Electrolyte engineering for optimizing anode/electrolyte interface towards superior aqueous zinc-ion batteries:A review

Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrite growth,hydrogen evolution reaction,and interfacial passivation occurring at the anode/electrolyte interface(AEI) have hindered their practical application.Constructing a stable AEI plays a key role in regulating zinc deposition and improving the cycle life of AZIBs.The fundamentals of AEI and the challenges faced by the Zn anode due to unstable interfaces are discussed.A comprehensive summary of electrolyte regulation strategies by electrolyte engineering to achieve a stable Zn anode is provided.The effectiveness evaluation techniques for stable AEI are also analyzed,including the interfacial chemistry and surface morphology evolution of the Zn anode.Finally,suggestions and perspectives for future research are offered about enabling a durable and stable AEI via electrolyte engineering,which may pave the way for developing high-performance AZIBs.

Designing Conformal Electrode-electrolyte Interface by Semi-solid NaK Anode for Sodium Metal Batteries

Solid-state Na metal batteries(SSNBs),known for its low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of NaK alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the intimate contact of electrode-electrolyte interface.Additionally,the filling of SiO_(2)nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 h.The full cell coupled with Na_(3)V_(3)(PO_(4))_(2)cathodes had an initial discharge capacity of 106.8 mAh·g^(-1)with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1)even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.

In-situ physical/chemical cross-linked hydrogel electrolyte achieving ultra-stable zinc anode-electrolyte interface towards dendrite-free zinc ion battery

Hydrogen evolution reaction(HER),zinc corrosion,and dendrites growth on zinc metal anode are the major issues limiting the practical applications of zinc-ion batteries.Herein,an in-situ physical/chemical cross-linked hydrogel electrolyte(carrageenan/polyacrylamide/ZnSO_(4),denoted as CPZ)has been developed to stabilize the zinc anode-electrolyte interface,which can eliminate side reactions and prevent dendrites growth.The in-situ CPZ hydrogel electrolyte improves the reversibility of zinc anode due to eliminating side reactions caused by active water molecules.Furthermore,the electrostatic interaction between the SO_(4)^(-)groups in CPZ and Zn^(2+)can encourage the preferential deposition of zinc atoms on(002)crystal plane,which achieve dendrite-free and homogeneous zinc deposition.The in-situ hydrogel electrolyte offers a streamlined approach to battery manufacturing by allowing for direct integration into the battery.Subsequently,the Zn//Zn half battery with CPZ hydrogel electrolyte can enable an ultra-long cycle over 5500 h at a current density of 0.5 mA cm^(-2),and the Zn//Cu half battery reach an average coulombic efficiency of 99.37%.The Zn//V_(2)O_5-GO full battery with CPZ hydrogel electrolyte demonstrates94.5%of capacity retention after 2100 cycles.This study is expected to open new thought for the development of commercial hydrogel electrolytes for low-cost and long-life zinc-ion batteries.

Mitigated reaction kinetics between lithium metal anodes and electrolytes by alloying lithium metal with low-content magnesium

Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.

Recent Advances in Nanoengineering of Electrode-Electrolyte Interfaces to Realize High-Performance Li-Ion Batteries

A suitable interface between the electrode and electrolyte is crucial in achieving highly stable electrochemical performance for Li-ion batteries,as facile ionic transport is required.Intriguing research and development have recently been conducted to form a stable interface between the electrode and electrolyte.Therefore,it is essential to investigate emerging knowledge and contextualize it.The nanoengineering of the electrode-electrolyte interface has been actively researched at the electrode/electrolyte and interphase levels.This review presents and summarizes some recent advances aimed at nanoengineering approaches to build a more stable electrode-electrolyte interface and assess the impact of each approach adopted.Furthermore,future perspectives on the feasibility and practicality of each approach will also be reviewed in detail.Finally,this review aids in projecting a more sustainable research pathway for a nanoengineered interphase design between electrode and electrolyte,which is pivotal for high-performance,thermally stable Li-ion batteries.

Facilitating prelithiation of silicon carbon anode by localized high-concentration electrolyte for high-rate and long-cycle lithium storage

The commercialization of silicon-based anodes is affected by their low initial Coulombic efficiency(ICE)and capacity decay,which are attributed to the formation of an unstable solid electrolyte interface(SEI)layer.Herein,a feasible and cost-effective prelithiation method under a localized highconcentration electrolyte system(LHCE)for the silicon-silica/graphite(Si-SiO_(2)/C@G)anode is designed for stabilizing the SEI layer and enhancing the ICE.The thin SiO_(2)/C layers with-NH_(2) groups covered on nano-Si surfaces are demonstrated to be beneficial to the prelithiation process by density functional theory calculations and electrochemical performance.The SEI formed under LHCE is proven to be rich in ionic conductivity,inorganic substances,and flexible organic products.Thus,faster Li+transportation across the SEI further enhances the prelithiation effect and the rate performance of Si-SiO_(2)/C@G anodes.LHCE also leads to uniform decomposition and high stability of the SEI with abundant organic components.As a result,the prepared anode shows a high reversible specific capacity of 937.5 mAh g^(-1)after 400 cycles at a current density of 1 C.NCM 811‖Li-SSGLHCE full cell achieves a high-capacity retention of 126.15 mAh g^(-1)at 1 C over 750 cycles with 84.82%ICE,indicating the great value of this strategy for Si-based anodes in large-scale applications.

High donor-number and low content electrolyte additive for stabilizing zinc metal anode

The aqueous zinc ion batteries(AZIBs)are thought as promising competitors for electrochemical energy storage,though their wide application is curbed by the uncontrollable dendrite growth and gas evolution side reactions.Herein,to stabilize both zinc anodes and water molecules,we developed a modified electrolyte by adding a trace amount of N,N-diethylformanmide(DEF)into the ZnSO_(4)electrolyte for the first time in zinc ion batteries.The effectiveness of DEF is predicted by the comparison of donor number and its preferential adsorption behavior on the zinc anode is further demonstrated by several spectroscopy characterizations,electrochemical methods,and molecular dynamics simulation.The modified electrolyte with 5%v.t.DEF content can ensure a stable cycling life longer than 3400 h of Zn‖Zn symmetric cells and an ultra-reversible Zn stripping/plating process with a high coulombic efficiency of 99.7%.The Zn‖VO_(2)full cell maintains a capacity retention of 83.5%and a 104 mA h g^(-1)mass capacity after 1000cycles.This work provides insights into the role of interfacial adsorption behavior and the donor number of additive molecules in designing low-content and effective aqueous electrolytes.

Unraveling the incompatibility mechanism of ethylene carbonate-based electrolytes in sodium metal anodes

Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.EC is also the most widely used electrolyte solvent in sodium ion batteries.However,compared to lithium metal,sodium metal(Na)shows higher activity and reacts violently with EC-based electrolyte(NaPF_(6)as solute),which leads to the failure of sodium metal batteries(SMBs).Herein,we reveal the electrochemical instability mechanism of EC on sodium metal battery,and find that the com-bination of EC and NaPF_(6) is electrically reduced in sodium metal anode during charging,resulting in the reduction of the first coulombic efficiency,and the continuous consumption of electrolyte leads to the cell failure.To address the above issues,an additive modified linear carbonate-based electrolyte is provided as a substitute for EC based electrolytes.Specifically,ethyl methyl carbonate(EMC)and dimethyl carbon-ate(DMC)as solvents and fluoroethylene carbonate(FEC)as SEI-forming additive have been identified as the optimal solvent for NaFP_(6)based electrolyte and used in Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))/Na batteries.The batter-ies exhibit excellent capacity retention rate of about 80%over 1000 cycles at a cut-off voltage of 4.3 V.

Stabilizing electrode-electrolyte interface for high-performance SiO_(x) anode by dual electrolyte additive

Macro-and micro-interface instability of SiO_(x)anode caused by its dramatic volume variation during cycling will result in low Coulombic efficiency and rapid capacity degradation.In this work,an organic-inorganic composite interfacial layer rich in benzene ring groups,polyisocyanates,and LiF was obtained on SiO_(x)anode by the introduction of 4-fluorophenyl isocyanate(FPI)and fluoroethylene carbonate(FEC)co-additives in electrolyte.The SiO_(x)anode material shows a capacity retention of 69.2%after 100 cycles at a current density of 1 A g^(-1)and rate capacity of 523 m A h g^(-1)at the current density of 3A g^(-1),while the SiO_(x)anode cycling in reference electrolyte has almost no capacity.

Unraveling the Fundamental Mechanism of Interface Conductive Network Influence on the Fast‑Charging Performance of SiO‑Based Anode for Lithium‑Ion Batteries

Progress in the fast charging of high-capacity silicon monoxide(SiO)-based anode is currently hindered by insufficient conductivity and notable volume expansion.The construction of an interface conductive network effectively addresses the aforementioned problems;however,the impact of its quality on lithium-ion transfer and structure durability is yet to be explored.Herein,the influence of an interface conductive network on ionic transport and mechanical stability under fast charging is explored for the first time.2D modeling simulation and Cryo-transmission electron microscopy precisely reveal the mitigation of interface polarization owing to a higher fraction of conductive inorganic species formation in bilayer solid electrolyte interphase is mainly responsible for a linear decrease in ionic diffusion energy barrier.Furthermore,atomic force microscopy and Raman shift exhibit substantial stress dissipation generated by a complete conductive network,which is critical to the linear reduction of electrode residual stress.This study provides insights into the rational design of optimized interface SiO-based anodes with reinforced fast-charging performance.

Interface and mechanical degradation mechanisms of the silicon anode in sulfide-based solid-state batteries at high temperatures

Silicon(Si)is a competitive anode material owing to its high theoretical capacity and low electrochemical potential.Recently,the prospect of Si anodes in solid-state batteries(SSBs)has been proposed due to less solid electrolyte interphase(SEI)formation and particle pulverization.However,major challenges arise for Si anodes in SSBs at elevated temperatures.In this work,the failure mechanisms of Si-Li_(6)PS_(5)Cl(LPSC)composite anodes above 80℃are thoroughly investigated from the perspectives of interface stability and(electro)chemo-mechanical effect.The chemistry and growth kinetics of Lix Si|LPSC interphase are demonstrated by combining electrochemical,chemical and computational characterizations.Si and/or Si–P compound formed at Lix Si|LPSC interface prove to be detrimental to interface stability at high temperatures.On the other hand,excessive volume expansion and local stress caused by Si lithiation at high temperatures damage the mechanical structure of Si-LPSC composite anodes.This work elucidates the behavior and failure mechanisms of Si-based anodes in SSBs at high temperatures and provides insights into upgrading Si-based anodes for application in SSBs.

Lithiophilic Li-Si alloy-solid electrolyte interface enabled by high-concentration dual salt-reinforced quasi-solid-state electrolyte

Solid polymer electrolytes(SPEs)are urgently required to achieve practical solid-state lithium metal batteries(LMBs)and lithium-ion batteries(LIBs),Herein,we proposed a mechanism for modulating interfacial conduction and anode interfaces in high-concentration SPEs by LiDFBOP.Optimized electrolyte exhibits superior ionic conductivity and remarkable interface compatibility with salt-rich clusters:(1)polymer-plastic crystal electrolyte(P-PCE,TPU-SN matrix)dissociates ion pairs to facilitate Li+transport in the electrolyte and regulates Li^(+)diffusion in the SEI.The crosslinking structure of the matrix compensates for the loss of mechanical strength at high-salt concentrations;(2)dual-anion TFSI^(-)_(n)-DFBOP^(-)_(m)in the Li^(+)solvation sheath facilitates facile Li^(+)desolvation and formation of salt-rich clusters and is conducive to the formation of Li conductive segments of TPU-SN matrix;(3)theoretical calculations indicate that the decomposition products of LiDFBOP form SEI with lower binding energy with LiF in the SN system,thereby enhancing the interfacial electrochemical redox kinetics of SPE and creating a solid interface SEI layer rich in LiF.As a result,the optimized electrolyte exhibits an excellent ionic conductivity of9.31×10^(-4)S cm^(-1)at 30℃and a broadened electrochemical stability up to 4.73 V.The designed electrolyte effectively prevents the formation of Li dendrites in Li symmetric cells for over 6500 h at0.1 mA cm^(-2).The specific Li-Si alloy-solid state half-cell capacity shows 711.6 mAh g^(-1)after 60 cycles at 0.3 A g^(-1).Excellent rate performance and cycling stability are achieved for these solid-state batteries with Li-Si alloy anodes and NCM 811 cathodes.NCM 811‖Prelithiated silicon-based anode solid-state cell delivers a discharge capacity of 195.55 mAh g^(-1)and a capacity retention of 97.8%after 120 cycles.NCM 811‖Li solid-state cell also delivers capacity retention of 84.2%after 450 cycles.

In situ atomic-scale tracking of unusual interface reaction circulation and phase reversibility in(de)potassiated alloy-typed anode

Alloy-typed anode materials,endowed innately with high theoretical specific capacity,hold great promise as an alternative to intercalation-typed counterparts for alkali-ion batteries.Despite tremendous efforts devoted to addressing drastic volume change and severe pulverization issues of such anodes,the underlying mechanisms involving dynamic phase evolutions and reaction kinetics have not yet been fully comprehended.Herein,taking antimony(Sb)anode as a representative paradigm,its microscopic operating mechanisms down to the atomic scale during live(de)potassiation cycling are systematically unraveled using in situ transmission electron microscopy.Highly reversible phase transformations at single-particle level,that are Sb←→KSb_(2)←→KSb←→K_5Sb_(4)←→K_(3)Sb,were revealed during cycling.Meanwhile,multiple phase interfaces associated with different reaction kinetics coexisted and this phenomenon was properly elucidated in the context of density functional theory calculations.Impressively,previously unexplored unidirectional circulation of reaction interfaces within individual Sb particle is confirmed for both potassiation and depotassiation.Based on the empirical results,the surface diffusion-mediated potassiation-depotassiation pathways at single-particle level are suggested.This work affords new insights into energy storage mechanisms of Sb anode and valuable guidance for targeted optimization of alloy-typed anodes(not limited to Sb)toward advanced potassium-ion batteries.

Inorganic/polymer hybrid layer stabilizing anode/electrolyte interfaces in solid-state Li metal batteries

Li1.5Al0.5Ge1.5(PO4)3(LAGP)is a solid-state electrolyte with high ionic conductivity and air stability but poor chemical stability and high interfacial impedance when directly contacted with Li metal.In this work,we develop an inorganic/polymer hybrid interlayer composed of Li bis(trifluoromethylsulfonyl)imide/poly(vinylene carbonate)polymer electrolyte and SiO2 submicrospheres to stabilize the Li/LAGP interface.The polymeric component renders high ionic conductance and low interfacial resistance,whereas the inorganic component imparts flame retardancy and a physical barrier to the known Li-LAGP side reaction,together enabling stable Li stripping/plating for more than 1,500 h at room temperature.With this interlayer at both electrodes,all-solid-state Li∥LiFePO4 full cells with stable cycling performance are also demonstrated.

Engineering homotype heterojunctions in hard carbon to induce stable solid electrolyte interfaces for sodium-ion batteries

Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this paper,homotype heterojunctions are designed on HC to induce the generation of stable solid electrolyte interfaces,which can effectively increase the ICE of HC from 64.7%to 81.1%.The results show that using a simple surface engineering strategy to construct a homotypic amorphous Al_(2)O_(3) layer on the HC could shield the active sites,and further inhibit electrolyte decomposition and side effects occurrence.Particularly,due to the suppression of continuous decomposition of NaPF 6 in ester-based electrolytes,the accumulation of NaF could be reduced,leading to the formation of thinner and denser solid electrolyte interface films and a decrease in the interface resistance.The HC anode can not only improve the ICE but elevate its sodium storage performance based on this homotype heterojunction composed of HC and Al_(2)O_(3).The optimized HC anode exhibits an outstanding reversible capacity of 321.5mAhg^(−1) at 50mAg^(−1).The cycling stability is also improved effectively,and the capacity retention rate is 86.9%after 2000 cycles at 1Ag^(−1) while that of the untreated HC is only 52.6%.More importantly,the improved sodium storage behaviors are explained by electrochemical kinetic analysis.

Regulating solid electrolyte interphases on phosphorus/carbon anodes via localized high-concentration electrolytes for potassium-ion batteries

The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.

Electrolyte Strategies Toward Optimizing Zn Anode for Zinc-Ion Batteries

Zinc-ion batteries(ZIBs)with low cost and high safety have become potential candidates for large-scale energy storage.However,the knotty Zn anode issues such as dendritic growth,hydrogen evolution reaction(HER)and corrosion and passivation are still unavoidable,which greatly limits the wide applications of ZIBs.The states and additives of electrolytes are closely related to these problems.However,there is a lack of systematic understanding and discussion about the intrinsic connection between the states and additives of electrolyte and Zn anode issues.In this review,the basic principles of dendritic growth,HER and corrosion and passivation are fi rstly introduced,and then,electrolyte optimization strategies with the corresponding electrochemical properties are systematically summarized.In particular,the action mechanism of electrolyte additives and the electrolyte states for Zn anode optimization is analyzed in detail.Finally,some unique views on the improvement of electrolyte for Zn anode optimization are put forward,which is expected to provide a certain professional reference for designing high-performance ZIBs.

Elucidating the suppression of lithium dendrite growth with a void-reduced anti-perovskite solid-state electrolyte pellet for stable lithium metal anodes

Solid-state lithium-metal batteries,with their high theoretical energy density and safety,are highly promising as a next-generation battery contender.Among the alternatives proposed as solid-state electrolyte,lithium-rich anti-perovskite(Li RAP)materials have drawn the most interest because of high theoretical Li^(+)conductivity,low cost and easy processing.Although solid-state electrolytes are believed to have the potential to physically inhibit the lithium dendrite growth,lithium-metal batteries still suffer from the lithium dendrite growth and thereafter the short circuiting.The voids in practical Li RAP pellets are considered as the root cause.Herein,we show that reducing the voids can effectively suppress the lithium dendrite growth.The voids in the pellet resulted in an irregular Li^(+)flux distribution and a poor interfacial contact with lithium metal anode;and hence the ununiform lithium dendrites.Consequently,the lithium-metal symmetric cell with void-reduced Li_(2)OHCl-HT pellet was able to display excellent cycling performance(750 h at 0.4 m A cm^(-2))and stability at high current density(0.8 m A cm^(-2)for 120 h).This study provides not only experimental evidence for the impact of the voids in Li RAP pellets on the lithium dendrite growth,but also a rational pellet fabrication approach to suppress the lithium dendrite growth.

Unraveling the heterogeneity of solid electrolyte interphase kinetically affecting lithium electrodeposition on lithium metal anode

The stability and uniformity of solid electrolyte interphase(SEI)are critical for clarifying the origin of capacity fade and safety issues for lithium metal anodes(LMA).However,understanding the interplay of SEI heterogeneity and Li electrodeposition is limited by the coupling of complex electrochemistry and mechanics processes.Herein,the correlation between the SEI failure behavior and Li deposition morphology is investigated through a quantitative electrochemical-mechanical model.The local deformation and stress of SEI during Li electrodeposition identify that the heterogeneous interface between different components first fails.Compared with the well-known mechanical strength,component uniformity plays the most important role in the initial SEI failure and uneven Li deposition,and a relative component uniformity(p>0.01)represents a proper balance to ensure the stability of the naturally heterogeneous SEI.Furthermore,the component regulation of SEI via the designed electrolyte experimentally demonstrates that improving component uniformity benefits SEI stability and the uniform Li electrodeposition for LMA,thereby increasing the capacity by~20%after 300 cycles.These fundamental understandings and proposed strategy can be not only used to guide the SEI optimization via the electrolyte regulation,but also extended to the rational designs of artificial SEI for high-performance LMA.

Toward stable and highly reversible zinc anodes for aqueous batteries via electrolyte engineering

Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the poor reversibility resulting from dendrite formation and side reactions poses a major obstacle for its practical application. Electrolyte, which is regarded as the “blood” of batteries, has a direct impact on reaction kinetics, mass transport, and side reactions and thus plays a key role in determining the electrochemical performance of Zn electrodes. Therefore, considerable efforts have been devoted to modulating the electrolytes to improve the performance of Zn electrodes. Although significant progress has been made, achieving stable and highly reversible Zn electrodes remains a critical challenge. This review aims to provide a systematic summary and discussion on electrolyte strategies for highperformance aqueous Zn batteries. The(electro)-chemical behavior and fundamental challenges of Zn electrodes in aqueous electrolytes are first discussed. Electrolyte modulation strategies developed to address these issues are then classified and elaborated according to the underlying mechanisms.Finally, remaining challenges and promising future research directions on aqueous electrolyte engineering are highlighted. This review offers insights into the design of highly efficient electrolytes for new generation of rechargeable Zn batteries.