Improving the performance of graphite anodes in rechargeable lithium batteries

A low cost graphite was examined as a negative electrode for rechargeable lithium batteries. The use of an electrolyte solution consisting of LiPF₆ (1 mol dm⁻³) in ethylene carbonate (EC) and dimethyl carbonate (DMC) at a volume ratio of 2:1 resulted in a capacity loss of 35% on the first cycle. When small quantities of dimethyl pyrocarbonate (DMPC) were added to the binary electrolyte system, the capacity loss on the first cycle was only 18% and thereafter a practical capacity value of 357 mA h g⁻¹ was sustained for more than 50 cycles, representing more than 2000 h of cycling.     

Comparative thermal stability of carbon intercalation anodes and lithium metal anodes for rechargeable lithium batteries

An accelerating rate calorimeter has been used to probe the thermal stability of Li_xC₆ in electrolyte as a function of specific surface area, lithium content, and solvent choice. The exotherm can be qualitatively modelled based on the reaction which produces the passivating film on the carbon surface.     

Microstructure and electrochemical properties of a nanometer-scale tin anode for lithium secondary batteries

The microstructure of nanometer-scale tin powder synthesized by the wire electric explosion (WEE) method is examined by transmission electron microscopy (TEM) at different Li insertion states, and then electrochemical properties of the tin power electrode are characterized by galvanostatic charge–discharge experiments. It is found that several Li/Sn inter-metalic compounds are formed during lithium insertion, namely Li_1−xSn, L₁₃Sn₅ and Li₇Sn₂. The passivation layer (or solid electrolyte interface, SEI) on the surface of particles cycled in an organic electrolyte electrochemical cell is characterized as Li₂CO₃ and ROCO₂Li by FT-IR spectroscopy. A great part of the passivation layer is amorphous, but a small is poorly crystallized.     

Silicon and carbon based composite anodes for lithium ion batteries

Composites comprising silicon (Si), graphite (C) and polyacrylonitrile-based disordered carbon (PAN-C), denoted as Si/C/PAN-C, have been synthesized by thermal treatment of mechanically milled silicon, graphite, and polyacrylonitrile (PAN) powder of nominal composition C–17.5 wt.% Si–30 wt.% PAN. PAN acts as a diffusion barrier to the interfacial diffusion reaction between graphite and Si to form the electrochemically inactive SiC during prolonged milling of graphite and Si, which could be easily formed in the absence of PAN. In addition, graphite, which contributes to the overall capacity of the composite and suppresses the irreversible loss, retains its graphitic structure during prolonged milling in the presence of PAN. The resultant Si/C/PAN-C based composites exhibit a reversible capacity of ∼660 mAh g⁻¹ with an excellent capacity retention displaying almost no fade in capacity when cycled at a rate of ∼C/4. Scanning electron microscopy (SEM) analysis indicates that the structural integrity and microstructural stability of the composite during the alloying/dealloying process appear to be the main reasons contributing to the good cyclability observed in the above composites.     

Low hydrogen containing amorphous carbon films—Growth and electrochemical properties as lithium battery anodes

Amorphous carbon films were deposited successfully on Cu foils by DC magnetron sputtering technique. Electrochemical performance of the film as lithium battery anode was evaluated across Li metal at 0.2 C rate in a non-aqueous electrolyte. The discharge curves showed unusually low irreversible capacity in the first cycle with a reversible capacity of ∼810 mAh g⁻¹, which is at least 2 times higher than that of graphitic carbon. For the first time we report here an amorphous carbon showing such a high reversibility in the first cycle, which is very much limited to the graphitic carbon. The deposited films were extensively characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and step profilometer for the structural and surface properties. The hydrogen content of the synthesized films was studied using residual gas analysis (RGA). The low hydrogen content and the low specific surface area of the synthesized amorphous carbon film are considered responsible for such a high first cycle columbic efficiency. The growth mechanism and the reasons for enhanced electrochemical performance of the carbon films are discussed.     

Morphology effect on the electrochemical performance of NiO films as anodes for lithium ion batteries

NiO films were prepared by chemical bath deposition and electrodeposition method, respectively, using nickel foam as the substrate. The films were characterized by scanning electron microscopy (SEM) and the images showed that their morphologies were distinct. The NiO film prepared by chemical bath deposition was highly porous, while the film prepared by electrodeposition was dense, and both of their thickness was about 1 μm. As anode materials for lithium ion batteries, the porous NiO film prepared by chemical bath deposition exhibited higher coulombic efficiency and weaker polarization and its specific capacity after 50 cycles was 490 mAh g⁻¹ at the discharge–charge current density of 0.5 A g⁻¹, and 350 mAh g⁻¹ at 1.5 A g⁻¹, higher than the electrodeposited film (230 mAh g⁻¹ at 0.5 A g⁻¹, and 170 mAh g⁻¹ at 1.5 A g⁻¹). The better electrochemical performances of the film prepared by chemical bath deposition are attributed to its highly porous morphology, which shorted diffusion length of lithium ions, and relaxed the volume change caused by the reaction between NiO and Li⁺.     

Improving electrochemical properties and structural stability of lithium manganese silicates as cathode materials for lithium ion batteries via introducing lithium excess

The serious capacity decay caused by structural amorphization is still a major issue for polyanion-type lithium manganese silicates (Li₂MnSiO₄) as cathode material for lithium ion batteries. In this work, a new strategy for alleviating the structural instability via the introduction of excess lithium into the host crystal lattice is provided. A comprehensive study demonstrates that the required energy for the extraction/insertion of lithium ions into host crystal lattice was decreased as a result of changed local environment of cations in the compound after the excess lithium occupancy in lattice. Importantly, it was found that Li-rich samples deliver higher reversible capacity and increased average potential than pristine sample, indicating the improved energy density of polyanion-type Li_{2 + 2x}Mn_{1 − x}SiO₄/C_. Additionally, the structure of Li2.2 sample was kept intact, while the Li2.0 sample was transformed to amorphous state at 200 mA h g⁻¹ during the initial charging process by controlling the charge cut-off potential. As expected, the introduction of a certain amount of excess lithium into Li₂MnSiO₄ is explored as a route to achieving increased capacity with more movable lithium, while maintaining its structural stability and cyclic stability.     

Camphor-based carbon nanotubes as an anode in lithium secondary batteries

Camphor vapour is pyrolysed in the presence of Fe, Ni and Co powder under a dinitrogen atmosphere at different temperatures (750–1050 °C). While Fe and Ni catalyse the formation of carbon nanotubes (CNs), Co facilitates carbon nanobead growth. The CNs, obtained using a Fe catalyst at 950 °C, are utilised as the anode in Li secondary batteries. The capacity of the batteries constructed in this way is as good as those prepared by graphitic carbon formed in the arc process.     

Improved electrochemical performance of modified natural graphite anode for lithium secondary batteries

Modified natural graphite is synthesized by surface coating and graphitizing process on the base of spherical natural graphite. The modified natural graphite is examined discharge capacity and coulombic efficiency for the initial charge–discharge cycle. Modification process results in marked improvement in electrochemical performance for a larger discharge capacity and better coulombic efficiency. The mechanism of the enhancement are investigated by means of X-ray powder diffraction, scan electron microscopy, and physical parameters examination. The proportion of rhombohedral crystal structure was reduced by the heat treatment process. The modified natural graphite exhibits 40 mAh g⁻¹ reduction in the first irreversible capacity while the reversible capacity increased by 16 mAh g⁻¹ in comparison with pristine graphite electrode. Also, it has an excellent capacity retention of ∼94% after 100 cycles and ∼87% after 300 cycles.     

Silicon,graphite and resin based hard carbon nanocomposite anodes for lithium ion batteries

Nanocomposite based on graphite (C), silicon (Si) and poly[(o-cresyl glycidyl ether)-co-formaldehyde] resin based amorphous hard carbon (HC), denoted as Si/C/HC, have been synthesized by thermal treatment of mechanically milled graphite, silicon and resin of nominal composition C–18 wt.% Si–40 wt.% resin at 973 K, 1073 K and 1173 K in ultrahigh purity argon atmosphere. The formation of the electrochemically inactive SiC is bypassed as well as the amorphization kinetics of graphite is reduced during prolonged milling of graphite and Si in the presence of the resin. Microstructural analysis has confirmed that the Si nanoparticle gets embedded, and is homogeneously dispersed and distributed on the graphite matrix after mechanical milling as well as after thermal treatment. Electrochemical studies have revealed that the Si/C/HC based nanocomposite, tested as a lithium ion anode, synthesized after thermal treatment at 1173 K exhibits a stable capacity of ∼640 mAh g⁻¹ with an excellent capacity retention when cycled at a rate of ∼160 mA g⁻¹. The nanocomposite anode also shows a moderate rate capability when cycled at different discharge/charge rates. Scanning electron microscopy analysis indicates that the structural integrity and the microstructural stability of the nanocomposite during the alloying/dealloying process contribute to the good cyclability observed in the above nanocomposites.     

Enhanced electrochemical properties of nanostructured bismuth-based composites for rechargeable lithium batteries

Nanostructured Bi/C and Bi/Al₂O₃/C composites, prepared by high-energy mechanical milling (HEMM), are investigated as anode materials for Li-ion rechargeable batteries. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) reveal that the Bi/C nanocomposite is composed of nano-sized Bi and amorphous C, while the Bi/Al₂O₃/C nanocomposite (obtained by the mechanochemical reduction of Bi₂O₃ and Al) is composed of nano-sized Bi, amorphous Al₂O₃, and amorphous C. The electrochemical reaction mechanism of the Bi/C nanocomposite electrode is identified by ex situ XRD analyses combined with a differential capacity plot. Electrochemical tests show that the Bi/C and Bi/Al₂O₃/C nanocomposites exhibit enhanced electrochemical performances compared with that of the pure Bi electrode.     

Silicon-oxycarbide based thin film anodes for lithium ion batteries

We show that anodes made by depositing thin films of polymer-derived silicon oxycarbide (SiCO) on copper have properties that are comparable to, or better than that of powder-based SiCO anodes. The great advantage of the thin film architecture is its simplicity, both in manufacturing and in application. The films are produced by spraying a film of the liquid polymer-precursor on copper, and then converting it into SiCO by heating at ∼1000 °C; at this point they are ready for constructing electrochemical cells. They show a capacity of ∼1000 mA h g⁻¹, 100% coulombic efficiency, good capacity at very high C-rates, and minimal fading at ∼60 cycles. However, if the films are thick they delaminate due to the volume change as lithium is cycled in and out. The transition from thin-film to thick-film behavior occurs when the SiCO films are approximately 1 μm thick. An analytical method for estimating this transition is presented.     

Electrochemical properties of new organic radical materials for lithium secondary batteries

The use of ionic liquid (IL)-supported organic radicals as cathode-active materials in lithium secondary batteries is reported in this article. Two different types of IL-supported organic radicals based on the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical and imidazolium hexafluorophosphate IL were synthesized. The first type is a mono-radical with one unit of TEMPO and the second is a symmetrical di-radical with 2 U of TEMPO; both are viscous liquids at 25 °C. The radicals exhibit electrochemical activity at ∼3.5 V versus Li/Li⁺ as revealed in the cyclic voltammetry tests. The organic radical batteries (ORBs) with these materials as the cathode, a lithium metal anode and 1 M LiPF₆ in EC/DMC electrolyte exhibited good performance at room temperature during the charge–discharge and cycling tests. The batteries exhibited specific capacities of 59 and 80 mAh g⁻¹ at 1 C-rate with the mono- and di-radicals as the cathodes, respectively, resulting in 100% utilization of the materials. The performance degradation with increasing C-rate is very minimal for the ORBs, thus demonstrating good rate capability.     

Towards creating reversible silicon-based composite anodes for lithium ion batteries

A new inexpensive method aimed at distinguishing the forms in which Li⁺ remains irreversibly trapped within composite silicon-based anodes was suggested and tested. It includes a life-cycle test at a fixed degree of lithiation during the initial cycles. The integral capacity values obtained from the test were then correlated with the various chemical species of Li⁺ present in the electrodes after various cycle numbers in both charged and discharged states. Such a technique may provide a quantitative analytical tool for developing this type of electrode.     

Microstructural controls of titanate nanosheet composites using carbon fibers and high-rate electrode properties for lithium ion secondary batteries

Composite electrodes of reassembled titanate and two kinds of carbon fibers were prepared and their high-rate electrode properties were examined. Multi-walled carbon nanotubes (MWNT) and vapor-grown carbon fibers (VGCF) were used for preparing the composites. The electronic conductivity of the MWNT composites increased with increasing contents of MWNT and exhibited a typical insulator-conductor transition. The MWNT composite with a MWNT content of 50 wt.% showed a capacity of 150 ± 5 mAh (g titanate)⁻¹ at a discharge rate of 0.67 C, and did not show a good high-rate capability due to the large content of hydrated water. The effect of the porous structure of the electrodes was revealed in the high-rate electrode properties of the microstructurally controlled composites with both MWNT and VGCF. The composites with 50 wt.% VGCF and 10 wt.% MWNT showed a reversible capacity of approximately 160 mAh (g titanate)⁻¹ at a discharge rate of 0.63 C and almost no capacity fading at relatively large discharge rate up to 19 C. A composite electrode with excellent high-rate capability was obtained by the microstructural control with carbon fibers.     

Improving electrochemical properties of lithium iron phosphate by addition of vanadium

The poor conductivity, resulting from the low lithium-ion diffusion rate and low electronic conductivity in the LiFePO₄ phase, has posed a bottleneck for commercial applications. Well-crystallized LiFePO₄-based powders with vanadium addition were synthesized with solution method. The synthesized powders are coated with carbon. The powder containing the well-mixed LiFePO₄ and Li₃V₂(PO₄)₃ phases (LFVP) with narrow distributed particle size ranging between 0.5 and 2.5 μm exhibits improved electrochemical performance. The small particle size and the presence of the electronically conductive mixed phases can be the reasons why the cells containing LFVP exhibit the high discharge capacity of about 100 mAh g⁻¹ at 10 C, whereas the samples with single phase, such as LiFePO₄ and Li₃V₂(PO₄)₃, have the discharge capacity less than 80 Ah g⁻¹ at the same rate.     

A review of the electrochemical performance of alloy anodes for lithium-ion batteries

Alloy anodes are promising anode materials for lithium-ion batteries due to their high-energy capacity and safety characteristics. However, the commercial use of alloy anodes has been hindered to date by their low cycle life and high initial capacity loss. This review highlights the recent progress in improving and understanding the electrochemical performance of various alloy anodes. The approaches used for performance improvement are summarized, and the causes of first-cycle irreversible capacity loss are discussed. The capacity retentions and irreversible capacity losses of various alloy anodes are compared. Several alloy anodes exhibited excellent cycle life (up to 300 cycles) with high initial coulombic efficiency (80-90%) and large reversible capacity (500-700 mAh g⁻¹).     

Effect of synthesis conditions on the properties of LiFePO4 for secondary lithium batteries

LiFePO₄ is one of the promising materials for cathode of secondary lithium batteries due to its high energy density, low cost, environmental friendliness and safety. However, LiFePO₄ has very poor electronic conductivity (∼10⁻⁹ S cm⁻¹) and Li-ion diffusion coefficient (∼1.8 × 10⁻¹⁴ cm² s⁻¹) at room temperature. In an attempt to improve electrochemical properties, Li_XFePO₄ with various amounts of Li contents were investigated in this study. Li_XFePO₄ (X = 0.7–1.1) samples were synthesized by solid-state reaction. High resolution X-ray diffraction, Rietveld analysis, BET, scanning electron microscopy, and hall effect measurement system were used to characterize these samples. Electronic conductivities of the samples with Li-deficient and Li-excess in Li_xFePO₄ were 10⁻³ to 10⁻¹ S cm⁻¹. Discharge capacities and rate capabilities of the samples with Li-deficient and Li-excess in Li_XFePO₄ were higher than those of stoichiometric LiFePO₄ sample. Li_0.9FePO₄ samples fired at 700 °C had discharge capacity of 156 and 140 mAh g⁻¹ at 0.1 C- and 2 C-rate, respectively.     

Cyclic stability and C-rate performance of amorphous silicon and carbon based anodes for electrochemical storage of lithium

Polymer-derived, amorphous ceramics (PDCs) constituted from silicon, carbon, oxygen and nitrogen are promising candidates as anodes for lithium ion (Li⁺) batteries, having a reversible capacity of up to 800 mAh g⁻¹. These measurements of lithium capacity are extended here to cyclic stability, high C-rate performance, and composition-range. The following new results are presented: (a) materials processed at 800 °C perform better than those synthesized at lower and higher temperatures, (b) materials with high oxygen content perform better than those with high nitrogen, (c) the SiCO materials are highly stable in cyclic loading, and (d) they are robust materials, capable of very high C-rates, without damage to their overall performance. Phenomenological analysis of composition dependent capacity suggests that Li is sequestered to mixed-bond tetrahedra of Si coordinated to both oxygen and carbon; it is argued that when oxygen is substituted by nitrogen the ability of these mixed bonds to bind to lithium in a reversible manner is severely diminished.     

Water-soluble binders for MCMB carbon anodes for lithium-ion batteries

We have investigated the suitability of four different binders for the conventional mesocarbon microbeads (MCMBs) anode material in Li-ion batteries. Unlike the conventional polyvinylidene fluoride (PVDF), the binders were water soluble and were either cellulose based, such as the lithium and sodium salts of carboxymethyl cellulose (NaCMC, and LiCMC) and Xanthan Gum (XG), or the conjugated polymer: poly(3,4-ethylendioxythiophene) (PEDOT, a.k.a. Baytron). All binders were commercially available except LiCMC, which was synthesized and characterized by FTIR and NMR. Thermal studies of the binders by TGA and DSC showed that, in air, the binders have a broad melting event at 100-150 °C, with an onset temperature for decomposition above 220 °C. Li/MCMB half-cell batteries were assembled using the studied binders. Slow scan voltammograms of all cells showed characteristic lithium insertion and de-insertion peaks including that of the SEI formation which was found to be embedded into the insertion peaks during the first cycle. Cycling of the cells showed that the one containing XG binder gave the highest capacities reaching 350 mAh g⁻¹ after 100 cycles at C/12, while the others gave comparable capacities to those of the conventional binder PVDF. The rate capabilities of cells were examined and found to perform well up to the studied C/2 rate with more than 50% capacity retained. Further studies of the XG-based MCMB electrodes were performed and concluded that an optimal thickness of 300-365 μm gave the highest capacities and sustained high C-rates.