New layered metal oxides as positive electrode materials for room-temperature sodium-ion batteries

In order to achieve better Na storage performance, most layered oxide positive electrode materials contain toxic and expensive transition metals Ni and/or Co, which are also widely used for lithium-ion batteries. Here we report a new quaternary layered oxide consisting of Cu, Fe, Mn, and Ti transition metals with O3-type oxygen stacking as a positive electrode for room-temperature sodium-ion batteries. The material can be simply prepared by a high-temperature solidstate reaction route and delivers a reversible capacity of 94 m Ah/g with an average storage voltage of 3.2 V. This paves the way for cheaper and non-toxic batteries with high Na storage performance.

Development of Magnesium-Insertion Positive Electrode for Rechargeable Magnesium Batteries

Magnesium-based rechargeable batteries might be an interesting future alternative to lithium-based batteries. It is so far well known that Mg2+ ion insertion into ion-transfer hosts proceeds slowly compared with Li+, so it is necessary to realize fast Mg2+ transport in the host in addition to other requirements as practical cathode materials for magnesium batteries. Positive electrode materials based on inorganic transition-metal oxides, sulfides, and borides are the only ones used up to now to insert magnesium ions. In this paper, the available results of research on materials suitable as possible, for secondary magnesium batteries, are reviewed.

Sucrose pyrolysis assembling carbon nanotubes on graphite felt using for vanadium redox flow battery positive electrode

In the present paper, multi-walled carbon nanotubes（MWCNTs） are successfully assembled on graphite felt（GF） using sucrose pyrolysis method for the first time. The in situ formed pyrolytic carbon is chosen as the binder because it is essentially carbon materials as well as CNTs and GF which has a natural tendency to achieve high bonding strength and low contact resistance. The MWCNTs/GF electrode is demonstrated to increase surface area, reduce polarization, lower charge transfer resistance and improve energy conversion efficiency comparing with GF. This excellent electrochemical performance is mainly ascribed to the high electro-catalytic activity of MWCNTs and increasing surface area.

CoO AS ADDITIVE IN POSITIVE ELECTRODE OF NICKEL-METAL HYDRIDE BATTERY

A series of positive electrodes for Ni/MH battery were fabricated by addition of CoO.The morphology and microstructure of the electrodes were examined by SEM and EDS, and electrochemical behavior was investigated in three-compartment appliances at room temperature.The electrochemical performance of the positive electrodes with CoO was improved. Under the same charge-discharge cycle, the electrodes with CoO showed higher specific capacity, lower charge mean voltage and higher discharge mean voltage. But ...

Metal-organic frameworks and their composites for advanced lithium-ion batteries:Synthesis,progress and prospects

Metal-organic frameworks(MOFs)are among the most promising materials for lithium-ion batteries(LIBs)owing to their high surface area,periodic porosity,adjustable pore size,and controllable chemical composition.For instance,their unique porous structures promote electrolyte penetration,ions transport,and make them ideal for battery separators.Regulating the chemical composition of MOF can introduce more active sites for electrochemical reactions.Therefore,MOFs and their related composites have been extensively and thoroughly explored for LIBs.However,the reported reviews solely include the applications of MOFs in the electrode materials of LIBs and rarely involve other aspects.A systematic review of the application of MOFs in LIBs is essential for understanding the mechanism of MOFs and better designing related MOFs battery materials.This review systematically evaluates the latest developments in pristine MOFs and MOF composites for LIB applications,including MOFs as the main materials(anode,cathode,separators,and electrolytes)to auxiliary materials(coating layers and additives for electrodes).Furthermore,the synthesis,modification methods,challenges,and prospects for the application of MOFs in LIBs are discussed.

Protective electrode/electrolyte interphases for high energy lithium-ion batteries with p-toluenesulfonyl fluoride electrolyte additive

High energy density lithium-ion batteries using Ni-rich cathode(such as LiNi0.6Co0.2Mn0.2O2) suffer from severe capacity decay.P-toluenesulfonyl fluoride(pTSF) has been investigated as a novel film-forming electrolyte additive to enhance the cycling performances of graphite/LiNi0.6Co0.2Mn0.2O2 pouch cell.In comparison with the baseline electrolyte,a small dose of pTSF can significantly improve the cyclic stability of the cell.Theoretical calculations together with experimental results indicate that pTSF would be oxidized and reduced to construct protective interphase film on the surfaces of LiNi0.6Co0.2Mn0.2O2 cathode and graphite anode,respectively.These S-containing surface films derived from pTSF effectively mitigate the decomposition of electrolyte,reduce the interphasial impedance,as well as prevent the dissolution of transition metal ions from Ni-rich cathode upon cycling at high voltage.This finding is beneficial for the practical application of high energy density graphite/LiNi0.6Co0.2Mn0.2O2 cells.

A chemo-mechanical model coupled with thermal effect on the hollow core–shell electrodes in lithium-ion batteries

Electrode is a key component to remain durability and safety of lithium-ion（Li-ion） batteries. Li-ion insertion/removal and thermal expansion mismatch may induce high stress in electrode during charging and discharging processes. In this paper, we present a continuum model based on COMSOL Multiphysics software, which involves thermal, chemical and mechanical behaviors of electrodes. The results show that,because of diffusion-induced stress and thermal mismatch, the electrode geometry plays an important role in diffusion kinetics of Li-ions. A higher local compressive stress results in a lower Li-ion concentration and thus a lower capacity when a particle is embedded another, which is in agreement with experimental observations.

Review on electrode-level fracture in lithium-ion batteries

Fracture occurred in electrodes of the lithium-ion battery compromises the integrity of the electrode structure and would exert bad influence on the cell performance and cell safety.Mechanisms of the electrode-level fracture and how this fracture would affect the electrochemical performance of the battery are of great importance for comprehending and preventing its occurrence.Fracture occurring at the electrode level is complex,since it may involve fractures in or between different components of the electrode.In this review,three typical types of electrode-level fractures are discussed:the fracture of the active layer,the interfacial delamination,and the fracture of metallic foils(including the current collector and the lithium metal electrode).The crack in the active layer can serve as an effective indicator of degradation of the electrochemical performance.Interfacial delamination usually follows the fracture of the active layer and is detrimental to the cell capacity.Fracture of the current collector impacts cell safety directly.Experimental methods and modeling results of these three types of fractures are concluded.Reasonable explanations on how these electrode-level fractures affect the electrochemical performance are sorted out.Challenges and unsettled issues of investigating these fracture problems are brought up.It is noted that the state-of-the-art studies included in this review mainly focus on experimental observations and theoretical modeling of the typical mechanical damages.However,quantitative investigations on the relationship between the electrochemical performance and the electrode-level fracture are insufficient.To further understand fractures in a multiscale and multi-physical way,advancing development of the cross discipline between mechanics and electrochemistry is badly needed.

Parameter-independent error correction for potential measurements by reference electrode in lithium-ion batteries

The safety monitoring of lithium-ion batteries(LIBs) is of great significance for realizing all-climate and full-lifespan battery management. In-situ measurement of anode potential with implanted reference electrodes(REs) has proven to be effective to monitor and avoid the occurrence of severe side reactions like Li plating to ensure the safe and fast charging. However, the intrinsic measurement errors caused by local blocking effects, which also can be referred to as potential artefacts, are seldom taken into consideration in existing studies, yet they highly dominate the correctness of conclusions inferred from REs. In this study, aiming at exploring the physical origin of the measurement errors and ensure reliable potential monitoring, electrochemical and post-mortem tests are conducted using commercial pouch cells with implanted REs. Corresponding electrochemical model which describes the blocking effects, is established to validate the abnormal absence of lithium plating that predicted by measured anode potentials under various charging rates. Theoretical derivation is further presented to explain the error sources, which can be attributed to increased local liquid potential of the RE position. Most importantly, with the guidance of error analysis, a novel parameter-independent error correction method for RE measurements is proposed for the first time, which is proven to be adequate to estimate the real anode potentials and deduce the critical C-rate of Li plating with extra safety margin. After error correction, the resulting critical C-rates are all within the range of 0.55 ± 0.03 C, which is close to the C-rate of 0.6–0.7 C obtained from experiments. In addition, this error correction method can be performed conveniently with only some simple RE measurements of polarization voltages, totally independent of battery electrochemical and geometric parameters. This study provides highly practical error correction method for RE measurements in real LIBs, substantially facilitating the fast diagnosis and safety evaluation of Li plating during charging of LIBs.

Electrode-compatible fluorine-free multifunctional additive regulating solid electrolyte interphase and solvation structure for high-performance lithium-ion batteries

The rapid development and widespread application of lithium-ion batteries(LIBs) have increased demand for high-safety and high-performance LIBs. Accordingly, various additives have been used in commercial liquid electrolytes to severally adjust the solvation structure of lithium ions, control the components of solid electrolyte interphase, or reduce flammability. While it is highly desirable to develop low-cost multifunctional electrolyte additives integrally that address both safety and performance on LIBs, significant challenges remain. Herein, a novel phosphorus-containing organic small molecule, bis(2-methoxyethyl) methylphosphonate(BMOP), was rationally designed to serve as a fluorine-free and multifunctional additive in commercial electrolytes. This novel electrolyte additive is low-toxicity,high-efficiency, low-cost, and electrode-compatible, which shows the significant improvement to both electrochemical performance and fire safety for LIBs through regulating the electrolyte solvation structure, constructing the stable electrode-electrolyte interphase, and suppressing the electrolyte combustion. This work provides a new avenue for developing safer and high-performance LIBs.

In-situ design and construction of lithium-ion battery electrodes on metal substrates with enhanced performances：A brief review

For the ever-growing demand of advanced lithium-ion batteries, it is highly desirable to grow self-supported micro-/nanostructured arrays on metal substrates as electrodes directly. The in-situ growth of electrode materials on the conducting substrates greatly simplifies the electrode fabrication process without using any binders or conductive additives. Moreover, the well-ordered arrays closely connected to the current collectors can provide direct electron transport pathways and enhanced accommodation of strains arisen from lithium ion lithiation/delithiation. This article summarizes our recent work on design and construction of lithium-ion battery electrodes on metal substrates. An aqueous solution-based process and a microemulsion-mediated process have been respectively presented to control the kinetic and thermodynamic processes for the micro-/nanostructured array growth on metal substrates, with particular attention to CuO nanorod arrays and microcog arrays successfully prepared on Cu foil substrates. They can be directly used as binder-free electrodes to build advanced lithium-ion batteries with high energy, high safety and high stability.

Analysis of diffusion induced elastoplastic bending of bilayer lithium-ion battery electrodes

Bilayer electrode, composed of a current collector layer and an active material layer, has great potential in applications of in-situ electrochemical experiments due to the bending upon lithiation. This paper establishes an elastoplastic theory for the lithiation induced deformation of bilayer electrode with consideration of the plastic yield of current collector. It is found that the plastic yield of current collector reduces the restriction of current collector to an active layer, and therefore, enhances in-plane stretching while lowers down the rate of electrode bending. Key parameters that influence the elastoplastic deformation are identified. It is found that the smaller thickness ratio and lower elastic modulus ratio of current collector to an active layer would lead to an earlier plastic yield of the current collector, the larger in-plane strain, and the smaller bending curvature, due to balance between the current collector and the active layer. The smaller yield stress and plastic modulus of current collector have similar impacts on the electrode deformation.

A comparative study on the reactivity of charged Ni-rich and Ni-poor positive electrodes with electrolyte at elevated temperatures using accelerating rate calorimetry

The reactivity between charged Li(Li_(0.115)Mn_(0.529)Ni_(0.339)Al_(0.017))O_(2)(Li-rich),single crystal Li(Ni_(0.8)Mn_(0.1)Co_(0.1))O_(2)(SC-NMC811),LiFePO_(4)(LFP) and LiMn_(0.8)Fe_(0.2)PO_(4)(LMFP) positive electrodes at different states of charge(SOCs) and traditional carbonate-based electrolyte at elevated temperatures is systematically studied using accelerating rate calorimetry(ARC).The results show that the SOC greatly affects the thermal stability of the Li-rich and SC-NMC811 when traditional carbonate-based electrolyte is used.Although an increase in the SOC increases the energy density of lithium-ion cells,it also increases the reactivity between charged Li-rich and SC-NMC811 samples with electrolyte at elevated temperatures.In comparison with SC-NMC811,the Li-rich samples are much more stable at elevated temperatures,and the latter have higher specific capacity.SC-NMC811 samples are less reactive than traditional polycrystalline NMC811.Both LFP and LMFP samples show excellent thermal stability at elevated temperatures.The substitution of Fe by Mn in the olivine series positive materials does not impact the reactivity with electrolyte.

A pre-strain strategy of current collectors for suppressing electrode debonding in lithium-ion batteries

The interfacial debonding between the active layer and the current collector has been recognized as a critical mechanism for battery fading,and thus has attracted great efforts focused on the related analyses.However,much still remains to be studied regarding practical methods for suppressing electrode debonding,especially from the perspective of mechanics.In this paper,a pre-strain strategy of current collectors to alleviate electrode debonding is proposed.An analytical model for a symmetric electrode with a deformable and limited-thickness current collector is developed to analyze the debonding behavior involving both a pre-strain of the current collector and an eigen-strain of the active layers.The results reveal that the well-designed pre-strain can significantly delay the debonding onset(by up to 100%)and considerably reduce the debonding size.The critical values of the pre-strain are identified,and the pre-strain design principles are also provided.Based on these findings,this work sheds light on the mechanical design to suppress electrode degradation.

High-Safety Anode Materials for Advanced Lithium-Ion Batteries

Lithium-ion batteries(LIBs)play a pivotal role in today's society,with widespread applications in portable electronics,electric vehicles,and smart grids.Commercial LIBs predominantly utilize graphite anodes due to their high energy density and cost-effectiveness.Graphite anodes face challenges,however,in extreme safety-demanding situations,such as airplanes and passenger ships.The lithiation of graphite can potentially form lithium dendrites at low temperatures,causing short circuits.Additionally,the dissolution of the solid-electrolyte-interphase on graphite surfaces at high temperatures can lead to intense reactions with the electrolyte,initiating thermal runaway.This review introduces two promising high-safety anode materials,Li_(4)Ti_(5)O_(12)and TiNb_(2)O_(7).Both materials exhibit low tendencies towards lithium dendrite formation and have high onset temperatures for reactions with the electrolyte,resulting in reduced heat generation and significantly lower probabilities of thermal runaway.Li_(4)Ti_(5)O_(12)and TiNb_(2)O_(7)offer enhanced safety characteristics compared to graphite,making them suitable for applications with stringent safety requirements.This review provides a comprehensive overview of Li_(4)Ti_(5)O_(12)and TiNb_(2)O_(7),focusing on their material properties and practical applicability.It aims to contribute to the understanding and development of high-safety anode materials for advanced LIBs,addressing the challenges and opportunities associated with their implementation in real-world applications.

A high Li-ion diffusion kinetics in multidimensional and compact-structured electrodes via vacuum filtration casting

Manufacturing process,diffusion co-efficient and areal capacity are the three main criteria for regulating thick electrodes for lithium-ion batteries(LIBs).However,simultaneously regulating these criteria for LIBs is desirable but remains a significant challenge.In this work,niobium pentoxide(Nb_(2)O_(5))anode and lithium iron phosphate(LiFePO_(4))cathode materials were chosen as the model materials and demonstrate that these three parameters can be simultaneously modulated by incorporation of micro-carbon fibers(MCF)and carbon nanotubes(CNT)with both Nb_(2)O_(5) and LFP via vacuum filtration approach.Both as-prepared MNC-20 anode and MLC-20 cathode achieves high reversible areal capacity of≈5.4 m A h cm^(-2)@0.1 C and outstanding Li-ion diffusion coefficients of≈10~(-8)cm~2 s~(-1)in the half-cell configuration.The assembled MNC-20‖MLC-20 full cell LIB delivers maximum energy and power densities of244.04 W h kg^(-1)and 108.86 W kg^(-1),respectively.The excellent electrochemical properties of the asprepared thick electrodes can be attributed to the highly conductive,mechanical compactness and multidimensional mutual effects of the MCF,CNT and active materials that facilitates rapid Li-ion diffusion kinetics.Furthermore,electrochemical impedance spectroscopy(EIS),symmetric cells analysis,and insitu Raman techniques clearly validates the enhanced Li-ion diffusion kinetics in the present architecture.

Magnetic resonance imaging techniques for lithium-ion batteries:Principles and applications

Operando monitoring of internal and local electrochemical processes within lithium-ion batteries(LIBs)is crucial,necessitating a range of non-invasive,real-time imaging characterization techniques including nuclear magnetic resonance(NMR)techniques.This review provides a comprehensive overview of the recent applications and advancements of non-invasive magnetic resonance imaging(MRI)techniques in LIBs.It initially introduces the principles and hardware of MRI,followed by a detailed summary and comparison of MRI techniques used for characterizing liquid/solid electrolytes,electrodes and commercial batteries.This encompasses the determination of electrolytes'transport properties,acquisition of ion distribution profile,and diagnosis of battery defects.By focusing on experimental parameters and optimization strategies,our goal is to explore MRI methods suitable to a variety of research subjects,aiming to enhance imaging quality across diverse scenarios and offer critical physical/chemical insights into the ongoing operation processes of LIBs.

Silicon micropillar electrodes of lithiumion batteries used for characterizing electrolyte additives

The 100 crystal-oriented silicon micropillar array platforms were prepared by microfabrication processes for the purpose of electrolyte additive identification. The silicon micropillar array platform was used for the study of fluorinated vinyl carbonate(FEC), vinyl ethylene carbonate(VEC), ethylene sulfite(ES), and vinyl carbonate(VC) electrolyte additives in the LiPF_6 dissolved in a mixture of ethylene carbonate and diethyl carbonate electrolyte system using charge/discharge cycles, electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, and x-ray photoelectron spectroscopy. The results show that the silicon pillar morphology displays cross-shaped expansion after lithiation/delithiation, the inorganic lithium salt keeps the silicon pillar morphology intact, and the organic lithium salt content promotes a rougher silicon pillar surface. The presence of poly-(VC) components on the surface of FEC and VC electrodes allows the silicon pillar to accommodate greater volume expansion while remaining intact. This work provides a standard, fast, and effective test method for the performance analysis of electrolyte additives and provides guidance for the development of new electrolyte additives.

Atomic Layer Deposition of High-Capacity Anodes for Next-Generation Lithium-Ion Batteries and Beyond

Electrification has great impacts on our modern society.To electrify future transportation,state-of-the-art lithium-ion batteries(LIBs)are still not sufficient in multiple aspects including cost,energy density,lifespan,and safety.To this end,next-generation high-energy LIBs and beyond are highly regarded.In this regard,high-capacity anodes are undergoing intensive investigation,such as silicon,SnO_(2),and lithium metal.However,such anode materials are commonly experiencing large volume changes and related issues,which are reflected on mechanical degradation,capacity fading,low efficiency,and unsatisfactory lifetime.To address these challenges,many technical strategies have been investigated.In the past decade,atomic layer deposition(ALD)has emerged as a new promising technique enabling atomic-scale surface modification and nanoscale design of high-capacity anodes for high performance.In this review,recent ALD studies on developing high-capacity anodes for LIBs and beyond are thoroughly summarized.In addition,ALD strategies and their effectiveness in pursing high-energy LIBs and beyond are discussed.Particularly,we highlighted the latest advances of ALD for addressing the notorious issues associated with Li metal anodes.It is expected that this work will promote the applications of ALD in new battery systems.

Computational design of promising 2D electrode materials for Li-ion and Li–S battery applications

Lithium-ion batteries(LIBs)and lithium-sulfur(Li–S)batteries are two types of energy storage systems with significance in both scientific research and commercialization.Nevertheless,the rational design of electrode materials for overcoming the bottlenecks of LIBs and Li–S batteries(such as low diffusion rates in LIBs and low sulfur utilization in Li–S batteries)remain the greatest challenge,while two-dimensional(2D)electrodes materials provide a solution because of their unique structural and electrochemical properties.In this article,from the perspective of ab-initio simulations,we review the design of 2D electrode materials for LIBs and Li–S batteries.We first propose the theoretical design principles for 2D electrodes,including stability,electronic properties,capacity,and ion diffusion descriptors.Next,classified examples of promising 2D electrodes designed by theoretical simulations are given,covering graphene,phosphorene,MXene,transition metal sulfides,and so on.Finally,common challenges and a future perspective are provided.This review paves the way for rational design of 2D electrode materials for LIBs and Li–S battery applications and may provide a guide for future experiments.