordinated with Li^(+),the electrolyte does not show incompatibility issue between neither metal lithium nor graphite anode.Therefore,it demonstrates excellent capability in stabilizing the interface of Ni-rich cathode and regulating lithium deposition morphology.The Li||LiNi_(0.87)Co_(0.08)Mn_(0.05)O_(2)(NCM87)batteries exhibit high capacity retention of more than 90%after 200 cycles even under the high cutoff voltage of 4.5 V,1 C rate.This study offers a prospective method to develop safe electrolytes suitable for high voltage applications,thus providing higher energy densities.
基金support from Batteries Sweden(Grant No.Vinnova-2019-00064)the Stand-Up for Energy consortium,the ISCF Faraday Challenge for the project on“Degradation of Battery Materials”(Grant No.EP/S003053/1,FIRG024)the ERC(Grant No.771777 FUN POLYSTORE).
文摘An electrolyte destined for use in a dual-ion battery(DIB)must be stable at the inherently high potential required for anion intercalation in the graphite electrode,while also protecting the Al current collector from anodic dissolution.A higher salt concentration is needed in the electrolyte,in comparison to typical battery electrolytes,to maximize energy density,while ensuring acceptable ionic conductivity and operational safety.In recent years,studies have demonstrated that highly concentrated organic electrolytes,ionic liquids,gel polymer electrolytes(GPEs),ionogels,and water-in-salt electrolytes can potentially be used in DIBs.GPEs can help reduce the use of solvents and thus lead to a substantial change in the Coulombic efficiency,energy density,and long-term cycle life of DIBs.Furthermore,GPEs are suited to manufacture compact DIB designs without separators by virtue of their mechanical strength and electrical performance.In this review,we highlight the latest advances in the application of different electrolytes in DIBs,with particular emphasis on GPEs.
基金funding from National Natural Science Foundation of China(52103053,52102312)Huxiang Young Talents of Hunan Province(2022RC1004)+1 种基金Macao Young Scholars Program(AM2021011)Foundation of State Key Laboratory of Utilization of Woody Oil Resource(GZKF202126)。
文摘The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previous studies using Zn I_(2)additive,this work designs an aqueous Bi I_(3)-Zn battery with selfsupplied I^(-).Ex situ tests reveal the conversion of Bi I_(3)into Bi(discharge)and Bi OI(charge)at the 1st cycle and the dissolved I^(-)in electrolyte.The active I^(-)species enhances the specific capacity and discharge medium voltage of electrode as well as improves the generation of Zn dendrite and by-product.Furthermore,the porous hard carbon is introduced to enhance the electronic/ionic conductivity and adsorb iodine species,proven by experimental and theoretical studies.Accordingly,the well-designed Bi I_(3)-Zn battery delivers a high reversible capacity of 182 m A h g^(-1)at 0.2 A g^(-1),an excellent rate capability with 88 m A h g^(-1)at 10 A g^(-1),and an impressive cyclability with 63%capacity retention over 20 K cycles at 10 A g^(-1).An excellent electrochemical performance is obtained even at a high mass loading of 6 mg cm^(-2).Moreover,a flexible quasi-solid-state Bi I_(3)-Zn battery exhibits satisfactory battery performances.This work provides a new idea for designing high-performance aqueous battery with dual mechanisms.
基金funding from the Natural Science Foundation of Hubei Province,China(Grant No.2022CFA031)supported by the Natural Science Foundation of China(Grant No.22309056).
文摘The stable operation of solid-state lithium metal batteries at low temperatures is plagued by severe restrictions from inferior electrolyte-electrode interface compatibility and increased energy barrier for Li^(+)migration.Herein,we prepare a dual-salt poly(tetrahydrofuran)-based electrolyte consisting of lithium hexafluorophosphate and lithium difluoro(oxalato)borate(LiDFOB).The Li-salt anions(DFOB−)not only accelerate the ring-opening polymerization of tetrahydrofuran,but also promote the formation of highly ion-conductive and sustainable interphases on Li metal anodes without sacrificing the Li^(+)conductivity of electrolytes,which is favorable for Li^(+)transport kinetics at low temperatures.Applications of this polymer electrolyte in Li||LiFePO_(4)cells show 82.3%capacity retention over 1000 cycles at 30℃and endow stable discharge capacity at−30℃.Remarkably,the Li||LiFePO4 cells retain 52%of their room-temperature capacity at−20℃and 0.1 C.This rational design of dual-salt polymer-based electrolytes may provide a new perspective for the stable operation of quasi-solid-state batteries at low temperatures.
基金financially supported by Science and Technology Foundation of Guizhou Province(QKHZC[2020]2Y037)the Science and Technology Innovation Program of Hunan Province(2020RC4005,2019RS1004)+2 种基金Research start-up funding from Central South University(202044019)Innovation Mover Program of Central South University(2020CX007)National Natural Science Foundation of China(U21A20284)
文摘Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,features the merits of high operating voltage,small volume change and favorable specific energy density.However,it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity.Herein,we propose an ingenious strategy targeting superior SIBs through cross-linked NVPF with multi-dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes(NVPF@C@CNTs).This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network,thus leading to enhanced charge transfer kinetics and superior cycling stability.Benefited from this unique structure,significantly improved electrochemical properties are obtained,including high specific capacity(126.9 mAh g^(-1)at 1 C,1 C=128 mA g^(-1))and remarkably improved long-term cycling stability with 93.9%capacity retention after 1000 cycles at 20 C.The energy density of 286.8 Wh kg^(-1)can be reached for full cells with hard carbon as anode(NVPF@C@CNTs//HC).Additionally,the electrochemical performance of the full cell at high temperature is also investigated(95.3 mAh g^(-1)after 100 cycles at 1 C at 50℃).Such nanoscale dual-carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large-scale energy storages.
基金supported by the National Natural Science Foundation of China(Nos.51872115 and 52272209)2020 International Cooperation Project of the Department of Science and Technology of Jilin Province(No.20200801001GH).
文摘It is challenging for precise governing of electronic configuration of the individually-atomic catalysts toward optimal electrocatalysis,as d-band configuration of a metal center determines the adsorption behavior of reactive species to the center in oxygen reduction reaction(ORR).The addition of Cu atom modifies the d-band center position of Fe central atom,thus strengthening the d-π*orbital interactions.Herein,FeCu-NC catalyst in the nitrogen-doped carbon(NC)support containing individual dual-metal CuN4/FeN4 sites was prepared by the surface confinement strategy of zeolitic imidazolate framework(ZIF),treated as a model catalyst.Experimentally and theoretically co-verified dual-metal CuN4/FeN4 sites highly dispersed in the NC support,enable transferring more electrons from FeN4 sites to*OH intermediates,thereby accelerating the desorption process of*OH species.Superior to those commercial Pt/C,Our FeCu-NC catalyst exhibited extraordinary ORR activity(with a E1/2 as high as 0.87 V)and cycling stability in 0.1 M KOH electrolyte,and thereof demonstrated excellent discharge performance in zinc-air batteries.Our construction of dual-atom catalysts(DACs)provides a strategy for atom-by-atom designing high-efficiency catalysts via orbital regulation.
基金supported by the National Natural Science Foundation of P.R.China(22001082)the Applied Science and Technology Planning Project of Guangdong Province,Guangzhou,China(2017B090917002)+5 种基金the Guangdong Basic and Applied Basic Research Fund Project(2019B1515120027)the Research and Development(R&D)Projects in Key Areas of Guangdong Province(2020B0101028005)the Guangdong Natural Science Foundation Project(No.2019A1515010841)the Guangdong Province International Science and Technology Cooperation Project(No.2019A050510038)the Guangzhou Science and Technology Association Young Talents Promotion Project(X20210201043)the Guangzhou Basic and Applied Basic Research Project(202102020624)。
文摘Lithium-sulfur batteries are severely restricted by low electronic conductivity of sulfur and Li_(2)S,shuttle effect,and slow conversion reaction of lithium polysulfides(LiPSs).Herein,we report a facile and highyield strategy for synthesizing dual-core single-atom catalyst(ZnCoN_(4)O_(2)/CN)with atomically dispersed nitrogen/oxygen-coordinated Zn-Co sites on carbon nanosheets.Based on density functional theory(DFT)calculations and LiPSs conversion catalytic ability,ZnCoN_(4)O_(2)/CN provides dual-atom sites of Zn and Co,which could facilitate Li^(+)transport and Li_(2)S diffusion,and catalyze LiPSs conversion more effectively than homonuclear bimetallic single-atom catalysts or their simple mixture and previously reported singleatom catalysts.Li-S cell with ZnCoN_(4)O_(2)/CN modified separator showed excellent rate performance(789.4 mA h g^(-1)at 5 C)and stable long cycle performance(0.05%capacity decay rate at 6C with 1000cycles,outperforming currently reported single atomic catalysts for LiPSs conversion.This work highlights the important role of metal active centers and provides a strategy for producing multifunctional dual-core single atom catalysts for high-performance Li-S cells.
基金financially supported by the National key Research & Development Program of China (2022YFE0115900, 2021YFA1501500)the National Natural Science Foundation of China (Nos. 22225902, U22A20436, 22209185)+3 种基金the CAS-Commonwealth Scientific and Industrial Research Organization (CSIRO) Joint Research Projects (121835KYSB20200039)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (Grant. YLUDNL Fund 2021011)Fujian Province Central Government Guides to Science and Technology Development Special Project (No. 2022L3024)Natural Science Foundation of Fujian Province, China (No. 2021J02020)。
文摘Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIBs featuring with high kinetics and long durability. Herein, we report the design and fabrication of N-doped carbon film-modified niobium sulfur–selenium(NbSSe/NC) nanosheets architecture, which holds favorable merits for Na^(+) storage of enlarged interlayer space, improved electrical conductivity, as well as enhanced reaction reversibility, endowing it with high capacity, high-rate capability and high cycling stability. The combined electrochemical studies with density functional theory calculation reveal that the enriched defects in such nanosheets architecture can benefit for facilitating charge transfer and Na+ adsorption to speed the electrochemical kinetics. The NbSSe/NC composites are studied as the anode of a full SDIBs by pairing the expanded graphite as cathode, which shows an impressively cyclic durability with negligible capacity attenuation over 1000 cycles at 0.5 A g^(-1), as well as an outstanding energy density of 230.6 Wh kg^(-1) based on the total mass of anode and cathode.
基金supported by the Innovation Foundation of Graduate Student of Harbin Normal University (HSDSSCX2022-111)the Natural Science Foundation of Heilongjiang Province of China(TD2020B001)the Opening Project of State Key Laboratory of Advanced Chemical Power Sources (SKL-ACPS-C-25)。
文摘The electronic and functional synergies between the twin metal centers make dual single-atom catalysts(DACs) attractive for oxygen electrocatalysis. The catalytic activities of DACs are largely decided by their surrounding micro-environment and supporting substrates. Modulating the micro-environment as well as engineering the efficient support is challenging tasks. Moreover, both are critical to optimizing the performance of DACs. Herein, a novel bio-cooperative strategy is developed to synthesize Fe Ni-DAC wherein Fe-Ni dual-atom sites are embedded in the N, P codoped tyre shaped carbon matrix. The configuration matching of Fe-Ni dual centers together with the local electronic engineering of N, P heteroatoms synergistically boost the catalytic activity on the oxygen reaction. Furthermore, the central-hollow highlyporous carbon matrix not only gives rise to a large amount of active sites, but also facilitates fast kinetics.Taking advantage of both the DAC and the substrate, the Fe Ni-NPC hollow tyre(HT) catalyst scores high in both oxygen reduction and evolution reactions, which exhibits the narrow potential difference and excellent durability. The aqueous Zn-air full battery(ZAB) integrating the Fe Ni-NPC HT air cathode has a high power density and a good stability over long-term cycling. Moreover, the flexible solid-state ZAB assembled with the polymer electrolyte obtains the high reliability over a wide range of temperatures or under diverse outside deformations. Therefore, this work offers a new green approach to prepare highly efficient DACs with built-in modulated micro-environment and tailor-made substrates. Moreover,it also paves a new way to develop highly-pliable power source for flexible electronics.
基金the funding support from“Hundred Talents Program”of Zhejiang University,the Fundamental Research Funds for the Central Universities(No.2021FZZX001-09)the National Natural Science Foundation of China(No.22005266)Zhejiang Provincial Natural Science Foundation(No.LR21E020003).
文摘Lithium-metal batteries(LMBs)based on high-voltage cathodes would deliver high specific energy density to meet the demand of future energy storage.However,developing liquid electrolytes with wide electrochemical window for high-energy LMBs is intrinsically challenging.Herein,we demonstrate metal-organic framework-functionalized separators(PE@MOF)with solvent sieving capability that implement dual electrolyte for LMBs.The capability of PE@MOF separator to block the diffusion of liquid electrolytes has been investigated.The PE@MOF separator notably suppresses solvents shuttling,enabling the independent optimization of cathode-electrolyte and anode-electrolyte interfaces.By adapting commercial carbonate and ether electrolytes on cathode and anode sides,respectively,robust cathode-electrolyte interphase(CEI)and solid electrolyte interface(SEI)have been built on both electrodes.The lifespan of LiCoO_(2)(LCO)|Li full cell has been notably extended when using dual electrolyte and the solvent-sieving PE@MOF separator.This work demonstrates a new strategy to separately optimize the local environments at electrodes and to develop high-energy LMBs using low-cost and commercially available electrolytes.
基金This work was financially supported by the National Natural Science Foundation of China Youth Fund(No.21703263)Open project of State Key Laboratory of Heavy Oil Processing in China University of Petroleum(No.Y7F1911191).
文摘Vanadium flow battery(VFB)is one of the most promising energy storage technologies because of its superior safety,reliability and cycle life,but the poor electrochemical performance at high cur-rent density limits its commercial application.Herein,an advanced design of the dual-gradient carbon nanofibers/graphite felt(DG-CNFs/GF)composite electrode is firstly proposed for the next-generation VFB with high power density.Specifically,there is a macro gradient distribution of CNFs along the thickness direction of the electrode,meanwhile a micro gradient distribution of CNFs is also existed along the ra-dial direction of a single fiber,and both the macro and micro gradient structure are verified through the physicochemical characterizations.In addition,the DG-CNFs/GF with a dual-gradient structure exhibits an excellent electrocatalytic activity and a fast mass transfer characteristic.It is worth noting that the energy conversion efficiencies,cycling stability in addition to power density of VFB with DG-CNFs/GF are much better than those with commercial GF,which make the dual-gradient DG-CNFs/GF to be a promis-ing alternative.Most importantly,the accomplishment of this work will provide a promising development direction of the highly efficient electrode for the next-generation VFB with high power density.
基金This work is supported by NSAF joint Fund(U1830106)Ningbo S&I Innovation 2025 Major Special Program(2018B10061)K.C.Wong Magna Fund in Ningbo University.
文摘Electrode materials which can reversibly react with anions are of interest for aqueous dual-ion batteries.Herein,we propose a novel anion electrode,Cu3(PO4)2,for constructing an aqueous dual-ion cell.The Cu3(PO4)2 electrode can operate in a quasi-neutral condition and deliver a reversible capacity of 115.6 mAh g^−1 with a well-defined plateau at−0.17 V versus Ag/AgCl.Its reaction mechanism shows that Cu3(PO4)2 decomposes into Cu2O and subsequently is converted into Cu during the initial discharge process.In the following charge process,Cu is oxidized into Cu2O.It suggests Cu3(PO4)2 reacts with OH−ions instead of PO43−ions after the initial discharge process and its potential thereby depends upon the OH−ions concentration in electrolyte.Additionally,an aqueous dual-ion cell is built by using pretreated Cu3(PO4)2 and Na0.44MnO2 as anode and cathode,respectively.During cycling,OH−ions and Na^+ions in electrolyte can be stored and released.Such a cell can provide a discharge capacity of 52.6 mAh g^−1 with plateaus at 0.70 and 0.45 V,exhibiting the potential of application.This work presents an available aqueous dual-ion cell and provides new insights into renewable energy storage and adjustment of the OH−ions concentration in aqueous buffer solution.
基金financially supported by the Hightech Research Key laboratory of Zhenjiang(SS2018002)Jiangsu Postdoctoral Research Funding Program(2020Z257)+3 种基金support from MOE Tier 1 grant(RG 157/19)from the China-Singapore International Joint Research Institute(204-A018002)financial support from the Guangdong Natural Science Funds(2019A1515010675)the Science and Technology Project of Shenzhen(JCYJ20210324094206019,KQJSCX20180328094001794)。
文摘While aqueous Zn-Na hybrid batteries have garnered widespread attention because of their low cost and high safety,it is still challenging to achieve long cycle-life and stable discharge-voltage due to sluggish reaction kinetics,zinc dendrite formation,and side reactions.Herein,we design a Zn^(2+)/Na^(+) dual-salt battery,in which sodiation of the NVP cathode favors zinc intercalation under an energy threshold,leading to decoupled redox reactions on the cathode and anode.Systematic investigations of the electrolyte effects show that the ion intercalation mechanism and the kinetics in the mixture of triflate-and acetate-based electrolytes are superior to those in the common acetate-only electrolytes.As a result,we have achieved fast discharging capability,suppressed zinc dendrites,a stable discharge voltage at 1.45 V with small polarization,and nearly 100%Coulombic efficiency in the dual-salt mixture electrolyte with optimized concentration of 1 M Zn(OAc)_(2)+1 M NaCF_(3)SO_(3).This work demonstrates the importance of electrolyte regulation in aqueous dual-salt hybrid batteries for the energy storage.
基金This research was financially supported by Soft Science Research Project of Guangdong Province(No.2017B030301013)the Shenzhen Science and Technology Research(Nos.CYJ20170818085823773 and ZDSYS201707281026184).
文摘Graphite as a positive electrode material of dual ion batteries(DIBs)has attracted tremendous attentions for its advantages including low lost,high working voltage and high energy density.However,very few literatures regarding to the real-time observation of anion intercalation behavior and surface evolution of graphite in DIBs have been reported.Herein,we use in situ atomic force microscope(AFM)to directly observe the intercalation/de-intercalation processes of PF6^-in graphite in real time.First,by measuring the change in the distance between graphene layers during intercalation,we found that PF6^-intercalates in one of every three graphite layers and the intercalation speed is measured to be 2μm-min^-1.Second,graphite will wrinke and suffer structural damnages at high voltages,along with severe electrolyte decomposition on the surface.These findings provide useful information for further optimizing the capacity and the stability of graphite anode in DIBs.
