Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,a...Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,achieving high energy density in Zn||MnO_(2)batteries remains challenging,highlighting the need to understand the electrochemical reaction mechanisms underlying these batteries more deeply and optimize battery components,including electrodes and electrolytes.This review comprehensively summarizes the latest advancements for understanding the electrochemistry reaction mechanisms and designing electrodes and electrolytes for Zn||MnO_(2)batteries in mildly and strongly acidic environments.Furthermore,we highlight the key challenges hindering the extensive application of Zn||MnO_(2)batteries,including high-voltage requirements and areal capacity,and propose innovative solutions to overcome these challenges.We suggest that MnO_(2)/Mn^(2+)conversion in neutral electrolytes is a crucial aspect that needs to be addressed to achieve high-performance Zn||MnO_(2)batteries.These approaches could lead to breakthroughs in the future development of Zn||MnO_(2)batteries,off ering a more sustainable,costeff ective,and high-performance alternative to traditional batteries.展开更多
The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)...The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.展开更多
Aqueous rechargeable Zn/MnO2 zinc-ion batteries(ZIBs)are reviving recently due to their low cost,non-toxicity,and natural abundance.However,their energy storage mechanism remains controversial due to their complicated...Aqueous rechargeable Zn/MnO2 zinc-ion batteries(ZIBs)are reviving recently due to their low cost,non-toxicity,and natural abundance.However,their energy storage mechanism remains controversial due to their complicated electrochemical reactions.Meanwhile,to achieve satisfactory cyclic stability and rate performance of the Zn/MnO2 ZIBs,Mn2+ is introduced in the electrolyte(e.g.,ZnSO4 solution),which leads to more complicated reactions inside the ZIBs systems.Herein,based on comprehensive analysis methods including electrochemical analysis and Pourbaix diagram,we provide novel insights into the energy storage mechanism of Zn/MnO2 batteries in the presence of Mn2+.A complex series of electrochemical reactions with the coparticipation of Zn2+,H+,Mn2+,SO42-,and OH-were revealed.During the first discharge process,co-insertion of Zn2+ and H+ promotes the transformation of MnO2 into ZnxMnO4,MnOOH,and Mn2O3,accompanying with increased electrolyte pH and the formation of ZnSO4·3 Zn(OH)2-5 H2O.During the subsequent charge process,ZnxMnO4,MnOOH,and Mn2O3 revert to a-MnO2 with the extraction of Zn2+ and H+,while ZnSO4·3Zn(OH)2·5H2O reacts with Mn2+ to form ZnMn3O7·3 H2O.In the following charge/discharge processes,besides aforementioned electrochemical reactions,Zn2+ reversibly insert into/extract from α-MnO2,ZnxMnO4,and ZnMn3O7·3H2O hosts;ZnSO4·3Zn(OH)2·5 H2O,Zn2Mn3O8,and ZnMn2O4 convert mutually with the participation of Mn2+.This work is believed to provide theoretical guidance for further research on high-performance ZIBs.展开更多
The commercialization of electrolytic MnO_(2)-Zn batteries is highly applauded owing to the advantages of cost-effectiveness,high safety,high energy density,and durable working performance.However,due to the low rever...The commercialization of electrolytic MnO_(2)-Zn batteries is highly applauded owing to the advantages of cost-effectiveness,high safety,high energy density,and durable working performance.However,due to the low reversibility of the cathode MnO_(2)/Mn^(2+)chemistry at high areal capacities and the severe Zn anode corrosion,the practical application of MnO_(2)-Zn batteries is hampered by inadequate lifespan.Leveraging the full advantage of an iodine redox mediator,here we design a highly rechargeable electrolytic MnO_(2)-Zn battery with a high areal capacity.The MnO_(2)-Zn battery coupled with an iodine mediator in a mild electrolyte shows a high discharge voltage of 1.85 V and a robust areal capacity of 10 mAh cm^(-2)under a substantial discharge current density of 160 mA cm^(-2).The MnO_(2)/I_(2)-Zn battery with an areal capacity of 10 mAh cm^(-2)exhibits prolonged stability of over 950 cycles under a high-capacity retention of~94%.The scaled-up MnO_(2)/I_(2)-Zn battery reveals a stable cycle life under a cell capacity of~600 mAh.Moreover,our constructed MnO_(2)/I_(2)-Zn battery demonstrates a practical energy density of~37 Wh kg^(-1)and a competitive energy cost of<18 US$kWh^(-1)by taking into account the cathode,anode,and electrolyte.The MnO_(2)/I_(2)-Zn battery,with its remarkable reversibility and reasonable energy density,enlightens a new arena of large-scale energy storage devices.展开更多
Aqueous rechargeable zinc-based batteries have attracted increasing interest and been considered potential alternatives for state-of-the-art lithium-ion batteries because of the low cost and high safety.Many cathode m...Aqueous rechargeable zinc-based batteries have attracted increasing interest and been considered potential alternatives for state-of-the-art lithium-ion batteries because of the low cost and high safety.Many cathode materials have been gradually developed and demonstrated excellent electrochemical performances.However,the complex electrochemistry,inevitable hydrogen release,and zinc corrosion severely hinder the practical application.The most concerned Zn-MnO_(2)batteries still suffer from the Mn dissolution and formation of byproducts.By adding organic solvents to inhibit the activity of water molecules,the hydrous organic electrolytes provide a sound solution for eliminating the unfavorable factors.Here we report a tetraethylene glycol dimethyl ether-based hydrous organic electrolyte consisting of LiClO_(4)·3H_(2)O and Zn(ClO4)2·6H2O,and a birnessite-type MnO_(2)cathode material for Zn-MnO_(2)batteries.The Li+/Zn2+ions co-(de)insertion mechanism is ascertained by the structural and morphological analyses.The electrostatic interaction between inserted ions and crystal structure is reduced effectively by employment of monovalent Li+ions,which ensures structural stability of cathode materials.Hydrous tetraglyme electrolyte inhibits the activity of water molecules and thus avoids the formation of byproduct Zn_(4)ClO_(4)(OH)7·Meanwhile,highly stable Zn plating/stripping for over 1500 h,an average coulombic efficiency of>99%in long-term cycling,and ultralong storage life(the cells can work well after stored over 1 year)are simultaneously realized in the novel electrolyte.Benefitting from these aspects,the Zn-MnO_(2)batteries manifest high specific capacity of 132 mA h g^(-1),an operating voltage of 1.25 V,and a capacity retention of>98%after 1000 cycles at a current density of 200 mA g^(-1).展开更多
Nanostructured MnO2/CNT composite was synthesized by a soft template approach in the presence of Pluronic P123 surfactant. The product was characterized by X-ray diffraction, thermogravimetric and differential thermal...Nanostructured MnO2/CNT composite was synthesized by a soft template approach in the presence of Pluronic P123 surfactant. The product was characterized by X-ray diffraction, thermogravimetric and differential thermal analyses, Fourier transformed infrared spectroscopy and high-resolution transmission electron microscopy. The results show that the sample consists of poor crystalline α-MnO2 nanorods with a diameter of about 10 nm and a length of 30-50 nm, which absorb on the carbon nanotubes. The electrochemical properties of the product as cathode material for Li-MnO2 cell are evaluated by galvanostatic charge-discharge and electrochemical impedance spectroscopy （EIS）. Compared with pure MnO2 electrode, the MnO2/CNT composite delivers a much larger initial capacity of 275.3 mA-h/g and better rate and cycling performance.展开更多
MnO2/MnO cathode material with superior Zn^2+storage performance is prepared through a simple physical mixing method.The MnO2/MnO nanocomposite with a mixed mass ratio of 12:1 exhibits the highest specific capacity(36...MnO2/MnO cathode material with superior Zn^2+storage performance is prepared through a simple physical mixing method.The MnO2/MnO nanocomposite with a mixed mass ratio of 12:1 exhibits the highest specific capacity(364.2 mA·h/g at 0.2C),good cycle performance(170.4 mA·h/g after 100 cycles)and excellent rate performance(205.7 mA·h/g at 2C).Analysis of cyclic voltammetry(CV)data at various scan rates shows that both diffusioncontrolled insertion behavior and surface capacitive behavior contribute to the Zn2+storage performance of MnO2/MnO cathodes.And the capacitive behavior contributes more at high discharge rates,due to the short paths of ion diffusion and the rapid transfer of electrons.展开更多
The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal‐air battery devices.Herein,an efficient liquid exfoliation strategy was designed for pro...The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal‐air battery devices.Herein,an efficient liquid exfoliation strategy was designed for producing silk‐like FeS2/NiS2 hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn‐air batteries.Because of the unique silk‐like morphology and interface nanocrystal structure,they can catalyze the oxygen evolution reaction(OER)efficiently with a low overpotential of 233 mV at j=10 mA cm?2.This is an improvement from the recently reported catalysts in 1.0 M KOH.Meanwhile,the oxygen reduction reaction(ORR)activity of the silk‐like FeS2/NiS2 hybrid nanocrystals showed an onset potential of 911 mV and a half‐wave potential of 640 mV.In addition,the reversible oxygen electrode activity of the silk‐like FeS2/NiS2 hybrid nanocrystals was calculated to be 0.823 V,based on the potential of the OER and ORR.Further,the homemade rechargeable Zn‐air batteries using FeS2/NiS2 hybrid nanocrystals as the air‐cathode displayed a high open‐circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h.The solid Zn‐air batteries exhibited an excellent rechargeable performance for 15 h.This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices.展开更多
文摘Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,achieving high energy density in Zn||MnO_(2)batteries remains challenging,highlighting the need to understand the electrochemical reaction mechanisms underlying these batteries more deeply and optimize battery components,including electrodes and electrolytes.This review comprehensively summarizes the latest advancements for understanding the electrochemistry reaction mechanisms and designing electrodes and electrolytes for Zn||MnO_(2)batteries in mildly and strongly acidic environments.Furthermore,we highlight the key challenges hindering the extensive application of Zn||MnO_(2)batteries,including high-voltage requirements and areal capacity,and propose innovative solutions to overcome these challenges.We suggest that MnO_(2)/Mn^(2+)conversion in neutral electrolytes is a crucial aspect that needs to be addressed to achieve high-performance Zn||MnO_(2)batteries.These approaches could lead to breakthroughs in the future development of Zn||MnO_(2)batteries,off ering a more sustainable,costeff ective,and high-performance alternative to traditional batteries.
基金financially supported by the National Natural Science Foundation of China(NSFC)(52203261)Natural Science Foundation of Jiangsu Province(BK20210474)the project of research on the industrial application of"controllable synthesis of nanocarbon-based polymer composites and their application in new energy”(N0.CJGJZD20210408092400002).
文摘The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.
基金the financial support from the International Science & Technology Cooperation Program of China (No. 2016YFE0102200)Shenzhen Technical Plan Project (No. JCYJ20160301154114273)+1 种基金National Key Basic Research(973) Program of China (No. 2014CB932400)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01N111)
文摘Aqueous rechargeable Zn/MnO2 zinc-ion batteries(ZIBs)are reviving recently due to their low cost,non-toxicity,and natural abundance.However,their energy storage mechanism remains controversial due to their complicated electrochemical reactions.Meanwhile,to achieve satisfactory cyclic stability and rate performance of the Zn/MnO2 ZIBs,Mn2+ is introduced in the electrolyte(e.g.,ZnSO4 solution),which leads to more complicated reactions inside the ZIBs systems.Herein,based on comprehensive analysis methods including electrochemical analysis and Pourbaix diagram,we provide novel insights into the energy storage mechanism of Zn/MnO2 batteries in the presence of Mn2+.A complex series of electrochemical reactions with the coparticipation of Zn2+,H+,Mn2+,SO42-,and OH-were revealed.During the first discharge process,co-insertion of Zn2+ and H+ promotes the transformation of MnO2 into ZnxMnO4,MnOOH,and Mn2O3,accompanying with increased electrolyte pH and the formation of ZnSO4·3 Zn(OH)2-5 H2O.During the subsequent charge process,ZnxMnO4,MnOOH,and Mn2O3 revert to a-MnO2 with the extraction of Zn2+ and H+,while ZnSO4·3Zn(OH)2·5H2O reacts with Mn2+ to form ZnMn3O7·3 H2O.In the following charge/discharge processes,besides aforementioned electrochemical reactions,Zn2+ reversibly insert into/extract from α-MnO2,ZnxMnO4,and ZnMn3O7·3H2O hosts;ZnSO4·3Zn(OH)2·5 H2O,Zn2Mn3O8,and ZnMn2O4 convert mutually with the participation of Mn2+.This work is believed to provide theoretical guidance for further research on high-performance ZIBs.
基金W.C.acknowledges the startup funds from USTC(Grant#KY2060000150)the Fundamental Research Funds for the Central Universities(WK2060000040).
文摘The commercialization of electrolytic MnO_(2)-Zn batteries is highly applauded owing to the advantages of cost-effectiveness,high safety,high energy density,and durable working performance.However,due to the low reversibility of the cathode MnO_(2)/Mn^(2+)chemistry at high areal capacities and the severe Zn anode corrosion,the practical application of MnO_(2)-Zn batteries is hampered by inadequate lifespan.Leveraging the full advantage of an iodine redox mediator,here we design a highly rechargeable electrolytic MnO_(2)-Zn battery with a high areal capacity.The MnO_(2)-Zn battery coupled with an iodine mediator in a mild electrolyte shows a high discharge voltage of 1.85 V and a robust areal capacity of 10 mAh cm^(-2)under a substantial discharge current density of 160 mA cm^(-2).The MnO_(2)/I_(2)-Zn battery with an areal capacity of 10 mAh cm^(-2)exhibits prolonged stability of over 950 cycles under a high-capacity retention of~94%.The scaled-up MnO_(2)/I_(2)-Zn battery reveals a stable cycle life under a cell capacity of~600 mAh.Moreover,our constructed MnO_(2)/I_(2)-Zn battery demonstrates a practical energy density of~37 Wh kg^(-1)and a competitive energy cost of<18 US$kWh^(-1)by taking into account the cathode,anode,and electrolyte.The MnO_(2)/I_(2)-Zn battery,with its remarkable reversibility and reasonable energy density,enlightens a new arena of large-scale energy storage devices.
基金supported by the National Natural Science Foundation of China(U1801255,91963210)the National Natural Science Foundation of Guangzhou,China(202201011414)。
文摘Aqueous rechargeable zinc-based batteries have attracted increasing interest and been considered potential alternatives for state-of-the-art lithium-ion batteries because of the low cost and high safety.Many cathode materials have been gradually developed and demonstrated excellent electrochemical performances.However,the complex electrochemistry,inevitable hydrogen release,and zinc corrosion severely hinder the practical application.The most concerned Zn-MnO_(2)batteries still suffer from the Mn dissolution and formation of byproducts.By adding organic solvents to inhibit the activity of water molecules,the hydrous organic electrolytes provide a sound solution for eliminating the unfavorable factors.Here we report a tetraethylene glycol dimethyl ether-based hydrous organic electrolyte consisting of LiClO_(4)·3H_(2)O and Zn(ClO4)2·6H2O,and a birnessite-type MnO_(2)cathode material for Zn-MnO_(2)batteries.The Li+/Zn2+ions co-(de)insertion mechanism is ascertained by the structural and morphological analyses.The electrostatic interaction between inserted ions and crystal structure is reduced effectively by employment of monovalent Li+ions,which ensures structural stability of cathode materials.Hydrous tetraglyme electrolyte inhibits the activity of water molecules and thus avoids the formation of byproduct Zn_(4)ClO_(4)(OH)7·Meanwhile,highly stable Zn plating/stripping for over 1500 h,an average coulombic efficiency of>99%in long-term cycling,and ultralong storage life(the cells can work well after stored over 1 year)are simultaneously realized in the novel electrolyte.Benefitting from these aspects,the Zn-MnO_(2)batteries manifest high specific capacity of 132 mA h g^(-1),an operating voltage of 1.25 V,and a capacity retention of>98%after 1000 cycles at a current density of 200 mA g^(-1).
基金Projects(21071153,20976198)supported by the National Natural Science Foundation of China
文摘Nanostructured MnO2/CNT composite was synthesized by a soft template approach in the presence of Pluronic P123 surfactant. The product was characterized by X-ray diffraction, thermogravimetric and differential thermal analyses, Fourier transformed infrared spectroscopy and high-resolution transmission electron microscopy. The results show that the sample consists of poor crystalline α-MnO2 nanorods with a diameter of about 10 nm and a length of 30-50 nm, which absorb on the carbon nanotubes. The electrochemical properties of the product as cathode material for Li-MnO2 cell are evaluated by galvanostatic charge-discharge and electrochemical impedance spectroscopy （EIS）. Compared with pure MnO2 electrode, the MnO2/CNT composite delivers a much larger initial capacity of 275.3 mA-h/g and better rate and cycling performance.
基金Project(21905304)supported by the National Natural Science Foundation of ChinaProject(ZR2019BEM031)supported by the Natural Science Foundation of Shandong Province,ChinaProjects(18CX02158A,19CX05001A)supported by the Fundamental Research Funds for the Central Universities,China。
文摘MnO2/MnO cathode material with superior Zn^2+storage performance is prepared through a simple physical mixing method.The MnO2/MnO nanocomposite with a mixed mass ratio of 12:1 exhibits the highest specific capacity(364.2 mA·h/g at 0.2C),good cycle performance(170.4 mA·h/g after 100 cycles)and excellent rate performance(205.7 mA·h/g at 2C).Analysis of cyclic voltammetry(CV)data at various scan rates shows that both diffusioncontrolled insertion behavior and surface capacitive behavior contribute to the Zn2+storage performance of MnO2/MnO cathodes.And the capacitive behavior contributes more at high discharge rates,due to the short paths of ion diffusion and the rapid transfer of electrons.
基金supported by the National Basic Research Program of China(21571089,21503102,51571125)the Fundamental Research Funds for the Central Universities(lzujbky-2016-k02,lzujbky-2018-k08,lzujbky-2017-it42)~~
文摘The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal‐air battery devices.Herein,an efficient liquid exfoliation strategy was designed for producing silk‐like FeS2/NiS2 hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn‐air batteries.Because of the unique silk‐like morphology and interface nanocrystal structure,they can catalyze the oxygen evolution reaction(OER)efficiently with a low overpotential of 233 mV at j=10 mA cm?2.This is an improvement from the recently reported catalysts in 1.0 M KOH.Meanwhile,the oxygen reduction reaction(ORR)activity of the silk‐like FeS2/NiS2 hybrid nanocrystals showed an onset potential of 911 mV and a half‐wave potential of 640 mV.In addition,the reversible oxygen electrode activity of the silk‐like FeS2/NiS2 hybrid nanocrystals was calculated to be 0.823 V,based on the potential of the OER and ORR.Further,the homemade rechargeable Zn‐air batteries using FeS2/NiS2 hybrid nanocrystals as the air‐cathode displayed a high open‐circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h.The solid Zn‐air batteries exhibited an excellent rechargeable performance for 15 h.This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices.
