Structural Engineering of Anode Materials for Low-Temperature Lithium-Ion Batteries:Mechanisms,Strategies,and Prospects

The severe degradation of electrochemical performance for lithium-ion batteries(LIBs)at low temperatures poses a significant challenge to their practical applications.Consequently,extensive efforts have been contributed to explore novel anode materials with high electronic conductivity and rapid Li^(+)diffusion kinetics for achieving favorable low-temperature performance of LIBs.Herein,we try to review the recent reports on the synthesis and characterizations of low-temperature anode materials.First,we summarize the underlying mechanisms responsible for the performance degradation of anode materials at subzero temperatures.Second,detailed discussions concerning the key pathways(boosting electronic conductivity,enhancing Li^(+)diffusion kinetics,and inhibiting lithium dendrite)for improving the low-temperature performance of anode materials are presented.Third,several commonly used low-temperature anode materials are briefly introduced.Fourth,recent progress in the engineering of these low-temperature anode materials is summarized in terms of structural design,morphology control,surface&interface modifications,and multiphase materials.Finally,the challenges that remain to be solved in the field of low-temperature anode materials are discussed.This review was organized to offer valuable insights and guidance for next-generation LIBs with excellent low-temperature electrochemical performance.

Two-dimensional layered In_(2)P_(3)S_(9): A novel superior anode material for sodium-ion batteries

Developing reliable and efficient anode materials is essential for the successfully practical application of sodium-ion batteries.Herein,employing a straightforward and rapid chemical vapor deposition technique,two-dimensional layered ternary indium phosphorus sulfide(In_(2)P_(3)S_(9)) nanosheets are prepared.The layered structure and ternary composition of the In_(2)P_(3)S_(9) electrode result in impressive electrochemical performance,including a high reversible capacity of 704 mA h g^(-1) at 0.1 A g^(-1),an outstanding rate capability with 425 mA h g^(-1) at 5 A g^(-1),and an exceptional cycling stability with a capacity retention of88% after 350 cycles at 1 A g^(-1).Furthermore,sodium-ion full cell also affords a high capacity of 308 and114 mA h g^(-1) at 0.1 and 5 A g^(-1).Ex-situ X-ray diffraction and ex-situ high-resolution transmission electron microscopy tests are conducted to investigate the underlying Na-storage mechanism of In_(2)P_(3)S_(9).The results reveal that during the first cycle,the P-S bond is broken to form the elemental P and In_(2)S_(3),collectively contributing to a remarkably high reversible specific capacity.The excellent electrochemical energy storage results corroborate the practical application potential of In_(2)P_(3)S_(9) for sodium-ion batteries.

Review and prospects on the low-voltage Na_(2)Ti_(3)O_(7) anode materials for sodium-ion batteries

Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in improving the energy density of NIBs.Low-voltage anode materials,however,are severely lacking in NIBs.Of all the reported insertion oxides anodes,the Na_(2)Ti_(3)O_(7) has the lowest operating voltage(an average potential of 0.3 V vs.Na^(+)/Na)and is less likely to deposit sodium,which has excellent potential for achieving NIBs with high energy densities and high safety.Although significant progress has been made,achieving Na_(2)Ti_(3)O_(7) electrodes with excellent performance remains a severe challenge.This paper systematically summarizes and discusses the physicochemical properties and synthesis methods of Na_(2)Ti_(3)O_(7).Then,the sodium storage mechanisms,key issues and challenges,and the optimization strategies for the electrochemical performance of Na_(2)Ti_(3)O_(7) are classified and further elaborated.Finally,remaining challenges and future research directions on the Na_(2)Ti_(3)O_(7) anode are highlighted.This review offers insights into the design of high-energy and high-safety NIBs.

Sol-gel synthesis of nanometer silicon/silicon suboxide/carbon anode material

A stacked Si/SiO_(x)/C composite anode material with carbon-coated structure was prepared by sol-gel method combined with carbothermal reduction using organic silicon.The results of X-ray diffractometry, scanning electron microscopy, and elemental analysis show that the Si/SiO_(x)/C material is a secondary particle with a porous micronanostructure, and the presence of nanometer silicon does not affect the carbothermal reduction and carbon coating.Electrochemical test results indicate that the specific capacity and first coulombic efficiency of SiO_(x)/C composite with nanometer silicon can be increased to 1 946.05 mAh/g and 76.49%,respectively.The reversible specific capacity of Si/SiO_(x)/C material blended with graphite is 749.69 mAh/g after 100 cycles at a current density of 0.1 C,and the capacity retention rate is up to 89.03%.Therefore, the composite has excellent electrochemical cycle stability.

A review on anode materials for lithium/sodium-ion batteries

Since lithium-ion batteries(LIBs) have been substantially researched in recent years, they now possess exceptional energy and power densities, making them the most suited energy storage technology for use in developed and developing industries like stationary storage and electric cars, etc. Concerns about the cost and availability of lithium have prompted research into alternatives, such as sodium-ion batteries(SIBs), which use sodium instead of lithium as the charge carrier. This is especially relevant for stationary applications, where the size and weight of battery are less important. The working efficiency and capacity of these batteries are mainly dependent on the anode, cathode, and electrolyte. The anode,which is one of these components, is by far the most important part of the rechargeable battery.Because of its characteristics and its structure, the anode has a tremendous impact on the overall performance of the battery as a whole. Keeping the above in view, in this review we critically reviewed the different types of anodes and their performances studied to date in LIBs and SIBs. The review article is divided into three main sections, namely:(i) intercalation reaction-based anode materials;(ii) alloying reaction-based anode materials;and(iii) conversion reaction-based anode materials, which are further classified into a number of subsections based on the type of material used. In each main section, we have discussed the merits and challenges faced by their particular system. Afterward, a brief summary of the review has been discussed. Finally, the road ahead for better application of Li/Na-ion batteries is discussed, which seems to mainly depend on exploring the innovative materials as anode and on the inoperando characterization of the existing materials for making them more capable in terms of application in rechargeable batteries.

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.

Two-dimensional dumbbell silicene as a promising anode material for(Li/Na/K)-ion batteries

Rechargeable ion batteries require anode materials with excellent performance,presenting a key challenge for researchers.This paper explores the potential of using two-dimensional dumbbell silicene as an anode material for alkali metal ion batteries through density functional theory(DFT)calculations.Our findings demonstrate that alkali metal ions have negative adsorption energies on dumbbell silicene,and the energy barriers for Li/Na/K ion diffusion are as low as0.032 e V/0.055 e V/0.21 e V,indicating that metal ions can easily diffuse across the entire surface of dumbbell silicene.Additionally,the average open circuit voltages of dumbbell silicene as anode for Li-ion,Na-ion,and K-ion batteries are 0.42 V,0.41 V,and 0.60 V,respectively,with corresponding storage capacities of 716 m Ah/g,622 m Ah/g,and 716 m Ah/g.These results suggest that dumbbell silicene is an ideal anode material for Li-ion,Na-ion,and K-ion batteries,with high capacity,low open circuit voltage,and high ion diffusion kinetics.Moreover,our calculations show that the theoretical capacities obtained using DFT-D2 are higher than those obtained using DFT-D3,providing a valuable reference for subsequent theoretical calculations.

Effects of anode material on the evolution of anode plasma and characteristics of intense electron beam diode

In this paper,three kinds of materials including graphite,titanium(Ti)and molybdenum(Mo)are used as anodes to figure out the influence factors of anode material on the characteristics of the intense electron beam diode.The results show that the characteristics of diode are mainly determined by the cathode plasma motion under a 15 mm diode gap,in which the typical electron beam parameters are 280 kV,3.5 kA.When the diode gap is reduced to 5 mm,the voltage of the electron beam reduces to about 200 kV,and its current increases to more than 8.2 kA.It is calculated that the surface temperatures of Ti and Mo anodes are higher than their melting points.The diode plasma luminescence images show that Ti and Mo anodes produce plasmas soon after the bombardment of electron beams.Ti and Mo lines are respectively found in the plasma composition of Ti and Mo anode diodes.Surface melting traces are also observed on Ti and Mo anodes by comparing the micromorphologies before and after bombardment of the electron beam.These results suggest that the time of anode plasma generation is closely related to the anode material.Compared with graphite,metal Ti and Mo anodes are more likely to produce large amounts of plasma due to their more significant temperature rise effect.According to the moment that anode plasma begins to generate,the average expansion velocities of cathode and anode plasma are estimated by fitting the improved space-charge limited flow model.This reveals that generation and motion of the anode plasma significantly affect the characteristics of intense electron beam diode.

The Microparticles SiOx Loaded on PAN-C Nanofiber as Three-Dimensional Anode Material for High-Performance Lithium-Ion Batteries

Three-dimensional C/SiOx nanofiber anode was prepared by polydimethylsiloxane(PDMS)and polyacrylonitrile(PAN)as precursors via electrospinning and freeze-drying successfully.In contrast to conventional carbon cover-ing Si-based anode materials,the C/SiOx structure is made up of PAN-C,a 3D carbon substance,and SiOx load-ing steadily on PAN-C.The PAN carbon nanofibers and loaded SiOx from pyrolyzed PDMS give increased conductivity and a stable complex structure.When employed as lithium-ion batteries(LIBs)anode materials,C/SiOx-1%composites were discovered to have an extremely high lithium storage capacity and good cycle per-formance.At a current density of 100 mA/g,its reversible capacity remained at 761 mA/h after 50 charge-dis-charge cycles and at 670 mA/h after 200 cycles.The C/SiOx-1%composite aerogel is a particularly intriguing anode candidate for high-performance LIBs due to these appealing qualities.

Synthesis of Cu_2O/reduced graphene oxide composites as anode materials for lithium ion batteries

A facile way was used to synthesize Cu2O/reduced graphene oxide （rGO） composites with octahedron-like morphology in aqueous solution without any surfactant. TEM images of the obtained Cu2O/rGOs reveal that the Cu2O particles and rGO distribute hierarchically and the primary Cu2O particles are encapsulated well in the graphene nanosheets. The electrochemical performance of Cu2O/rGOs is enhanced compared with bare Cu2O when they are employed as anode materials for lithium ion batteries. The Cu2O/rGO composites maintain a reversible capacity of 348.4 mA？h/g after 50 cycles at a current density of 100 mA/g. In addition, the composites retain 305.8 mA？h/g after 60 cycles at various current densities of 50, 100, 200, 400 and 800 mA/g.

Preparation and electrochemical performance of tantalum-doped lithium titanate as anode material for lithium-ion battery

The electrochemical performance of Ta-doped Li4Ti5O12 in the form of Li4Ti4.95Ta0.05O12 was characterized.X-ray diffraction（XRD） and scanning electron microscopy（SEM） were employed to characterize the structure and morphology of Li4Ti4.95Ta0.05O12.Ta-doping does not change the phase composition and particle morphology,while improves remarkably its cycling stability at high charge/discharge rate.Li4Ti4.95Ta0.05O12 exhibits an excellent rate capability with a reversible capacity of 116.1 mA·h/g at 10C and even 91.0 mA·h/g at 30C.The substitution of Ta for Ti site can enhance the electronic conductivity of Li4Ti5O12 via the generation of mixing Ti4＋/Ti3＋,which indicates that Li4Ti4.95Ta0.05O12 is a promising candidate material for anodes in lithium-ion battery application.

Effect of germanium on electrochemical performance of chain-like Co-P anode material for Ni/Co rechargeable batteries

Co-P （4.9% P） powders with a chain-like morphology were prepared by a novel chemical reduction method. The Co-P and germanium powders were mixed at various mass ratios to form Co-P composite electrodes. Charge and discharge test and electrochemical impedance spectroscopy （EIS） were carried out to investigate the electrochemical performance, which can be significantly improved by the addition of germanium. For instance, when the mass ratio of Co-P powders to germanium is 5：1, the sample electrode shows a reversible discharge capacity of 350.3 mA·h/g and a high capacity retention rate of 95.9% after 50 cycles. The results of cyclic voltammmetry （CV） show the reaction mechanism of Co/Co（OH）2 within Co-P composite electrodes and EIS indicates that this electrode shows a low charge-transfer resistance, facilitating the oxidation of Co to Co（OH）2.

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.

Recent progress of advanced anode materials of lithium-ion batteries

The rapid development of electric vehicles and mobile electronic devices is the main driving force to improve advanced high-performance lithium ion batteries(LIBs).The capacity,rate performance and cycle stability of LIBs rely directly on the electrode materials.As far as the development of the advanced LIBs electrode is concerned,the improvement of anode materials is more urgent than the cathode materials.Industrial production of anode materials superior to commercial graphite still faces some challenges.This review sets out the most basic LIBs anode material design.The reaction principles and structural design of carbon materials,various transition metal oxides,silicon and germanium are summarized,and then the progress of other anode materials are analyzed.Due to the rapid development of metal organic frameworks(MOFs)in energy storage and conversion in recent years,the synthesis process and energy storage mechanism of nanostructures derived from MOF precursors are also discussed.From the perspective of novel structural design,the progress of various MOFs-derived materials for alleviating the volume expansion of anode materials is discussed.Finally,challenges for the future development of advanced anode materials for LIBs will be considered.

Tempura-like carbon/carbon composite as advanced anode materials for K-ion batteries

Graphite as a promising anode candidate of K-ion batteries(KIBs)has been increasingly studied currently,but corresponding rate performance and cycling stability are usually inferior to amorphous carbon materials.To protect the layer structure and further boost performance,tempura-like carbon/carbon nanocomposite of graphite@pitch-derived S-doped carbon(G@PSC)is designed and prepared by a facile and low-temperature modified molten salt method.This robust encapsulation structure makes their respective advantages complementary to each other,showing mutual promotion of electrochemical performances caused by synergy effect.As a result,the G@PSC electrode is applied in KIBs,delivering impressive rate capabilities(465,408,370,332,290,and 227 m A h g^(-1)at 0.05,0.2,0.5,1,2,and 5 A g^(-1))and ultralong cyclic stability(163 m A g^(-1)remaining even after 8000 cycles at 2 A g^(-1)).On basis of ex-situ studies,the sectionalized K-storage mechanism with adsorption(pseudocapacitance caused by S doping)-intercalation(pitch-derived carbon and graphite)pattern is revealed.Moreover,the exact insights into remarkable rate performances are taken by electrochemical kinetics tests and density functional theory calculation.In a word,this study adopts a facile method to synthesize high-performance carbon/carbon nanocomposite and is of practical significance for development of carbonaceous anode in KIBs.

Template-Free Synthesis of Sb_2S_3 Hollow Microspheres as Anode Materials for Lithium-Ion and Sodium-Ion Batteries

Hierarchical Sb_2S_3 hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated by X-ray diffraction, focused-ion beam-scanning electron microscopy dual-beam system, and transmission electron microscopy. When used as the anode material for lithium-ion batteries, Sb_2S_3 hollow microspheres manifest excellent rate property and enhanced lithium-storage capability and can deliver a discharge capacity of 674 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. Even at a high currentdensity of 5000 m A g^(-1), a discharge capacity of541 m Ah g^(-1) is achieved. Sb_2S_3 hollow microspheres also display a prominent sodium-storage capacity and maintain a reversible discharge capacity of 384 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. The remarkable lithium/sodium-storage property may be attributed to the synergetic effect of its nanometer size and three-dimensional hierarchical architecture, and the outstanding stability property is attributed to the sufficient interior void space,which can buffer the volume expansion.

A ternary phased SnO_2-Fe_2O_3/SWCNTs nanocomposite as a high performance anode material for lithium ion batteries

A new SnO2-Fe2O3/SWCNTs（single-walled carbon nanotubes） ternary nanocomposite was first synthesized by a facile hydrothermal approach.SnO2 and Fe2O3 nanoparticles（NPs） were homogeneously located on the surface of SWCNTs,as confirmed by X-ray diffraction（XRD）,transmission electron microscope（TEM） and energy dispersive X-ray spectroscopy（EDX）.Due to the synergistic effect of different components,the as synthesized SnO2-Fe2O3/SWCNTs composite as an anode material for lithium-ion batteries exhibited excellent electrochemical performance with a high capacity of 692 mAh·g-1 which could be maintained after 50 cycles at 200 mA·g-1.Even at a high rate of2000 mA·g-1,the capacity was still remained at 656 mAh·g-1.

Effective regeneration of high-performance anode material recycled from the whole electrodes in spent lithium-ion batteries via a simplified approach

Along with the extensive application of energy storage devices,the spent lithium-ion batteries(LIBs)are unquestionably classified into the secondary resources due to its high content of several valuable metals.However,current recycling methods have the main drawback to their tedious process,especially the purification and separation process.Herein,we propose a simplified process to recycle both cathode(LiCoO_(2))and anode(graphite)in the spent LIBs and regenerate newly high-performance anode material,CoO/CoFe2O4/expanded graphite(EG).This process not only has the advantages of succinct procedure and easy control of reaction conditions,but also effectively separates and recycles lithium from transition metals.The 98.43%of lithium is recovered from leachate when the solid product CoO/CoFe2O4/EG is synthesized as anode material for LIBs.And the product exhibits improved cyclic stability(890 mAh g^(-1) at 1 A g^(-1) after 700 cycles)and superior rate capability(208 mAh g^(-1) at 5 A g^(-1)).The merit of this delicate recycling design can be summarized as three aspects:the utilization of Fe impurity in waste LiCoO_(2),the transformation of waste graphite to EG,and the regeneration of anode material.This approach properly recycles the valuable components of spent LIBs,which introduces an insight into the future recycling.

Impact of Morphology of Conductive Agent and Anode Material on Lithium Storage Properties

In this study,the impact of morphology of conductive agent and anode material(Fe3O4)on lithium storage properties was throughly investigated.Granular and belt-like Fe3O4active materials were separately blended with two kinds of conductive agents(i.e.,granular acetylene black and multi-walled carbon nanotube)as anodes in lithium-ion batteries(LIBs),respectively.It was found that the morphology of conductive agent is of utmost importance in determining LIBs storage properties.In contrast,not as the way we anticipated,the morphology of anode material merely plays a subordinate role in their electrochemical performances.Further,the morphology-matching principle of electrode materials was discussed so as to render their utilization more rational and effective in LIBs.

CoFe_2O_4-Graphene Nanocomposites Synthesized through An Ultrasonic Method with Enhanced Performances as Anode Materials for Li-ion Batteries

Co Fe2O4-graphene nanosheets(Co Fe2O4-GNSs) were synthesized through an ultrasonic method, and their electrochemical performances as Li-ion battery electrode were improved by annealing processes. The nanocomposites obtained at 350 °C maintained a high specific capacity of 1,257 m Ah g-1even after 200 cycles at 0.1 A g-1. Furthermore,the obtained materials also have better rate capability, and it can be maintained to 696, 495, 308, and 254 m Ah g-1at 1, 2,5, and 10 A g-1, respectively. The enhancements realized in the reversible capacity and cyclic stability can be attributed to the good improvement in the electrical conductivity achieved by annealing at appropriate temperature, and the electrochemical nature of Co Fe2O4 and GNSs during discharge–charge processes.