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.

Polypyrrole-coated triple-layer yolk-shell Fe_(2)O_(3)anode materials with their superior overall performance in lithium-ion batteries

Iron oxide(Fe_(2)O_(3))emerges as a highly attractive anode candidate among rapidly expanding energy storage market.Nonethe-less,its considerable volume changes during cycling as an electrode material result in a vast reduced battery cycle life.In this work,an ap-proach is pioneered for preparing high-performance Fe_(2)O_(3)anode materials,by innovatively synthesizing a triple-layer yolk-shell Fe_(2)O_(3)uniformly coated with a conductive polypyrrole(Ppy)layer(Fe_(2)O_(3)@Ppy-TLY).The uniform polypyrrole coating introduces more reac-tion sites and adsorption sites,and maintains structure stability through charge-discharge process.In the uses as lithium-ion battery elec-trodes,Fe_(2)O_(3)@Ppy-TLY demonstrates high reversible specific capacity(maintaining a discharge capacity of 1375.11 mAh·g^(−1)after 500 cycles at 1 C),exceptional cycling stability(retaining the steady charge-discharge performance at 544.33 mAh·g^(−1)after 6000 ultrafast charge-discharge cycles at a 10 C current density),and outstanding high current charge-discharge performance(retaining a reversible ca-pacity of 156.75 mAh·g^(−1)after 10000 cycles at 15 C),thereby exhibiting superior lithium storage performance.This work introduces in-novative advancements for Fe_(2)O_(3)anode design,aiming to enhance its performance in energy storage fields.

Carbon-coated ZnO Nanocomposite Microspheres as Anode Materials for Lithium-ion Batteries

The carbon-coated ZnO nanospheres materials have been synthesized via a simple hydrothermal method.The effect of carbon content on the microstructure,morphology and electrochemical performance of the materials was investigated by XRD,Raman spectroscopy,transmission electron microscopy,scanning electron microscopy and electrochemical techniques.Research results show that the spherical ZnO/C material with a carbon cladding content of 10%is very homogeneous and approximately 200 nm in size.The electrochemical performances of the ZnO/C nanospheres as an anode materials are examines.The ZnO/C exhibits better stability than pure ZnO,excellent lithium storage properties as well as improved circulation performance.The Coulomb efficiency of the ZnO/C with 10%carbon coated content reaches 98%.The improvement of electrochemical performance can be attributed to the carbon layer on the ZnO surface.The large volume change of ZnO during the charge-discharge process can be effectively relieved.

Emerging two-dimensional Mo-based materials for rechargeable metal-ion batteries:Advances and perspectives

With the rapid development of rechargeable metal-ion batteries(MIBs)with safety,stability and high energy density,significant efforts have been devoted to exploring high-performance electrode materials.In recent years,two-dimensional(2D)molybdenum-based(Mo-based)materials have drawn considerable attention due to their exceptional characteristics,including low cost,unique crystal structure,high theoretical capacity and controllable chemical compositions.However,like other transition metal compounds,Mo-based materials are facing thorny challenges to overcome,such as slow electron/ion transfer kinetics and substantial volume changes during the charge and discharge processes.In this review,we summarize the recent progress in developing emerging 2D Mo-based electrode materials for MIBs,encompassing oxides,sulfides,selenides,carbides.After introducing the crystal structure and common synthesis methods,this review sheds light on the charge storage mechanism of several 2D Mo-based materials by various advanced characterization techniques.The latest achievements in utilizing 2D Mo-based materials as electrode materials for various MIBs(including lithium-ion batteries(LIBs),sodium-ion batteries(SIBs)and zinc-ion batteries(ZIBs))are discussed in detail.Afterwards,the modulation strategies for enhancing the electrochemical performance of 2D Mo-based materials are highlighted,focusing on heteroatom doping,vacancies creation,composite coupling engineering and nanostructure design.Finally,we present the existing challenges and future research directions for 2D Mo-based materials to realize high-performance energy storage systems.

Outstanding Lithium Storage Performance of a Copper-Coordinated Metal-Covalent Organic Framework as Anode Material for Lithium-Ion Batteries

Metal-covalent organic frameworks(MCOF)as a bridge between covalent organic framework(COF)and metal organic framework(MOF)possess the characteristics of open metal sites,structure stability,crystallinity,tunability as well as porosity,but still in its infancy.In this work,a covalent organic framework DT-COF with a keto-enamine structure synthesized from the condensation of 3,3'-dihydroxybiphenyl diamine(DHBD)and triformylphloroglucinol(TFP)was coordinated with Cu^(2+)by a simple post-modification method to a obtain a copper-coordinated metal-covalent organic framework of Cu-DT COF.The isomerization from a keto-enamine structure of DT-COF to a enol-imine structure of Cu-DT COF is induced due to the coordination interaction of Cu^(2+).The structure change of Cu-DT COF induces the change of the electron distribution in the Cu-DT COF,which greatly promotes the activation and deep Li-storage behavior of the COF skeleton.As anode material for lithium-ion batteries(LIBs),Cu-DT COF exhibits greatly improved electrochemical performance,retaining the specific capacities of 760 mAh g^(-1)after 200 cycles and 505 mAh g^(-1)after 500 cycles at a current density of 0.5 A g^(-1).The preliminary lithium storage mechanism studies indicate that Cu^(2+)is also involved in the lithium storage process.A possible mechanism for Cu-DT COF was proposed on the basis of FT-IR,XPS,EPR characterization and electrochemical analysis.This work enlightens a novel strategy to improve the energy storage performance of COF and promotes the application of COF and MCOF in LIBs.

Enhanced Electrochemical Performances of Ni Doped Cr_(8)O_(21)Cathode Materials for Lithium-ion Batteries

Cathode materials,nickel doped Cr_(8)O_(21),were synthesized by a solid-state method.The effects of Ni doping on the electrochemical performances of Cr_(8)O_(21) were investigated.The experimental results show that the discharge capacities of the samples depend on the nickel contents,which increases firstly and then decreases with increasing Ni contents.Optimized Ni_(0.5)Cr_(7.5)O_(21)delivers a first capacity up to 392.6 m Ah·g^(-1)at 0.1C.In addition,Ni doped sample also demonstrates enhanced cycling stability and rate capability compared with that of the bare Cr_(8)O_(21).At 1 C,an initial discharge capacity of 348.7 m Ah·g^(-1)was achieved for Ni_(0.5)Cr_(7.5)O_(21),much higher than 271.4 m Ah·g^(-1)of the un-doped sample,with an increase of more than 28%.Electrochemical impedance spectroscopy results confirm that Ni doping reduces the growth of interface resistance and charge transfer resistance,which is conducive to the electrochemical kinetic behaviors during charge-discharge.

Hydrothermal synthesis of spindle-like Li_2FeSiO_4-C composite as cathode materials for lithium-ion batteries

In this paper,we report on the preparation of Li2FeSiO4,sintered Li2FeSiO4,and Li2FeSiO4-C composite with spindle-like morphologies and their application as cathode materials of lithium-ion batteries.Spindle-like Li2FeSi04 was synthesized by a facile hydrothermal method with（NH4）2Fe（SO4）2 as the iron source.The spindle-like Li2FeSiO4 was sintered at 600 ℃ for 6 h in Ar atmosphere.Li2FeSiO4-C composite was obtained by the hydrothermal treatment of spindle-like Li2FeSiO4 in glucose solution at 190 ℃ for 3 h.Electrochemical measurements show that after carbon coating,the electrode performances such as discharge capacity and high-rate capability are greatly enhanced.In particular.Li2FeSiO4-C with carbon content of 7.21 wt%delivers the discharge capacities of 160.9 mAh·g-1 at room temperature and 213 mAh·g-1 at45℃（0.1 C）,revealing the potential application in lithium-ion batteries.

Effect of lithium content on electrochemical property of Li_(1+x)(Mn_(0.6)Ni_(0.2)Co_(0.2))_(1-x)O_2(0≤x≤0.3) composite cathode materials for rechargeable lithium-ion batteries

In order to confirm the optimal Li content of Li-rich Mn-based cathode materials(a fixed mole ratio of Mn to Ni to Co is0.6:0.2:0.2),Li1+x(Mn0.6Ni0.2Co0.2)1-xO2(x=0,0.1,0.2,0.3)composites were obtained,which had a typical layered structure with R3m and C2/m space group observed from X-ray powder diffraction(XRD).Electron microscopy micrograph(SEM)reveals that the particle sizes in the range of0.4-1.1μm increase with an increase of x value.Li1.2(Mn0.6Ni0.2Co0.2)0.8O2sample delivers a larger initial discharge capacity of275.7mA·h/g at the current density of20mA/g in the potential range of2.0-4.8V,while Li1.1(Mn0.6Ni0.2Co0.2)0.9O2shows a better cycle performance with a capacity retention of93.8%at0.2C after50cycles,showing better reaction kinetics of lithium ion insertion and extraction.

Influences of transition metal on structural and electrochemical properties of Li[Ni_xCo_yMn_z]O_2(0.6≤x≤0.8) cathode materials for lithium-ion batteries

Li[NixCoyMn2]O2（0.6≤x≤0.8） cathode materials with a typical hexagonal α-NaFeO2 structure were prepared utilizing a co-precipitation method.It is found that the ratio of peak intensities of（003） to（104） observed from X-ray diffraction（XRD）increases with decreasing the Ni content or increasing the Co content.The scanning electron microscopy（SEM） images reveal that the small primary particles are agglomerated to form the secondary ones.As the Mn content increases,the primary and secondary particles become larger and the resulted particle size for the Li[Ni（0.6）Co（0.2）Mn（0.2）]O2 is uniformly distributed in the range of100-300 nm.Although the initial discharge capacity of the Li/Li[NixCoyMn2]O2 cells reduces with decreasing the Ni content,the cyclic performance and rate capability are improved with higher Mn or Co content.The Li[Ni（0.6）Co（0.2）Mn（0.2）]O2 can deliver excellent cyclability with a capacity retention of 97.1%after 50 cycles.

TiO_2/graphene nanocomposites as anode materials for high rate lithium-ion batteries

A simple strategy to prepare a hybrid of nanocomposites of anatase TiO2/graphene nanosheets （GNS） as anode materials for lithium-ion batteries was reported.The morphology and crystal structure were studied by X-ray diffraction （XRD）,field emission scanning electron microscopy （FE-SEM） and transmission electron microscopy （TEM）.The electrochemical performance was evaluated by galvanostatic charge-lischarge tests and alternating current （AC） impedance spectroscopy.The results show that the TiO2/GNS electrode exhibit higher electrochemical performance than that of TiO2 electrode regardless of the rate.Even at 500 mA/g,the capacity of TiO2/GNS is 120.3 mAh/g,which is higher than that of TiO2 61.6 mAh/g.The high performance is attributed to the addition of graphene to improve electrical conductivity and reduce polarization.

Preparation of layered Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2 as positive material for lithium-ion secondary battery

The uniform layered Li(Ni1/3Co1/3Mn1/3)O2 cathode material for lithium-ion secondary batteries were synthesized by using(Ni1/3Co1/3Mn1/3)(OH)2 synthesized by a liquid phase co-precipitated method as precursors and with NiSO4,CoSO4,MnSO4 and NH3·H2O as raw materials. The influence of the preparation conditions such as precursors preparation,calcinations temperature and calcinations time on the structural and electrochemical properties of the Li(Ni1/3Co1/3Mn1/3)O2 were systematicelly studied. The result of XRD shows the I003/I104 value of the Li(Ni1/3Co1/3Mn1/3)O2 powder synthesized at 950 ℃ for 10 h is 1.26,which illustrates the well-ordered layer-structure. The average particle size of uniform Li(Ni1/3Co1/3Mn1/3)O2 powder is about 400 nm in diameter as observed by scanning electron microscopy. The first discharge capacity of Li(Ni1/3Co1/3Mn1/3)O2 electrode is 174.6 mA·h/g at 16 mA/g between 2.8 V and 4.5 V versus Li at room temperature,and the capacity retention is 95.2% of the initial discharge capacity after 50 cycles at 32 mA/g.

Modification strategies improving the electrochemical and structural stability of high-Ni cathode materials

With the increasing spotlight in electric vehicles,there is a growing demand for high-energy-density batteries to enhance driving range.Consequently,several studies have been conducted on high-energy-density LiNi_(x)Co_(y)Mn_(z)O_(2)cathodes.However,there is a limit to permanent performance deterioration because of side reactions caused by moisture in the atmosphere and continuous microcracks during cycling as the Ni content to express high energy increases and the content of Mn and Co that maintain structural and electrochemical stabilization decreases.The direct modification of the surface and bulk regions aims to enhance the capacity and long-term performance of high-Ni cathode materials.Therefore,an efficient modification requires a study based on a thorough understanding of the degradation mechanisms in the surface and bulk region.In this review,a comprehensive analysis of various modifications,including doping,coating,concentration gradient,and single crystals,is conducted to solve degradation issues along with an analysis of the overall degradation mechanism occurring in high-Ni cathode materials.It also summarizes recent research developments related to the following modifications,aims to provide notable points and directions for post-studies,and provides valuable references for the commercialization of stable high-energy-density cathode materials.

Recent progress in Ni-rich layered oxides and related cathode materials for Li-ion cells

Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.

Progress in doping and crystal deformation for polyanions cathode based lithium-ion batteries

Polyanion-based materials are considered one of the most attractive and promising cathode materials for lithiumion batteries(LIBs)due to their good stability,safety,cost-effectiveness,suitable voltages,and minimal environmental impact.However,these materials suffer from poor rate capability and low-temperature performance owing to limited electronic and ionic conductivity,which restricts their practical applicability.Recent developments,such as coating material particles with carbon or a conductive polymer,crystal deformation through the doping of foreign metal ions,and the production of nanostructured materials,have significantly enhanced the electrochemical performances of these materials.The successful applications of polyanion-based materials,especially in lithium-ion batteries,have been extensively reported.This comprehensive review discusses the current progress in crystal deformation in polyanion-based cathode materials,including phosphates,fluorophosphates,pyrophosphates,borates,silicates,sulfates,fluorosilicates,and oxalates.Therefore,this review provides detailed discussions on their synthesis strategies,electrochemical performance,and the doping of various ions.

Ultrasonic synthesis of CoO/graphene nanohybrids as high performance anode materials for lithium-ion batteries

A facile ultrasonic method was used to synthesize CoO/graphene nanohybrids by employing Co4（CO）12 as a cobalt precursor. The nanohybrids were characterized by SEM, TEM and XPS, and the results show that CoO nanoparticles （3-5 nm） distribute uniformly on the surface of graphene. The CoO/graphene nanohybrids display high performance as an anode material for lithium-ion battery, such as high reversible lithium storage capacity （650 mA-h/g after 50 cycles, almost twice that of commercial graphite anode）, high coulombic efficiency （over 95%） and excellent cycling stability. The extraordinary performance arises from the structure of the nanohybrids： the nanosized CoO particles with high dispersity on conductive graphene substrates are beneficial for lithium-ion insertion/extraction, shortening diffusion length for lithium ions and improving conductivity, thus the lithium storage performance was improved.

Solid-state mechanochemistry advancing two dimensional materials for lithium-ion storage applications:A mini review

The vigorous development of two-dimensional(2D)materials brings about numerous opportunities for lithiumion batteries(LIBs)due to their unique 2D layered structure,large specific surface area,outstanding mechanical and flexibility properties,etc.Modern technologies for production of 2D materials include but are not limited to mechanochemical(solid-state/liquid-phase)exfoliation,the solvothermal method and chemical vapor deposition.In this review,strategies leading to the production of 2D materials via solid-state mechanochemistry featuring traditional high energy ball-milling and Sichuan University patented pan-milling are highlighted.The mechanism involving exfoliation,edge selective carbon radical generation of the 2D materials is delineated and this is followed by detailed discussion on representative mechanochemical techniques for tailored and improved lithium-ion storage performance.In the light of the advantages of the solid-state mechanochemical method,there is great promise for the commercialization of 2D materials for the next-generation high performance LIBs.

Empowering the Future: Exploring the Construction and Characteristics of Lithium-Ion Batteries

Lithium element has attracted remarkable attraction for energy storage devices, over the past 30 years. Lithium is a light element and exhibits the low atomic number 3, just after hydrogen and helium in the periodic table. The lithium atom has a strong tendency to release one electron and constitute a positive charge, as Li . Initially, lithium metal was employed as a negative electrode, which released electrons. However, it was observed that its structure changed after the repetition of charge-discharge cycles. To remedy this, the cathode mainly consisted of layer metal oxide and olive, e.g., cobalt oxide, LiFePO4, etc., along with some contents of lithium, while the anode was assembled by graphite and silicon, etc. Moreover, the electrolyte was prepared using the lithium salt in a suitable solvent to attain a greater concentration of lithium ions. Owing to the lithium ions’ role, the battery’s name was mentioned as a lithium-ion battery. Herein, the presented work describes the working and operational mechanism of the lithium-ion battery. Further, the lithium-ion batteries’ general view and future prospects have also been elaborated.

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.

A review of cathode and electrolyte recovery from spent lithium-ion batteries: Recent technologies, processes and policies

Recently,lithium-ion batteries(LIBs),due to their superior performance,have been vastly applied in electronic,auto,and other industries,resulting in the generation of an increasing amount of spent LIBs.What’s worse,LIBs contained potentially toxic substances,including heavy metals,toxic and flammable electrolyte containing LiBF_(4),LiClO_(4),and LiPF_(6).Conventional disposal of spent LIBs via landfill or incineration exerts tremendous pressure on the environment.It was necessary to adopt efficient,low-cost,and environmentally friendly approaches to valorizing spent LIBs,which could not only alleviate the shortage of rare resources by recycling valuable ele-ments such as Cu,Li,Mn,Ni,Co,and Al,but also eliminate the pollution of harmful components in batteries and realize the recycling and sustainable industry related to consumer electronics and electric vehicles(EVs).Given this,this paper summarized the recycling technologies of spent LIBs,including pyrometallurgy(melting reduction and roasting methods)and hydrometallurgy(leaching,precipitation,extraction,ion-exchange,elec-trochemical,sol-gel methods),and electrolyte recycling(organic solvent extraction and supercritical extraction methods).Pyrometallurgy technologies had relatively decent metal recovery rates but were associated with high energy consumption and atmospheric emission issues.Hydrometallurgical technologies were more environ-mentally friendly and efficient in recovering spent LIBs,although disposing of the wastewater generated from the process remained a challenge.In addition,the different industrial processes and various countries’related policies of recycling spent LIBs were investigated.In the end,the outlooks and future directions of recycling spent LIBs were proposed.

Overlooked impact of precursor mixing:Implications in the electrochemical performance of battery electrode materials

Solid-state reactions are an essential part of the synthesis of various cathode materials for lithium-ion batteries(LIBs).Despite the simplicity and effectiveness for mass production,a subtle variation in synthesis conditions can often give rise to unexpectedly different physical properties,significantly affecting the electrochemical performance of electrode materials.However,this aspect has long been overlooked in the LIB community,which should focus on advancement in understanding the influence of synthesis conditions.As solid-state reactions occur only at the interface of precursor materials,maximizing the interfacial contact area between mixed precursor powders is crucial.Mechanical milling and/or mixing are common practices that have been performed in both academia and industry for this purpose.Unlike the common belief that this pre-treatment before calcination would be of great benefit for the preparation of high-performance LIB materials,we revealed in this work that this practice is not always successful for this goal.In our case study of the preparation of LiCoO_(2),we demonstrated that mechanical mixing-a routinely implemented process for homogeneous mixing of precursors-can be harmful if it is performed without assuring optimal working conditions for mixing.The underlying reasons for this surprising result are elucidated in this work,and we hope that this new insight can help avoid the potential pitfall of routine implementations performed for LIB materials.