Tamarind seed skin-derived fiber-like carbon nanostructures as novel anode material for lithium-ion battery

Demand of low-cost carbonaceous anode materials for lithium-ion batteries has led to the development of anode materials from different bio-sources. In this regard, tamarind seed (skin) was used as a precursor to prepare disordered carbon as an anode material for lithium-ion batteries. The carbon was prepared through simple hydrothermal method and was characterized by X-ray diffraction (XRD), Raman spectroscopy, Brunauer–Emmett–Teller (BET) measurements, field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM) techniques. It exhibited amorphous carbon particles arranged in a fiber-like morphology with high surface area of 508 m² g^?1. The binder content was optimized for the carbon to achieve high and stable capacity. Electrochemical performance of the as-prepared carbon with optimized binder content showed a stable reversible specific capacity of 224 mAhg^?1 after 300 cycles at 1 C-rate. The stable cycling performance of carbon at high current rate is explained by electrochemical impedance spectroscopy (EIS) and FE-SEM data of cycled electrodes. The low cost and stable specific capacity make the carbon as potential anode material for lithium-ion battery.

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Graphical abstract Fiber-like carbon nanostructures from tamarind seed (skin) (TDC) via simple and effective hydrothermal method and its application as a novel anode material for lithium-ion battery.

     

Sn/carbon nanotube composite anode with improved cycle performance for lithium-ion battery

Anode material for lithium-ion battery based on Sn/carbon nanotube (CNT) composite is synthesized via a chemical reduction method. The Sn/CNT composite is characterized by thermogravimetry, X-ray diffraction, and transition electron microscopy. The Sn/CNT composite delivers high initial reversible capacity of 630.5 mAh g^?1 and exhibits stable cycling performance with a reversible capacity of 413 mAh g^?1 at the 100th cycle. The enhanced electrochemical performance of the Sn/CNT composite could be mainly attributed to the well dispersion of Sn nanoparticles on CNT and partially filling Sn nanoparticles inside the CNT. It is proposed that the chemical treatment of CNT with concentrated nitric acid, which cuts carbon nanotube into short pieces and increases the amount of oxygen-functional groups on the surface, plays an important role in the anchoring of Sn nanoparticles on carbon nanotube and inhibiting the agglomeration of Sn nanoparticles during the charge–discharge process.     

Surface-modification of anode carbon for lithium-ion battery using chemical vapor infiltration technique

To reduce the high irreversible capacity of the low crystalline carbon fiber for the anode material of lithium-ion battery, pyrolytic carbon (pyrocarbon) was coated at 950 °C from C₃H₈(30%)-H₂ gas system using pressure-pulsed chemical vapor infiltration. Carbon fiber was coated with the dense pyrocarbon film having the laminar texture and the low surface area of 1.9 m² g⁻¹. It was revealed from XRD and Raman spectroscopy that the crystallinity of pyrocarbon is higher than that of the core carbon. Electrochemical properties were measured in ethylene carbonate (EC) and propylene carbonate (PC) base electrolytes. Irreversible capacity was reduced in EC-based electrolyte by coating with 8 mass% pyrocarbon, which would be attributed to the high crystallinity, laminar structure and low surface area of pyrocarbon. Irreversible capacity was also decreased in PC-based electrolyte. The crystallinity of pyrocarbon was not so high as PC-based electrolyte was decomposed in the case of the high crystalline graphite.     

Study of metal-supported carbon matrix as a high-capacity anode for Li-ion battery

Tin–graphite composite with 20 wt. % metal content as well as its structural and electrochemical characteristics are presented. Synthetic graphite—super flake type—was used as object for the modification experiment. Chemical reduction was applied for the loading process, which was carried out under inert argon atmosphere. Composite with specific morphology and improved electrochemical behavior was prepared. The obtained material shows higher discharge capacity as well as increased initial charge–discharge coulomb efficiency, compared with the unmodified one. The supporting metal morphology, the type of graphite, and the preparation process taken together generally affect the improvement of the electrochemical performance. This work was presented at the 11th Euro Conference on Science and Technology of Ionics, Batz-sur-Mer, France, Sept. 9–15, 2007.     

Silicon/carbon nanocomposites used as anode materials for lithium-ion batteries

Silicon/carbon nanocomposites are prepared by dispersing nano-sized silicon in mesophase pitch and a subsequent pyrolysis process. In the nanocomposites, silicon nanoparticles are homogeneously distributed in the carbon networks derived from the mesophase pitch. The silicon/carbon nanocomposite delivers a high reversible capacity of 841 mAh g^?1 at the current density of 100 mA g^?1 at the first cycle, high capacity retention of 98 % over 30 cycles, and good rate performance. The superior electrochemical performance of nanocomposite is attributed to the carbon networks with turbostratic structure, which enhance the conductivity and alleviate the volume change of silicon.     

Tin oxide nano-flower-anchored graphene composites as high-performance anode materials for lithium-ion batteries

The SnO₂ nano-flower/graphene (SnO₂-NF/GN) composites were synthesized by using graphene (GN) and SnO₂ nano-flower (SnO₂-NF). Among them, the SnO₂-NFs were prefabricated by using sodium hydroxide and stannic chloride pentahydrate (SnCl₄·5H₂O) as raw materials. The results of SEM show that the SnO₂-NFs are uniformly dispersed on the surface of GN. Furthermore, compared with the pure SnO₂, the as-prepared SnO₂-NF/GN composites displayed superior cycle performace and high rate capability. The SnO₂-NF/GN composite delivers a specific capacity of 650 mAh g^?1 after 60 cycles and an excellent rate capability of 480 mAh g^?1 at 2000 mA g^?1.     

Chemically shortened multi-walled carbon nanotubes used as anode materials for lithium-ion batteries

An easy chemically cutting process, modified Hummers' method, was proposed to treat multi-walled carbon nanotubes, successfully cutting pristine long, entangled carbon nanotubes into hydrosoluble pieces, mostly less than 200 nm. This short, chemically oxidized carbon nanotube was then applied as an anode material for lithium-ion batteries. The as-prepared material possessed higher reversible capacity and coulombic efficiency. The intrinsic factors were explored by X-ray photoelectron spectroscopy and cyclic voltammetry.     

Electrochemical properties of SnO2 nanorods as anode materials in lithium-ion battery

Well-dispersed SnO2 nanorods with diameter of 4-15 nm and length of 100-200 nm are synthesised through a hydrothermal route and their potential as anode materials in lithium-ion batteries is investigated. The observed initial discharge capacity is as high as 1778 mA·h/g, much higher than the theoretical value of the bulk SnO2 (1494 mA·h/g). During the following 15 cycles, the reversible capacity decreases from 929 to 576 mA·h/g with a fading rate of 3.5% per cycle. The fading mechanism is discussed. Serious capacity fading can be avoided by reducing the cycling voltages from 0.05-3.0 to 0.4-1.2 V. At the end, SnO2 nanorods with much smaller size are synthesized and their performance as anode materials is studied. The size effect on the electrochemical properties is briefly discussed.     

PAN-based carbon fiber@SnO<Subscript>2</Subscript> for highly reversible structural lithium-ion battery anode

The carbon fiber (CF) is frequently preferred because it is considered as a multifunctional lightweight composite, where the CF is not only acted as one completely integrated part of the device with high-performance structural reinforcement, but also served as one of the battery electrode to storage energy. However, the limitation of electrochemical capacity of commercial CFs for the structural lithium-ion battery (SLIB) is an urgent issue should be solved. Therefore, in this work, a novel strategy to fabricate CF@SnO₂ composite is developed by employing one-step tin tetrachloride solvothermal method. The performance of the CFs could be improved by growing the stannic oxide firmly on each CF to form a synergetic electrode. When tested as anode materials, a high reversible capacity of 510 mAh g^?1 at a current density of 100 mAh g^?1 is maintained without obvious decay up to 150 cycles (a huge increase as high as 637.5% than that of the pure CFs). Furthermore, our strategy reveals an attainable route, which could be as a promising way to make a sustainable anode for SLIBs and carbon-based multi-functional composite for other practical applications.     

Graphene-Co/CoO shaddock peel-derived carbon foam hybrid as anode materials for lithium-ion batteries

A novel graphene (G)-Co/CoO shaddock peel-derived carbon foam (SPDCF) hybrid was fabricated as anode materials for lithium-ion batteries. The preparation of G-Co/CoO SPDCF was according to the following two steps. Firstly, the dried shaddock peels were immersed into the mixture of Co(NO₃)₂/graphene oxide for about 12 h. Then, the shaddock peels were taken out and heated at 800 °C for 2 h under N₂ atmosphere. The strategy is simple, low-cost, and environmentally friendly because the shaddock peel is abundant and renewable. The obtained G-Co/CoO SPDCF hybrid were carefully characterized by SEM, EDS, XPS, XRD, TGA, BET, TEM, and electrochemical techniques. The results showed that the carbonized shaddock peels had hierarchical porous nanoflakes structures and graphene was uniformly dispersed into the SPDCF. The nanosized Co/CoO was formed on the G-SPDCF. The resulted G-Co/CoO SPDCF hybrid could maintain a high capacity of 600 mA h g^?1 at 0.2 A g^?1 after 80 cycles, which was much higher than that of commercial graphite (372 mA h g^?1). The enhanced performance might be ascribed to the existence of lots of uniform Co/CoO and the hierarchical G-SPDCF alleviating the mechanical stress during the process of lithiation/delithiation.     

Growth and morphology of carbon nanostructures on nickel oxide nanoparticles in catalytic chemical vapor deposition

The present study explores the conditions favorable for the growth of cylindrical carbon nanostructures such as multi-walled carbon nanotube (MWCNT) and carbon nanofiber by catalytic chemical vapor deposition (CCVD) method using nickel oxide-based catalyst nanoparticles of different average sizes as well as different levels of doping by copper oxide. The role of doping and the average size have been related to the observed melting behavior of nanoparticles of nickel oxide by thermal and diffraction analysis, and the importance of melting has been highlighted in the context of growth of cylindrical nanostructures. In the reducing environment prevailing in the CCVD chamber due to decomposition of flowing acetylene gas at elevated temperature, there is extensive reduction of oxide nanoparticles. Lack of melting and faster flow of carbon-bearing gases favor the formation of a carbon deposit cover over the catalyst nanoparticles giving rise to the formation of nanobeads. Melting allows rapid diffusion of carbon from the surface to inside catalyst particles, and reduced flow of gas lowers the rate of carbon deposit, both creating conditions favorable for the formation of cylindrical nanostructures, which grows around the catalyst particles. Smaller particle size and lower doping favor growth of MWCNT, while growth of fiber is commonly observed on larger particles having relatively higher level of doping.     

Lithium titanate as anode material for lithium-ion cells: a review

Lithium titanate (Li₄Ti₅O₁₂) has emerged as a promising anode material for lithium-ion (Li-ion) batteries. The use of lithium titanate can improve the rate capability, cyclability, and safety features of Li-ion cells. This literature review deals with the features of Li₄Ti₅O₁₂, different methods for the synthesis of Li₄Ti₅O₁₂, theoretical studies on Li₄Ti₅O₁₂, recent advances in this area, and application in Li-ion batteries. A few commercial Li-ion cells which use lithium titanate anode are also highlighted.     

Effects of nitrogen on the carbon anode of a lithium secondary battery

Nitrogen-containing carbons have been made from different polymer precursors at 600°C. Their composition and structure have been studied by chemical analysis, X-ray powder diffraction and X-ray photoelectron spectroscopy. These results show that this kind of carbon is disordered, and nitrogen exists as two kinds of forms in the polymeric carbons: graphene nitrogen (N_1s binding energy 398.5 eV) and conjugated nitrogen (N_1s binding energy 400.2 eV). The discharge and charge process suggests that these two kinds of nitrogen are bonded satisfactorily and could not result in irreversible reaction with Li. The increase of reversible capacity mainly results from the graphene nitrogen, and the higher the content of nitrogen, the higher the charge capacity. Part of the irreversible capacity is derived from the formed lithium carbide and lithium atoms which are intercalated and could not be deintercalated.     

Montmorillonite-based ceramic membranes as novel lithium-ion battery separators

Novel montmorillonite-based ceramic membrane (CM) has been prepared with poly(vinylidene fluoride-co-hexafluoropropene) (PVdF-HFP) copolymer as binder. Physical properties such as surface morphology, porosity, liquid electrolyte uptake and thermal stability were analysed. The ceramic membrane was activated by soaking it in a non-aqueous liquid electrolyte (1.0 M LiPF₆ solution in 1/1 v/v ethylene carbonate/diethyl carbonate mixture) for 10 min. The compatibility of the membrane with lithium metal anode as a function of storage time was analysed by assembling a Li/CM/Li symmetric cell. Finally, a lab-scale cell composed of Li/CM/LiFePO₄ is assembled and its cycling performance analysed at different C-rates. Although the ceramic membrane is not flexible, it shows high thermal stability and stable interfacial properties when in contact with the lithium metal anode. A stable cycling behaviour is demonstrated even at 1C-rate with limited fade in capacity.     

Effect of fluoroethylene carbonate as an electrolyte additive on the cycle performance of silicon-carbon composite anode in lithium-ion battery

The cycling performance of silicon-carbon anodes in the electrolyte with different content (0, 2, 5, 10 wt%) fluorinated ethylene carbonate (FEC) was studied. Among all the electrolytes the injection of 2 wt% FEC into carbonate electrolyte, the retention capacity of silicon carbon anode enhanced from 54.81 to 83.82% after 50 cycles. The performance of SEI layer on the anode was characterized by SEM, EIS, FTIR, and XPS analysis. These studies reveal that the SEI layer formed in the FEC-containing electrolyte effectively reduced the capacity loss of the material and reduced the interfacial impedance.     

Red phosphorus encapsulated in porous carbon derived from cigarette filter solid waste as a promising anode material for lithium-ion batteries

Red phosphorus (RP) is considered to be one of the promising anode materials for lithium-ion batteries (LIBs) on account of its high theoretical capacity (2596 mAh g^?1), abundant resources, and environmental friendliness. However, the intrinsic insulating nature and large volume change during lithium insertion/extraction process lead to drastic capacity loss upon cycling. Recently, great attention has been devoted to constructing P-based composites via mixing with carbon materials. Here, a novel P/C composite, in which red P nanoparticles were homogeneously distributed in cigarette filter-derived porous carbon (CPC), was fabricated by vaporization-condensation method. Due to the unique characteristics of porous carbon, including high specific area, good conductivity, and rich internal porous structure, CPC obtained by means of heat treatment that serves as conductive matrix to load red P could be of great benefits, which can not only improve the overall electrical conductivity but also mitigate the volume expansion issues. As a result, the RP/CPC composite as an anode material for LIBs delivers a good cycling stability (500 mAh g^?1 at 100 mA g^?1 with a high Coulombic efficiency above 99% after 50 cycles) and rate capability (355 mAh g^?1 even at 1000 mA g^?1).     

Preparation of carbon nanoparticles from electrolysis of molten carbonates and use as anode materials in lithium-ion batteries

The electrochemical reduction of molten Li–Na–K carbonates at 450 °C provides “quasi-spherical” carbon nanoparticles with size comprised between 40 and 80 nm (deduced from AFM measurements). XRD analyses performed after washing and heat-treatment at various temperatures have revealed the presence of graphitised and amorphous phases. The d₀₀₂ values were close to the ideal one obtained for pure graphite. Raman spectroscopy has pointed out surface disordering which increases with increasing temperature of the heat-treatment. The presence of Na and Li on the surface of the carbon powder has been evidenced by SIMS. The maximum Na and Li contents were observed for carbon samples heat-treated at 400 °C. Their electrochemical performances vs. the insertion/deinsertion of lithium cations were studied in 1 M LiPF₆–EC : DEC : DMC (2 : 1 : 2). The first charge–discharge cycle is characterised by a high irreversible capacity as in the case of hard-disordered carbon materials. However, the potential profile in galvanostatic mode is intermediate between that usually observed for graphite and amorphous carbon: rather continuous charge–discharge curves sloping between 1.5 and 0.3 V vs. Li / Li⁺, and successive phase transformations between 0.3 and 0.02 V vs. Li / Li⁺. The best electrochemical performances were obtained with carbon powders heat-treated at 400 °C which exhibits a reversible capacity value of 1080 mAh g^− 1 (composition of Li_2.9C₆). This sample has also both the lowest surface disordering (deduced from Raman spectroscopy), and the highest Na and Li surface contents (deduced from SIMS).     

The centrifugally constructed and thermally activated three-dimensional graphene toward a binder-free highly performed anode of the lithium-ion battery

A binder-free three-dimensional porous interconnected graphene (a-3DrGO@NF) was centrifugally constructed and KOH-activated at 800 °C, leading a mechanically strong and pore-developed anode candidate for lithium ion batteries (LIBs). The unique approach of the integration of the mechanical construction and thermal activation demonstrated favorable frameworks to facilitate the stable and fast migrations of both ion and electron during the galvanostatic charge/discharge process, thus significantly improving its durability and electrochemical performance compared to those without the activated and thermal treatment. The a-3DrGO@NF LIBs showed a highly reversible capacity of 1250 mAh g^?1 at a current density of 0.1 A g^?1 after 50 cycles without degradation relative to the first cycle. More importantly, the a-3DrGO@NF LIBs exhibited excellent large current discharge property and cyclic stability of 965 mAh g^?1 in its first cycle and 545 mAh g^?1 after 150 cycles at a current density of 4 A g^?1. Furthermore, it can be quickly charged and discharged in a very short time of 92 s together with high-rate capability of 256 mAh g^?1 after 200 cycles at 10 A g^?1. At both lower and higher its current density as to 10 A g^?1, the coulombic efficiency was close to 100% and showed the reliability of a-3DrGO@NF LIBs.