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 of the carbon coating of the silicon anode in highperformance lithium-ion batteries

In the development of rechargeable lithium ion batteries(LIBs),silicon anodes have attracted much attention because of their extremely high theoretical capacity,relatively low Li-insertion voltage and the availability of silicon resources.However,their large volume expansion and fragile solid electrolyte interface(SEI)film hinder their commercial application.To solve these problems,Si has been combined with various carbon materials to increase their structural stability and improve their interface properties.The use of different carbon materials,such as amorphous carbon and graphite,as three-dimensional(3D)protective anode coatings that help buffer mechanical strain and isolate the electrolyte is detailed,and novel methods for applying the coatings are outlined.However,carbon materials used as a protective layer still have some disadvantages,necessitating their modification.Recent developments have focused on modifying the protective carbon shells,and substitutes for the carbon have been suggested.

A review of anode materials for sodium ion batteries

Lithium-ion batteries(LIBs)are used in electric vehicles and portable smart devices,but lithium resources are dwindling and there is an increasing demand which has to be catered for.Sodium ion batteries(SIBs),which are less costly,are a promising replacement for LIBs because of the abundant natural reserves of sodium.The anode of a SIB is a necessary component of the battery but is less understood than the cathode.This review outlines the development of various types of anodes,including carbonbased,metallic and organic,which operate using different reaction mechanisms such as intercalation,alloying and conversion,and considers their challenges and prospects.Strategies for modifying their structures by doping and coating,and also modifying the solid electrolyte interface are discussed.In addition,this review also discusses the challenges encountered by the anode of SIBs and the solutions.

Research Progress of Carbon-Silicone Composite Materials

Silicone is a kind of polymer material with high cross-linked structure,which is com-posed by Si-O-Si main chain.Due to the special molecular chain structure,silicone mate-rials are characterized by oxidation resistance,aging resistance,high and low temperature resistance and chemical corrosion resistance.Moreover,silicone materials have process-able properties,simple forming process,good mechanical property,non-toxic and pollution-free.Therefore,silicone has been widely concerned by researchers at home and abroad.In this paper,the main research progress and application directions of carbon-silicone composite at home and abroad in recent years are reviewed.

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.

Carbon-based interface engineering and architecture design for high-performance lithium metal anodes

Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electrochemical potential.However,owing to inhomogeneous Li-ion flux,Li anodes undergo uncontrollable Li deposition,leading to limited power output and practical applications.Carbon materials and their composites with controllable structures and properties have received extensive attention to guide the homogeneous growth of Li to achieve high-performance Li anodes.In this review,the correlation between the behavior of Li anode and the properties of carbon materials is proposed.Subsequently,we review emerging strategies for rationally designing high-performance Li anodes with carbon materials,including interface engineering(stabilizing solid electrolyte interphase layer and other functionalized interfacial layer)and architecture design of host carbon(constructing three-dimension structure,preparing hollow structure,introducing lithiophilic sites,optimizing geometric effects,and compositing with Li).Based on the insights,some prospects on critical challenges and possible future research directions in this field are concluded.It is anticipated that further innovative works on the fundamental chemistry and theoretical research of Li anodes are needed.

Stabilizing porous micro-sized silicon anodes via construction of tough composite interface networks for high-energy-density lithium-ion batteries

Compared to nanostructured Si/C materials, micro-sized Si/C anodes for lithium-ion batteries (LIBs) have gained significant attention in recent years due to their higher volumetric energy density, reduced side reactions and low costs. However, they suffer from more severe volume expansion effects, making the construction of stable micro-sized Si/C anode materials crucial. In this study, we proposed a simple wet chemistry method to obtain porous micro-sized silicon (μP-Si) from waste AlSi alloys. Then, the μP-Si@carbon nanotubes (CNT)@C composite anode with high tap density was prepared by wrapping with CNT and coated with polyvinylpyrrolidone (PVP)-derived carbon. Electrochemical tests and finite element (FEM) simulations revealed that the introduction of CNTs and PVP-derived carbon synergistically optimize the stability and overall performance of the μP-Si electrode via construction of tough composite interface networks. As an anode material for LIBs, the μP-Si@CNT@C electrode exhibits boosted reversible capacity (∼ 3500 mAh·g^(−1) at 0.2 A·g^(−1)), lifetime and rate performance compared to pure μP-Si. Further full cell assembly and testing also indicates that μP-Si@CNT@C is a highly promising anode, with potential applications in future advanced LIBs. It is expected that this work can provide valuable insights for the development of micro-sized Si-based anode materials for high-energy-density LIBs.

Research progress on silicon/carbon composite anode materials for lithium-ion battery

Silicon （Si） has been considered as one of the most promising anode material for tHe next generation lithium-ion batteries （LIBs） with high energy densities, due to its high theoretical capacity, abundant availability and environmental friendliness. However. silicon materials with low intrinsic electric and ionic conductivity suffer from huge volume variation during lithiation/delithiation processes leading to the pulverization of Si and subsequently resulting in severe capacity fading of the electrodes. Coupling of Si with carbon （C） realizes a favorable combination of the two materials properties, such as high lithiation capacity of Si and excellent mechanical and conductive properties of C. making silicon/carbon composite （Si/C） ideal candidates for LIBs anodes. In this review, recent progresses of Si/C materials utilized in LIBs are summarized in terms of structural design principles, material synthesis methods, morphological characteristics and electrochemical performances by highlighting the material structures. The mechanisms behind the performance enhancement are also discussed. Moreover, other factors that affect the performance of Si/C anodes, such as prelithiation, electrolyte additives, and binders, are also discussed. We aim to present a full scope of the Si/C-based anodes, and help understand and design future structures of Si/C anodes in LIBs,

Recent Progress in Improving Rate Performance of Cellulose-Derived Carbon Materials for Sodium-Ion Batteries

Cellulose-derived carbon is regarded as one of the most promising candidates for high-performance anode materials in sodium-ion batteries;however,its poor rate performance at higher current density remains a challenge to achieve high power density sodium-ion batteries.The present review comprehensively elucidates the structural characteristics of cellulose-based materials and cellulose-derived carbon materials,explores the limitations in enhancing rate performance arising from ion diffusion and electronic transfer at the level of cellulose-derived carbon materials,and proposes corresponding strategies to improve rate performance targeted at various precursors of cellulose-based materials.This review also presents an update on recent progress in cellulose-based materials and cellulose-derived carbon materials,with particular focuses on their molecular,crystalline,and aggregation structures.Furthermore,the relationship between storage sodium and rate performance the carbon materials is elucidated through theoretical calculations and characterization analyses.Finally,future perspectives regarding challenges and opportunities in the research field of cellulose-derived carbon anodes are briefly highlighted.

Pioneering the direct large-scale laser printing of flexible“graphenic silicon”self-standing thin films as ultrahigh-performance lithium-ion battery anodes

Recent technological advancements,such as portable electronics and electric vehicles,have created a pressing need for more efficient energy storage solutions.Lithium-ion batteries(LIBs)have been the preferred choice for these applications,with graphite being the standard anode material due to its stability.However,graphite falls short of meeting the growing demand for higher energy density,possessing a theoretical capacity that lags behind.To address this,researchers are actively seeking alternative materials to replace graphite in commercial batteries.One promising avenue involves lithiumalloying materials like silicon and phosphorus,which offer high theoretical capacities.Carbon-silicon composites have emerged as a viable option,showing improved capacity and performance over traditional graphite or pure silicon anodes.Yet,the existing methods for synthesizing these composites remain complex,energy-intensive,and costly,preventing widespread adoption.A groundbreaking approach is presented here:the use of a laser writing strategy to rapidly transform common organic carbon precursors and silicon blends into efficient“graphenic silicon”composite thin films.These films exhibit exceptional structural and energy storage properties.The resulting three-dimensional porous composite anodes showcase impressive attributes,including ultrahigh silicon content,remarkable cyclic stability(over 4500 cycles with∼40%retention),rapid charging rates(up to 10 A g^(-1)),substantial areal capacity(>5.1 mAh cm^(-2)),and excellent gravimetric capacity(>2400 mAh g^(-1) at 0.2 A g^(-1)).This strategy marks a significant step toward the scalable production of high-performance LIB materials.Leveraging widely available,cost-effective precursors,the laser-printed“graphenic silicon”composites demonstrate unparalleled performance,potentially streamlining anode production while maintaining exceptional capabilities.This innovation not only paves the way for advanced LIBs but also sets a precedent for transforming various materials into high-performing electrodes,promising reduced complexity and cost in battery production.

Low‐temperature synthesis of graphitic carbon‐coated silicon anode materials

We report the synthesis of a high‐performance graphitic carbon‐coated silicon(Si@GC)composite material for lithium‐ion batteries via a scalable production route.Porous Si is produced from the magnesiothermic reduction of commercial silica(SiO2)precursor followed by low‐temperature graphitic carbon coating using glucose as the precursor.The obtained Si@GC composite achieves an excellent reversible specific capacity of 1195 mAh g−1 and outstanding cycle stability.The thick Si@GC anode(3.4 mg cm^−2)in full cells with commercial lithium iron phosphate cathode delivers a remarkable performance of 800 mAh g^−1 specific capacity and 2.7 mAh cm^−2 areal capacity as well as 93.6%capacity retention after 200 cycles.

Interfacial design of silicon/carbon anodes for rechargeable batteries:A review

Silicon(Si)has been studied as a promising alloying type anode for lithium-ion batteries due to its high specific capacity,low operating potential and abundant resources.Nevertheless,huge volume expansion during alloying/dealloying processes and low electronic conductivity of Si anodes restrict their electrochemical performance.Thus,carbon(C)materials with special physical and chemical properties are applied in Si anodes to effectively solve these problems.This review focuses on current status in the exploration of Si/C anodes,including the lithiation mechanism and solid electrolyte interface formation,various carbon sources in Si/C anodes,such as traditional carbon sources(graphite,pitch,biomass),and novel carbon sources(MXene,graphene,MOFs-derived carbon,graphdiyne,etc.),as well as interfacial bonding modes of Si and C in the Si/C anodes.Finally,we summarize and prospect the selection of carbonaceous materials,structural design and interface control of Si/C anodes,and application of Si/C anodes in all-solid-state lithium-ion batteries and sodium-ion batteries et al.This review will help researchers in the design of novel Si/C anodes for rechargeable batteries.

In Situ Formation of LiF-Rich Carbon Interphase on Silicon Particles for Cycle-Stable Battery Anodes

Silicon(Si)is a potential high-capacity anode material for the next-generation lithium-ion battery with high energy density.However,Si anodes suff er from severe interfacial chemistry issues,such as side reactions at the electrode/electrolyte interface,leading to poor electrochemical cycling stability.Herein,we demonstrate the fabrication of a conformal fl uorine-containing carbon(FC)layer on Si particles(Si-FC)and its in situ electrochemical conversion into a LiF-rich carbon layer above 1.5 V(vs.Li^(+)/Li).The as-formed LiF-rich carbon layer not only isolates the active Si and electrolytes,leading to the suppression of side reactions,but also induces the formation of a robust solid-electrolyte interface(SEI),leading to the stable interfacial chemistry of as-designed Si-FC particles.The Si-FC electrode has a high initial Coulombic effi ciency(CE)of 84.8%and a high reversible capacity of 1450 mAh/g at 0.4 C(1000 mA/g)for 300 cycles.In addition,a hybrid electrode consisting of 85 wt%graphite and 15 wt%Si-FC,and mass 2.3 mg/cm^(2) loading delivers a high areal capacity of 2.0 mAh/cm^(2) and a high-capacity retention of 93.2%after 100 cycles,showing the prospects for practical use.

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.

Carbon materials for stable Li metal anodes: Challenges, solutions, and outlook

Lithium(Li)metal is regarded as the ultimate anode for next-generation Li-ion batteries due to its highest specific capacity and lowest electrochemical potential.However,the Li metal anode has limitations,including virtually infinite volume change,nonuniform Li deposition,and an unstable electrode-electrolyte interface,which lead to rapid capacity degradation and poor cycling stability,significantly hindering its practical application.To address these issues,intensive efforts have been devoted toward accommodating and guiding Li deposition as well as stabilizing the interface using various carbon materials,which have demonstrated excellent effectiveness,benefiting from their vast variety and excellent tunability of the structure-property relationship.This review is intended as a guide through the fundamental challenges of Li metal anodes to the corresponding solutions utilizing carbon materials.The specific functionalities and mechanisms of carbon materials for stabilizing Li metal anodes in these solutions are discussed in detail.Apart from the stabilization of the Li metal anode in liquid electrolytes,attention has also been paid to the review of anode-free Li metal batteries and solid-state batteries enabled by strategies based on carbon materials.Furthermore,we have reviewed the unresolved challenges and presented our outlook on the implementation of carbon materials for stabilizing Li metal anodes in practical applications.

Functional carbon materials for high-performance Zn metal anodes

The realization of“carbon peak”and“carbon neutralization”highly depends on the efficient utilization of renewable energy sources.Exploring reliable and low-cost electrochemical energy storage systems is an ever-growing demand for renewable energy integration.Among available candidates,aqueous zinc-ion batteries(AZIBs)receive extensive researchers'attention because of their material abundance,high capacity,high safety,and environmental friendliness.However,the irreversible issues of Zn anode in terms of notorious dendric Zn growth,Zn corrosion/hydrogen evolution,and passivation significantly impede the commercialization of high-performance AZIBs.Carbon materials have advantages of large specific surface area,low cost,high electrical conductivity,controllable structure,and good stability.Their application provides remedies for improving the comprehensive performance of Zn anodes.In this review,the fundamentals and issues of Zn anodes,and the research progress with functional carbon materials for Zn anodes in recent years are presented.Three major strategies are described in detail,including the use of carbon materials(carbon nanotubes,graphene,carbon fiber,metal-organic framework(MOF)derived host,etc.)as Zn plating/stripping substrates,as protective coating layers on Zn,and as electrolyte additives.Finally,the remaining challenges and perspectives of carbon materials in high-performance AZIBs are outlined.

Bi nanoparticles in situ encapsulated by carbon film as high-performance anode materials for Li-ion batteries

Bismuth (Bi) has indeed inspired great interests in lithium-ion batteries (LIBs) due to the high capacity,but was still limited by the low electrical conductivity and large volume variation.Herein,a composite material based on Bi nanoparticles in situ encapsulated by carbon film (Bi@CF) is prepared successfully through a facile metal–organic framework (MOF)-engaged approach.As anode materials for LIBs,the Bi@CF composites achieved high reversible capacities of 705 and 538 mAh g^(-1)at 0.2 and 0.5 A g^(-1) after200 cycles,and long cycling performance with a stable capacity of 306 mAh g^(-1)at 1.0 A g^(-1) even after 900 cycles.In situ X-ray diffraction (XRD) measurements clearly revealed the conversion between Bi and Li_(3)Bi during the alloying/dealloying process,confirming the good electrochemical reversibility of Bi@CF for Li-storage.The reaction kinetics of this Bi@CF composite was further studied by galvanostatic intermittent titration technique (GITT).This work may provide an inspiration for the elaborate design and facile preparation of alloy-type anode materials for high-performance rechargeable batteries.

Influence of carbon coating on the electrochemical performance of SiO@C/graphite composite anode materials

Silicon monoxide(SiO) has been considered as one of the most promising anode materials for next generation highenergy-density Li-ion batteries(LiBs) thanks to its high theoretical capacity. However, the poor intrinsic electronic conductivity and large volume change during lithium intercalation/de-intercalation restrict its practical applications. Fabrication of SiO/C composites is an effective way to overcome these problems. Herein, a series of micro-sized SiO@C/graphite(Si0@C/G) composite anode materials, with designed capacity of 600 mAh·g-1, are successfully prepared through a pitch pyrolysis reaction method. The electrochemical performance of SiO@C/G composite anodes with different carbon coating contents of 5 wt%, 10 wt%, 15 wt%, and 35 wt% is investigated. The results show that the SiO@C/G composite with15-wt% carbon coating content exhibits the best cycle performance, with a high capacity retention of 90.7% at 25℃ and90.1% at 45 0 C after 100 cycles in full cells with LiNi0.5Co0.2Mn0.3O2 as cathodes. The scanning electron microscope(SEM) and electrochemistry impedance spectroscopy(EIS) results suggest that a moderate carbon coating layer can promote the formation of stable SEI film, which is favorable for maintaining good interfacial conductivity and thus enhancing the cycling stability of SiO electrode.

Effects of carbon sources on electrochemical performance of Li_4Ti_5O_(12)/C composite anode materials

Li4Ti5O12/C composite materials were synthesized by two-step solid state reaction method with glucose, sucrose, and starch as carbon sources, respectively. The effects of carbon sources on the structure, morphology, and electrochemical performance of Li4Ti5O12/C composite materials were investigated by SEM, XRD and electrochemical tests. The results indicate that carbon sources have almost no effect on the structure of Li4Ti5O12/C composite materials. The initial discharge capacities of the Li4Ti1O12/C composite materials are slightly lower than those of as-synthesized Li4Ti5O12. However, Li4Ti5O12/C composite materials show better electrochemical rate performance than the as-synthesized Li4Ti5O12. The capacity retention （79%） of the Li4Ti5O12/C composite materials with starch as carbon source, is higher than that of Li4Ti5O12/C composite materials with glucose and sucrose as carbon source at current rate of 2.0C.

Multilevel carbon architecture of subnanoscopic silicon for fast‐charging high‐energy‐density lithium‐ion batteries

Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.