Contrasting with Fe-based Prussian blue analogues(PBAs),Mn-based PBAs with higher energy density are more promising cathode materials for Na-ion batteries.However,fast capacity fading has severely impeded its practica...Contrasting with Fe-based Prussian blue analogues(PBAs),Mn-based PBAs with higher energy density are more promising cathode materials for Na-ion batteries.However,fast capacity fading has severely impeded its practical use,which is still not well understood.To elucidate the fading mechanism,in situ and ex situ electron paramagnetic resonance are employed here.The results first demonstrate the charge delocalization of Mn2+and Mn dissolution during cycles,which are further proved to be highly related.Our work reveals the inherent shortcoming of Mn-based PBA cathodes in liquid electrolyte.展开更多
Layered manganese dioxide(δ-MnO_(2))is a promising cathode material for aqueous zinc-ion batteries(AZIBs)due to its high theoretical capacity,high operating voltage,and low cost.However,its practical application face...Layered manganese dioxide(δ-MnO_(2))is a promising cathode material for aqueous zinc-ion batteries(AZIBs)due to its high theoretical capacity,high operating voltage,and low cost.However,its practical application faces challenges,such as low electronic conductivity,sluggish diffusion kinetics,and severe dissolution of Mn^(2+).In this study,we developed a δ-MnO_(2) coated with a 2-methylimidazole(δ-MnO_(2)@2-ML)hybrid cathode.Density functional theory(DFT)calculations indicate that 2-ML can be integrated into δ-MnO_(2) through both pre-intercalation and surface coating,with thermodynamically favorable outcomes.This modification expands the interlayer spacing of δ-MnO_(2) and generates Mn-N bonds on the surface,enhancing Zn^(2+)accommodation and diffusion kinetics as well as stabilizing surface Mn sites.The experimentally prepared δ-MnO_(2)@2-ML cathode,as predicted by DFT,features both 2-ML pre-intercalation and surface coating,providing more zinc-ion insertion sites and improved structural stability.Furthermore,X-ray diffraction shows the expanded interlayer spacing,which effectively buffers local electrostatic interactions,leading to an enhanced Zn^(2+)diffusion rate.Consequently,the optimized cathode(δ-MnO_(2)@2-ML)presents improved electrochemical performance and stability,and the fabricated AZIBs exhibit a high specific capacity(309.5mAh/g at 0.1 A/g),superior multiplicative performance(137.6mAh/g at 1 A/g),and impressive capacity retention(80%after 1350 cycles at 1 A/g).These results surpass the performance of most manganese-based and vanadium-based cathode materials reported to date.This dual-modulation strategy,combining interlayer engineering and interface optimization,offers a straightforward and scalable approach,potentially advancing the commercial viability of low-cost,high-performance AZIBs.展开更多
Reducing the dissolution of Mn from LiMn_(2)O_(4)(LMO)and enhancing the stability of film electrodes are critical and challenging for Li+ions selective extraction via electrochemically switched ion exchange technology...Reducing the dissolution of Mn from LiMn_(2)O_(4)(LMO)and enhancing the stability of film electrodes are critical and challenging for Li+ions selective extraction via electrochemically switched ion exchange technology.In this work,we prepared a nitrogen-doped carbon cladding LMO(C-N@LMO)by polymerization of polypyrrole and high-temperature annealing in the N2 gas to achieve the above purpose.The modified C-N@LMO film electrode exhibited lower Mn dissolution and better cyclic stability than the LMO film electrode.The dissolution ratio of Mn from the C-N@LMO film electrode decreased by 42%compared to the LMO film electrode after 10 cycles.The cladding layer not only acted as a protective layer but also functioned as a conductive shell,accelerating the migration rate of Li+ions.The intercalation equilibrium time of the C-N@LMO film electrode reached within an hour during the extraction of Li+ions,which was 33%less compared to the pure LMO film electrode.Meanwhile,the C-N@LMO film electrode retained evident selectivity toward Li+ions,and the separation factor was 118.38 for Li+toward Mg2+in simulated brine.Therefore,the C-N@LMO film electrode would be a promising candidate for the recovery of Li+ions from salt lakes.展开更多
A low-carbon future demands more affordable batteries utilizing abundant elements with sustainable end-of-life battery management.Despite the economic and environmental advantages of Li-MnO_(2)batteries,their applica-...A low-carbon future demands more affordable batteries utilizing abundant elements with sustainable end-of-life battery management.Despite the economic and environmental advantages of Li-MnO_(2)batteries,their applica-tion so far has been largely constrained to primary batteries.Here,we demonstrate that one of the major limiting factors preventing the stable cycling of Li-MnO_(2)batteries,Mn dissolution,can be effectively mitigated by employing a common ether electrolyte,1 mol/L lithium bis(trifluorometha-nesulfonyl)imide(LiTFSI)in 1,3-dioxane(DOL)/1,2-dimethoxyethane(DME).We discover that the suppression of this dissolution enables highly reversible cycling of the MnO_(2)cathode regardless of the synthesized phase and morphology.Moreover,we find that both the LiPF_(6)salt and carbonate solvents present in conventional electrolytes are responsible for previous cycling challenges.The ether electrolyte,paired with MnO_(2)cathodes is able to demonstrate stable cycling performance at various rates,even at elevated temperature such as 60℃.Our discovery not only represents a defining step in Li-MnO_(2)batteries with extended life but provides design criteria of electrolytes for vast manganese-based cathodes in rechargeable batteries.展开更多
基金supported by grants from the National Natural Science Foundation of China(grant no.22272055)Scientific and Technological Project in Henan Province(grant no.222102240081)+1 种基金Key Scientific Research Projects in Universities of Henan Province(grant no.22A140014)Technological Project of Anyang City(grant no.201710).
文摘Contrasting with Fe-based Prussian blue analogues(PBAs),Mn-based PBAs with higher energy density are more promising cathode materials for Na-ion batteries.However,fast capacity fading has severely impeded its practical use,which is still not well understood.To elucidate the fading mechanism,in situ and ex situ electron paramagnetic resonance are employed here.The results first demonstrate the charge delocalization of Mn2+and Mn dissolution during cycles,which are further proved to be highly related.Our work reveals the inherent shortcoming of Mn-based PBA cathodes in liquid electrolyte.
基金supported by the the National Natural Science Foundation of China(52203303)the Shenzhen Science and Technology Program(SGDX20211123151002003 and GJHZ20220913142812025)+1 种基金the International Partnership Program of the Chinese Academy of Sciences(321GJHZ2023189FN)the SIAT International Joint Lab(E5G108).
文摘Layered manganese dioxide(δ-MnO_(2))is a promising cathode material for aqueous zinc-ion batteries(AZIBs)due to its high theoretical capacity,high operating voltage,and low cost.However,its practical application faces challenges,such as low electronic conductivity,sluggish diffusion kinetics,and severe dissolution of Mn^(2+).In this study,we developed a δ-MnO_(2) coated with a 2-methylimidazole(δ-MnO_(2)@2-ML)hybrid cathode.Density functional theory(DFT)calculations indicate that 2-ML can be integrated into δ-MnO_(2) through both pre-intercalation and surface coating,with thermodynamically favorable outcomes.This modification expands the interlayer spacing of δ-MnO_(2) and generates Mn-N bonds on the surface,enhancing Zn^(2+)accommodation and diffusion kinetics as well as stabilizing surface Mn sites.The experimentally prepared δ-MnO_(2)@2-ML cathode,as predicted by DFT,features both 2-ML pre-intercalation and surface coating,providing more zinc-ion insertion sites and improved structural stability.Furthermore,X-ray diffraction shows the expanded interlayer spacing,which effectively buffers local electrostatic interactions,leading to an enhanced Zn^(2+)diffusion rate.Consequently,the optimized cathode(δ-MnO_(2)@2-ML)presents improved electrochemical performance and stability,and the fabricated AZIBs exhibit a high specific capacity(309.5mAh/g at 0.1 A/g),superior multiplicative performance(137.6mAh/g at 1 A/g),and impressive capacity retention(80%after 1350 cycles at 1 A/g).These results surpass the performance of most manganese-based and vanadium-based cathode materials reported to date.This dual-modulation strategy,combining interlayer engineering and interface optimization,offers a straightforward and scalable approach,potentially advancing the commercial viability of low-cost,high-performance AZIBs.
基金supported by the National Natural Science Foundation of China(Grant Nos.U21A20303,22078217 and U20A20141).
文摘Reducing the dissolution of Mn from LiMn_(2)O_(4)(LMO)and enhancing the stability of film electrodes are critical and challenging for Li+ions selective extraction via electrochemically switched ion exchange technology.In this work,we prepared a nitrogen-doped carbon cladding LMO(C-N@LMO)by polymerization of polypyrrole and high-temperature annealing in the N2 gas to achieve the above purpose.The modified C-N@LMO film electrode exhibited lower Mn dissolution and better cyclic stability than the LMO film electrode.The dissolution ratio of Mn from the C-N@LMO film electrode decreased by 42%compared to the LMO film electrode after 10 cycles.The cladding layer not only acted as a protective layer but also functioned as a conductive shell,accelerating the migration rate of Li+ions.The intercalation equilibrium time of the C-N@LMO film electrode reached within an hour during the extraction of Li+ions,which was 33%less compared to the pure LMO film electrode.Meanwhile,the C-N@LMO film electrode retained evident selectivity toward Li+ions,and the separation factor was 118.38 for Li+toward Mg2+in simulated brine.Therefore,the C-N@LMO film electrode would be a promising candidate for the recovery of Li+ions from salt lakes.
基金supported by NSF through the UC San Diego Materials Research Science and Engineering Center(UCSD MRSEC)DMR-2011924Part of the work used the UCSD-MTI Battery Fabrication Facility and the UCSDArbin Battery Testing Facility.Electron microscopic characterization was performed at the San Diego Nanotechnology Infrastructure(SDNI)of UCSD,a member of the National Nanotechnology Coordinated Infrastructure,which is supported by the National Science Foundation(Grant No.ECCS-1542148)Use of the Stanford Synchrotron Radiation Light source,SLAC National Accelerator Laboratory,is supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,under Contract No.DE-AC02-76SF00515.
文摘A low-carbon future demands more affordable batteries utilizing abundant elements with sustainable end-of-life battery management.Despite the economic and environmental advantages of Li-MnO_(2)batteries,their applica-tion so far has been largely constrained to primary batteries.Here,we demonstrate that one of the major limiting factors preventing the stable cycling of Li-MnO_(2)batteries,Mn dissolution,can be effectively mitigated by employing a common ether electrolyte,1 mol/L lithium bis(trifluorometha-nesulfonyl)imide(LiTFSI)in 1,3-dioxane(DOL)/1,2-dimethoxyethane(DME).We discover that the suppression of this dissolution enables highly reversible cycling of the MnO_(2)cathode regardless of the synthesized phase and morphology.Moreover,we find that both the LiPF_(6)salt and carbonate solvents present in conventional electrolytes are responsible for previous cycling challenges.The ether electrolyte,paired with MnO_(2)cathodes is able to demonstrate stable cycling performance at various rates,even at elevated temperature such as 60℃.Our discovery not only represents a defining step in Li-MnO_(2)batteries with extended life but provides design criteria of electrolytes for vast manganese-based cathodes in rechargeable batteries.
