Preparation and electrochemical performance of bramble-like ZnO array as anode materials for lithium-ion batteries

A bramble-like ZnO array with a special three-dimensional (3D) nanostructure was successfully fabricated on Zn foil through a facile two-step hydrothermal process. A possible growth mechanism of the bramble-like ZnO array was proposed. In the first step of hydrothermal process, the crystal nucleus of Zn(OH) ₄ ^2? generated by the zinc atoms and OH^? ions fold together preferentially along the positive polar (0001) to form the needle-like ZnO array. In the second step of hydrothermal process, the crystal nuclei of Zn(OH) ₄ ^2? adjust their posture to keep their c-axes vertical to the perching sites due to the sufficient environmental force and further grow preferentially along the (0001) direction so as to form bramble-like ZnO array. The electrochemical properties of the needle- and bramble-like ZnO arrays as anode materials for lithium-ion batteries were investigated and compared. The results show that the bramble-like ZnO material exhibits much better lithium storage properties than the needle-like ZnO sample. Reasons for the enhanced electrochemical performance of the bramble-like ZnO material were investigated.     

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.     

Modified carbothermal synthesis and electrochemical performance of LiFePO4/C composite as cathode materials for lithium-ion batteries

LiFePO₄/C active materials were synthesized via a modified carbothermal method, with a low raw material cost and comparatively simple synthesis process. Rheological phase technology was introduced to synthesize the precursor, which effectively decreased the calcination temperature and time. The LiFePO₄/C composite synthesized at 700 °C for 12 h exhibited an optimal performance, with a specific capacity about 130 mAh g^?1 at 0.2C, and 70 mAh g^?1 at 20C, respectively. It also showed an excellent capacity retention ratio of 96 % after 30 times charge–discharge cycles at 20C. EIS was applied to further analyze the effect of the synthesis process parameters. The as-synthesized LiFePO₄/C composite exhibited better high-rate performance as compared to the commercial LiFePO₄ product, which implied that the as-synthesized LiFePO₄/C composite was a promising candidate used in the batteries for applications in EVs and HEVs.     

Sn-Sb and Sn-Bi alloys as anode materials for lithium-ion batteries

Sn/SnSb, Sn/Bi, and Sn/SnSb/Bi multi-phase materials were synthesised via reduction of cationic precursors with NaBH₄ and with Zn, and were tested for their suitability as anode materials for Li-ion batteries by galvanostatic cycling. The rapid reduction with NaBH₄ yielded the finer materials with the better cycling stabilities, whereas the reduction with Zn yielded the purer materials with the lower irreversible capacities in the first cycle. Reversible capacities of ∼ 600 mAh g⁻¹, ∼ 350 – 400 mAh g⁻¹, and ∼ 500 mAh g⁻¹ were obtained for Sn/SnSb, Sn/Bi, and Sn/SnSb/Bi, respectively. The cycling stability of the materials decreased in the order Sn/SnSb>Sn/SnSb/Bi>Sn/Bi, which is in part attributed to the presence / absence of intermetallic phases which undergo phase-separation during lithiation. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Synthesis and electrochemical investigation of highly dispersed ZnO nanoparticles as anode material for lithium-ion batteries

Highly dispersed ZnO nanoparticles were prepared by a versatile and scalable sol-gel synthetic technique. High-resolution transmission electronic microscopy (HRTEM) showed that the as-prepared ZnO nanoparticles are spherical in shape and exhibit a uniform particle size distribution with the average size of about 7 nm. Electrochemical properties of the resulting ZnO were evaluated by galvanostatic discharge/charge cycling as anode for lithium-ion battery. A reversible capacity of 1652 mAh g^?1 was delivered at the initial cycle and a capacity of 318 mAh g^?1 was remained after 100 cycles. Furthermore, the system could deliver a reversible capacity of 229 mAh g^?1 even at a high current density of 1.5 C. This outstanding electrochemical performance could be attributed to the nano-sized features of highly dispersed ZnO particles allowing for the better accommodation of large strains caused by particle expansion/shrinkage along with providing shorter diffusion paths for Li⁺ ions upon insertion/deinsertion.     

High-rate Li4Ti5O12/C composites as anode for lithium-ion batteries

The Li₄Ti₅O₁₂/C composites were synthesized by a simple solid-state reaction at 800 °C for 12 h by using Super P® conductive carbon black as carbon source. X-ray diffraction analysis shows that the Li₄Ti₅O₁₂ with 0, 5, 7.5, and 10 wt% carbon shows similar patterns with cubic spinel structure. Scanning electron microscope shows that Li₄Ti₅O₁₂ aggregated seriously, but the aggregation was inhibited by the addition of Super P® carbon. The results indicate that the addition of 5 wt% carbon during sintering and a further 5 wt% carbon during slurry preparation shows the best rate capability of 110 mAh/g when the cells were charge/discharged at 10 C rate. The comparison of the charge–discharge curves shows that the higher rate improvement should further decrease the particle size of LTO or improve the conductivity of LTO itself.     

Preparation of Si-PPy-Ag composites and their electrochemical performance as anode for lithium-ion batteries

The nanosilicon connected by polypyrrole (PPy) and silver (Ag) particles was simply synthesized by a chemical polymerization process in order to prepare Si-based anodes for Li-ion batteries. The phase structure, surface morphology, and electrochemical properties of the as-synthesized powders were analyzed by X-ray diffraction, FT-IR, scanning electron microscopy, and galvanostatic charge/discharge measurements. The cycle stability of the Si-PPy-Ag composites was greatly enhanced compared with the pure nanosilicon. A high capacity of more than 823 mA h g^?1 was maintained after 100 cycles. The improved electrochemical characteristics are attributed to the volume buffering effect as well as effective electronic conductivity of the polypyrrole and silver in the composite electrode.     

Synthesis and electrochemical performances of Li4Ti4.95Al0.05O12/C as anode material for lithium-ion batteries

Spinel compounds Li₄Ti_5−xAl_xO₁₂/C (x=0, 0.05) were synthesized via solid state reaction in an Ar atmosphere, and the electrochemical properties were investigated by means of electronic conductivity, cyclic voltammetry, and charge-discharge tests at different discharge voltage ranges (0-2.5 V and 1-2.5 V). The results indicated that Al³⁺ doping of the compound did not affect the spinel structure but considerably improved the initial capacity and cycling performance, implying the spinel structure of Li₄Ti₅O₁₂ was more stable when Ti⁴⁺ was substituted by Al³⁺, and Al³⁺ doping was beneficial to the reversible intercalation and deintercalation of Li⁺. Al³⁺ doping improved the reversible capacity and cycling performance effectively especially when it was discharged to 0 V.     

Sn and SnO2-graphene composites as anode materials for lithium-ion batteries

Sn and SnO₂-graphene composites were synthesized using hydrothermal process, followed by annealing in Ar/H₂ atmosphere, and characterized using x-ray diffraction, scanning electron microscopy, and transition electron microscopy. The results indicated that the polycrystalline metallic Sn forms nanospheres with a diameter of 100?～?300 nm, while the SnO₂ nanoparticles are much smaller with a size below 15 nm, which adsorb tightly on the surface of graphene sheets. The Sn and SnO₂-gaphene composites showed good electrochemical performance. After 55 charging/discharging cycles, the capacity remains above 440 mAh/g at a cycling rate of 400 mA/g and the coulombic efficiency is 99.1 %. The good electrochemical properties of the composites are partially contributed to the graphene component with good mechanical flexibility and electrical conductivity, which is an excellent carbon matrix for dispersing the Sn and SnO₂ nanostructures and provides the electron transport pathways as well.     

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.     

Theoretical prediction of borophene monolayer as anode materials for high-performance lithium-ion batteries

Three morphologies of two-dimension Boron with metallicity have been successfully synthetized by experiments. To access the potential of β₁₂ borophene (□) and χ₃ borophene monolayer (◇) as anode materials for lithium ion batteries, first-principles calculations based on density functional theory (DFT) are performed. Lithium atom is preferentially absorbed over the center of the hexagonal B atom hollow of β₁₂ and χ₃ borophene monolayer. The fully lithium storage phase of β₁₂ and χ₃ borophene monolayer corresponds to Li₈B₁₀ and Li₈B₁₆ with a theoretical specific capacity of 1983 and 1240 mA h g^?1, respectively, much larger than other two-dimension materials. Interestingly, lithium ion diffusion on β₁₂ borophene (□) monolayer is extremely fast with a low-energy barrier of 41 meV. Meanwhile, lithiated-borophene monolayer shows enhanced metallic conductivity during the whole lithiation process. Compared to the buckled borophene (△), the extremely enhanced lithium adsorption energy of β₁₂ and χ₃ phase with vacancies weakens lithium ion diffusion. Therefore, it is important to control the generation of vacancy in the buckled borophene (△) anode for lithium ion batteries. Borophene is a promising candidate with high capacity and high rate capability for anode material in lithium ion batteries.     

Synthesis and electrochemical performance of hole-rich Li4Ti5O12 anode material for lithium-ion secondary batteries

Hole-rich Li₄Ti₅O₁₂ composites are synthesized by spray drying using carbon nanotubes as additives in precursor solution, subsequently followed calcinated at high temperature in air. The structure, morphology, and texture of the as-prepared composites are characterized with XRD, Raman, BET and SEM techniques. The electrochemical properties of the as-prepared composites are investigated systematically by charge/discharge testing, cyclic voltammograms and AC impedance spectroscopy, respectively. In comparison with the pristine Li₄Ti₅O₁₂, the hole-rich Li₄Ti₅O₁₂ induced by carbon nanotubes exhibits superior electrochemical performance, especially at high rates. The obtained excellent electrochemical performances of should be attributed to the hole-rich structure of the materials, which offers more connection-area with the electrolyte, shorter diffusion-path length as well faster migration rate for both Li ions and electrons during the charge/discharge process.     

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.     

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.     

Synthesis,characterization, and electrochemical properties of lithium-based fluorosulfate nanoparticles as cathode for lithium-ion batteries

Lithium-based fluorosulfate nanoparticles were synthesized by a simple and fast solid state reaction from the precursors FeSO₄?7H₂O and LiF ground by high energy ball milling. Through the introduction of excess of LiF, relatively pure LiFeSO₄F phase with polycrystalline structure was obtained. The structure, morphology, and element valence state were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS). The results demonstrate uniformly distributed particles and larger particles consisted of single crystalline structure, besides the valence states for different elements were analyzed and Fe²⁺ was confirmed. The cyclic voltammograms (CV) and charge-discharge cycling performances were employed to characterize electrochemical properties of prepared cathode material. It is very interesting that double redox peaks appeared reversibly. Meanwhile, it exhibited a relatively higher first-discharge capacity of 115 mAh/g at 0.05C and it still maintained above 60 mAh/g capacity after experiencing 30 times cycles at final 2C rate.     

Synthesis and characterization of mixed vanadium oxide cathode materials for lithium-ion batteries

A family of mixed vanadium oxides LiCo_yNi_(1−y)VO₄ (x=0.2, 0.5 and 0.8) of potential use as high voltage cathode materials in lithium batteries, has been synthesized and characterized. In general the x-ray diffraction analysis showed that these compounds have an inverse spinel structure where about 85 % of the Ni²⁺ and Co²⁺ ions occupies octahedral sites and the rest tetrahedral sites along with the V⁵⁺ ions. Moreover, the annealing temperature plays a key role in determining the particle size, as demonstrated by scanning electron microscope analysis. Cycling voltammetry tests showed that the lithium insertion-extraction process in the LiCo_yNi_(1−y)VO₄ electrode materials occurs reversibly at around 4.3–4.4 V vs. Li and these results are confirmed by cycling tests. The cycling capacity is modest; however the trend of the cycling curves leads to foresee that an increase in capacity may be obtained by extending the charging process beyond 4.6 V vs. Li, once a stable electrolyte will be available. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Synthesis of three-dimensional cross-linked MnO@C composite as high-performance anode material for lithium-ion batteries

MnO@C composites with three-dimensional cross-linked structure were designed and fabricated through hydrothermal treatment. Cation exchange resin was used as the precursor to create a three-dimensional cross-linked porous carbon structure, which was evenly decorated by nanosized MnO particles. When compared with pristine MnO, those MnO@C composites showed much better stability during charge-discharge cycling, retaining a specific capacity of 615 mAh g^?1 (62.5 wt% MnO) after 100 cycles at a current density of 0.2 A g^?1. This could be ascribed to the special three-dimensional cross-linked porous carbon that not only accelerated the transport of Li⁺ ions but also buffered the volume change and prevented agglomeration of MnO particles during the repeated lithiation and delithiation process.     

Excellent long-term electrochemical performance of graphite oxide as cathode materials for lithium-ion batteries

A facile, scalable route has been adopted to synthesize graphite oxides with different degrees of oxidation. Subsequently, graphite oxides with rationally designed functional groups have been utilized as cathode materials for lithium-ion batteries (LIBs). The electrodes deliver the initial and second discharge capacities of 332 and 172 mAh g^?1 at a current density of 0.1 A g^?1, respectively. More importantly, a remarkable long-term cycling performance of 130 mAh g^?1 after 800 cycles has been gathered, with an ultralow capacity fading of 0.03% per cycle from the second cycle. The root cause of excellent cycling stability should be ascribed to the admirable reversibility of epoxy and carbonyl groups in graphite oxides during the Li-cycling. Meanwhile, the deep study has provided a novel way to avoid complex and expensive post-treatment process of graphite oxides, whose synthesis conditions are also optimized. Those striking features make graphite oxides as promising cathode materials for lithium-ion batteries.