Three-in-one LaNiO_(3) functionalized separator boosting electrochemical stability and redox kinetics for high-performance Li-S battery

The lithium-sulfur(Li-S)battery,as one of the energy storage devices,has been in the limelight due to its high theoretical energy density.However,the poor redox kinetics and the"shuttle effect"of polysulfides severely restrict the use of Li-S batteries in practical applications.Herein,a novel bimetallic LaNiO_(3) functional material with high electrical conductivity and catalytic property is prepared to act as a high-efficiency polysulfide shuttling stopper.The three LaNiO_(3) samples with different physical/chemical characteristics are obtained by controlling the calcination temperature.In conjunction with the high electrical conductivity and excellent catalytic properties of the as-prepared materials,the appropriate chemisorption toward polysulfides offers great potential to enhance electrochemical stability for highperformance Li-S batteries.Particularly,the Li-S cell with the separator modified by such functional material gives a specific capacity of 658 mA h g^(-1) after 500 cycles at a high current density of 2 C.Even with high sulfur loading of 6.05 mg cm^(-2),the Li-S battery still exhibits an areal specific capacity of 2.81 m A h cm^(-2)after 150 cycles.This work paves a new avenue for the rational design of materials for separator modification in high-performance Li-S batteries.

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.

Crystal Structure, Spectroscopic Characterization, and Electrochemical and Thermal Stability Properties of a Dinuclear Nickel(Ⅱ) Complex

A new nickel（Ⅱ） complex Ni2（L）2（2,2＇-bipy）2·5.5H2O with methy-bicycle[2.2.1]hept-5-ene-2,3-dicarboxylic acid（H2L） and 2,2？-bipyridine（2,2＇-bipy） as ligands has been synthesized in the mixed solvent DMF and water（v：v = 5：2）. It crystallizes in the triclinic space group P1 with a = 10.414（2）, b = 12.884（3）, c = 16.176（4） A, α = 70.715（5）, β = 80.599（5）, γ = 77.383（6）°, V = 1989.4（8） A^3, Dc = 1.531 g/cm^3, Z = 2, F（000） = 958, GOOF = 1.028, the final R = 0.0808 and w R = 0.2036. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two nickel ions are bridged by two μ2-η1：η0 3-carboxylate groups of L2- anions. The coordination environment of Ni（Ⅱ） ion is Ni N2O3, giving a distorted square pyramidal geometry. The thermal stability and electrochemical properties of the complex were investigated.

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.

Boosting the Activity and Stability with Dual-Metal-N Couplings for Li–O_(2)Battery

Electrocatalysts with high efficiency are crucial for improving the storage capacity and electrochemical stability of lithium–oxygen batteries(LOBs).In this work,through a facile hydrothermal method,cobalt–nitrogen-doped carbon nanocubes(Co–N/C),the calcination products of zeolitic imidazolate framework(ZIF–67)are encapsulated by ultrathin C–MoS_(2) nanosheets to obtain Co–N/C@C–MoS_(2) composites which are used as host materials for the oxygen cathode.The synergistic effect between Co–N_(x) active sites and Mo–N coupling centers effectively promotes the formation and decomposition of Li_(2)O_(2) during repeated discharge and charge process.The mesoporous C–MoS_(2) nanosheets with delicately designed morphology facilitate charge transfer and account for improved reaction kinetics and more importantly,suppressed side reactions between the carbon materials and the electrolyte.The oxygen cathode with the Co–N/C@C–MoS_(2)host shows a high initial discharge specific capacity of 21197 mAh g^(-1)and a long operation life of 332 cycles.Theoretical calculation provides in-depth explanation for the reaction mechanism and offers insights for the rational design of electrocatalysts for LOBs.

Electrochemical behaviors of novel composite polymer electrolytes for lithium batteries

A novel composite polymer electrolyte was prepared by blending an appropriateamount of LiClO_4 and 10 percent (mass fraction) fumed SiO_2 with the block copolymer of poly(ethylene oxide) (PEO) synthesized by poly (ethylene glycol) (PEG) 400 and CH_2C1_2 The ionicconductivity, electrochemical stability, interfacial characteristic and thermal behavior of thecomposite polymer electrolyte were studied by the measurements of AC impedance spectroscopy, linearsweep voltammetry and differential scanning calorimetry (DSC), respectively. The glass transitiontemperature acts as a function of salt concentration, which increases with the LiClO_4 content.Lewis acid-base model interaction mechanism was introduced to interpret the interactive relationbetween the filled fumed SiO_2 and the lithium salt in the composite polymer electrolyte. Over thesalt concentration range and the measured temperature, the maximum ionic conductivity of thecomposite polymer electrolyte (10^(-4.41) S/cm) appeared at EO/Li=25 (mole ratio) and 30 deg C, andthe beginning oxidative degradation potential versus Li beyond 5 V.

MoO2 nanoparticles/carbon textiles cathode for high performance flexible Li-O2 battery

Conventional Li-O2 battery is hardly considered as a next-generation flexible electronics thus far,since it is inflexible,bulk,and limited by the absence of the adjustable cell configuration.Here,we report a binder-free and flexible electrode of x wt%MoO2 NPs/CTs(x=6,16,and 28).A cell with 16 wt% MoO2 NPs/CTs displays a good cyclability over 240 cycles with a low overpotential of 0.33 V on the 1st cycle at a constant current density of 0.2 mA cm-2,a considerable rate performance,a superior reversibility associated with the desired formation and degradation of Li2O2,and a high electrochemical stability even under stringent bending and twisting conditions.Our work represents a promising progress in the material development and architecture design of O2 electrode for flexible Li-O2 batteries.

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.

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.

Construction of LiCl/LiF/LiZn hybrid SEI interface achieving high-performance sulfide-based all-solid-state lithium metal batteries

Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have received extensive attention due to their high energy density and high safety,while the poor interface stability between sulfide electrolyte and lithium metal anode limits their development.Hence,a hybrid SEI(LICl/Li F/Li Zn)was constructed at the interface between Li_(5.5)PS_(4.5)Cl_(1.5)sulfide electrolyte and lithium metal.The Li Cl and Li F interface phases with high interface energy effectively induce the uniform deposition of Li^(+)and reduce the overpotential of Li^(+)deposition,while the Li Zn alloy interface phase accelerates the diffusion of lithium ions.The synergistic effect of the above functional interface phases inhibits the growth of lithium dendrites and stabilizes the interface between the sulfide electrolyte and lithium metal.The hybrid SEI strategy exhibits excellent electrochemical performance on symmetric batteries and all-solid-state batteries.The symmetrical cell exhibits stable cycling performance over long duration over 500 h at 1.0 mA cm^(-2).Moreover,the LiNbO_(3)@NCM712/Li_(5.5)PS_(4.5)Cl_(1.5)/Li-10%Zn F_(2)battery exhibits excellent cycle stability at a high rate of 0.5 C,with a capacity retention rate of 76.4%after 350 cycles.

An in-situ polymerized interphase engineering for high-voltage allsolid- state lithium-metal batteries

All-solid-state lithium batteries(ASSLBs)have attracted great interest due to their promising energy density and strong safety.However,the interface issues,including large interfacial resistance between electrode and electrolyte and low electrochemical stability of solid-state electrolytes against high-voltage cathodes,have restricted the development of high-voltage ASSLBs.Herein,we report an ASSLB with stable cycling by adopting a conformal polymer interlayer in-situ formed at the Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)–cathode interfaces.The polymer can perfectlyfill the voids and create a stable interface contact between LLZTO and cathodes.In addition,the electric field across the polymer interlayer is reduced compared with pure solid polymer electrolyte(SPE),which facilitates the electrochemical stability with high-voltage cathode.The all-solid-state Li|LLZTO-SPE|LiFe_(0.4)Mn_(0.6)PO_(4)(LMFP)cells achieve a low interface impedance,high specific capacity,and excellent cycling performance.This work presents an effective and practical strategy to rationally design the electrode–electrolyte interface for the application of high-voltage ASSLBs.

Annealing effects on the optical and electrochemical properties of tantalum pentoxide films

Tantalum pentoxide(Ta_(2)O_(5)) has attracted intensive attention due to their excellent physicochemical properties.Ta_(2)O_(5) films were synthesized via electron beam evaporation(EBE)and subsequently annealed at different temperatures ranging from 300 to 900℃.X-ray diffraction(XRD)results show that amorphous Ta_(2)O_(5) thin films form from 300 to 700℃ and then a phase transition to polycrystalline β-Ta_(2)O_(5) films occurs since 900℃.The surface morphology of the Ta_(2)O_(5) films is uniform and smooth.The resulted Ta_(2)O_(5)films exhibit excellent transmittance properties for wavelengths ranging from 300 to 1100 nm.The bandgap of the Ta_(2)O_(5) films is broadened from 4.32 to 4.46 eV by annealing.The 900℃ polycrystalline film electrode has improved electrochemical stability,compared to the other amorphous counterparts.

Enhance Stability and in vitro Cell Response to a Bioinspired Coating on Zr Alloy with Increasing Chitosan Content

The aim of the present paper is to characterize bioinspired chitosan （CS） ＋ hydroxyapatite （HA） coatings with various components ratio on a zirconium alloy with titanium. The coatings were characterized by FT-IR, SEM, hydrophilic/hydrophobic balance, adherence, roughness, electrochemical stability and in vitro cell response. Electrochemical tests, including potentio- dynamic polarization curves and electrochemical impedance spectroscopy, were performed in normal saline physiological solution. Cell viability of MC3T3-E1 osteoblasts, lactate dehydrogenase, nitric oxide, and Reactive Oxygen Species （ROS） levels, as well as actin cytoskeleton morphology, were evaluated as biological in vitro tests. The results on in vitro cell response indicated good cell membrane integrity and viability for all samples, but an increased cell number, a decreased ROS level and a better cytoskeleton organization were noticed for the sample with a higher CS content. The coating with highest CS concen- tration indicated the best performance based on the experimental data. The highest hydrophilic character, highest resistance to corrosion and best biocompatibility as well recommend this coating for bioapplications in tissue engineering.

Computational insights into the ionic transport mechanism and interfacial stability of the Li_(2)OHCl solid-state electrolyte

Lithium-rich antiperovskites are promising solid-state electrolytes for all-solid-state lithium-ion batteries because of their high structural tolerance and good formability.However,the experimentally reported proton-free Li_(3)OCl is plagued by its inferior interfacial compatibility and harsh synthesis conditions.In contrast,Li_(2)OHCl is a thermodynamically favored phases and is easier to achieve than Li_(3)OCl.Due to the proton inside this material,it exhibits interesting lithium diffusion mechanisms.Herein,we present a systematic investigation of the ionic transport,phase stability,and electrochemicalchemical stability of Li_(2)OHCl using first-principles calculations.Our results indicate that Li_(2)OHCl is thermodynamically metastable and is an electronic insulator.The wide electrochemical stability window and high chemical stability of Li_(2)OHCl against various electrodes are confirmed.The charged defects are the dominant conduction mechanism for Li-transport,with a low energy barrier of~0.50 eV.The Li-ion conductivity estimated by ab initio molecular dynamics simulations is about 1.3×10^(-4) S cm^(-1) at room temperature.This work identifies the origin of the high interfacial stability and ionic conductivity of Li_(2)OHCl,which can further lead to the design of such as a cathode coating.Moreover,all computational methods for calculating the properties of Li_(2)OHCl are general and can guide the design of highperformance solid-state electrolytes.

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.

Epitaxial interface stabilizing iridium dioxide toward the oxygen evolution reaction under high working potentials

Proton exchange membrane water electrolyzer(PEMWE)driven by renewable electricity is a promising technique toward green hydrogen production,but the corrosive environment and high working potential pose severe challenges for developing advanced electrocatalysts for the oxygen evolution reaction(OER).Although Ir-based materials possess relatively balanced activity and stability for the OER,their dissolution behavior cannot be neglected,in particular under high working potentials.In this work,iridium dioxide(IrO_(2))nanoparticles(NPs)were anchored on the surface of exfoliated h-boron nitride(BN)nanosheets(NSs)toward the OER reaction in acid media.Highly active Ir(V)species were stabilized by the epitaxial interface between IrO_(2)and h-BN,and therefore the IrO_(2)/BN delivered stable performance at increased working potentials,while the activity of bare IrO_(2)NPs without h-BN support decreased rapidly.Also,the smaller lattice spacing of h-BN induced compressive strain for IrO_(2),resulting in improved activity.Our results demonstrate the feasibility of stabilizing highly active Ir(V)species for the OER in acid media by constructing robust interface and provide new possibilities toward designing advanced heterostructured electrocatalysts.

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.

Anti-perovskite materials for energy storage batteries

Anti-perovskites X3BA,as the electrically inverted derivatives of perovskites ABX3,have attracted tremendous attention for their good performances in multiple disciplines,especially in energy storage batteries.The Li/Na-rich antiperovskite(LiRAP/NaRAP)solid-state electrolytes(SSEs)typically show high ionic conductivities and high chemical/electrochemical stability toward the Li-metal anode,illustrating their great potential for applications in the Limetal batteries(LMBs)using nonaqueous liquid electrolyte or all-solid-state electrolyte.The antiperovskites have been studied as artificial solid electrolyte interphase for Li-metal anode protection,film SSEs for thin-film batteries,and low melting temperature solid electrolyte enabling melt-infiltration for the manufacture of all-solid-state lithium batteries.Transition metal-doped LiRAPs as cathodes have demonstrated a high discharge specific capacity and good rate capability in the Li-ion batteries(LIBs).Additionally,the underlying scientific principles in antiperovskites with flexible structural features have also been extensively studied.In this review,we comprehensively summarize the development,structural design,ionic conductivity and ion transportation mechanism,chemical/electrochemical stability,and applications of some antiperovskite materials in energy storage batteries.The perspective for enhancing the performance of the antiperovskites is also provided as a guide for future development and applications in energy storage.

Electrolyte design for rechargeable anion shuttle batteries

As an emerging new type of battery chemistry,the anion shuttle battery(ASB),based on the shuttling and storage of anions,is considered a sustainable alternative to gigawatt-scale energy storage due to the associated resource abundance,low cost,high safety,and high energy density.Although significant progress has been achieved,practical applications of ASBs are still hindered by tough challenges,such as short lifetime,limited reversible capacity,and low Coulombic efficiency.Therefore,it is very necessary to design and explore new electrolyte systems with high electrochemical/chemical stability,sufficient compatibility towards electrodes,and excellent kinetics/reversibility for anion electrochemical reactions.Here,we review the recent achievements and main challenges in developing electrolytes for ASBs,which include solid,non-aqueous,and aqueous electrolytes.We mainly focus on the unique properties and basic principles of designing these electrolytes,and their various performance parameters.Perspectives on design strategies for ASB electrolytes are also presented,which could facilitate the development of advanced ASBs for grid-scale energy storage.