A novel calculation strategy for optimized prediction of the reduction of electrochemical window at anode

The reduction of the electrochemical window(EW)of electrolytes plays a significant role in assessing their compatibility with the anode in lithium-ion batteries.However,the accurate calculation of the reduction of EW is still challenging due to missing the solvation effects,condensation effects,kinetic factors,and the passivation on anodes.The theoretical prediction of the intrinsic and apparent EW is confirmed by a comprehensive experimental analysis of ethylene carbonatedimethyl carbonate(EC-DMC)electrolytes,combining linear sweep voltammetry(LSV)and gas chromatography-mass spectrometry(GC-MS).The proposed novel kinetic normal distribution theory model can quantitatively explain the current density from LSV and affirm acetaldehyde(MeCHO)as one of the primary reduction products of EC.The solvent effect restricts the intrinsic EW of EC-DMC without lithium salt to 2.6 V(vs.Li^(+)/Li)arising from the Marcus-Gerischer theory and the passivation of MeCHO on the anode broadens the apparent EW to 0.3 V(vs.Li^(+)/Li)arising from the normal distribution of the lowest unoccupied molecular orbital(LUMO)for MeCHO produced by thermal motion.In addition,the passivation on the anode depends intensively on the lithium salt,resulting in more complicated influences on the apparent EW.

Challenges of polymer electrolyte with wide electrochemical window for high energy solid-state lithium batteries

With the rapid development of energy storage technology,solid-state lithium batteries with high energy density,power density,and safety are considered as the ideal choice for the next generation of energy storage devices.Solid electrolytes have attracted considerable attention as key components of solid-state batteries.Compared with inorganic solid electrolytes,solid polymer electrolytes have better flexibility,machinability,and more importantly,better contact with the electrode,and low interfacial impedance.However,its low ionic conductivity,narrow electrochemical stability window(ESW),and poor mechanical properties at room temperature limit its development and practical applications.In recent years,many studies have focused on improving the ionic conductivity of polymer electrolytes;however,few systematic studies and reviews have been conducted on their ESWs.A polymer electrolyte with wide electrochemical window will aid battery operation at a high voltage,which can effectively improve their energy density.Moreover,their stability toward lithium metal anode is also important.Therefore,this review summarizes the recent progress of solid polymer electrolytes on the ESW,discusses the factors affecting ESW of polymer electrolytes,and analyzes a strategy to broaden the window from the perspective of molecular interaction,polymer structural design,and interfacial tuning.The development trends of polymer electrolytes with wide electrochemical windows are also presented.

Recovering the electrochemical window by forming a localized solvation nanostructure in ionic liquids with trace water

Motivated by the fascinating merits of wide electrochemical stability window(ESW)and nonflammability,ionic liquids(ILs)have been utilized as advanced electrolytes in various emerging electrochemical energy storage technologies.However,ILs are hygroscopic to the water in the air and the presence of trace water will narrow the ESW of ILs.In this article,we report that a localized solvation nanostructure(LSNS)is formed in ILs,which plays an important role in fully recovering the originally decreased ESW of[EMIM][TFSI]IL owing to the trace water.Such LSNS is consisted of Li^(+)ions with water molecules as the center,TFSI-anions as the secondary periphery and EMIM^(+)cations as the outermost layer after adding the proper amount of LiTFSI.This nanostructure can restrain the possibility of trace water to approach the electrode/electrolyte interfaces and adverse redox reactions,thereby recovering the ESW.Moreover,the effectiveness of this strategy in different kinds of ILs to fully recover ESW decreasing is verified.This article comes up with a feasible method to eliminate the trace water caused ESW drop for ILbased electrolytes and provides a new insight for understanding the molecular-level interaction between different ions in ILs with water molecules.

Trend of Developing Aqueous Liquid and Gel Electrolytes for Sustainable,Safe,and High‑Performance Li‑Ion Batteries

Current lithium-ion batteries(LIBs)rely on organic liquid electrolytes that pose significant risks due to their flammability and toxicity.The potential for environmental pollution and explosions resulting from battery damage or fracture is a critical concern.Water-based(aqueous)electrolytes have been receiving attention as an alternative to organic electrolytes.However,a narrow electrochemicalstability window,water decomposition,and the consequent low battery operating voltage and energy density hinder the practical use of aqueous electrolytes.Therefore,developing novel aqueous electrolytes for sustainable,safe,high-performance LIBs remains challenging.This Review first commences by summarizing the roles and requirements of electrolytes–separators and then delineates the progression of aqueous electrolytes for LIBs,encompassing aqueous liquid and gel electrolyte development trends along with detailed principles of the electrolytes.These aqueous electrolytes are progressed based on strategies using superconcentrated salts,concentrated diluents,polymer additives,polymer networks,and artificial passivation layers,which are used for suppressing water decomposition and widening the electrochemical stability window of water of the electrolytes.In addition,this Review discusses potential strategies for the implementation of aqueous Li-metal batteries with improved electrolyte–electrode interfaces.A comprehensive understanding of each strategy in the aqueous system will assist in the design of an aqueous electrolyte and the development of sustainable and safe high-performance batteries.

Asymmetric Electrolytes Design for Aqueous Multivalent Metal Ion Batteries

With the rapid development of portable electronics and electric road vehicles,high-energy-density batteries have been becoming front-burner issues.Traditionally,homogeneous electrolyte cannot simultaneously meet diametrically opposed demands of high-potential cathode and low-potential anode,which are essential for high-voltage batteries.Meanwhile,homogeneous electrolyte is difficult to achieve bi-or multi-functions to meet different requirements of electrodes.In comparison,the asymmetric electrolyte with bi-or multi-layer disparate components can satisfy distinct requirements by playing different roles of each electrolyte layer and meanwhile compensates weakness of individual electrolyte.Consequently,the asymmetric electrolyte can not only suppress by-product sedimentation and continuous electrolyte decomposition at the anode while preserving active substances at the cathode for high-voltage batteries with long cyclic lifespan.In this review,we comprehensively divide asymmetric electrolytes into three categories:decoupled liquid-state electrolytes,bi-phase solid/liquid electrolytes and decoupled asymmetric solid-state electrolytes.The design principles,reaction mechanism and mutual compatibility are also studied,respectively.Finally,we provide a comprehensive vision for the simplification of structure to reduce costs and increase device energy density,and the optimization of solvation structure at anolyte/catholyte interface to realize fast ion transport kinetics.

Sodium Nitrate/Formamide Deep Eutectic Solvent as Flame-Retardant and Anticorrosive Electrolyte Enabling 2.6 V Safe Supercapacitors with Long Cyclic Stability

Safe operation of electrochemical capacitors(supercapacitors)is hindered by the flammability of commercial organic electrolytes.Non-flammable Water-in-Salt(WIS)electrolytes are promising alternatives;however,they are plagued by the limited operation voltage window(typically≤2.3 V)and inherent corrosion of current collectors.Herein,a novel deep eutectic solvent(DES)-based electrolyte which uses formamide(FMD)as hydrogen-bond donor and sodium nitrate(NaNO_(3))as hydrogen-bond acceptor is demonstrated.The electrolyte exhibits the wide electrochemical stability window(3.14 V),high electrical conductivity(14.01 mScm^(-1)),good flame-retardance,anticorrosive property,and ultralow cost(7%of the commercial electrolyte and 2%of WIS).Raman spectroscopy and Density Functional Theory calculations reveal that the hydrogen bonds between the FMD molecules and NO_(3)^(-)ions are primarily responsible for the superior stability and conductivity.The developed NaNO_(3)/FMD-based coin cell supercapacitor is among the best-performing state-of-art DES and WIS devices,evidenced by the high voltage window(2.6 V),outstanding energy and power densities(22.77 Wh kg^(-1)at 630 W kg^(-1)and 17.37 kW kg^(-1)at 12.55 Wh kg^(-1)),ultralong cyclic stability(86%after 30000 cycles),and negligible current collector corrosion.The NaNO_(3)/FMD industry adoption potential is demonstrated by fabricating 100 F pouch cell supercapacitors using commercial aluminum current collectors.

Realizing high-voltage aqueous zinc-ion batteries with expanded electrolyte electrochemical stability window

Aqueous zinc-ion batteries(AZIBs) have aroused significant research interest around the world in the past decade. The use of low-cost aqueous electrolytes and a metallic Zn anode with a suitable redox potential and high energy density make AZIBs a potential alternative to commercial Li-ion batteries in the development of next-generation batteries. However, owing to the narrow electrochemical stability window(ESW) of aqueous electrolytes, the choice of cathode materials is limited, because of which AZIBs exhibit a relatively low operating voltage and energy density. Hence, expanding the ESW of aqueous electrolytes is important for the development of practical AZIBs. This paper systematically reviews the electrolyte engineering strategies being explored to broaden the ESW of AZIBs. An in-depth analysis of high-voltage AZIBs is also presented. We suggest that the realization of high-voltage AZIBs depends on the synergistic development of suitable electrolytes and cathode materials. In addition, the cost associated with their fabrication as well as the use of standardized electrochemical tests should be considered during the design of high-voltage AZIBs.

Cooperative Chloride Hydrogel Electrolytes Enabling Ultralow-Temperature Aqueous Zinc Ion Batteries by the Hofmeister Effect

Aqueous zinc ion batteries have high potential applicability for energy storage due to their reliable safety,environmental friendliness,and low cost.However,the freezing of aqueous electrolytes limits the normal operation of batteries at low temperatures.Herein,a series of high-performance and low-cost chloride hydrogel electrolytes with high concentrations and low freezing points are developed.The electrochemical windows of the chloride hydrogel electrolytes are enlarged by>1 V under cryogenic conditions due to the obvious evolution of hydrogen bonds,which highly facilitates the operation of electrolytes at ultralow temperatures,as evidenced by the low-temperature Raman spectroscopy and linear scanning voltammetry.Based on the Hofmeister effect,the hydrogen-bond network of the cooperative chloride hydrogel electrolyte comprising 3 M ZnCl_(2)and 6 M LiCl can be strongly interrupted,thus exhibiting a sufficient ionic conductivity of 1.14 mS cm;and a low activation energy of 0.21 e V at-50℃.This superior electrolyte endows a polyaniline/Zn battery with a remarkable discharge specific capacity of 96.5 mAh g;at-50℃,while the capacity retention remains~100%after 2000 cycles.These results will broaden the basic understanding of chloride hydrogel electrolytes and provide new insights into the development of ultralow-temperature aqueous batteries.

Bi-salt electrolyte for aqueous rechargeable aluminum battery

The exertion of superior high-energy density based on multivalent ions transfer of rechargeable aluminum batteries is greatly hindered by limited electrochemical stability window of typical water in salt electrolyte(Wi SE). Recently, it is reported that a second salt addition to the Wi SE can offer further suppression of water activities, and achieves a much wider electrochemical window compared with aqueous Wi SE electrolytes. Hence, we demonstrate a class of water in bi-salt electrolyte containing the trifluoromethanesulfonate(OTF), which exhibits an ultra-wide electrochemical window of 4.35 V and a very low overpotential of 14.6 m V. Moreover, the interface chemistry between cathode and electrolyte is also confirmed via kinetic analysis. Surprisingly, we find the electrolyte can effectively suppress Mn dissolution from the cathode, alleviate self-discharge behavior, and ensure a stable electrode–electrolyte interface based on the interface concentrated-confinement effect. Owing to these unique merits of water in bi-salt electrolyte, the AlxMnO_(2)·nH_(2)O material delivers a high capacity of 364 m Ah g;and superb long-term cycling performance > 150 cycles with a capacity decay rate of 0.37% per cycle with coulombic efficiency at ca. 95%.

Reshaping Electrolyte Solvation Structure for High-Energy Aqueous Batteries

A highlight on reshaping aqueous electrolyte solvation structure for highenergy batteries is provided.Firstly,the recent key design routes for regulating solvation structure to widen electrochemical stability window(ESW)of aqueous electrolyte are briefly summarized.Then,the groundbreaking work of Wang et al.on reshaping electrolyte structure using urea as the diluent is elaborated.Finally,the significance of Wang's work is highlighted.

The electrochemical stability of ionic liquids and deep eutectic solvents

Room temperature ionic liquids （ILs） composed of cations and anions, as well as deep eutectic solvents （DESs） composed of hydrogen bond donors （HBDs） and hydrogen bond acceptors （HBAs）, are regarded as green solvents due to their low volatility. They have been used widely for electrochemically driven reactions because they exhibit high conductivity and excellent elec- trochemical stability. However, no systematic investigations on the electrochemical potential windows （EPWs）, which could be used to characterize the electrochemical stability, have been reported. In this regard, the EPWs of 33 ILs and 23 DESs have been studied utilizing cyclic voltammetry （CV） method and the effects of structural factors （cations and anions of ILs, and HBDs and HBAs of DESs） and external factors （electrode, water content） on the EPWs have been comprehensively investi- gated. The electrochemical stability of selected 1Ls comprising five traditional cations, namely imidazolium, pyridinium, pyr- rolidinium, piperidinium and ammonium and 13 kinds of versatile anions was studied. The results show that for ILs, both cati- on and anion play an important role on the reductive and oxidative potential limit. For a same IL at different working electrode, for example, glassy carbon （GC）, gold （Au） and platinum （Pt） electrode, the largest potential window is almost observed on the GC working electrode. The investigations on the EPWs of choline chloride （ChCl）, choline bromide （ChBr）, choline iodide （ChI）, and methyl urea based DESs show that the DES composed of ChCl and methyl urea has the largest potential window. This work may aid the selection of ILs or DESs for use as a direct electrolyte or a solvent in electrochemical applications.

Electrochemically stable lithium-ion and electron insulators(LEIs)for solid-state batteries

Rechargeable solid-state Li metal batteries demand ordered flows of Li-ions and electrons in and out of solid structures,with repeated waxing and waning of Ubcc phase near contact interfaces which gives rise to various electro-chemo-mechanical challenges.There have been approaches that adopt three-dimensional(3D)nanoporous architectures consisting of mixed ion-electron conductors(MIECs)to combat these challenges.However,there has remained an issue of LiBcc nucleation at the interfaces between different solid components(e.g.,solid electrolyte/MlEC interface),which could undermine the interfacial bonding,thereby leading to the evolution of mechanical instability and the loss of ionic/electronic percolation.In this regard,the present work shows that the Li-ion and electron insulators(LEIs)that are thermodynamically stable against LiBcc could combat such challenges by blocking transportation of charge carriers on the interfaces,analogous to dielectric layers in transistors.We searched the ab initio database and have identified 48 crystalline compounds to be LEI candidates(46 experimentally reported compounds and 2 hypothetical compounds predicted to be stable)with a band gap greater than 3 eV and vanishing Li solubility.Among these compounds,those with good adhesion to solid electrolyte and mixed ion-electron conductor of interest,but are lithiophobic,are expected to be the most useful.We also extended the search to Na or K metal compatible alkali-ion and electron insulators,and identified some crystalline compounds with a property to resist corresponding alkali-ions and electrons.

Enhanced room-temperature Na^(+) ionic conductivity in Na_(4.92)Y_(0.92)Zr_(0.08)Si_(4)O_(12)

Developing cost-effective and reliable solid-state sodium batteries with superior performance is crucial for stationary energy storage.A key component in facilitating their application is a solid-state electrolyte with high conductivity and stability.Herein,we employed aliovalent cation substitution to enhance ionic conductivity while preserving the crystal structure.Optimized substitution of Y^(3+)with Zr^(4+)in Na_(5)YSi_(4)O_(12) introduced Naþion vacancies,resulting in high bulk and total conductivities of up to 6.5 and 3.3 mS cm^(-1),respectively,at room temperature with the composition Na_(4.92)Y_(0.92)Zr_(0.08)Si_(4)O_(12)(NYZS).NYZS shows exceptional electrochemical stability(up to 10 V vs.Naþ/Na),favorable interfacial compatibility with Na,and an excellent critical current density of 2.4 mA cm^(-2).The enhanced conductivity of Naþions in NYZS was elucidated using solid-state nuclear magnetic resonance techniques and theoretical simulations,revealing two migration routes facilitated by the synergistic effect of increased Naþion vacancies and improved chemical environment due to Zr^(4+)substitution.NYZS extends the list of suitable solid-state electrolytes and enables the facile synthesis of stable,low-cost Naþion silicate electrolytes.

Hydrogen isotope effects: A new path to high-energy aqueous rechargeable Li/Na-ion batteries

Aqueous rechargeable Li/Na-ion batteries have shown promise for sustainable large-scale energy storage due to their safety,low cost,and environmental benignity.However,practical applications of aqueous batteries are plagued by water's intrinsically narrow electrochemical stability window,which results in low energy density.In this perspective article,we review several strategies to broaden the electrochemical window of aqueous electrolytes and realize high-energy aqueous batteries.Specifically,we highlight our recent findings on stabilizing aqueous Li storage electrochemistry using a deuterium dioxide-based aqueous electrolyte,which shows significant hydrogen isotope effects that trigger a wider electrochemical window and inhibit detrimental parasitic processes.

A quasi-solid-state electrolyte with high ionic conductivity for stable lithium-ion batteries

The practical applications of solid-state electrolytes in lithium-ion batteries(LIBs)are hindered by their low ionic conductivity and high interfacial resistance.Herein,an ethoxylated trimethylolpropane triacrylate based quasi-solid-state electrolyte(ETPTAQSSE)with a three-dimensional(3D)network is prepared by a one-step in-situ photopolymerization method.The 3D network is designed to overcome the contradiction between the plasticizer-related ionic conductivity and the thickness-dependent mechanical property of quasi-solid-state electrolytes.The ETPTA-QSSE achieves superb room-temperature ionic conductivity up to 4.55×10^(−3)S cm^(−1),a high lithium ion transference number of 0.57,along with a wide electrochemical window of 5.3 V(vs.Li+/Li),which outperforms most ever of the reported solid-state electrolytes.Owing to the robust network structure and the cathodeelectrolyte integrated electrode design,Li metal symmetrical cells show reduced interface resistance and reinforced electrode/electrolyte interface stability.When applying the ETPTA-QSSE in LiFePO_(4)||Li cells,the quasi-solid-state cell demonstrates an enhanced initial discharge capacity(155.5 mAh g^(−1)at 0.2 C)accompanied by a high average Coulombic efficiency of greater than 99.3%,offering capacity retention of 92%after 200 cycles.Accordingly,this work sheds light on the strategy of enhancing ionic conductivity and reducing interfacial resistance of quasi-solid-state electrolytes,which is promising for high-voltage LIBs.

“Water in salt/ionic liquid”electrolyte for 2.8 V aqueous lithium-ion capacitor

Development of high-voltage electrolytes with non-flammability is significantly important for future energy storage devices.Aqueous electrolytes are inherently non-flammable,easy to handle,and their electrochemical stability windows(ESWs)can be considerably expanded by increasing electrolyte concentrations.However,further breakthroughs of their ESWs encounter bottlenecks because of the limited salt solubility,leading to that most of the high-energy anode materials can hardly function reversibly in aqueous electrolytes.Here,by introducing a non-flammable ionic liquid as co-solvent in a lithium salt/water system,we develop a"water in salt/ionic liquid"(WiSIL)electrolyte with extremely low water content.In such WiSIL electrolyte,commercial niobium pentoxide(Nb2O5)material can operate at a low potential(-1.6 V versus Ag/AgCl)and contribute its full capacity.Consequently,the resultant Nb2O5-based aqueous lithium-ion capacitor is able to operate at a high voltage of 2.8 V along with long cycling stability over 3000 cycles,and displays comparable energy and power performance(51.9 Wh kg^-1 at 0.37 kW kg^-1 and 16.4 Wh kg^-1 at 4.9 kW kg^-1)to those using non-aqueous electrolytes but with improved safety performance and manufacturing efficiency.