Understanding of the charge storage mechanism of MnO_(2)-based aqueous zinc-ion batteries:Reaction processes and regulation strategies

Though secondary aqueous Zn ion batteries(AZIBs)have been received broad concern in recent years,the development of suitable cathode materials of AZIBs is still a big challenge.The MnO_(2) has been deemed as one of most hopeful cathode materials of AZIBs on account of some extraordinary merits,such as richly natural resources,low toxicity,high discharge potential,and large theoretical capacity.However,the crystal structure diversity of MnO_(2) results in an obvious various of charge storage mechanisms,which can cause great differences in electrochemical performance.Furthermore,several challenges,including intrinsic poor conductivity,dissolution of manganese and sluggish ion transport dynamics should be conquered before real practice.This work focuses on the reaction mechanisms and recent progress of MnO_(2)-based materials of AZIBs.In this review,a detailed review of the reaction mechanisms and optimal ways for enhancing electrochemical performance for MnO_(2)-based materials is proposed.At last,a number of viewpoints on challenges,future development direction,and foreground of MnO_(2)-based materials of aqueous zinc ions batteries are put forward.This review clarifies reaction mechanism of MnO_(2)-based materials of AZIBs,and offers a new perspective for the future invention in MnO_(2)-based cathode materials,thus accelerate the extensive development and commercialization practice of aqueous zinc ions batteries.

Anti-aggregation growth and hierarchical porous carbon encapsulation enables the C@VO_(2) cathode with superior storage capability for aqueous zinc-ion batteries

Self-aggregation and sluggish transport kinetics of cathode materials would usually lead to the poor electrochemical performance for aqueous zinc-ion batteries(AZIBs).In this work,we report the construction of C@VO_(2) composite via anti-aggregation growth and hierarchical porous carbon encapsulation.Both of the morphology of composite and pore structure of carbon layer can be regulated by tuning the adding amount of glucose.When acting as cathode applied for AZIBs,the C@VO_(2)-3:3 composite can deliver a high capacity of 281 m Ah g^(-1) at 0.2 A g^(-1).Moreover,such cathode also exhibits a remarkably rate capability and cyclic stability,which can release a specific capacity of 195 m Ah g^(-1) at 5 A g^(-1) with the capacity retention of 95.4%after 1000 cycles.Besides that,the evolution including the crystal structure,valence state and transport kinetics upon cycling were also deeply investigated.In conclusion,benefited from the synergistic effect of anti-aggregation morphology and hierarchical porous carbon encapsulation,the building of such C@VO_(2) composite can be highly expected to enhance the ion accessible site,boost the transport kinetics and thus performing a superior storage performance.Such design concept can be applied for other kinds of electrode materials and accelerating the development of highperformance AZIBs.

Novel Insights into Energy Storage Mechanism of Aqueous Rechargeable Zn/MnO2 Batteries with Participation of Mn2+

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.

Recent advances in energy storage mechanism of aqueous zinc-ion batteries

Aqueous rechargeable zinc-ion batteries(ZIBs)have recently attracted increasing research interest due to their unparalleled safety,fantastic cost competitiveness and promising capacity advantages compared with the commercial lithium ion batteries.However,the disputed energy storage mechanism has been a confusing issue restraining the development of ZIBs.Although a lot of efforts have been dedicated to the exploration in battery chemistry,a comprehensive review that focuses on summarizing the energy storage mechanisms of ZIBs is needed.Herein,the energy storage mechanisms of aqueous rechargeable ZIBs are systematically reviewed in detail and summarized as four types,which are traditional Zn^(2+)insertion chemistry,dual ions co-insertion,chemical conversion reaction and coordination reaction of Zn^(2+)with organic cathodes.Furthermore,the promising exploration directions and rational prospects are also proposed in this review.

Sn-doped BiOCl nanosheet with synergistic H^(+)/Zn^(2+)co-insertion for“rocking chair”zinc-ion battery

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.

A novel improvement strategy and a comprehensive mechanism insight for α-MnO_(2) energy storage in rechargeable aqueous zinc-ion batteries

Aqueous zinc-ion batteries have been regarded as the most potential candidate to substitute lithium-ion batteries.However,many serious challenges such as suppressing zinc dendrite growth and undesirable reactions,and achieving fully accepted mechanism also have not been solved.Herein,the commensal composite microspheres withα-MnO_(2) nano-wires and carbon nanotubes were achieved and could effectively suppress ZnSO_(4)·3Zn(OH)_(2)·nH_(2)O rampant crystallization.The electrode assembled with the microspheres delivered a high initial capacity at a current density of 0.05 A g^(-1) and maintained a significantly prominent capacity retention of 88%over 2500 cycles.Furthermore,a novel energy-storage mechanism,in which multivalent manganese oxides play a synergistic effect,was comprehen-sively investigated by the quantitative and qualitative analysis for ZnSO_(4)·3Zn(OH)_(2)·nH_(2)O.The capacity contribution of multivalent manganese oxides and the crystal structure dissection in the transformed processes were completely identified.Therefore,our research could provide a novel strategy for designing improved electrode structure and a comprehensive understanding of the energy storage mechanism of α-MnO_(2) cathodes.

Non-desolvation Zn^(2+)storage mechanism enables MoS_(2)anode with enhanced interfacial charge-transfer kinetics for low temperature zinc-ion batteries

The emerging rocking-chair aqueous zinc-ion battery(AZIB)configuration provides a promising approach for realizing their practical applications by avoiding the critical drawbacks of Zn metal anodes including unsatisfactory Coulombic efficiency and low Zn utilization.Therefore,exploiting appropriate insertion-type anodes with fast charge-transfer kinetics is of great importance,and many modifications focusing on the improvement of electron transport and bulk Zn^(2+)diffusion have been proposed.However,the interfacial Zn^(2+)transfer determined by the desolvation process actually dominates the kinetics of overall battery reactions,which is mainly overlooked.Herein,the interlayer structure of Mo S_(2)is rationally co-intercalated with water and ethylene glycol(EG)molecules(Mo S2@EG),giving rise to a fast non-desolvation Zn^(2+)storage mechanism,which is verified by the extraordinarily smaller activation energy of interfacial Zn^(2+)transfer(4.66 k J mol^(-1))compared with that of pristine Mo S_(2)(56.78 k J mol^(-1)).Furthermore,the results of theoretical calculations,in-situ Raman and ex-situ characterizations also indicate the enhanced structural integrity of Mo S2@EG during cycling due to the enlarged interlayer spacing and charge screening effect induced by interlaminar EG molecules.Consequently,the Mo S_(2)@EG anode enables excellent cycling stability of both high-energy-density Mo_S2@EG||PVO(polyaniline intercalated V_(2)O_(5))and high-voltage Mo S2@EG||Na_(3)V_(2)(PO_(4))_2O_(2)F(NVPF)full batteries with neglectable capacity decay at-20℃.

2D Materials Boost Advanced Zn Anodes:Principles,Advances,and Challenges

Aqueous zinc-ion battery(ZIB)featuring with high safety,low cost,environmentally friendly,and high energy density is one of the most promising systems for large-scale energy storage application.Despite extensive research progress made in developing high-performance cathodes,the Zn anode issues,such as Zn dendrites,corrosion,and hydrogen evolution,have been observed to shorten ZIB’s lifespan seriously,thus restricting their practical application.Engineering advanced Zn anodes based on two-dimensional(2D)materials are widely investigated to address these issues.With atomic thickness,2D materials possess ultrahigh specific surface area,much exposed active sites,superior mechanical strength and flexibility,and unique electrical properties,which confirm to be a promising alternative anode material for ZIBs.This review aims to boost rational design strategies of 2D materials for practical application of ZIB by combining the fundamental principle and research progress.Firstly,the fundamental principles of 2D materials against the drawbacks of Zn anode are introduced.Then,the designed strategies of several typical 2D materials for stable Zn anodes are comprehensively summarized.Finally,perspectives on the future development of advanced Zn anodes by taking advantage of these unique properties of 2D materials are proposed.

PVA-assisted hydrated vanadium pentoxide/reduced graphene oxide films for excellent Li^(+)and Zn^(2+)storage properties

Low-cost,high safety and environment-friendly aqueous energy storage systems(ESSs)are huge potential for grid-level energy storage,but the(de)intercalation of metal ions in the electrode materials(e.g.vanadium oxides)to obtain superior long-term cycling stability is a significant challenge.Herein,we demonstrate that polyvinyl alcohol(PVA)-assisted hydrated vanadium pentoxide/reduced graphene oxide(V_(2)O_(5)·n H_(2)O/r GO/PVA,denoted as the VGP)films enable long cycle stability and high capacity for the Li^(+)and Zn^(2+)storages in both the VGP//Li Cl(aq)//VGP and the VGP//Zn SO4(aq)//Zn cells.The binderfree VGP films are synthesized by a one-step hydrothermal method combination with the filtration.The extensive hydrogen bonds are formed among PVA,GO and H_(2)O,and they act as structural pillars and connect the adjacent layers as glue,which contributes to the ultrahigh specific capacitance and ultralong cyclic performance of Li^(+)and Zn^(2+)storage properties.As for Li^(+)storage,the binder-free VGP4 film(4mg PVA)electrode achieves the highest specific capacitance up to 1381 F g^(-1)at 1.0 A g^(-1)in the three-electrode system and 962 F g^(-1)at 1.0 A g^(-1)in the symmetric two-electrode system.It also behaves the outstanding cyclic performance with the capacitance retention of 96.5%after 15000 cycles in the three-electrode system and 99.7%after 25000 cycles in the symmetric two-electrode system.As for Zn^(2+)storage,the binder-free VGP4 film electrode exhibits the high specific capacity of 184 m A h g^(-1)at 0.5A g^(-1)in the VGP4//Zn SO4(aq)//Zn cell and the superb cycle performance of 98.5%after 25000 cycles.This work not only provides a new strategy for the construction of vanadium oxides composites and demonstrates the potential application of PVA-assisted binder-free film with excellent electrochemical properties,but also extends to construct other potential electrode materials for metal ion storage cells.

Deciphering H^(+)/Zn^(2+) co-intercalation mechanism of MOF-derived2D MnO/C cathode for long cycle life aqueous zinc-ion batteries

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.

Proton storage chemistry in aqueous zinc-organic batteries:A review

Benefiting from the advantageous features of structural diversity and resource renewability,organic electroactive compounds are considered as attractive cathode materials for aqueous Zn-ion batteries(ZIBs).In this review,we discuss the recent developments of organic electrode materials for aqueous ZIBs.Although the proton(H^(+))storage chemistry in aqueous Zn-organic batteries has triggered an overwhelming literature surge in recent years,this topic remains controversial.Therefore,our review focuses on this significant issue and summarizes the reported electrochemical mechanisms,including pure Zn^(2+)intercalation,pure H^(+)storage,and H^(+)/Zn^(2+)co-storage.Moreover,the impact of H^(+)storage on the electrochemical performance of aqueous ZIBs is discussed systematically.Given the significance of H^(+)storage,we also highlight the relevant characterization methods employed.Finally,perspectives and directions on further understanding the charge storage mechanisms of organic materials are outlined.We hope that this review will stimulate more attention on the H^(+)storage chemistry of organic electrode materials to advance our understanding and further its application.

Coupling N-doping and rich oxygen vacancies in mesoporous ZnMn_(2)O_(4)nanocages toward advanced aqueous zinc ion batteries

The development of a high specific capacity and stable manganese(Mn)-based cathode material is very attractive for aqueous zinc-ion(Zn^(2+))batteries(ZIBs).However,the inherent low electrical conductivity and volume expansion challenges limit its stability improvement.Here,a mesoporous ZnMn_(2)O_(4)(ZMO)nanocage(N-ZMO)coupled with nitrogen doping and oxygen vacancies is prepared by defect engineering and rational structural design as a high-performance cathode material for rechargeable ZIBs.The oxygen vacancies enhance the electrical conductivity of the material and the nitrogen doping releases the strong electrostatic force of the material to maintain a higher structural stability.Interestingly,N-ZMO exhibits excellent ability of Zn^(2+)storage(225.4 mAh·g^(−1)at 0.3 A·g^(−1)),good rate,and stable cycling performance(88.4 mAh·g^(−1)after 1,000 cycles at 3 A·g^(−1)).Furthermore,a flexible quasi-solid-state device with high energy density(261.6 Wh·kg^(−1))is assembled,demonstrating long-lasting durability.We believe that the strategy in this study can provide a new approach for developing aqueous ZIBs.

Ethylene glycol-regulated ammonium vanadate with stable layered structure and favorable interplanar spacing as high-performance cathode for aqueous zinc ion batteries

Ammonium vanadate compounds featuring large capacity,superior rate capability and light weight are regarded as promising cathode materials for aqueous zinc ion batteries(AZIBs).However,the controllable synthesis of desired ammonium vanadates remains a challenge.Herein,various ammonium vanadate compounds were successfully prepared by taking advantage of ethylene glycol(EG)regulated polyolreduction strategy and solvent effect via hydrothermal reaction.The morphology and crystalline phase of resultant products show an evolution from dendritic(NH_(4))_(2)V_(6)O_(16)to rod-like NH_(4)V_(4)O_(10)and finally to lamellar(NH4)2V4O9 as increasing the amount of EG.Specifically,the NH_(4)V_(4)O_(10)product exhibits a high initial capacity of 427.5 mAh/g at 0.1 A/g and stable cycling with a capacity retention of 90.4%after 5000 cycles at 10 A/g.The relatively excellent electrochemical performances of NH_(4)V_(4)O_(10)can be ascribed to the stable open-framework layered structure,favorable(001)interplanar spacing,and peculiar rod-like morphology,which are beneficial to the highly reversible Zn^(2+)storage behaviors.This work offers a unique way for the rational design of high-performance cathode materials for AZIBs.