Fabrication of Silicon/Carbon Composite Material with Silicon Waste and Carbon Nanofiber Applied in Lithium-Ion Battery

Silicon (Si) is regarded as a promising material for lithium-ion battery anode because of high theoretical capacity. Nevertheless, Si faces particle pulverization and rapid capacity fading due to serious volume change during the lithiation and the delithiation process. In this work, a silicon/carbon composite constituted to Si powder and carbon nanofiber (CNF) is produced to solve the above issues as a new design structure of anode material. The Si powder was recycled from the silicon slicing waste in photovoltaic industry and the CNF was from dry rice straws. By mixing the purified Si powder with CNF, the composite was synthesized by the freeze-drying method and calcination. In the cyclic test, Si adding with 1 wt% CNF showed 3091 mAh/g capacity in the first cycle and 1079 mAh/g capacity after 100 cycles at the current density of 0.5 A/g, which were both better than pristine Si. SEM images also show the composite structure can eliminate cracks on the surface of the electrode during cycling. CNF attaching on Si particles can increase specific surface area, so binder can easily combine the active materials and the conductive materials together. This strategy enhances the structure stability and prevents the electrode from delamination.

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,

Multi-scale design of silicon/carbon composite anode materials for lithium-ion batteries:A review

Silicon/carbon composites,which integrate the high lithium storage performance of silicon with the exceptional mechanical strength and conductivity of carbon,will replace the traditional graphite electrodes for high-energy lithium-ion batteries.Various strategies have been designed to synthesize silicon/carbon composites for tackling the issues of anode pulverization and poor stability in the anodes,thereby improving the lithium storage ability.The effect of the regulation method at each scale on the final negative electrode performance remains unclear.However,it has not been fully clarified how the regulation methods at each scale influence the final anode performance.This review will categorize the materials structure into three scales:molecular scale,nanoscale,and microscale.First,the review will examine modification methods at the molecular scale,focusing on the interfacial bonding force between silicon and carbon.Next,it will summarize various nanostructures and special shapes in the nanoscale to explore the construction of silicon/carbon composites.Lastly,the review will provide an analysis of microscale control approaches,focusing on the formation of composite particle with micron size and the utilization of micro-Si.This review provides a comprehensive overview of the multi-scale design of silicon/carbon composite anode materials and their optimization strategies to enhance the performance of lithium-ion batteries.

One-Step Solution Synthesis of Carbon Cloth@SiO_(2) Composite for Flexible Anode of Advanced Lithium-Ion Battery

A flexible anode composite,carbon cloth@SiO_(2)composite(CC@SiO_(2)),was synthesized by a one-step solution method using tetraethyl orthosilicate(TEOS)as the silica source.CC@SiO_(2)can be directly used as the negative electrode material for lithium-ion battery,and its initial reversible deintercalation capacity reaches 1358.7 mA·h·g^(-1).The electrode shows a capacity of 863.8 mA·h·g^(-1)up to 130 cycles at 0.5 A·g^(-1),displaying excellent rate performance and cycle stability.

Annihilating the Formation of Silicon Carbide:Molten Salt Electrolysis of Carbon-Silica Composite to Prepare the Carbon-Silicon Hybrid for Lithium-lon Battery Anode

Silicon(Si)and carbon(C)composites hold the promise for replacing the commercial graphite anode,thus increasing the energy density of lithium-ion batteries(LIBs).To mitigate the formation of SiC,this paper reports a molten salt electrolysis approach to prepare C-Si composite by the electrolysis of C-SiO2 composites.Unlike the conventional way of making a C coating on Si,C-SiO2 composites were prepared by pyrolyzing the low-cost sucrose and silica.The electrochemical deoxidation of the C-SiO2 composites not only produces nanostructured Si inside the C matrix but also introduces voids between the C and Si owing to the volume shrinkage from converting SiO2 to Si.More importantly,the use of Mg ion-containing molten salts precludes the generation of SiC,and the electrolytic Si@C composite anode delivers a capacity of about 1500 mAh g-1 after 100 cycles at a current density of 500 mA g-1.Further,the Si@C‖LiNi0.6Co0.2Mn0.2O2 full cell delivers a high energy density of 608 Wh kg-1.Overall,the molten salt approach provides a one-step electrochemical way to convert oxides@C to metals@C functional materials.

N-doped porous carbon nanofibers sheathed pumpkin-like Si/C composites as free-standing anodes for lithium-ion batteries

Dramatic capacity fading and poor rate performance are two main obstacles that severely hamper the widespread application of the Si anode owing to its large volume variation during cycling and low intrinsic electrical conductivity.To mitigate these issues,free-standing N-doped porous carbon nanofibers sheathed pumpkin-like Si/C composites(Si/C-ZIF-8/CNFs)are designed and synthesized by electrospinning and carbonization methods,which present greatly enhanced electrochemical properties for lithium-ion battery anodes.This particular structure alleviates the volume variation,promotes the formation of stable solid electrolyte interphase(SEI)film,and improves the electrical conductivity.As a result,the as-obtained free-standing Si/C-ZIF-8/CNFs electrode delivers a high reversible capacity of 945.5 mAh g^(-1) at 0.2 A g^(-1) with a capacity retention of 64% for 150 cycles,and exhibits a reversible capacity of 538.6 mA h g^(-1) at 0.5 A g^(-1) over 500 cycles.Moreover,the full cell composed of a freestanding Si/C-ZIF-8/CNFs anode and commercial LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)(NCM)cathode shows a capacity of 63.4 mA h g^(-1) after 100 cycles at 0.2 C,which corresponds to a capacity retention of 60%.This rational design could provide a new path for the development of high-performance Si-based anodes.

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.

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.

Interconnected sandwich structure carbon/Si-SiO_2/carbon nanospheres composite as high performance anode material for lithium-ion batteries

In the present work,an interconnected sandwich carbon/Si-SiO2/carbon nanospheres composite was prepared by template method and carbon thermal vapor deposition（TVD）.The carbon conductive layer can not only efficiently improve the electronic conductivity of Si-based anode,but also play a key role in alleviating the negative effect from huge volume expansion over discharge/charge of Si-based anode.The resulting material delivered a reversible capacity of 1094 mAh/g,and exhibited excellent cycling stability.It kept a reversible capacity of 1050 mAh/g over 200 cycles with a capacity retention of 96%.

Optimization of mixing speed and time to disperse the composite conductive agent composed of carbon black and graphene in lithium-ion battery slurry

This paper proposed an optimal approach to disperse the composite conductive agent which is composed of carbon black(CB)and graphene(Gr)within lithium-ion battery(LIB)slurry with different mixing speeds and mixing times.The internal structures of LIB slurry are characterized by Electrochemical Impedance Spectroscopy,Scanning Electron Microscopy,and Raman experiment.Initially,a composite conductive solution is prepared by mixing the composite conductive agent with NMP solvent under the conditions of five different mixing speeds n_(1)(n_(1)=1000,1100,1200,1300,1400 rpm)in the case of mixing time t_(1)=10 min.Subsequently,LIB slurry is prepared by blending the composite conductive solution,LiCoO_(2)and PVDF-NMP solution under the conditions of five different mixing speeds n_(2)(n_(2)=1000±280,1100±280,1200±280,1300±280,1400±280 rpm)in the case of mixing time t_(2)=6 min.By analyzing the internal structure of different LIB slurries,it shows that in the case of n_(1)=n_(2)=1200 rpm,a conductive network structure is well formed within LIB slurry.Additionally,in order to determine the optimal time to prepare the composite conductive solution for LIB slurry,nine different t_(1)(t_(1)=0,10,20,30,40,50,60,70,80 min)are selected.By analyzing the internal structure of different LIB slurries,a well-formed conductive network structure and a uniformly distributed composite conductive agent are deduced in LIB slurry when t_(1)=50 min.Therefore,it can be concluded that the composite conductive agent composed of CB and Gr is able to be uniformly dispersed in LIB slurry by establishing a well-formed conductive network structure under the optimal mixing speed n_(1)=n_(2)=1200 rpm and the optimal mixing time t_(1)=50 min,t_(2)=6 min.This kind of the internal structure has the potential to be used to further analyze the dispersion characterizations of LIB slurry under different composite conductive agent and CB/Gr ratios with the aim of improving the final performance of LIB.

Rational architecture design of yolk/double-shells Si-based anode material with double buffering carbon layers for high performance lithium-ion battery

Among the many strategies to fabricate the silicon/carbon composite,yolk/double-shells structure can be regarded as an effective strategy to overcome the intrinsic defects of Si-based anode materials for Li-ion batteries(LIBs).Hereon,a facile and inexpensive technology to prepare silicon/carbon composite with yolk/double-shells structure is proposed,in which the double buffering carbon shells are fabricated.The silicon/carbon nanoparticles with core-shell structure are encapsulated by SiO_(2)and external carbon layer,and it shows the yolk/double-shells structure via etching the SiO_(2)sacrificial layer.The multiply shells structure not only significantly improves the electrical conductivity of composite,but also effectively prevents the exposure of Si particles from the electrolyte composition.Meanwhile,the yolk/double-shells structure can provide enough space to accommodate the volume change of the electrode during charge/discharge process and avoid the pulverization of Si particles.Moreover,the as-prepared YDS-Si/C shows excellent performance as anode of LIBs,the reversible capacity is as high as 1066 mA h g^(-1) at the current density of 0.5 A g^(-1) after 200 cycles.At the same time,the YDS-Si/C has high capacity retention and good cyclic stability.Therefore,the unique architecture design of yolk/double-shells for Si/C composite provides an instructive exploration for the development of next generation anode materials of LIBs with high electrochemical performances and structural stability.

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.

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.

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.

Mechanochemically Metamorphosed Composites of Homogeneous Nanoscale Silicon and Silicate Oxides with Lithium and Metal Compounds

An active anode material for Li-ion batteries was synthesized using a simple mechanochemical process to minimize the large change in Si volume observed during charge-discharge operation and to compensate for the associated irreversible loss of Li or irreversible capacity loss, which are obstacles to achieve high-performance electrochemical properties during charge-discharge. The composite was mechanochemically milled with Si, lithium oxide, and copper oxide as raw materials;the composite contains Si nanoparticles, amorphous silicon monoxide, and Si-Li or Si-Cu alloy compounds, and it exhibits improved electrochemical properties. In particular, this composite achieved a better capacity retention, higher coulombic efficiency (over 100%), and longer cycling performance than Si alone, indicating considerable optimization of the electrical and ionic conductivity in the composite. The developed method allowed for control of the Li content to compensate for the lack of Li ions in the composite, and the cycling performance was optimized using the Cu alloy, oxide, and Li compounds within the composite.

Construction of three-dimensional carbon framework-loaded silicon nanoparticles anchored by carbon film for highperformance lithium-ion battery anode materials

Si materials are widely considered to be the next-generation anode to replace the current commercial graphite-based anode due to its high energy density.However,the large volume variation of silicon during(de)lithiation process leads to rapid capacity decay,hindering its commercial application.Although the various hollow structure designs of Si nanomaterials have improved their cycling stability in the laboratory,the high-pressure calendering process in the current industrial electrode preparation process might collapse the hollow structure and weaken the structural advantages of hollow silicon anode materials.In this work,a silicon carbon composite material(Si@3DC)in which Si nanoparticles were anchored on a three-dimensional carbon framework through carbon films was prepared by a simple proton exchange method.The three-dimensional carbon framework with multiple hierarchical pores of Si@3DC was compatible with the high-pressure calendering process,but also could provide expansion space for Si nanoparticles during the lithiation process,and ensure good electronic and ionic conductivity.The carbon film on the surface of Si nanoparticles promoted the formation of stable solid electrolyte interphase(SEI)films,ensuring the good cycle stability of Si@3DC.

Hybrid Silicon-Carbon Nanostructured Composites as Superior Anodes for Lithium Ion Batteries

We have successfully fabricated a hybrid silicon-carbon nanostructured composite with large area （about 25.5 in^2） in a simple fashion using a conventional sputtering system. When used as the anode in lithium ion batteries, the uniformly deposited amorphous silicon （a-Si） works as the active material to store electrical energy, and the pre-coated carbon nanofibers （CNFs） serve as both the electron conducting pathway and a strain/stress relaxation layer for the sputtered a-Si layers during the intercalation process of lithium ions. As a result, the as-fabricated lithium ion batteries, with deposited a-Si thicknesses of 200 nm or 300 nm, not only exhibit a high specific capacity of 〉2000 mA.h/g, but also show a good capacity retention of over 80% and Coulombic efficiency of 〉98% after a large number of charge/discharge experiments. Our approach offers an efficient and scalable method to obtain silicon-carbon nanostructured composites for application in lithium ion batteries.

Carbon dot-modified silicon nanoparticles for lithium-ion batteries

Silicon(Si)particles were functionalized using carbon dots(CDs)to enhance the interaction between the Si particles and the binders.First,CDs rich in polar groups were synthesized using a simple hydrothermal method.Then,CDs were loaded on the Si surface by impregnation to obtain the functionalized Si particles(Si/CDs).The phases and microstructures of the Si/CDs were observed using Fourier-transform infrared reflection,X-ray diffraction,scanning electron microscopy,and high-resolution transmission electron microscopy.Si/CDs were used as the active material of the anode for electrochemical performance experiments.The electrochemical performance of the Si/CD electrode was assessed using cyclic voltammetry,electrochemical impedance spectroscopy,and constant current charge and discharge experiment.The electrodes prepared with Si/CDs showed good mechanical structure stability and electrochemical performance.After 150 cycles at 0.2 C,the capacity retention rate of the Si/CD electrode was 64.0%,which is twice as much as that of pure Si electrode under the same test conditions.

The influence of compact and ordered carbon coating on solid-state behaviors of silicon during electrochemical processes

To address the issues of large volume change and low conductivity of silicon(Si)materials,carbon coatings have been widely employed as surface protection agent and conductive medium to encapsulate the Si materials,which can improve the electrochemical performance of Si-based electrodes.There has been a strong demand to gain a deeper understanding of the impact of efficient carbon coating over the lithiation and delithiation process of Si materials.Here,we report the first observation of the extended two-phase transformation of carbon-coated Si nanoparticles(Si/C)during electrochemical processes.The Si/C nanoparticles were prepared by sintering Si nanoparticles with polyvinylidene chloride precursor.The Si/C electrode underwent a two-phase transition during the first 20 cycles at 0.2 C,but started to engage in solid solution reaction when the ordered compact carbon coating began to crack.Under higher current density conditions,the electrode was also found to be involved in solid solution reaction,which,however,was due to the overwhelming demand of kinetic property rather than the breaking of the carbon coating.In comparison,the Si/C composites prepared with sucrose possessed more disordered and porous carbon structures,and presented solid solution reaction throughout the entire cycling process.

Regeneration of photovoltaic industry silicon waste toward high-performance lithium-ion battery anode

The diamond-wire sawing silicon waste(DWSSW)from the photovoltaic industry has been widely considered as a low-cost raw material for lithium-ion battery silicon-based electrode,but the effect mechanism of impurities presents in DWSSW on lithium storage performance is still not well understood;meanwhile,it is urgent to develop a strategy for changing DWSSW particles into high-performance electrode materials.In this work,the occurrence state of impurities presents in DWSSW was carefully analyzed using in situ Ar ion etching technology Then,the novel Si@C@SiO_(x)@PAl-NDC composite was designed through in situ encapsulation strategy.The obtained Si@C@SiO_(x)@PAl-NDC electrode shows a high first capacity of 2343.4 mAh·g^(-1)with an initial Coulombic efficiency(ICE)of 84.4%under current density of 1.0 A·g^(-1),and can deliver an impressive capacity of 984.9 mAh·g^(-1)after 200 cycles.Combined numerical simulation modeling calculations,the increase in proportion of Si^(4+)/Si^(0)and Si^(3+)/Si^(0)valence states in SiO_(x)layer leads to a decrease in von Mises stress,which ultimately improves the cycling structural stability.Meanwhile,the porous 2D-3D aluminum/nitrogen(Al/N)co-doped carbon layer and nanowires on SiO_(x)layer can provide abundant active sites for lithium storage due to its developed hierarchical pores structure,which facilitates ion transport What is more,the performance of Si@C@SiO_(x)@PAl-NDC//LiFePO_(4)full cell shows its great potential in practical application.