Template-free reverse micelle process for the synthesis of a rod-like LiFePO4/C composite cathode material for lithium batteries

The synthesis of rod-like LiFePO₄/C cathodes using template-free reverse micelle process is reported for high performance lithium batteries. We have demonstrated that the size of the primary particles could be controlled based on sintering temperature and sintering time and size of the large aggregates is adjustable based on the carbon content of the sample. Thermogravimetry and differential thermal analysis have been used to propose a possible mechanism for the formation rod-like LiFePO₄/C cathode material. X-ray diffraction, scanning electron microscopy, impedance spectroscopy and charge-discharge measurements have been used to characterize the material. Electrochemical performance of rod-like LiFePO₄/C cathode material offers higher initial capacity and excellent rate capability than that obtained by loose porous LiFePO₄/C material due to unique rod-like composite material formed by primary nanoparticles. Hence, it can be suggested that that the rod-like nanostructured morphology improves structural stability, lithium ion diffusion and electronic conductivity of the LiFePO₄/C composite material. The template-free reverse micelle process for the synthesis of the rod-like LiFePO₄/C cathode material opens up a new route to synthesize lithium transition metal oxides with controlled morphologies for applications in high power lithium batteries.     

Effect of FePO4 coating on electrochemical and safety performance of LiCoO2 as cathode material for Li-ion batteries

LiCoO₂ was surface modified by a coprecipitation method followed by a high-temperature treatment in air. FePO₄-coated LiCoO₂ was characterized with various techniques such as X-ray diffraction (XRD), auger electron spectroscopy (AES), field emission scanning electron microscope (FE-SEM), energy dispersive spectroscopy (EDS), transmission electron microscope (TEM), electrochemical impedance spectroscopy (EIS), 3 C overcharge and hot-box safety experiments. For the 14500R-type cell, under a high charge cutoff voltage of 4.3 and 4.4 V, 3 wt.% FePO₄-coated LiCoO₂ exhibits good electrochemical properties with initial discharge specific capacities of 146 and 155 mAh g⁻¹ and capacity retention ratios of 88.7 and 82.5% after 400 cycles, respectively. Moreover, the anti-overcharge and thermal safety performance of LiCoO₂ is greatly enhanced. These improvements are attributed to the FePO₄ coating layer that hinders interaction between LiCoO₂ and electrolyte and stabilizes the structure of LiCoO₂. The FePO₄-coated LiCoO₂ could be a high performance cathode material for lithium-ion battery.     

Studies of selected synthesis procedures of the conducting LiFePO4-based composite cathode materials for Li-ion batteries

In this paper technological aspects of a synthesis of phospho-olivine LiFePO₄ based composite cathode materials for lithium batteries are presented. An effective synthesis route yielding a highly conductive composite cathode material was developed. The structural, electrical and electrochemical properties of these materials were investigated. It was shown that the enhanced conductivity of the cathode material is due to the presence of a thin layer of the reduced material which has metallic properties, which is formed on the grain surfaces of the phospho-olivine. We propose a synthesis route yielding LiFePO₄/Fe₂P composite material.     

Synthesis and characterization of macroporous tin oxide composite as an anode material for Li-ion batteries

A macroporous SnO₂/C composite anode material was synthesized using an organic template-assisted method. Polystyrene spheres were synthesized and used as template and lead to macroporous morphology with pores of 300-500 nm in diameter and a surface area of 54.7 m² g⁻¹. X-ray diffraction showed that the SnO₂ nanoparticles are crystallized in a rutile P42/mnm lattice with the presence of Sn metal traces. The synthesized macroporous SnO₂/C composite provided promising performance in lithium half cells showing a discharge capacity of 607 mAh g⁻¹ after 55 cycles. It was found that the macroporous SnO₂/C composite is stable and resistant to pulverization upon cycling.     

Hydrometallurgical process for recovery of cobalt from waste cathodic active material generated during manufacturing of lithium ion batteries

The paper presents a new leaching-solvent extraction hydrometallurgical process for the recovery of a pure and marketable form of cobalt sulfate solution from waste cathodic active material generated during manufacturing of lithium ion batteries (LIBs). Leaching of the waste was carried out as a function of the leachant H₂SO₄ concentration, temperature, pulp density and reductant H₂O₂ concentration. The 93% of cobalt and 94% of lithium were leached at suitable optimum conditions of pulp density: 100 g L⁻¹, 2 M H₂SO₄, 5 vol.% of H₂O₂, with a leaching time 30 min and a temperature 75 °C. In subsequent the solvent extraction study, 85.42% of the cobalt was recovered using 1.5 M Cyanex 272 as an extractant at an O/A ratio of 1.6 from the leach liquor at pH 5.00. The rest of the cobalt was totally recovered from the raffinate using 0.5 M of Cyanex 272 and an O/A ratio of 1, and a feed pH of 5.35. Then the co-extracted lithium was scrubbed from the cobalt-loaded organic using 0.1 M Na₂CO₃. Finally, the cobalt sulfate solution with a purity 99.99% was obtained from the cobalt-loaded organic by stripping with H₂SO_4.     

Enhanced electrochemical properties of LiFePO4 cathode for Li-ion batteries with amorphous NiP coating

Here we show that the intrinsic low electrical conductivity of LiFePO₄ which seriously hinders the application of LiFePO₄ for Li-ion batteries is overcome with conductive metallic NiP nano-coating. High resolution transmission electron microscopy image reveals that the NiP coating is a nanoscale amorphous layer, which was deposited on the LiFePO₄ particles to form a so-called core/shell structure via electroless plating at room temperature. The electrochemical performances of NiP coated LiFePO₄ show that both of the rate performance and cycleability of LiFePO₄ against graphite anode are improved by the NiP coating. Analysis of electrochemical impedance spectra of the LiFePO₄/graphite cells demonstrates that the NiP coating decreases both of the surface film resistance and charge transfer resistance. The dissolution of Fe from LiFePO₄ in the LiPF₆ based electrolyte is remarkably suppressed by the protective NiP coating.     

Physical and electrochemical properties of LiFePO4/C composite cathode prepared from various polymer-containing precursors

The goal of this research was to study the effect of various polymer-containing precursors on the performance of LiFePO₄/C composite. A coprecipitation method was applied to prepare a series of LiFePO₄/C materials by calcinating amorphous LiFePO₄ with various polymer compounds at 600 °C. The materials were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, particle size analysis, thermal analysis, BET specific surface area, Raman spectral analysis and electrochemical methods. The results showed that the structure of polymer precursors played an important role in improving the performance of LiFePO₄/C composites. The residual carbon produced by the pyrolysis of polymers with functionalized aromatic groups exhibited a better capacity in the LiFePO₄/C composites. A polyaromatic compound, e.g. polystyrene, with more functionalized aromatic groups displayed improved performance because its decomposition temperature was close to the temperature of the LiFePO₄ phase transformation, which resulted in fine particle size and uniform carbon distribution on the composite surface. According to Raman spectral analysis, polystyrene with more aromatic groups has a lower I_D/I_G and sp³/sp² peak ratio indicating more highly graphite-like carbon formation during polymer pyrolysis and exhibited a better capacity.     

Electrochemical properties of LiFe0.9Mn0.1PO4/Fe2P cathode material by mechanical alloying

LiFePO₄, olivine-type LiFe_0.9Mn_0.1PO₄/Fe₂P composite was synthesized by mechanical alloying of carbon (acetylene back), M₂O₃ (M = Fe, Mn) and LiOH·H₂O for 2 h followed by a short-time firing at 900 °C for only 30 min. By varying the carbon excess different amounts of Fe₂P second phase was achieved. The short firing time prevented grain growth, improving the high-rate charge/discharge capacity. The electrochemical performance was tested at various C/x-rate. The discharge capacity at 1C rate was increased up to 120 mAh g⁻¹ for the LiFe_0.9Mn_0.1PO₄/Fe₂P composite, while that of the unsubstituted LiFePO₄/Fe₂P and LiFePO₄ showed only 110 and 60 mAh g⁻¹, respectively. Electronic conductivity and ionic diffusion constant were measured. The LiFe_0.9Mn_0.1PO₄/Fe₂P composite showed higher conductivity and the highest diffusion coefficient (3.90 × 10⁻¹⁴ cm² s⁻¹). Thus the improvement of the electrochemical performance can be attributed to (1) higher electronic conductivity by the formation of conductive Fe₂P together with (2) an increase of Li⁺ ion mobility obtained by the substitution of Mn²⁺ for Fe²⁺.     

A new phosphate-based nonflammable electrolyte solvent for Li-ion batteries

A new fire-retardant—dimethyl(2-methoxyethoxy)methylphosphonate (DMMEMP) has been synthesized and evaluated as a high safe electrolyte solvent for lithium-ion batteries. This report summarizes the physical and electrochemical properties of the new compound. It is found that, this nonflammable phosphonate has a moderate viscosity, a high dielectric constant and a good thermal stability. It can provide a wide electrochemical stability window of 0–5.5 V (vs. Li⁺/Li), a high conductivity of 2.0 mS cm⁻¹ at 20 °C with 1 M LiTFSI. The electrochemical performance investigated with the Li/LiFePO₄ half-cells shows a good capacity of 148.1 mAh g⁻¹ and a coulombic efficiency close to 100% at the 10th cycle.     

Structure and performance of LiFePO4 cathode materials: A review

LiFePO₄ has been considered a promising battery material in electric vehicles. However, there are still a number of technical challenges to overcome before its wide-spread applications. In this article, the structure and electrochemical performance of LiFePO₄ are reviewed in light of the major technical requirements for EV batteries. The rate capability, capacity density, cyclic life and low-temperature performance of various LiFePO₄ materials are described. The major factors affecting these properties are discussed, which include particle size, doping, carbon coating, conductive carbon loading and synthesis techniques. Important future research for science and engineering is suggested.     

Improved electrolytes for Li-ion batteries: Mixtures of ionic liquid and organic electrolyte with enhanced safety and electrochemical performance

Physical and electrochemical characteristics of Li-ion battery systems based on LiFePO₄ cathodes and graphite anodes with mixture electrolytes were investigated. The mixed electrolytes are based on an ionic liquid (IL), and organic solvents used in commercial batteries. We investigated a range of compositions to determine an optimum conductivity and non-flammability of the mixed electrolyte. This led us to examine mixtures of ILs with the organic electrolyte usually employed in commercial Li-ion batteries, i.e., ethylene carbonate (EC) and diethylene carbonate (DEC). The IL electrolyte consisted of (trifluoromethyl sulfonylimide) (TFSI) as anion and 1-ethyl-3-methyleimidazolium (EMI) as the cation. The physical and electrochemical properties of some of these mixtures showed an improvement characteristics compared to the constituents alone. The safety was improved with electrolyte mixtures; when IL content in the mixture is ≥40%, no flammability is observed. A stable SEI layer was obtained on the MCMB graphite anode in these mixed electrolytes, which is not obtained with IL containing the TFSI-anion. The high-rate capability of LiFePO₄ is similar in the organic electrolyte and the mixture with a composition of 1:1. The interface resistance of the LiFePO₄ cathode is stabilized when the IL is added to the electrolyte. A reversible capacity of 155 mAh g⁻¹ at C/12 is obtained with cells having at least some organic electrolyte compared to only 124 mAh g⁻¹ with pure IL. With increasing discharge rate, the capacity is maintained close to that in the organic solvent up to 2 C rate. At higher rates, the results with mixture electrolytes start to deviate from the pure organic electrolyte cell. The evaluation of the Li-ion cells; LiFePO₄//Li₄Ti₅O₁₂ with organic and, 40% mixture electrolytes showed good 1st CE at 98.7 and 93.0%, respectively. The power performance of both cell configurations is comparable up to 2 C rate. This study indicates that safety and electrochemical performance of the Li-ion battery can be improved by using mixed IL and organic solvents.     

LiFePO4 water-soluble binder electrode for Li-ion batteries

A new water-soluble elastomer from ZEON Corp. was evaluated as binder with LiFePO₄ cathode material in Li-ion batteries. The mechanical characteristic of this cathode was compared to that with PVdF-based cathode binder. The elastomer-based cathode shows high flexibility with good adhesion. The electrochemical performance was also evaluated and compared to PVdF-based cathodes at 25 and at 60 °C. A lower irreversible capacity loss was obtained with the elastomer-based cathode, however, aging at 60 °C shows a comparable cycle life to that observed with PVdF-based cathodes. The LiFePO₄–WSB at high rate shows a good performance with 120 mAh g⁻¹ at 10C rate at 60 °C.     

A novel sol-gel synthesis route to NaVPO4F as cathode material for hybrid lithium ion batteries

Sodium vanadium fluorophosphate, NaVPO₄F, a cathode material for hybrid lithium ion batteries has been synthesized via a modified sol-gel method followed by heat treatment. The vanadium (Ш) gel precursor as the reaction intermediate phase can be facilely prepared in ethanol under ambient conditions, and this synthesis considerably simplifies the conventional high-temperature fabrication of VPO₄. X-ray diffraction (XRD) results indicate a phase transition of NaVPO₄F from the monoclinic crystal to the tetragonal symmetry structure. Meanwhile, the scanning electron microscope (SEM) images show the obvious spatial rearrangements on the morphology of samples. The hybrid lithium ion batteries based on the tetragonal NaVPO₄F exhibit an even discharge plateau at 3.6 V vs. Li in the limited voltage range of 3.0-4.2 V, and the discharge capacity retention is up to 98.7% after 100 cycles at C/4 rate. With voltage excursion to 3.0-4.5 V, the initial charge and discharge deliver the reversible storage capacity of 117.3 and 106.8 mAh g⁻¹, respectively. Furthermore, the prepared NaVPO₄F has a capacity retention of 83% after 100th cycle at 2 C rate. The electrochemical properties reveal the reversible mixed alkali ion (Li⁺, Na⁺) insertion reactions for this fluorophosphate material.     

Synthesis and characterization of Nd doped LiMn2O4 cathode for Li-ion rechargeable batteries

Spinel powders of LiMn_1.99Nd_0.01O₄ have been synthesized by chemical synthesis route to prepare cathodes for Li-ion coin cells. The structural and electrochemical properties of these cathodes were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, cyclic voltammetry, and charge-discharge studies. The cyclic voltammetry of the cathodes revealed the reversible nature of Li-ion intercalation and deintercalation in the electrochemical cell. The charge-discharge characteristics for LiMn_1.99Nd_0.01O₄ cathode materials were obtained in 3.4–4.3 V voltage range and the initial discharge capacity of this material were found to be about 149 mAh g⁻¹. The coin cells were tested for up to 25 charge-discharge cycles. The results show that by doping with small concentration of rare-earth element Nd, the capacity fading is considerably reduced as compared to the pure LiMn₂O₄ cathodes, making it suitable for Li-ion battery applications.     

Interfacial resistance of the LiFePO4-C/PEO-LiTFSI composite electrode for dry-polymer lithium-ion batteries

The interfacial resistance between the composite electrode and PEO-based solid polymer electrolyte was examined using two different symmetrical cells and AC impedance measurements in the temperature range of 30-60 °C. Of the four major resistance components identified in our previous study, three components due to the resistances of the polymer electrolyte and the charge transfer resistance between LiFePO₄-C and the electrolyte were assigned; however, one resistance component, in the medium frequency range has not yet been assigned. In this report, the medium frequency range resistance component was investigated using a symmetrical cell with composite electrodes composed of active and inactive materials (LiCoO₂, LiMn₂O₄ and SiO₂), solid polymer electrolyte, and carbon fiber as an electron conductor. The resistance was not affected by the carbon coating in LiFePO₄-C and the conductive carbon additive (VGCF). An electron blocking cell was also prepared and the resistance was measured in the temperature range of 30-60 °C to confirm the effect of the electrode thickness and the electrode composition. The resistance was not affected by the thickness, and decreased with decreasing PEO-LiTFSI electrolyte content in the composite electrode. However, no significant change in the activation energy was evident with the change in the electrode composition.     

A study on the electrochemical characteristics of LiFePO4 cathode for lithium polymer batteries by hydrothermal method

Phospho-olivine LiFePO₄ cathode materials were prepared by hydrothermal reaction at 150 °C. Carbon black was added to enhance the electrical conductivity of LiFePO₄. LiFePO₄-C powders (0, 3, 5 and 10 wt.%) were characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM). LiFePO₄-C/solid polymer electrolyte (SPE)/Li cells were characterized electrochemically by charge/discharge experiments at a constant current density of 0.1 mA cm⁻² in a range between 2.5 and 4.3 V vs. Li/Li⁺, cyclic voltammetry (CV) and ac impedance spectroscopy. The results showed that initial discharge capacity of LiFePO₄ was 104 mAh g⁻¹. The discharge capacity of LiFePO₄-C/SPE/Li cell with 5 wt.% carbon black was 128 mAh g⁻¹ at the first cycle and 127 mAh g⁻¹ after 30 cycles, respectively. It was demonstrated that cycling performance of LiFePO₄-C/SPE/Li cells was better than that of LiFePO₄/SPE/Li cells.     

Fabrication and electrochemical characteristics of electrospun LiFePO4/carbon composite fibers for lithium-ion batteries

LiFePO₄/C composite fibers were synthesized by using a combination of electrospinning and sol-gel techniques. Polyacrylonitrile (PAN) was used as an electrospinning media and a carbon source. LiFePO₄ precursor materials and PAN were dissolved in N,N-dimethylformamide separately and they were mixed before electrospinning. LiFePO₄ precursor/PAN fibers were heat treated, during which LiFePO₄ precursor transformed to energy-storage LiFePO₄ material and PAN was converted to carbon. The surface morphology and microstructure of the obtained LiFePO₄/C composite fibers were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and elemental dispersive spectroscopy (EDS). XRD measurements were also carried out in order to determine the structure of LiFePO₄/C composite fibers. Electrochemical performance of LiFePO₄/carbon composite fibers was evaluated in coin-type cells. Carbon content and heat treatment conditions (such as stabilization temperature, calcination/carbonization temperature, calcination/carbonization time, etc.) were optimized in terms of electrochemical performance.     

Improvement in the Ppy/V2O5 hybrid as a cathode material for Li ion batteries using PSA as an organic additive

With the aim of improving the electrochemical properties of this candidate cathodic material for lithium ion batteries, a vanadium oxide (V₂O₅) and polypyrrole (Ppy) hybrid was prepared using pyridinesulfonic acid (PSA) as additive. The hybrid synthesis has been carried out in the literature by chemical polymerization of pyrrole in the host inorganic matrix, using the V₂O₅ dispersed in an acidic solution as an oxidizing agent. In this work the hybrid has been synthesised with PSA giving good results compared to other samples of the pristine V₂O₅ and to the Ppy/V₂O₅ hybrid without additive. An improvement of about 20% in the charge storage capacity has been achieved. The reasons for this improvement are discussed and analyzed using different experimental techniques. The hybrid material has the added advantage of an improved performance without the addition of any binder or conducting element as a cathode in a lithium ion battery.     

Preparation and characterization of Na-doped LiFePO4/C composites as cathode materials for lithium-ion batteries

To improve the performance of LiFePO₄, single phase Li_1−xNa_xFePO₄/C (x = 0, 0.01, 0.03, 0.05) samples are synthesized by in situ polymerization restriction-carbonthermal reduction method. The effects of Na doping are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results indicate that doped Na ion does not destroy the lattice structure of LiFePO₄, while enlarges the lattice volume. Electrochemical test results show that the Li_0.97Na_0.03FePO₄/C sample exhibits the best electrochemical performance with initial special discharge capacity of 158 mAh g⁻¹ at 0.1 C. EIS results demonstrate that the charge transfer resistance of the sample decreases greatly by doping an appropriate amount of Na.     

Preparation of C-LiFePO4/polypyrrole lithium rechargeable cathode by consecutive potential steps electrodeposition

In this work carbon coated lithium iron phosphate (C-LiFePO₄)/polypyrrole (PPy) composite preparation has been carried out using electrochemical techniques. This composite has been deposited on a stainless steel mesh in order to use it as a cathode in a lithium-ion battery. When an oxidation potential is applied to the working electrode, the pyrrole monomer is polymerized and the C-LiFePO₄ particles are incorporated into the polymer matrix and bound to the polymer and mesh. An experimental procedure was performed in order to understand how the composite formation is carried out and what the oxidation state of the composite material is during the charge-discharge process. As the electrochemical method of synthesis has a big influence in the electrochemical properties of the polymer, the use of consecutive potential steps has been studied in order to improve the charge-storage capacity of the composite material. The influence on the final composite properties of the oxidation-deposition time and potential and the effect of the number of cycles has been analyzed. An improvement of about 20% has been achieved using short oxidation times (3 s) at 0.9 V vs. Ag/AgCl. The reasons for this improvement are discussed and analyzed using different experimental techniques.