Optimized LiVOPO4 for cathodes in Li-ion rechargeable batteries

Improvement of the rate properties of orthorhombic LiVOPO₄ by using a milling approach and acetylene black additives as electronic binder is investigated. The average particle size of orthorhombic LiVOPO₄ was reduced from 12.0 μm to 6.1 μm by milling process by which the Li intercalation capacity into LiVOPO₄ increased to 40 mAhg⁻¹ at 0.4 mAcm⁻² (C/5). At an optimized acetylene black amount of 15 wt.%, a better uniformity in particle size distribution and dispersion of the current distribution was obtained. Thus, enhancing the kinetic performance a fairly large reversible intercalation capacity of Li was achieved with values of 100 and 60 mAhg⁻¹ at high rate conditions of C/5 (0.4 mAcm⁻²) and 1C (2 mAcm⁻²), respectively. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

The use of carbonaceous materials as field-emission cathodes

The advantages and disadvantages of carbon fibers and graphite plates with a developed surface as field-emission cathode materials are discussed. Experimental data for the chemical composition of the materials and the effect of thermal annealing on their structure and emission properties are presented. A correlation between the work function and the amount of cesium implant is studied. The feasibility of preparing planar cold cathodes with a developed surface by means of radiation technologies is considered, and the evolution of the emitting surface during bombardment by low-energy residual gas ions is traced. Cold cathode designs for various applications are recommended.     

Li2MnSiO4/carbon nanofiber cathodes for Li-ion batteries

Pure single-phase Li₂MnSiO₄ nanoparticle-embedded carbon nanofibers have been prepared for the first time via a simple sol-gel and electrospinning technique. They exhibit an improved electrochemical performance over conventional carbon-coated Li₂MnSiO₄ nanoparticle electrodes, including a high discharge capacity of ～200 mAh g^?1, at a C/20 rate, with the retention of 77 % over 20 cycles and a 1.6-fold higher discharge capacity at a 1 C rate.     

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO’s properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li₂O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.     

Synthesis and characterization of LiMn1-x Fe x PO4/carbon nanotubes composites as cathodes for Li-ion batteries

Carbon nanotubes (CNT) coated with LiMn_1-x Fe _x PO₄ (0.2?≤?x?≤?0.8), as possible cathode materials, was synthesized by using a sol–gel process (Polyol method), after annealing under flowing nitrogen. X-ray diffraction (XRD) patterns of the composites confirmed the formation of the olivine structured LiMn_1-x Fe _x PO₄ phase and no secondary phases were detected. The morphological investigation revealed the formation of agglomerates with particles size ranging between 300 and 700 nm. XRD investigation of composites shows difference of the morphology by doping CNT and carbon black in the composites. Transmission electron microscopy shows the growth of nano-sized particles on CNT (20–70 nm) and the agglomeration of primary particles to form secondary particles. The X-ray photoelectron spectroscopy showed that the Fe and Mn ions are in divalent states in the LiMn_1-x Fe _x PO₄ composites. The cyclic voltamograms showed the oxidation peaks of iron and manganese ions at 3.53–3.63 and 4.05–4.33 V, respectively, while the reduction peaks were found at 3.21–3.42 V (iron reduction) and 3.85–3.93 V (manganese reduction) depending on the iron content in the composition. The LiMn_0.6Fe_0.4PO₄/CNT composite (x?=?0.4) (with 20 %?wt CNT) delivered a specific capacity of 120 mAhg^?1 (at a discharge rate of C/20 and RT).     

Phosphate materials for cathodes in lithium ion secondary batteries

Olivine phosphates of general formula LiMPO₄ (M=Fe, Co, Ni) were prepared and characterised in order to evaluate new potential cathode materials for secondary lithium ion batteries. The synthesis was performed by soft chemistry methods to avoid problematical and energetic expensive solid state reactions. In all the compounds no secondary phase was detected and the powder morphology was found to be suitable for cathode layers preparation. Only LiFePO₄ and LiCoPO₄ showed reversible lithium deintercalation-intercalation at 3.5 and 4.8 V vs. Li⁺/Li, respectively. The LiCoPO₄ high potential makes this compound very attractive for high energy batteries, but unfortunately its lifetime appears to be too poor. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Combined operando studies of new electrode materials for Li-ion batteries

The performances of Li-ion batteries depend on many factors amongst which the important ones are the electrode materials and their structural and electronic evolution upon cycling. For a better understanding of lithium reactivity mechanism of many materials the combination of X-Ray Powder Diffraction (XRPD) and Transmission Mössbauer Spectroscopy (TMS) providing both structural and electronic information during the electrochemical cycling has been carried out. Thanks to the design of a specific electrochemical cell, derived from a conventional Swagelock cell, such measurements have been realised in operando mode. Two examples illustrate the greatness of combining XRPD and TMS for the study of LiFe_0.75Mn_0.25PO₄ as positive electrode and TiSnSb as negative electrode. Different kinds of insertion or conversion reactions have been identified leading to a better optimization and design of performing electrodes.     

Electrochemical performances of nano-Co3O4 with different morphologies as anode materials for Li-ion batteries

Three kinds of Co₃O₄ nanomaterials with different morphologies were synthesized controllably by a post-anneal-assisted hydrothermal method in this study. X-ray diffraction and scanning electron microscopy indicated that all three kinds of samples were pure cubic phase of Co₃O₄ with morphologies of nanorods, nanoclusters, and nanoplates. Moreover, the transmission electron microscopy (TEM) and high-resolution TEM showed that the Co₃O₄ nanorods were bamboo-like and highly crystalline structures. When these materials were applied to the lithium-ion batteries (LIBs) as anode materials, the Co₃O₄ of nanorods demonstrated the best performance. It has a stable reversible capacity of 954 mAh g^?1 as the anode of a LIB, much higher than the other two kinds of Co₃O₄ of rod-like nanoclusters and nanoplates, even after 35 cycles. All results showed that the morphology and microstructure take very important roles in the performance of Co₃O₄ as the anode materials in LIBs.     

Si/polyaniline-based porous carbon composites with an enhanced electrochemical performance as anode materials for Li-ion batteries

Silicon/polyaniline-based porous carbon (Si/PANI-AC) composites have been prepared by a three-step method: coating polyaniline on Si particles using in situ polymerization, carbonizing, and further activating by steam. The morphology and structure of Si/PANI-AC composites have been characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectra, respectively. The content and pore structure of the carbon coating layer in Si/PANI-AC have been measured by thermogravimetric analysis and N₂ adsorption-desorption isotherm, respectively. The results indicate some micropores about 1~2 nm in the carbon layer appear during activation and that crystal structure and morphology of Si particles can be retained during preparation. Si/PANI-AC composites exhibit high discharge capacity about 1000 mAh g^?1 at 1.5 A g^?1; moreover, when the current density returns to 0.2 A g^?1, the discharge capacity is still 1692 mAh g^?1 and remains 1453 mAh g^?1 after 70 cycles. The results indicate that the porous carbon coating layer in composites plays an important role in the improvement of the electrochemical performance of pure Si.     

Ceramic materials as supports for low-temperature fuel cell catalysts

The performance and durability of low-temperature fuel cells seriously depend on catalyst support materials. Catalysts supported on high surface area carbons are widely used in low temperature fuel cells. However, the corrosion of carbonaceous catalyst-support materials such as carbon black has been recognized as one of the causes of performance degradation of low-temperature fuel cells, in particular under repeated start-stop cycles or high-potential conditions. To improve the stability of the carbon support, materials with a higher graphitic character such as carbon nanotubes and carbon nanofibers have been tested in fuel cell conditions. These nanostructured carbons show a several-fold lower intrinsic corrosion rate, however, do not prevent carbon oxidation, but rather simply decrease the rate. Due their high stability in fuel cell environment, ceramic materials (oxides and carbides) have been investigated as carbon-substitute supports for fuel cell catalysts. Moreover, the higher specific electrocatalytic activity of some ceramic supported metals than unsupported and carbon supported ones, suggests the possibility of a synergistic effect by supporting metal catalyst on ceramic supports. This paper presents an overview of ceramic materials tested as a support for fuel cell catalysts, with particular attention addressed to the electrochemical activity and stability of the supported catalysts.     

Synthesis and characterization of LiFePO4/3-dimensional carbon nanostructure composites as possible cathode materials for Li-ion batteries

Composites of three-dimensional (3D) carbon nanostructures coated with olivine-structured lithium iron phosphates (LiFePO₄) as cathode materials for lithium ion batteries have been prepared through a Pechini-assisted reversed polyol process for the first time. The coating has been successfully performed on nonfunctionalized commercially available 3D carbon used as catalysts. Thermal analysis revealed no phase transitions till crystallization occurred at 579 °C. Morphological investigation of the prepared composites showed a very good quality of the coating on the 3D carbon structures. A great enhancement of the crystallinity of the olivine structure and of the composites was revealed by the structural investigation performed on pure LiFePO₄ and composites after annealing at 600 °C for 10 h under nitrogen atmosphere. The cyclic voltammetry curves of the composites show well-defined peaks and smaller value of the polarization overpotential indicating an enhancement of electrode reaction reversibility compared to the LiFePO₄ phase.     

Two-dimensional MnN utilized as high-capacity anode for Li-ion batteries

When developing high performance lithium-ion batteries,high capacity is one of the key indicators.In the last decade,the progress of two-dimensional(2 D) materials has provided new opportunities for boosting the storage capacity.Here,based on first-principles calculation method,we predict that MnN monolayer,a recently proposed 2 D nodal-loop halfmetal containing the metallic element Mn,can be used as a super high-capacity lithium-ion batteries anode.Its theoretical capacity is above 1554 mA-h/g,more than four times that of graphite.Meanwhile,it also satisfies other requirements for a good anode material.Specifically,we demonstrate that MnN is mechanically,dynamically,and thermodynamically stable.The configurations before and after lithium adsorption exhibit good electrical conductivity.The study of Li diffusion on its surface reveals a very low diffusion barrier(～ 0.12 eV),indicating excellent rate performance.The calculated average open-circuit voltage of the corresponding half-cell at full charge is also very low(～0.22 V),which facilitates higher operating voltage.In addition,the lattice changes of the material during lithium intercalation are very small(～ 1.2%-～4.8%),which implies good cycling performance.These results suggest that 2 D MnN can be a very promising anode material for lithium-ion batteries.     

Lithium-enriched polypyrrole as a prospective cathode material for Li-ion cells

Lithium substitution in polypyrrole can be accomplished by a variety of approaches and the present work introduces one of the cost-effective techniques using a relatively less expensive lithium salt, n-butyllithium in hexanes (n-BuLi), as the dopant. Chemical oxidative polymerization method is employed to synthesize polypyrrole (PPy) using anhydrous ferric chloride as the oxidant and it is dedoped using NH₄OH solution in the fully reduced state. The dedoped polypyrrole is treated with n-butyllithium in hexanes (n-BuLi) in an argon-filled glove box to get the lithiated form of polypyrrole (PPyL) and the concentration of n-BuLi is varied to improve metalation. The lithiated PPy is characterized by FTIR spectroscopy, XRD, FESEM, and TEM techniques to understand the structural and the morphological details. The lithium content in the lithiated samples is estimated using ICP-AES analysis. The thermal studies using the TGA technique show that the lithiated polypyrrole has good thermal stability. Coin cells are assembled in the argon-filled glove box using Li-substituted polypyrrole as the cathode, lithium metal foil as the anode, and lithium hexafluorophosphate (LiPF₆) as the electrolyte. The assembled cells are electrochemically characterized using cyclic voltammetry and charge–discharge cycling techniques and it is seen that the Li-substituted polypyrrole-based Li-ion cells are electrochemically active.     

Nanoflake CoN as a high capacity anode for Li-ion batteries

CoN films with nanoflake morphology are prepared by RF magnetron sputtering on Cu and oxidized Si substrates and characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) techniques. The thickness and composition of the films are determined by the Rutherford back scattering (RBS) technique confirming the stoichiometric composition of CoN with a thickness, 200 (± 10) nm. Li-storage and cycling behavior of nanoflake CoN have been evaluated by galvanostatic discharge–charge cycling and cyclic voltammetry (CV) in cells with Li–metal as counter electrode in the range of 0.005–3.0 V at ambient temperature. Results show that a first-cycle reversible capacity of 760 (± 10) mAhg^? 1 at a current rate 250 mAg^? 1(0.33 C) increases consistently to yield a capacity of 990 (± 10) mAhg^? 1 after 80 cycles. The latter value corresponds to 2.7 mol of cyclable Li/mol of CoN vs. the theoretical, 3.0 mol of Li. Very good rate capability is shown when cycled at 0.59 C (up to 80 cycles) and at 6.6 C (up to 50 cycles). The coloumbic efficiency is found to be 96–98% in the range of 10–80 cycles. The average charge and discharge potentials are 0.7 and 0.2 V, respectively for the decomposition/formation of Li₃N as determined by CV. However, cycling to an upper cut-off voltage of 3.0 V is essential for the completion of the “conversion reaction”. Based on the ex-situ-XRD, -HR-TEM and -SAED data, the plausible Li-cycling mechanism is discussed. The results show that nanoflake CoN film is a prospective anode material for Li-ion batteries.     

Preparation and characteristics of Sb-doped LiNiO2 cathode materials for Li-ion batteries

Compounds LiNi_1−xSb_xO₂ (x=0, 0.1, 0.15, 0.2, 0.25) were synthesized by the two-step calcination method. The structural and morphological properties of the products were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD analysis confirms that the uniform solid solution has been formed in the as-prepared compounds without any impurities. It is shown that the crystal lattice parameters (a, c) of the Sb-doped compounds are bigger than those of pure LiNiO₂ and the Sb-doped compound with x=0.2 consists of spherical-like nanoparticles with a mean grain size of 50 nm. The electrochemical performances of as-prepared samples were studied via galvanostatic charge-discharge cycling tests. The compound with x=0.2 exhibits excellent capacity retention during the charge-discharge processes due to its reinforced structural stability, and a discharge capacity of 102.4 mAh/g is still obtained in the voltage range of 2.5-4.5 V after 20 cycles. Thermal analysis further confirms that the structural stability of LiNi_0.8Sb_0.2O₂ is superior to that of pure LiNiO₂.     

Characterization of the surface of positive electrodes for Li-ion batteries using 7Li MAS NMR

The growth and evolution of the interphase, due to contact with the ambient atmosphere or electrolyte, are followed using ⁷Li magic-angle spinning nuclear magnetic resonance (MAS NMR) in the case of two materials amongst the most promising candidates for positive electrodes for lithium batteries: LiFePO₄ and LiMn_0.5Ni_0.5O₂. The use of appropriate experimental conditions to acquire the NMR signal allows observing only the «diamagnetic» lithium species at the surface of the grains of active material. The reaction of LiMn_0.5Ni_0.5O₂ with the ambient atmosphere or LiPF₆ (1 M in Ethylene Carbonated/DiMéthyl Carbonate (EC/DMC)) electrolyte is extremely fast and leads to an important amount of lithium-containing diamagnetic species compared to what can be observed in the case of LiFePO₄. The two studied materials display a completely different surface chemistry in terms of reactivity and/or kinetics of the surface towards electrolyte. Moreover, these results show that MAS NMR is a very promising tool to monitor phenomena taking place at the interface between electrode and electrolyte.     

Synthesis and characterization of TiO2-coated magnetite clusters (nFe3O4@TiO2) as anode materials for Li-ion batteries

TiO₂-coated magnetite clusters (nFe₃O₄@TiO₂) were facilely prepared through the sol–gel reaction between Ti alkoxides (TEOT) and magnetite clusters (nFe₃O₄) with terminated alkoxy groups. The composite particles represented a core–shell nanostructure (nFe₃O₄@TiO₂) consisting of a Fe₃O₄ cluster core and a TiO₂ capsule layer. The capsule layer of nFe₃O₄@TiO₂ was increased with increasing amounts of TEOT (150, 300, 500 μl) in sol–gel reaction. The Fe₃O₄@TiO₂ (150 μl of TEOT) with a thin TiO₂ layer (ca. 10 nm) exhibited two kinds of cathodic (0.79 V and 1.61 V) and anodic (1.78 and 2.1 V) peaks attributed to the reduction and oxidation process by Fe₃O₄ core and TiO₂ layer, respectively. The thin nFe₃O₄@TiO₂ (150 μl of TEOT) exhibited the enhanced capacity retention by ca. 40% probably due to the buffering effect of TiO₂ capsule layer. However, the thick nFe₃O₄@TiO₂ (300–500 μl of TEOT) exhibited a rapid capacity fading due to the disintegrated core–shell nanostructure, i.e., unfavorable hetero-junction between TiO₂ matrix and magnetite clusters.