Cyclability study of silicon–carbon composite anodes for lithium-ion batteries using electrochemical impedance spectroscopy

The effects of carbonization process and carbon nanofiber/nanotube additives on the cycling stability of silicon–carbon composite anodes were investigated by monitoring the impedance evolution during charge/discharge cycles with electrochemical impedance spectroscopy (EIS). Three types of Si–C anodes were investigated: the first type consisted of Si nanoparticles incorporated into a network of carbon nanofibers (CNFs) and multi-walled carbon nanotubes (MWNTs), with annealed polymer binder. The second type of Si–C anodes was prepared by further heat treatment of the first Si–C anodes to carbonize the polymer binder. The third Si–C anode was as same as the second one except no CNFs and MWNTs being added. Impedance analysis revealed that the carbonization process stabilized the Si–C anode structure and decreased the charge transfer resistance, thus improving the cycling stability. On the other hand, although the MWNTs/CNFs additives could enhance the electronic conductivity of the Si–C anodes, the induced inhomogeneous structure decreased the integrity of the electrode, resulting in a poor long term cycling stability.     

A novel nanosized silicon-based composite as anode material for high performance lithium ion batteries

A new kind of silicon-based composite anode with high initial coulombic efficiency and good cycling performance is synthesized by a wet high energy mechanical milling technique and characterized by X-ray diffraction, transmission electron microscope and high resolution transmission electron microscope. It is demonstrated that the in situ formed Si particles with size of 5–10 nm are uniformly distributed in the elastic matrices consisting of the in situ formed Li-containing compounds, amorphous P₂O₅, SiP₂O₇, Ni, Si–Ni alloys and conductive graphite. The elastic matrices can effectively alleviate the volume variations of the active Si particles during long-term cycling. The as-prepared silicon-based composite electrode reveals an initial discharge and charge capacity of 549 and 565.3 mAh g⁻¹, respectively, with an initial coulombic efficiency of 103%. After 80 cycles, the reversible capacity of the composite electrode is up to 560.7 mAh g⁻¹ with a capacity retention rate of 99%.     

Novel carbon nanofibers of high graphitization as anodic materials for lithium ion secondary batteries

Carbon nanofibers (CNFs) of high graphitization degree were prepared by a CVD process at 550-700 °C. They showed different structures according to catalyst and preparation temperatures. The structure of CNF prepared from CO/H₂ over an iron catalyst was controlled from platelet (P) to tubular (T) by raising the decomposition temperature from 550 to 700 °C. The CNFs prepared over a copper-nickel catalyst from C₂H₄/H₂ showed the typical herringbone (HB) structure regardless of the reaction temperatures. The CNFs prepared over Fe showed d₀₀₂ of 0.3363-0.3381 nm, similar to that of graphite, indicating very high graphitization degree in spite of the low preparation temperature. Such CNFs of high graphitization degree showed high capacity of 297-431 mA h/g, especially in the low potential region. However, low first cycle coulombic efficiency of ≈60% is a problem to be solved. The graphitization of the CNF preserved the platelet texture, however, and formed the loops to connect the edges of the graphene sheets. Higher graphitization temperatures made the loop more definite. The graphitized CNF showed high capacity (367 mA h/g); however, its coulombic efficiency was not so large despite its modified edges by graphitization, indicating that the graphene edges were not so influential for the irreversible reaction of Li ion battery.     

Electrochemical properties of Si–Ge–Mo anode composite materials prepared by magnetron sputtering for lithium ion batteries

Si–Ge–Mo composites are prepared using an RF/DC magnetron sputtering method, and their potential use as anode materials for rechargeable lithium-ion batteries is investigated. The Si–Ge–Mo composite films present an amorphous structure. The reaction mechanism of the Si–Ge–Mo with Li is investigated by various analytical techniques. The fabricated Si_0.41Ge_0.34Mo_0.25 composite film shows excellent electrochemical properties, including a high energy density (1st charge: 1193 mAh g⁻¹), long cycleability (ca. 870 mAh g⁻¹ over 100 cycles), and good initial Coulombic efficiency (ca. 96%). Additionally, when coupled with a LiCoO₂ cathode, the Si_0.55Ge_0.22Mo_0.23 composite electrode used as an anode shows excellent cycleability with a high energy density. The excellent electrochemical properties demonstrated by the Si–Ge–Mo composite film electrode confirm its potential as an alternative anode material for lithium-ion batteries.     

Enhancing particle erosion resistance of glass‐reinforced polymeric composites using carbon nanofiber‐based nanopaper coatings

Sand erosion may cause severe damage of blades in wind turbine and helicopter blades as well as many surface components of airplanes. In this study, thin nanopapers made of carbon nanofibers (CNFs) are used to enhance the resistance of solid particle erosion of glass fiber (GF)/wind epoxy composites. Finite element computer simulations are used to elucidate the underlying mechanisms. The much higher particle erosion resistance of nanopapers compared to GF‐reinforced epoxy composites is attributed to the high strength of CNFs and their nanoscale structure. The excellent performance in particle erosion resistance makes the CNF‐based nanopaper a prospective protective coating material for the turbine blades in the wind energy industry. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Analysis of the interaction of vinyl and carbonyl silanes with carbon nanofiber surfaces

Carbon nanofibers (CNFs) have been treated with vinyltryethoxy silane (VTS) and 3-metacryloxypropyltrimethoxy silane (MPS). CNF–silane interactions have been analyzed by means of TGA, FTIR-ATR, TEM, HRTEM, SEM and nitrogen adsorption. For similar silane concentration solutions TG analysis has shown that VTS and MPS form one and three silane monolayers, respectively. This has also been corroborated by the presence of an FTIR-ATR band at 1250 cm⁻¹ assigned to Si–O–Si bonds of silica layers. For low silane concentrations, the vinyl group of VTS is bonded to the graphene CNF surface mainly through π–π interactions. However, MPS interacts through the carbonyl group with hydroxyl groups of graphene defect sheets existing probably in micropores. Silanol–CNF hydroxyl interactions are also expected at these silane concentrations. For high silane concentration, when the silica layer is formed, both silanes present vinyl free and carbonyl free groups, as observed by the 1370 and 1686 cm⁻¹ FTIR-ATR bands, respectively. Nitrogen adsorption has shown that while VTS is adsorbed mainly on the defect free graphene surface, MPS is adsorbed on the micropores and, therefore on the hydroxyl defect graphene sites. These results are finally correlated with the dispersion stability of both silanes on water and styrene solutions.     

Characterization of carbon nanofiber composites synthesized by shaping process

Catalytically grown carbon nanofibers (CNFs) are shaped into pellets in desired size and configuration by a conventional molding process so as to extend the potential applications of CNFs in industrial heterogeneous catalysis. After shaping, a novel carbon nanofiber composite with sufficient mechanical strength is produced, in which isolated CNFs are connected by a carbon network formed through polymer binder carbonization. Characterization of the synthesized CNF composite is performed by using HRTEM, XRD, Raman, N₂ physisorption, TPD and TGA. A comparison of the textural and structural properties, as well as the surface chemistry is made amongst the CNFs, the CNF composite, and a commercial coal-based activated carbon, in order to attain a comprehensive understanding of the CNF composite. The results show that the CNF composite preserves the mesoporous texture of the CNFs which will be beneficial to those reactions of mass transfer control. The modification effect of oxidative treatments on physico-chemical properties of the CNF composite is also investigated. More surface oxygen-containing groups are introduced to the composite by treating the material either in boiling HNO₃ solution or in static air at 400 °C.     

Effects of surface modification,carbon nanofiber concentration,and dispersion time on the mechanical properties of carbon‐nanofiber–polycarbonate composites

The time effect of ultrasonication was investigated for dispersing carbon nanofibers (CNFs) into a polycarbonate (PC) matrix on the mechanical properties of thus‐produced composites. The effects of CNF surface modification by plasma treatment and the CNF concentration in composites on their mechanical properties were also explored. The plasma coating was characterized by HRTEM and FT‐IR. Furthermore, the plasma polymerization (10 w) treatment on the CNF enhanced the CNF dispersion in the polymer matrix. The mechanical properties of the CNF–PC composites varied with the dispersion time, at first increasing to a maximum value and then dropping down. After a long ultrasonic treatment (24 h), the properties increased again. At a high concentration, the CNF‐PC suspension became difficult to disperse. Additionally, the possible mechanisms for these behaviors are simply proposed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3792–3797, 2007     

锂离子电池Si薄膜负极材料的制备及性能

采用直流磁控溅射法成功制备了钾离子电池用Si薄膜负极材料.通过SEM、恒电流充放电对薄膜材料的形貌及电化学性能进行了表征.结果表明,样品表面颗粒呈球状,表面较粗糙.电化学性能测试表明,Si电极存在较大的初期不可逆容量损失,其首次库仑效率为53%,首次嵌钾容量为1300 mAh/g,10次循环后,嵌锂容量维持在530 mAh/g,容量保持率为41%.     

Synthesis and electrochemical evaluation of carbon coated Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> alloy-graphite composite lithium battery anodes

With a view to minimize the unavoidable large volume changes of tin based Cu₆Sn₅ alloy anodes, a composite Cu₆Sn₅/graphite anode has been prepared via. a mechanical alloying process and subsequently coated with disordered carbon through pyrolysis of PVC. Phase pure products with better crystallinity and preferred surface morphology were obtained, as evident from PXRD and SEM respectively. Upon electrochemical charge-discharge, the intermetallic Cu₆Sn₅ alloy-graphite composite anode was found to exhibit an enhanced initial discharge capacity of 564 mAh g⁻¹ followed by significant capacity fade (>20%) especially after five cycles. On the other hand, carbon coated Cu₆Sn₅ alloy-graphite composite demonstrated promising electrochemical properties such as steady reversible capacity (∼200 mAh g⁻¹), excellent cycle performance (<5% capacity fade) and high coulombic efficiency (∼98%) via. significant reduction of volume changes. The carbon coating offers buffering and conductive actions on the anode active material and thereby enhances the electrochemical behavior of carbon coated Cu₆Sn₅ alloy/graphite composite anode material.     

Si–Al thin film anode material with superior cycle performance and rate capability for lithium ion batteries

To improve the electrochemical performance of Si thin film, we have investigated the effect of the addition of Al in the film. The Si–Al thin film were prepared by co-deposition from Si target embedded with Al rods on Cu foil. The atomic ratio of Al in the film is 18.69% estimated by energy-dispersive spectroscopy. The XRD and TEM analysis revealed that the Si–Al thin film was a complete amorphous structure. The electrochemical performance of the Si–Al thin film as anode material for lithium ion battery was investigated by the cyclic voltammetry and charge/discharge tests. The Si–Al thin film delivered a high reversible capacity of 2257.8 mAh g⁻¹ and an initial Coulombic efficiency of 85.9% at 0.05C rates. Compared with pure Si thin film with the same thickness, Si–Al thin film showed superior rate capability and cycle performance. And the Li⁺ diffusion coefficient of Si–Al thin film is much higher than that of Si thin film.     

Effect of polyaniline surface modification of carbon nanofibers on cure kinetics of epoxy resin

Polyaniline (PANI) “nanograss” was grown on carbon nanofibers (CNFs). The cure behavior of an epoxy resin with and without unmodified CNFs or PANI modified CNFs was studied by means of non‐isothermal and isothermal differential scanning calorimetry (DSC). CNFs accelerated the reaction of epoxy and diamine. PANI surface modification further increased the reaction rate and the extent of reaction. An autocatalytic cure kinetic model was used to fit the reaction curves. It was found that activation energies of the epoxy reaction decreased in the presence of CNFs and PANI modified CNFs. The observed catalytic effect of CNF and PANI surface coating can be very useful for low temperature cure of large epoxy composite products. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhancement of electrosorption capacity of activated carbon fibers by grafting with carbon nanofibers

The composite films of activated carbon fibers (ACFs) and carbon nanofibers (CNFs) are prepared via chemical vapor deposition of CNFs onto ACFs in different times from 0.5 to 2 h and their electrosorption behaviors in NaCl solution are investigated. The morphology, structure, porous and electrochemical properties are characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, N₂ adsorption at 77 K, contact angle goniometer and electrochemical workstation, respectively. The results show that CNFs have been hierarchically grown on the surface of ACFs and the as grown ACF/CNF composite films have less defects, higher specific capacitances, more suitable mesoporous structure and more hydrophilic surface than the pristine ACFs, which is beneficial to their electrosorption performance. The ACFs/CNFs with CNFs deposited in 1 h exhibit an optimized NaCl removal ratio of 80%, 55% higher than that of ACFs and the NaCl electrosorption follows a Langmuir isotherm with a maximum electrosorption capacity of 17.19 mg/g.     

一维纳米结构SnO2的制备及其电化学性能研究

用SnCl4·5H2O、水合肼为原料,采用水热法制备一维纳米结构SnO2。X射线衍射（XRD）、扫描电镜（SEM）和透射电镜（TEM）结果表明：制备的一维纳米结构的SnO2为四方相结构,其直径为0．5—2．5μm,长度约几百微米。恒电流充放电测试结果显示：在电流密度为160mAhg^-1（0．2C）时,该SnO2材料的首次放电容量为1780mAhg^-1,第二十周期放电容量保持到468mAhg^-1;从第三周期开始,库仑效率均保持在90％以上。以上结果表明这种材料具有较高的储锂容量和较好的可逆性能,是一种有前景的锂离子电池负极材料。     

Vanadium nitride and carbon nanofiber composite membrane as an interlayer for extended life cycle lithium-sulphur batteries

In this study, carbon nanofibre (CNF) and vanadium-nitride-modified CNF (VNCNF) were fabricated by the electrospinning method, followed by carbonisation. The fabricated VNCNF and CNF were sandwiched between the cathode and separator to be used as interlayers. The lithium-sulphur (Li–S) cell employing the VNCNF interlayer exhibited high initial charge and discharge capacities of 1452 and 1480 mAh g^?1, corresponding a coulombic efficiency higher than 100% at a rate of 0.5 C, whereas the cell with the CNF interlayer delivered the initial charge and discharge capacities of 858 and 772 mAh g^?1, respectively, corresponding to a coulombic efficiency of 89.97%. Even after 400 cycles, the cell with the VNCNF interlayer retained a remarkable high capacity of 923 mAh g^?1, whereas the cell with the CNF interlayer showed only 586 mAh g^?1 at a rate of 0.5 C. Furthermore, the cell with the VNCNF interlayer exhibited an excellent rate capability of up to 2 C, which was much higher than those of the cells with CNF and without an interlayer. The better performance of Li–S cell with the VNCNF interlayer is attributed to the strong adsorption ability of VNCNF for polysulphide by suppressing the shuttle effect. In addition, the catalytic effect of VN in CNF accelerated the capturing and utilisation of the dissolved active materials, thereby enhancing the Red-Ox kinetics and capacity.     

Long-term-durable anti-icing superhydrophobic composite coatings

We prepared carbon-based superhydrophobic composite coatings through a quick technique, merging multiwalled carbon nanotubes (MWCNTs) and carbon nanofibers (CNFs) to obtain hierarchical nanostructures on fiber-reinforced polymer (FRP) sheets; this was followed by supercritical fluid (SCF) processing and physical mixing (PM). The prepared SCF–MWCNT–CNF and PM–MWCNT–CNF composite coatings showed high water contact angles of 171.6 and 160°. The surface morphologies of the composite coatings revealed a lot of even nanostructures and folding at high magnifications. A high number of CNFs were added to the MWCNTs to initiate different nanoroughnesses in the composite coatings. The as-prepared superhydrophobic composite coatings showed excellent anti-icing properties, as indicated by the supercooled water droplet (-20°C) test under environmental conditions. Also, the surface of the SCF–MWCNT–CNF superhydrophobic composite coating showed excellent antifouling properties. We studied the surface wettability increasing different temperatures (30–180°C) in the SCF–MWCNT–CNF composite; this exposed the fact that the FRP sheets were thermally stable up to 100°C, and a while later, they changed from a superhydrophobic state to a superhydrophilic state at 180°C. This study revealed an economically workable method for the preparation of MWCNT–CNF composites with SCF techniques. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47059.     

Study of Co–Sn and Ni–Sn alloys prepared in molten chlorides and used as negative electrode in rechargeable lithium battery

Ni₃Sn₂ and several Co–Sn alloys prepared by electrodeposition in molten LiCl–KCl were studied as anode materials in rechargeable Li-ion battery. In the case of Ni₃Sn₂, the charge–discharge curves do not exhibit any plateau in contrast with Co–Sn alloys. For Ni₃Sn₂, the reversible capacity and the coulombic efficiency tend to constant values of about 225 mAh/g and 85%, respectively, after subsequent cycles. Among the studied Co–Sn alloys, the best electrochemical performances was observed when CoSn₂ was used as anode material: the reversible capacity and the coulombic efficiency observed after 60 cycles were about 530 mAh/g and 96%, respectively. Whatever the alloys, SEM investigations performed before and after cycling do not reveal any significant difference between the original material and the cycled material, indicating a good stability of the electrodeposited films upon cycling.     

Nano-scale copper-coated graphite as anode material for lithium-ion batteries

Nano-scale copper particles were homogeneously deposited on the surface of natural graphite through electroless plating. The co-intercalation of solvated lithium ion and reduction of the electrolyte were effectively depressed after coating of copper particles. Consequently, the graphite showed a significant improvement in charge–discharge properties such as coulombic efficiency, cycle characteristics, and high rate performance as an anode material for lithium ion batteries.     

Hydrophilization by coating of silylated polyoxazoline using sol–gel process

Hybrid films prepared from TEOS and polyoxazolines (Si–POx–Si) crosslinking agents were coated on different substrates in order to modify their surface properties. The film cohesion and adhesion on substrates were expected through the hydrogen bonding of the polyoxazoline crosslinked network. Low molecular-weight α,ω-unsaturated polyoxazolines (DA-PMOx)s were synthesized by a one step cationic ring-opening polymerization (CROP) of 2-methyl-2-oxazoline (MOx) with a good control over the molecular weight. Based on double thiol-ene coupling (d-TEC) a post-functionalization of DA-PMOx end chains gave in good yield polyoxazoline cross linker (Si–POx–Si). Glass and various polymer substrates (PP, PEI, POM, etc.) were spin coated by the organic–inorganic hybrid films through sol–gel process. AFM, SEM, visible reflectance spectroscopy and contact angle experiments allowed the full characterization of targeted surfaces and demonstrated the efficiency of the polyoxazoline coating.     

Biomimetic synthesis and characterization of carbon nanofiber/hydroxyapatite composite scaffolds

Three dimensional electrospun carbon nanofiber (CNF)/hydroxyapatite (HAp) composites were biomimetically synthesized in simulated body fluid (SBF). The CNFs with diameter of ∼250 nm were first fabricated from electrospun polyacrylonitrile precursor nanofibers by stabilization at 280 °C for 2 h, followed by carbonization at 1200 °C. The morphology, structure and water contact angle (WCA) of the CNFs and CNF/HAp composites were characterized. The pristine CNFs were hydrophobic with a WCA of 139.6°, resulting in the HAp growth only on the very outer layer fibers of the CNF mat. Treatment in NaOH aq. solutions introduced carboxylic groups onto the CNFs surfaces, and hence making the CNFs hydrophilic. In the SBF, the surface activated CNFs bonded with Ca²⁺ to form nuclei, which then easily induced the growth of HAp crystals on the CNFs throughout the CNF mat. The fracture strength of the CNF/HAp composite with a CNF content of 41.3% reached 67.3 MPa. Such CNF/HAp composites with strong interfacial bondings and high mechanical strength can be potentially useful in the field of bone tissue engineering.