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 Zn metal batteries(AZMBs)with intrinsic safety,high energy density and low cost have been regarded as promising electrochemical energy storage devices.However,the parasitic reaction on metallic Zn anode and th...Aqueous Zn metal batteries(AZMBs)with intrinsic safety,high energy density and low cost have been regarded as promising electrochemical energy storage devices.However,the parasitic reaction on metallic Zn anode and the incompatibility between electrode and electrolytes lead to the deterioration of electrochemical performance of AZMBs during the cycling.The critical point to achieve the stable cycling of AZMBs is to properly regulate the zinc ion solvated structure and transfer behavior between metallic Zn anode and electrolyte.In recent years,numerous achievements have been made to resolve the formation of Zn dendrite and interface incompatible issues faced by AZMBs via optimizing the sheath structure and transport capability of zinc ions at electrode-electrolyte interface.In this review,the challenges for metallic Zn anode and electrode-electrolyte interface in AZMBs including dendrite formation and interface characteristics are presented.Following the influences of different strategies involving designing advanced electrode structu re,artificial solid electrolyte interphase(SEI)on Zn anode and electrolyte engineering to regulate zinc ion solvated sheath structure and transport behavior are summarized and discussed.Finally,the perspectives for the future development of design strategies for dendrite-free Zn metal anode and long lifespan AZMBs are also given.展开更多
As an alternative to Li-ion batteries,aqueous Zn batteries have gained attention due to the abundance of Zn metal,low reduction potential(-0.76 V vs.standard hydrogen electrode),and high theoretical capacity(820 mAh g...As an alternative to Li-ion batteries,aqueous Zn batteries have gained attention due to the abundance of Zn metal,low reduction potential(-0.76 V vs.standard hydrogen electrode),and high theoretical capacity(820 mAh g^(-1))of multivalent Zn2+ion.However,the growth of Zn dendrites and the formation of irreversible surface reaction byproducts pose challenges for ensuring a long battery lifespan and commercialization.Herein,the Cu foil coated with a single-walled carbon nanotube(SWCNT)layer using a facile doctor blade casting method is utilized.The SWCNT-coated Cu foil demonstrates a significantly longer battery lifespan compared to the bare Cu in the half-cell tests.Through operando optical microscopy imaging,we are able to provide intuitive evidence that Zn deposition occurs between the carbon nanotube(CNT)coating and Cu substrate,in agreement with the computational results.Also,with various imaging techniques,the flat morphology and homogeneous distribution of Zn beneath the SWCNT layer are demonstrated.In addition,the full-cell using CNT-coated Cu exhibits a long cycle life compared to the control group,thereby demonstrating improved electrochemical performance with limited Zn for the cycling process.展开更多
The construction of Zn based hybrid battery through the combination of Zn-air and Zn-Co3O4 batteries at cell level is a feasible strategy to integrate high voltage,specific capacity and energy density in one power sup...The construction of Zn based hybrid battery through the combination of Zn-air and Zn-Co3O4 batteries at cell level is a feasible strategy to integrate high voltage,specific capacity and energy density in one power supply equipment.For Zn based hybrid battery,an efficient cathode material with high specific capacitance and excellent ORR,OER activities is a vital component,which determines its performance in great extent.In this work,with Co based coordination polymer as precursor,oxygen vacancy-rich Co3 O4 based cathode material is synthesized.In this material Co3O4 particles with the size about 20 to 35 nm reside evenly in mesoporous carbon matrix doped by nitrogen atoms.In OER,the overpotential of this cathode material is merely 330 m V.Its ORR proceeds with a typical four electron process with half wave achieving 0.76 V.If charge/discharge at 1 A·g^-1,specific capacitance of this cathode material is 254.4 mAh·g^-1.As current density increases to 20 A·g^-1,the specific capacitance still arrives at 122.5 mAh·g^-1 with nearly 50%retained.Based on attractive performance of this cathode material,Zn based hybrid battery is assembled.When discharge at 1 m A·cm-2,it presences two voltage platforms at 1.71 and 1.14 V.In this situation,specific capacitance reaches 790 m Ah·g^-1 with energy density 928 Wh·kg^-1.Hybrid battery shows promising stability after 300-cycle continuous test.展开更多
The development of aqueous Zn batteries is limited by parasitic water reactions,corrosion,and dendrite growth.To address these challenges,an inner Helmholtz plane(IHP)regulation method is proposed by employing low-cos...The development of aqueous Zn batteries is limited by parasitic water reactions,corrosion,and dendrite growth.To address these challenges,an inner Helmholtz plane(IHP)regulation method is proposed by employing low-cost,non-toxic maltitol as the electrolyte additive.The preferential adsorption behavior of maltitol can expel the water from the inner Helmholtz plane,and thus hinder the immediate contact between Zn metal and H_(2)O.Meanwhile,strong interaction between maltitol and H_(2)O molecules can restrain the activity of H_(2)O.Besides,the"IHP adsorption effect"along with the low LUMO energy level of maltitol-CF_(3)SO_(3)^(-)can promote the in-situ formation of an organic-inorganic complex solid electrolyte interface(SEI)layer.As a result,the hydrogen/oxygen evolution side reaction,corrosion,and dendrites issues are effectively suppressed,thereby leading to highly reversible and dendrite-free Zn plating/stripping.The Zn‖I_(2)battery with hybrid electrolytes also demonstrates high electrochemical performance and ultralong cycling stability,showing a capacity retention of 75%over 20000 charge-discharge cycles at a large current density of 5 A g^(-1).In addition,the capacity of the device has almost no obvious decay over20000 cycles even at-30℃.This work offers a successful electrolyte regulation strategy via the IHP adsorption effect to design electrolytes for high-performance rechargeable Zn-ion batteries.展开更多
Developing an e cient and durable oxygen reduction electrocatalyst is critical for clean-energy technology, such as fuel cells and metal–air batteries. In this study, we developed a facile strategy for the preparatio...Developing an e cient and durable oxygen reduction electrocatalyst is critical for clean-energy technology, such as fuel cells and metal–air batteries. In this study, we developed a facile strategy for the preparation of flexible, porous, and well-dispersed metal–heteroatom-doped carbon nanofibers by direct carbonization of electrospun Zn/Co-ZIFs/PAN nanofibers(Zn/Co-ZIFs/PAN). The obtained Zn/Co and N co-doped porous carbon nanofibers carbonized at 800 °C(Zn/Co–N@PCNFs-800) presented a good flexibility, a continuous porous structure, and a superior oxygen reduction reaction(ORR) catalytic activity to that of commercial 20 wt% Pt/C, in terms of its onset potential(0.98 V vs. RHE), half-wave potential(0.89 V vs. RHE), and limiting current density(-5.26 mA cm^(-2)). In addition, we tested the suitability and durability of Zn/Co–N@PCNFs-800 as the oxygen cathode for a rechargeable Zn–air battery. The prepared Zn–air batteries exhibited a higher power density(83.5 mW cm^(-2)), a higher specific capacity(640.3 mAh g^(-1)), an excellent reversibility, and a better cycling life than the commercial 20 wt% Pt/C + RuO_2 catalysts. This design strategy of flexible porous non-precious metal-doped ORR electrocatalysts obtained from electrospun ZIFs/polymer nanofibers could be extended to fabricate other novel, stable, and easy-to-use multi-functional electrocatalysts for clean-energy technology.展开更多
An in situ coupling strategy to prepare Co_9S_8/S and N dual?doped graphene composite(Co_9S_8/NSG) has been proposed. The key point of this strategy is the function?oriented design of organic compounds. Herein, cobalt...An in situ coupling strategy to prepare Co_9S_8/S and N dual?doped graphene composite(Co_9S_8/NSG) has been proposed. The key point of this strategy is the function?oriented design of organic compounds. Herein, cobalt porphyrin derivatives with sulfo groups are employed as not only the coupling agents to form and anchor Co_9S_8 on the graphene in situ, but also the heteroatom?doped agent to generate S and N dual?doped graphene. The tight coupling of multiple active sites endows the composite materials with fast electrochemical kinetics and excellent stability for both oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The obtained electrocatalyst exhibits better activity parameter(ΔE = 0.82 V) and smaller Tafel slope(47.7 mV dec^(-1) for ORR and 69.2 mV dec^(-1) for OER) than commercially available Pt/C and RuO_2. Most importantly, as electrocatalyst for rechargeable Zn–air battery, Co_9S_8/NSG displays low charge–discharge voltage gap and outstanding long?term cycle stability over 138 h compared to Pt/C–RuO_2. To further broaden its application scope, a homemade all?solid?state Zn–air battery is also prepared, which displays good charge–discharge performance and cycle performance. The function?oriented design of N_4?metallomacrocycle derivatives might open new avenues to strategic construction of high?performance and long?life multifunctional electrocatalysts for wider electro?chemical energy applications.展开更多
The development of e cient earth-abundant electrocatalysts for oxygen reduction, oxygen evolution, and hydrogen evolution reactions(ORR, OER, and HER) is important for future energy conversion and energy storage devic...The development of e cient earth-abundant electrocatalysts for oxygen reduction, oxygen evolution, and hydrogen evolution reactions(ORR, OER, and HER) is important for future energy conversion and energy storage devices, for which both rechargeable Zn–air batteries and water splitting have raised great expectations. Herein, we report a single-phase bimetallic nickel cobalt sulfide((Ni,Co)S_2) as an e cient electrocatalyst for both OER and ORR. Owing to the synergistic combination of Ni and Co, the(Ni,Co)S_2 exhibits superior electrocatalytic performance for ORR, OER, and HER in an alkaline electrolyte, and the first principle calculation results indicate that the reaction of an adsorbed O atom with a H_2O molecule to form a *OOH is the potential limiting step in the OER. Importantly, it could be utilized as an advanced air electrode material in Zn–air batteries, which shows an enhanced charge–discharge performance(charging voltage of 1.71 V and discharge voltage of 1.26 V at 2 mA cm^(-2)), large specific capacity(842 mAh g_(Zn)^(-1) at 5 mA cm^(-2)), and excellent cycling stability(480 h). Interestingly, the(Ni,Co)S_2-based Zn–air battery can e ciently power an electrochemical water-splitting unit with(Ni,Co)S_2 serving as both the electrodes. This reveals that the prepared(Ni,Co)S_2 has promising applications in future energy conversion and energy storage devices.展开更多
The overall electrochemical performances of Ni-Zn batteries are still far from satisfactory, specifically for rate performance and cycling stability Herein, we demonstrated a high-performance flexible Ni//Zn battery w...The overall electrochemical performances of Ni-Zn batteries are still far from satisfactory, specifically for rate performance and cycling stability Herein, we demonstrated a high-performance flexible Ni//Zn battery with outstanding durability and high power density based on selfsupported NiCo_2 O_4 nanosheets as cathode and Zn nanosheets as anode. This Ni//Zn battery is able to deliver a remarkable capacity of183.1 mAh g^(-1) and a good cycling performance(82.7% capacity retention after 3500 cycles). More importantly, this battery achieves an admirable power density of 49.0 kW kg^(-1) and energy density of 303.8 Wh kg^(-1), substantially higher than most recently reported batteries. With such excellent electrochemical performance, this battery will have great potential as an ultrafast power source in practical application.展开更多
High-performance flexible one-dimensional(1D)electrochemical energy storage devices are crucial for the applications of wearable electronics.Although much progress on various 1D energy storage devices has been made,ch...High-performance flexible one-dimensional(1D)electrochemical energy storage devices are crucial for the applications of wearable electronics.Although much progress on various 1D energy storage devices has been made,challenges involving fabrication cost,scalability,and efficiency remain.Herein,a highperformance flexible all-fiber zinc-ion battery(ZIB)is fabricated using a low-cost,scalable,and efficient continuous wet-spinning method.Viscous composite inks containing cellulose nanofibers/carbon nanotubes(CNFs/CNTs)binary composite network and either manganese dioxide nanowires(MnO_(2) NWs)or commercial Zn powders are utilized to spinning fiber cathodes and anodes,respectively.MnO_(2) NWs and Zn powders are uniformly dispersed in the interpenetrated CNFs/CNTs fibrous network,leading to homogenous composite inks with an ideal shear-thinning property.The obtained fiber electrodes demonstrate favorable uniformity and flexibility.Benefiting from the well-designed electrodes,the assembled flexible fiber-shaped ZIB delivers a high specific capacity of 281.5 m Ah g^(-1) at 0.25 A g^(-1) and displays excellent cycling stability over 400 cycles.Moreover,the wet-spun fiber-shaped ZIBs achieve ultrahigh gravimetric and volumetric energy densities of 47.3 Wh kg^(-1) and 131.3 m Wh cm^(-3),respectively,based on both cathode and anode and maintain favorable stability even after 4000 bending cycles.This work offers a new concept design of 1D flexible ZIBs that can be potentially incorporated into commercial textiles for wearable and portable electronics.展开更多
Combining the unique advantages of aqueous electrolytes and metallic Zn anode, rechargeable aqueous Zn-ion batteries(ZIBs) are of great promise for large-scale energy storage applications due to their inherent high sa...Combining the unique advantages of aqueous electrolytes and metallic Zn anode, rechargeable aqueous Zn-ion batteries(ZIBs) are of great promise for large-scale energy storage applications due to their inherent high safety, low cost, and environmental friendliness. As the essential component of ZIBs, Zn metal anode suffers from severe dendrite formation and inevitable side reactions(e.g. corrosion and hydrogen evolution)in aqueous electrolytes, which leads to low Coulombic efficiency and inferior cycling stability, impeding their large-scale applications. To be compatible with satisfactory aqueous ZIBs, Zn anode has been modified from various perspectives and focus areas. Herein, based on their intrinsic characteristics, we review the related improvement strategies for Zn anode, including interphase, substrate, and bulk design, so as to achieve an in-depth understanding of Zn anode optimization. Furthermore, the timely summary of characterization methods for Zn anodes are also performed for the first time, from both thermodynamic and kinetics perspectives, which is particularly helpful for beginners to understand the complicated characterizations and employ suitable methods. Finally, certain noteworthy points are put forward for subsequent investigation of aqueous ZIBs. It is expected that this review will enlighten researchers to explore more efficient optimization strategies for Zn anode in aqueous electrolytes.展开更多
One approach to accelerate the stagnant kinetics of both the oxygen reduction and evolution reactions(ORR/OER)is to develop a rationally designed multiphase nanocomposite,where the functions arising from each of the c...One approach to accelerate the stagnant kinetics of both the oxygen reduction and evolution reactions(ORR/OER)is to develop a rationally designed multiphase nanocomposite,where the functions arising from each of the constituent phases,their interfaces,and the overall structure are properly controlled.Herein,we successfully synthesized an oxygen electrocatalyst consisting of Ni nanoparticles purposely interpenetrated into mesoporous NiO nanosheets(porous Ni/NiO).Benefiting from the contributions of the Ni and NiO phases,the well-established pore channels for charge transport at the interface between the phases,and the enhanced conductivity due to oxygen-deficiency at the pore edges,the porous Ni/NiO nanosheets show a potential of 1.49 V(10 mA cm^-2)for the OER and a half-wave potential of 0.76 V for the ORR,outperforming their noble metal counterparts.More significantly,a Zn-air battery employing the porous Ni/NiO nanosheets exhibits an initial charging-discharging voltage gap of 0.83 V(2 mA cm^-2),specific capacity of 853 mAh gZn^-1 at 20 mA cm^-2,and long-time cycling stability(120 h).In addition,the porous Ni/NiO-based solid-like Zn-air battery shows excellent electrochemical performance and flexibility,illustrating its great potential as a next-generation rechargeable power source for flexible electronics.展开更多
The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries(AZMBs).However,the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commerci...The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries(AZMBs).However,the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commercial applications.To address these issues,a novel anode-free Zniodine battery(AFZIB)was designed via a simple,low-cost and scalable approach.Iodine plays bifunctional roles in improving the AFZIB overall performance:enabling high-performance Zn-rich cathode and modulating Zn deposition behavior.On the cathode side,the ZnI_(2) serves as Zn-rich cathode material.The graphene/polyvinyl pyrrolidone heterostructure was employed as an efficient host for ZnI_(2) to enhance electron conductivity and suppress the shuttle effect of iodine species.On the anode side,trace I_(3)^(−) additive in the electrolyte creates surface reconstruction on the commercial Cu foil.The in situ formed zincophilic Cu nanocluster allows ultralow-overpotential and uniform Zn deposition and superior reversibility(average coulombic efficiency>99.91% over 7,000 cycles).Based on such a configuration,AFZIB exhibits significantly increased energy density(162 Wh kg^(−1)) and durable cycle stability(63.8% capacity retention after 200 cycles)under practical application conditions.Considering the low cost and simple preparation methods of the electrode materials,this work paves the way for the practical application of AZMBs.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supported by the National Key Research and Development Programs(2021YFB2400400)Major Science and Technology Innovation Project of Hunan Province(2020GK10102020GK1014-4)+7 种基金National Natural Science Foundation of China(32201162)the 70th general grant of China Postdoctoral Science Foundation(2021M702947)Natural Science Foundation of Henan(232300420404)Key Scientific and Technological Project of Henan Province(232102320290,232102311156)Key Research Project Plan for Higher Education Institutions in Henan Province(24A150009,23B430011)Doctor Foundation of Henan University of Engineering(D2022002)the Science and Technology Innovation Program of Hunan Province(2023RC3154)the scientific research projects of Education Department of Hunan Province(23A0188)。
文摘Aqueous Zn metal batteries(AZMBs)with intrinsic safety,high energy density and low cost have been regarded as promising electrochemical energy storage devices.However,the parasitic reaction on metallic Zn anode and the incompatibility between electrode and electrolytes lead to the deterioration of electrochemical performance of AZMBs during the cycling.The critical point to achieve the stable cycling of AZMBs is to properly regulate the zinc ion solvated structure and transfer behavior between metallic Zn anode and electrolyte.In recent years,numerous achievements have been made to resolve the formation of Zn dendrite and interface incompatible issues faced by AZMBs via optimizing the sheath structure and transport capability of zinc ions at electrode-electrolyte interface.In this review,the challenges for metallic Zn anode and electrode-electrolyte interface in AZMBs including dendrite formation and interface characteristics are presented.Following the influences of different strategies involving designing advanced electrode structu re,artificial solid electrolyte interphase(SEI)on Zn anode and electrolyte engineering to regulate zinc ion solvated sheath structure and transport behavior are summarized and discussed.Finally,the perspectives for the future development of design strategies for dendrite-free Zn metal anode and long lifespan AZMBs are also given.
基金Ministry of Science and ICT,South Korea,Grant/Award Number:C310200National Research Foundation of Korea(NRF),Grant/Award Number:2020R1C1C1012308。
文摘As an alternative to Li-ion batteries,aqueous Zn batteries have gained attention due to the abundance of Zn metal,low reduction potential(-0.76 V vs.standard hydrogen electrode),and high theoretical capacity(820 mAh g^(-1))of multivalent Zn2+ion.However,the growth of Zn dendrites and the formation of irreversible surface reaction byproducts pose challenges for ensuring a long battery lifespan and commercialization.Herein,the Cu foil coated with a single-walled carbon nanotube(SWCNT)layer using a facile doctor blade casting method is utilized.The SWCNT-coated Cu foil demonstrates a significantly longer battery lifespan compared to the bare Cu in the half-cell tests.Through operando optical microscopy imaging,we are able to provide intuitive evidence that Zn deposition occurs between the carbon nanotube(CNT)coating and Cu substrate,in agreement with the computational results.Also,with various imaging techniques,the flat morphology and homogeneous distribution of Zn beneath the SWCNT layer are demonstrated.In addition,the full-cell using CNT-coated Cu exhibits a long cycle life compared to the control group,thereby demonstrating improved electrochemical performance with limited Zn for the cycling process.
基金supported by the National Natural Science Foundation of China(21303010)Fundamental Research Funds for the Central University(N170504025)。
文摘The construction of Zn based hybrid battery through the combination of Zn-air and Zn-Co3O4 batteries at cell level is a feasible strategy to integrate high voltage,specific capacity and energy density in one power supply equipment.For Zn based hybrid battery,an efficient cathode material with high specific capacitance and excellent ORR,OER activities is a vital component,which determines its performance in great extent.In this work,with Co based coordination polymer as precursor,oxygen vacancy-rich Co3 O4 based cathode material is synthesized.In this material Co3O4 particles with the size about 20 to 35 nm reside evenly in mesoporous carbon matrix doped by nitrogen atoms.In OER,the overpotential of this cathode material is merely 330 m V.Its ORR proceeds with a typical four electron process with half wave achieving 0.76 V.If charge/discharge at 1 A·g^-1,specific capacitance of this cathode material is 254.4 mAh·g^-1.As current density increases to 20 A·g^-1,the specific capacitance still arrives at 122.5 mAh·g^-1 with nearly 50%retained.Based on attractive performance of this cathode material,Zn based hybrid battery is assembled.When discharge at 1 m A·cm-2,it presences two voltage platforms at 1.71 and 1.14 V.In this situation,specific capacitance reaches 790 m Ah·g^-1 with energy density 928 Wh·kg^-1.Hybrid battery shows promising stability after 300-cycle continuous test.
基金supported by the National Natural Science Foundation of China(52261160384)the Shenzhen Science and Technology Innovation Commission(RCYX20221008092934093)+1 种基金the Shenzhen Science and Technology Program(KJZD20230923114107014)the support from Testing Technology Center of Materials and Devices,Tsinghua Shenzhen International Graduate School。
文摘The development of aqueous Zn batteries is limited by parasitic water reactions,corrosion,and dendrite growth.To address these challenges,an inner Helmholtz plane(IHP)regulation method is proposed by employing low-cost,non-toxic maltitol as the electrolyte additive.The preferential adsorption behavior of maltitol can expel the water from the inner Helmholtz plane,and thus hinder the immediate contact between Zn metal and H_(2)O.Meanwhile,strong interaction between maltitol and H_(2)O molecules can restrain the activity of H_(2)O.Besides,the"IHP adsorption effect"along with the low LUMO energy level of maltitol-CF_(3)SO_(3)^(-)can promote the in-situ formation of an organic-inorganic complex solid electrolyte interface(SEI)layer.As a result,the hydrogen/oxygen evolution side reaction,corrosion,and dendrites issues are effectively suppressed,thereby leading to highly reversible and dendrite-free Zn plating/stripping.The Zn‖I_(2)battery with hybrid electrolytes also demonstrates high electrochemical performance and ultralong cycling stability,showing a capacity retention of 75%over 20000 charge-discharge cycles at a large current density of 5 A g^(-1).In addition,the capacity of the device has almost no obvious decay over20000 cycles even at-30℃.This work offers a successful electrolyte regulation strategy via the IHP adsorption effect to design electrolytes for high-performance rechargeable Zn-ion batteries.
基金the Natural Science Foundation of Jiangsu Province (Grant No. BK20171200) for their financial support
文摘Developing an e cient and durable oxygen reduction electrocatalyst is critical for clean-energy technology, such as fuel cells and metal–air batteries. In this study, we developed a facile strategy for the preparation of flexible, porous, and well-dispersed metal–heteroatom-doped carbon nanofibers by direct carbonization of electrospun Zn/Co-ZIFs/PAN nanofibers(Zn/Co-ZIFs/PAN). The obtained Zn/Co and N co-doped porous carbon nanofibers carbonized at 800 °C(Zn/Co–N@PCNFs-800) presented a good flexibility, a continuous porous structure, and a superior oxygen reduction reaction(ORR) catalytic activity to that of commercial 20 wt% Pt/C, in terms of its onset potential(0.98 V vs. RHE), half-wave potential(0.89 V vs. RHE), and limiting current density(-5.26 mA cm^(-2)). In addition, we tested the suitability and durability of Zn/Co–N@PCNFs-800 as the oxygen cathode for a rechargeable Zn–air battery. The prepared Zn–air batteries exhibited a higher power density(83.5 mW cm^(-2)), a higher specific capacity(640.3 mAh g^(-1)), an excellent reversibility, and a better cycling life than the commercial 20 wt% Pt/C + RuO_2 catalysts. This design strategy of flexible porous non-precious metal-doped ORR electrocatalysts obtained from electrospun ZIFs/polymer nanofibers could be extended to fabricate other novel, stable, and easy-to-use multi-functional electrocatalysts for clean-energy technology.
基金supported by the National Natural Science Foundation of China (Grant No. 21404014)the Science & Technology Department of Jilin Province (No. 20170101177JC)
文摘An in situ coupling strategy to prepare Co_9S_8/S and N dual?doped graphene composite(Co_9S_8/NSG) has been proposed. The key point of this strategy is the function?oriented design of organic compounds. Herein, cobalt porphyrin derivatives with sulfo groups are employed as not only the coupling agents to form and anchor Co_9S_8 on the graphene in situ, but also the heteroatom?doped agent to generate S and N dual?doped graphene. The tight coupling of multiple active sites endows the composite materials with fast electrochemical kinetics and excellent stability for both oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The obtained electrocatalyst exhibits better activity parameter(ΔE = 0.82 V) and smaller Tafel slope(47.7 mV dec^(-1) for ORR and 69.2 mV dec^(-1) for OER) than commercially available Pt/C and RuO_2. Most importantly, as electrocatalyst for rechargeable Zn–air battery, Co_9S_8/NSG displays low charge–discharge voltage gap and outstanding long?term cycle stability over 138 h compared to Pt/C–RuO_2. To further broaden its application scope, a homemade all?solid?state Zn–air battery is also prepared, which displays good charge–discharge performance and cycle performance. The function?oriented design of N_4?metallomacrocycle derivatives might open new avenues to strategic construction of high?performance and long?life multifunctional electrocatalysts for wider electro?chemical energy applications.
基金supported by the National Natural Science Foundation of China (Grant Nos. 11474137 and 11674143)Program for Changjiang Scholars and Innovative Research Team in University (IRT 16R35)+1 种基金the Fundamental Research Funds for the Central Universities (Grant Nos. LZUMMM2018017, lzujbky-2018-121)the support of Ministry of Education (MOE2016-T2-2-138,Singapore),for research conducted at the National University of Singapore
文摘The development of e cient earth-abundant electrocatalysts for oxygen reduction, oxygen evolution, and hydrogen evolution reactions(ORR, OER, and HER) is important for future energy conversion and energy storage devices, for which both rechargeable Zn–air batteries and water splitting have raised great expectations. Herein, we report a single-phase bimetallic nickel cobalt sulfide((Ni,Co)S_2) as an e cient electrocatalyst for both OER and ORR. Owing to the synergistic combination of Ni and Co, the(Ni,Co)S_2 exhibits superior electrocatalytic performance for ORR, OER, and HER in an alkaline electrolyte, and the first principle calculation results indicate that the reaction of an adsorbed O atom with a H_2O molecule to form a *OOH is the potential limiting step in the OER. Importantly, it could be utilized as an advanced air electrode material in Zn–air batteries, which shows an enhanced charge–discharge performance(charging voltage of 1.71 V and discharge voltage of 1.26 V at 2 mA cm^(-2)), large specific capacity(842 mAh g_(Zn)^(-1) at 5 mA cm^(-2)), and excellent cycling stability(480 h). Interestingly, the(Ni,Co)S_2-based Zn–air battery can e ciently power an electrochemical water-splitting unit with(Ni,Co)S_2 serving as both the electrodes. This reveals that the prepared(Ni,Co)S_2 has promising applications in future energy conversion and energy storage devices.
基金supported by the Guangdong Natural Science Funds for Distinguished Young Scholar (2014A030306048)National Natural Science Foundation of China (21403306)+3 种基金Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program (2015TQO1C205)Pearl River Nova Program of Guangzhou (201610010080)Open Fund of Jiangsu Key Laboratory of Materials and Technology for Energy Conversion (MTEC-2015M05)Training Program of Scientific and Technological Innovation for Undergraduates (pdjh2017a0003)
文摘The overall electrochemical performances of Ni-Zn batteries are still far from satisfactory, specifically for rate performance and cycling stability Herein, we demonstrated a high-performance flexible Ni//Zn battery with outstanding durability and high power density based on selfsupported NiCo_2 O_4 nanosheets as cathode and Zn nanosheets as anode. This Ni//Zn battery is able to deliver a remarkable capacity of183.1 mAh g^(-1) and a good cycling performance(82.7% capacity retention after 3500 cycles). More importantly, this battery achieves an admirable power density of 49.0 kW kg^(-1) and energy density of 303.8 Wh kg^(-1), substantially higher than most recently reported batteries. With such excellent electrochemical performance, this battery will have great potential as an ultrafast power source in practical application.
基金financially supported by the National Science Fund for Distinguished Young Scholars(52025133)the Beijing Natural Science Foundation(JQ18005)+7 种基金the Tencent Foundation through the XPLORER PRIZE,the National Key R&D Program of China(2017YFA0206701)the BIC-ESAT fundingthe financial support of the Central Universities(2232020D-13)the Shanghai Sailing Program(20YF1400700)the National Natural Science Foundation of China(52003045)the financial support from the Young Elite Scientist Sponsorship Program by CAST(2019QNRC001)the“1000-Plan program”of Shaanxi Provincethe“Young Talent Support Plan”of Xi’an Jiaotong University。
文摘High-performance flexible one-dimensional(1D)electrochemical energy storage devices are crucial for the applications of wearable electronics.Although much progress on various 1D energy storage devices has been made,challenges involving fabrication cost,scalability,and efficiency remain.Herein,a highperformance flexible all-fiber zinc-ion battery(ZIB)is fabricated using a low-cost,scalable,and efficient continuous wet-spinning method.Viscous composite inks containing cellulose nanofibers/carbon nanotubes(CNFs/CNTs)binary composite network and either manganese dioxide nanowires(MnO_(2) NWs)or commercial Zn powders are utilized to spinning fiber cathodes and anodes,respectively.MnO_(2) NWs and Zn powders are uniformly dispersed in the interpenetrated CNFs/CNTs fibrous network,leading to homogenous composite inks with an ideal shear-thinning property.The obtained fiber electrodes demonstrate favorable uniformity and flexibility.Benefiting from the well-designed electrodes,the assembled flexible fiber-shaped ZIB delivers a high specific capacity of 281.5 m Ah g^(-1) at 0.25 A g^(-1) and displays excellent cycling stability over 400 cycles.Moreover,the wet-spun fiber-shaped ZIBs achieve ultrahigh gravimetric and volumetric energy densities of 47.3 Wh kg^(-1) and 131.3 m Wh cm^(-3),respectively,based on both cathode and anode and maintain favorable stability even after 4000 bending cycles.This work offers a new concept design of 1D flexible ZIBs that can be potentially incorporated into commercial textiles for wearable and portable electronics.
基金supported by the National Natural Science Foundation of China (Grant Nos.51872196)。
文摘Combining the unique advantages of aqueous electrolytes and metallic Zn anode, rechargeable aqueous Zn-ion batteries(ZIBs) are of great promise for large-scale energy storage applications due to their inherent high safety, low cost, and environmental friendliness. As the essential component of ZIBs, Zn metal anode suffers from severe dendrite formation and inevitable side reactions(e.g. corrosion and hydrogen evolution)in aqueous electrolytes, which leads to low Coulombic efficiency and inferior cycling stability, impeding their large-scale applications. To be compatible with satisfactory aqueous ZIBs, Zn anode has been modified from various perspectives and focus areas. Herein, based on their intrinsic characteristics, we review the related improvement strategies for Zn anode, including interphase, substrate, and bulk design, so as to achieve an in-depth understanding of Zn anode optimization. Furthermore, the timely summary of characterization methods for Zn anodes are also performed for the first time, from both thermodynamic and kinetics perspectives, which is particularly helpful for beginners to understand the complicated characterizations and employ suitable methods. Finally, certain noteworthy points are put forward for subsequent investigation of aqueous ZIBs. It is expected that this review will enlighten researchers to explore more efficient optimization strategies for Zn anode in aqueous electrolytes.
基金the National Natural Science Foundation of China(Grant Nos.11474137,11674143)the Fundamental Research Funds for the Central Universities(Grant No.Lzujbky-2019-cd02).
文摘One approach to accelerate the stagnant kinetics of both the oxygen reduction and evolution reactions(ORR/OER)is to develop a rationally designed multiphase nanocomposite,where the functions arising from each of the constituent phases,their interfaces,and the overall structure are properly controlled.Herein,we successfully synthesized an oxygen electrocatalyst consisting of Ni nanoparticles purposely interpenetrated into mesoporous NiO nanosheets(porous Ni/NiO).Benefiting from the contributions of the Ni and NiO phases,the well-established pore channels for charge transport at the interface between the phases,and the enhanced conductivity due to oxygen-deficiency at the pore edges,the porous Ni/NiO nanosheets show a potential of 1.49 V(10 mA cm^-2)for the OER and a half-wave potential of 0.76 V for the ORR,outperforming their noble metal counterparts.More significantly,a Zn-air battery employing the porous Ni/NiO nanosheets exhibits an initial charging-discharging voltage gap of 0.83 V(2 mA cm^-2),specific capacity of 853 mAh gZn^-1 at 20 mA cm^-2,and long-time cycling stability(120 h).In addition,the porous Ni/NiO-based solid-like Zn-air battery shows excellent electrochemical performance and flexibility,illustrating its great potential as a next-generation rechargeable power source for flexible electronics.
基金This work was financially supported by Shaanxi Yanchang Petroleum CO.,Ltd(18529)Yiwu Research Institute of Fudan University(21557),the National Science Foundation of China(22075048)the Shanghai International Collaboration Research Project(19520713900).
文摘The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries(AZMBs).However,the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commercial applications.To address these issues,a novel anode-free Zniodine battery(AFZIB)was designed via a simple,low-cost and scalable approach.Iodine plays bifunctional roles in improving the AFZIB overall performance:enabling high-performance Zn-rich cathode and modulating Zn deposition behavior.On the cathode side,the ZnI_(2) serves as Zn-rich cathode material.The graphene/polyvinyl pyrrolidone heterostructure was employed as an efficient host for ZnI_(2) to enhance electron conductivity and suppress the shuttle effect of iodine species.On the anode side,trace I_(3)^(−) additive in the electrolyte creates surface reconstruction on the commercial Cu foil.The in situ formed zincophilic Cu nanocluster allows ultralow-overpotential and uniform Zn deposition and superior reversibility(average coulombic efficiency>99.91% over 7,000 cycles).Based on such a configuration,AFZIB exhibits significantly increased energy density(162 Wh kg^(−1)) and durable cycle stability(63.8% capacity retention after 200 cycles)under practical application conditions.Considering the low cost and simple preparation methods of the electrode materials,this work paves the way for the practical application of AZMBs.
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.