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
The development of insertion-type anodes is the key to designing“rocking chair”zinc-ion batteries.However,there is rare report on high mass loading anode with high performances.Here,{001}-oriented Bi OCl nanosheets ...The development of insertion-type anodes is the key to designing“rocking chair”zinc-ion batteries.However,there is rare report on high mass loading anode with high performances.Here,{001}-oriented Bi OCl nanosheets with Sn doping are proposed as a promising insertion-type anode.The designs of cross-linked CNTs conductive network,{001}-oriented nanosheet,and Sn doping significantly enhance ion/electron transport,proved via experimental tests and theoretical calculations(density of states and diffusion barrier).The H^(+)/Zn^(2+)synergistic co-insertion mechanism is proved via ex situ XRD,Raman,XPS,and SEM tests.Accordingly,this optimized electrode delivers a high reversible capacity of 194 m A h g^(-1)at 0.1 A g^(-1)with a voltage of≈0.37 V and an impressive cyclability with 128 m A h g^(-1)over 2500 cycles at 1 A g^(-1).It also shows satisfactory performances at an ultrahigh mass loading of 10 mg cm^(-2).Moreover,the Sn-Bi OCl//MnO_(2)full cell displays a reversible capacity of 85 m A h g^(-1)at 0.2 A g^(-1)during cyclic test.展开更多
Nowadays,multivalent batteries are not widely commercialized in contrast with monovalent batteries because their development faces more obstacles,which partly derive from the typically higher charge density of multiva...Nowadays,multivalent batteries are not widely commercialized in contrast with monovalent batteries because their development faces more obstacles,which partly derive from the typically higher charge density of multivalent ions.This property results in poor capacity retention and reversibility,and low coulombic efficiency since the insertion of multivalent ions strongly destabilizes the host structure.To overcome these issues,a close-to-amorphous cathode material has been prepared containing cations(Ca)larger than those to be inserted(Mg).Specifically,low-crystallinity CaMn_(2)O_(4)(CMO)has been prepared and tested as a cathode for aqueous magnesium and calcium batteries.Employing XPS and ICP-OES,calcium and magnesium ions are shown to be inserted-extracted into-from the cathode,the performance being better for magnesium insertion because of its higher diffusion coefficient.In situ Raman analysis reveals that CMO evolves into a birnessite-type structure during the initial electrochemical cycles in both aqueous magnesium and calcium media.The gravimetric capacity obtained for cycle 50 at 263 mA g^(-1)in aqueous 1.0 M Mg(NO_(3))_(2)has a value of 93 mAh g^(-1),while for aqueous 1.0 M Ca(NO_(3))_(2),it is only of 46 mAh g^(-1).The results obtained for the magnesium electrolyte compare well with other cathode materials based on manganese oxides.展开更多
Poor conductivity,sluggish ion diffusion kinetics and short cycle life hinder the further development of manganese oxide in aqueous zinc-ion batteries(AZIBs).Exploring a cathode with high capacity and long cycle life ...Poor conductivity,sluggish ion diffusion kinetics and short cycle life hinder the further development of manganese oxide in aqueous zinc-ion batteries(AZIBs).Exploring a cathode with high capacity and long cycle life is critical to the commercial development of AZIBs.Herein,a two-dimensional(2D) MnO/C composite derived from metal organic framework(MOF) was prepared.The 2D MnO/C cathode exhibits a remarkably cyclic stability with the capacity retention of 90.6% after 900 cycles at 0.5 A·g^(-1) and maintains a high capacity of 120.2 mAh·g^(-1)after 4500 cycles at 1.0 A·g^(-1).It is demonstrated that MnO is converted into Mn_(3)O_(4) through electrochemical activation strategy and shows a Zn^(2+)and H^(+)co-intercalation mechanism.In general,this work provides a new path for the development of high-performance AZIBs cathode with controllable morphology.展开更多
Sodium ions(Na+)and ether electrolyte coinserted graphite possesses a considerable volume expansion effect.However,the mechanism fails to clearly explain its stability.In response to this deficiency,the co-inserted re...Sodium ions(Na+)and ether electrolyte coinserted graphite possesses a considerable volume expansion effect.However,the mechanism fails to clearly explain its stability.In response to this deficiency,the co-inserted reaction is proposed,which is affected by the Lorentz force of the applied electric field under the high-current condition.The Na^(+)ions are separated out,while the ethylene glycol dimethyl ether molecules remain between the graphite layers.This insight provides a reasonable explanation for the extraordinary stability of this material.In situ X-ray diffraction and density functional theory calculations confirm the separation and release of Na+.On the basis of this result,unmodified commercial graphite was stably cycled 6400 times at a current density of up to 10 A g^(-1),and the capacity retention rate was as high as 97.2%.The full battery assembled in the laboratory has a maximum output power of 14,846 W kg^(-1)and an output energy density of 103 W h kg^(-1)(relative to the weight of anodic and cathodic active materials).The new mechanism provides innovative ideas for the design of large-scale energy storage devices.展开更多
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.
基金supported by the Natural Science Foundation of China (52102312,51672234,and 52072325)the Natural Science Foundation of Hunan Province of China (2021JJ40528)+2 种基金the China Postdoctoral Science Foundation (2020M682581)the Macao Young Scholars Program (AM2021011)the College Student Innovation and Entrepreneurship Training Program (S202210530051)。
文摘The development of insertion-type anodes is the key to designing“rocking chair”zinc-ion batteries.However,there is rare report on high mass loading anode with high performances.Here,{001}-oriented Bi OCl nanosheets with Sn doping are proposed as a promising insertion-type anode.The designs of cross-linked CNTs conductive network,{001}-oriented nanosheet,and Sn doping significantly enhance ion/electron transport,proved via experimental tests and theoretical calculations(density of states and diffusion barrier).The H^(+)/Zn^(2+)synergistic co-insertion mechanism is proved via ex situ XRD,Raman,XPS,and SEM tests.Accordingly,this optimized electrode delivers a high reversible capacity of 194 m A h g^(-1)at 0.1 A g^(-1)with a voltage of≈0.37 V and an impressive cyclability with 128 m A h g^(-1)over 2500 cycles at 1 A g^(-1).It also shows satisfactory performances at an ultrahigh mass loading of 10 mg cm^(-2).Moreover,the Sn-Bi OCl//MnO_(2)full cell displays a reversible capacity of 85 m A h g^(-1)at 0.2 A g^(-1)during cyclic test.
基金supported by MCIN with funding from European Union Next Generation EU (PRTR-C17.I1)Generalitat Valenciana+1 种基金the MCIN, European Union and Generalitat Valenciana for financial support under the Advanced Materials programme project MFA/2022/062the Universitat d’Alacant for the award of an FPU grant.
文摘Nowadays,multivalent batteries are not widely commercialized in contrast with monovalent batteries because their development faces more obstacles,which partly derive from the typically higher charge density of multivalent ions.This property results in poor capacity retention and reversibility,and low coulombic efficiency since the insertion of multivalent ions strongly destabilizes the host structure.To overcome these issues,a close-to-amorphous cathode material has been prepared containing cations(Ca)larger than those to be inserted(Mg).Specifically,low-crystallinity CaMn_(2)O_(4)(CMO)has been prepared and tested as a cathode for aqueous magnesium and calcium batteries.Employing XPS and ICP-OES,calcium and magnesium ions are shown to be inserted-extracted into-from the cathode,the performance being better for magnesium insertion because of its higher diffusion coefficient.In situ Raman analysis reveals that CMO evolves into a birnessite-type structure during the initial electrochemical cycles in both aqueous magnesium and calcium media.The gravimetric capacity obtained for cycle 50 at 263 mA g^(-1)in aqueous 1.0 M Mg(NO_(3))_(2)has a value of 93 mAh g^(-1),while for aqueous 1.0 M Ca(NO_(3))_(2),it is only of 46 mAh g^(-1).The results obtained for the magnesium electrolyte compare well with other cathode materials based on manganese oxides.
基金financially supported by the National Natural Science Foundation of China (Nos.22078200 and 51874199)Guangdong Basic and Applied Basic Research Foundation (No.2021A1515010162)。
文摘Poor conductivity,sluggish ion diffusion kinetics and short cycle life hinder the further development of manganese oxide in aqueous zinc-ion batteries(AZIBs).Exploring a cathode with high capacity and long cycle life is critical to the commercial development of AZIBs.Herein,a two-dimensional(2D) MnO/C composite derived from metal organic framework(MOF) was prepared.The 2D MnO/C cathode exhibits a remarkably cyclic stability with the capacity retention of 90.6% after 900 cycles at 0.5 A·g^(-1) and maintains a high capacity of 120.2 mAh·g^(-1)after 4500 cycles at 1.0 A·g^(-1).It is demonstrated that MnO is converted into Mn_(3)O_(4) through electrochemical activation strategy and shows a Zn^(2+)and H^(+)co-intercalation mechanism.In general,this work provides a new path for the development of high-performance AZIBs cathode with controllable morphology.
基金supported by the National Natural Science Foundation of China(21978088,91534202 and 51673063)sponsored by the Program of Shanghai Academic/Technology Research Leader(20XD1433600)+4 种基金the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutes of High Learningthe Basic Research Program of Shanghai(17JC1402300)the Social Development Program of Shanghai(17DZ1200900)the Shanghai City Board of education research and innovation projectthe Fundamental Research Funds for the Central Universities(222201718002)。
文摘Sodium ions(Na+)and ether electrolyte coinserted graphite possesses a considerable volume expansion effect.However,the mechanism fails to clearly explain its stability.In response to this deficiency,the co-inserted reaction is proposed,which is affected by the Lorentz force of the applied electric field under the high-current condition.The Na^(+)ions are separated out,while the ethylene glycol dimethyl ether molecules remain between the graphite layers.This insight provides a reasonable explanation for the extraordinary stability of this material.In situ X-ray diffraction and density functional theory calculations confirm the separation and release of Na+.On the basis of this result,unmodified commercial graphite was stably cycled 6400 times at a current density of up to 10 A g^(-1),and the capacity retention rate was as high as 97.2%.The full battery assembled in the laboratory has a maximum output power of 14,846 W kg^(-1)and an output energy density of 103 W h kg^(-1)(relative to the weight of anodic and cathodic active materials).The new mechanism provides innovative ideas for the design of large-scale energy storage devices.
