Synthesis of LiFePO4/C cathode material from ferric oxide and organic lithium salts

LiFePO₄/C cathode material has been simply synthesized via a modified in situ solid-state reaction route using the raw materials of Fe₂O₃, NH₄H₂PO₄, Li₂C₂O₄ and lithium polyacrylate (PAALi). The sintering temperature of LiFePO₄/C precursor is studied by thermo-gravimetric (TG)/differential thermal analysis (DTA). The physical properties of LiFePO₄/C are then investigated through analysis using by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and the electrochemical properties are investigated by electrochemical impedance spectra (EIS), cyclic voltammogram (CV) and constant current charge/discharge test. The LiFePO₄/C composite with the particle size of ∼200 nm shows better discharge capacity (156.4 mAh g⁻¹) than bare LiFePO₄ (52.3 mAh g⁻¹) at 0.2 C due to the improved electronic conductivity which is demonstrated by EIS. The as-prepared LiFePO₄/C through this method also shows excellent high-rate characteristic and cycle performance. The initial discharge capacity of the sample is 120.5 mAh g⁻¹ and the capacity retention rate is 100.6% after 50 cycles at 5 C rate. The results prove that the using of organic lithium salts can obtain a high performance LiFePO₄/C composite.     

Synthesis and characterization of high-density LiFePO4/C composites as cathode materials for lithium-ion batteries

To achieve a high-energy-density lithium electrode, high-density LiFePO₄/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO₄ as a precursor, glucose as a C source, and Li₂CO₃ as a Li source, in a pipe furnace under an atmosphere of 5% H₂-95% N₂. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO₄/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO₄/carbon composite powder with a carbon content of 7% reached 1.80 g m⁻³. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g⁻¹, respectively, with a volume capacity of 300.6 mAh cm⁻³, at a 0.1C rate. At a rate of 5C, the LiFePO₄/carbon composite shows a high discharge capacity of 98.3 mAh g⁻¹ and a volume capacity of 176.94 mAh cm⁻³.     

Preparation and electrochemical properties of a LiFePO4/C composite cathode material by a polymer-pyrolysis–reduction method

A LiFePO₄/C composite was successfully prepared by a polymer-pyrolysis–reduction method, using FePO₄·2H₂O and lithium polyacrylate (PAALi) as raw materials. The structure of the LiFePO₄/C composites was investigated by X-ray diffraction (XRD). The micromorphology of the precursor and LiFePO₄/C powders was observed using scanning electron microscopy (SEM), and the in situ coating of carbon on the particles was observed by transmission electron microscopy (TEM). Furthermore, the electrochemical properties were evaluated by cyclic voltammograms (CVs), electrochemical impedance spectra (EIS) and constant current charge/discharge cycling tests. The results showed that the sample synthesized at 700 °C had the best electrochemical performance, exhibiting initial discharge capacities of 157, 139 and 109 mAh g⁻¹ at rates of 0.1, 1 and 5 C, respectively. Moreover, the sample presented excellent capacity retention as there was no significant capacity fade after 50 cycles.     

Enhanced rate performance of nano–micro structured LiFePO4/C by improved process for high-power Li-ion batteries

A spherical carbon-coated nano–micro structured LiFePO₄ composite is synthesized for use as a cathode material in high-power lithium-ion batteries. The composites are synthesized through carbothermal reduction with two sessions of ball milling (before and after pre-sintering of precursor) followed by spray-drying with the dispersant of polyethylene glycol added. The structure, particle size, and surface morphology of the cathode active material and the properties of the coated carbon are investigated by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. Results indicate that the LiFePO₄/C composite has a spherical micro-porous morphology composed of a large number of carbon-coated nano-spheres linked together with an ordered olivine structure. The carbon on the surface of LiFePO₄ effectively reduces inter-particle agglomeration of the LiFePO₄ particles. A galvanostatic charge–discharge test indicates that the LiFePO₄/C composites exhibit initial discharge capacities of 155 mAh g⁻¹ and 88 mAh g⁻¹ at 0.2 C and 20 C rates with the end of discharge voltage of 2.5 V, respectively. This behavior is ascribed to the unique spherical structure, which shortens lithium ions diffusion length and improves the electric contact between LiFePO₄ particles.     

Enhanced rate performance of carbon-coated LiNi0.5Mn1.5O4 cathode material for lithium ion batteries

Conductive carbon has been coated on the surface of LiNi_0.5Mn_1.5O₄ cathode material by the carbonization of sucrose for the purpose of improving the rate performance. The effect of carbon coating on the physical and electrochemical properties is discussed through the characterizations of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), cycling and rate tests. Results demonstrate that the carbon coating can greatly enhance the discharge capacity, rate capability and cycling stability of the LiNi_0.5Mn_1.5O₄ without degrading the spinel structure. The sample modified with 1 wt.% sucrose displays the best performance. A large capacity of 130 mAh g⁻¹ at 1 C discharge rate with a high retention of 92% after 100 cycles and a stable 114 mAh g⁻¹ at 5 C discharge rate can be delivered. The remarkably improved rate properties of the carbon-coated samples are due to the suppression of the solid electrolyte interfacial (SEI) layer development and faster kinetics of both the Li⁺ diffusion and the charge transfer reaction.     

Effect of carbon coating on low temperature electrochemical performance of LiFePO4/C by using polystyrene sphere as carbon source

Carbon perfectly coated LiFePO₄ cathode materials are synthesized by carbon-thermal reduction method using polystyrene (PS) spheres as carbon source. The PS spheres with diameters of 150–300 nm used for the pyrolysis reaction not only inhibit the particle growth but also lead to uniform distribution of carbon coating on the surface of LiFePO₄ particles. Rate capability and cycling stability of LiFePO₄/C with the carbon contents ranging from 1.4 wt% to 3.7 wt% are investigated at −20 °C. The LiFePO₄/C with 3.0 wt% C exhibits excellent electrochemical capability at low temperature, which delivers 147 mAh g⁻¹ at 0.1 C. After 100 cycles at a charge–discharge rate of 1 C, there is still 100% of initial capacity retained for the LiFePO₄/C electrode at −20 °C. According to the transmission electron microscope analysis and cyclic voltammetry measurement, this can be attributed to the good carbon coating morphology and optimal carbon coating thickness.     

In situ construction of carbon nano-interconnects between the LiFePO4 grains using ultra low-cost asphalt

LiFePO₄/C composite cathode materials with carbon nano-interconnect structures were synthesized by one-step solid state reaction using low-cost asphalt as both carbon source and reducing agent. Based on the thermogravimetry, differential scanning calorimetry, transmission electron microscopy and high-resolution transmission electron microscopy, a growth model was proposed to illustrate the formation of the carbon nano-interconnect between the LiFePO₄ grains. The LiFePO₄/C composite shows enhanced discharge capacity (150 mAh g⁻¹) with excellent capacity retention compared with the bare LiFePO₄ (41 mAh g⁻¹) due to the electronically conductive nanoscale networking provided by the asphalt-based carbon. The results prove that the asphalt is a perfect carbon source and reduction agent for cost-effective production of high performance LiFePO₄/C composite.     

Synthesis of spindle-shaped nanoporous C–LiFePO4 composite and its application as a cathodes material in lithium ion batteries

In this work, LiFePO₄/C composites were prepared in hydrothermal system by using iron gluconate as iron source, and two feeding sequences during the preparation were comparatively studied. The morphology, crystal structure and charge–discharge performance of the prepared samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and galvanostatic charge–discharge testing. The results showed that the feeding sequences and iron gluconate seriously affected the microstructures and electrochemical properties of the resulting LiFePO₄ cathodes in lithium ion batteries. The spindle-shaped LiFePO₄ with hierarchical microporous structure self-assembled by nanoparticles has been successfully synthesized by synthesis route B. In addition, the cell performance of the synthesized LiFePO₄ by synthesis route B was better than that of LiFePO₄ by synthesis route A. Specially at high rates, the superior rate performance of the spindle-shaped LiFePO₄/C microstructure (LFP/C-B) was revealed. And special reversible capacities of ∼118 and ∼95 mAh g⁻¹ were obtained at rates of 2 C and 5 C, comparing to ∼96 and ∼68 mAh g⁻¹ for LFP/C-A.     

Enhanced electrochemical properties of LiFePO4/C synthesized with two kinds of carbon sources,PEG-4000 (organic) and Super p (inorganic)

Olivine structured LiFePO₄/C cathode was synthesized via a freeze-drying route and followed by microwave heating with two kinds of carbon sources: PEG-4000 (organic) and Super p (inorganic). XRD patterns indicate that the as-prepared sample has an olivine structure and carbon modification does not affect the structure of the sample. Image of SEM shows a uniform and optimized particles size, which greatly improves the electrochemical properties. TEM result reveals the amorphous carbon around the surface of the particles. At a low rate of 0.1 C, the LiFePO₄/C sample presents a high discharge capacity of 157.8 mAh g⁻¹ which is near the theoretical capacity (170 mAh g⁻¹), and it still attains to 149.1 mAh g⁻¹ after 200 cycles. It also exhibits an excellent rate capacity with high discharge capacities of 143.2 mAh g⁻¹, 137.5 mAh g⁻¹, 123.7 mAh g⁻¹ and 101.6 mAh g⁻¹ at 0.5 C, 1.0 C, 2.0 C and 5.0 C, respectively. EIS results indicate that the charge transfer resistance of LiFePO₄ decreases greatly after carbon coating.     

Effects of neodymium aliovalent substitution on the structure and electrochemical performance of LiFePO4

LiFe_1−xNd_xPO₄/C (x = 0-0.08) cathode material was synthesized using a solid-state reaction. The synthesis conditions were optimized by thermal analysis of the precursor and magnetic properties of LiFePO₄/C. The structure and electrochemical performances of the material were studied using XRD, FE-SEM, EDS, electrochemical impedance spectroscopy and galvanostatic charge-discharge. The results show that a small amount of aliovalent Nd³⁺ ion-dopant substitution on Fe²⁺ ions can effectively reduce the particle size of LiFePO₄/C. Cell parameters of LiFe_1−xNd_xPO₄ (x = 0.04-0.08) were calculated, and the results showed that LiFe_1−xNd_xPO₄/C had the same olivine structure as LiFePO₄. LiFe_0.4Nd_0.6PO₄/C delivers the discharge capacity of 165.2 mAh g⁻¹ at rate of 0.2 C and the capacity retention rate is 92.8% after 100 cycles. Charge-transfer resistance decreases with the addition of glucose and Nd³⁺ ions. Poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) was synthesized and PZS nanorods were used as a carbon source to coat LiFePO₄. All of the results show that aliovalent doping substitution of Fe in LiFePO₄ is well tolerated.     

Properties of Li-graphite and LiFePO4 electrodes in LiPF6–sulfolane electrolyte

Sulfolane (also referred to as tetramethylene sulfone, TMS) containing LiPF₆ and vinylene carbonate (VC) was tested as a non-flammable electrolyte for a graphite |LiFePO₄ lithium-ion battery. Charging/discharging capacity of the LiFePO₄ electrode was ca. 150 mAh g⁻¹ (VC content 5 wt%). The capacity of the graphite electrode after 10 cycles establishes at the level of ca. 350 mAh g⁻¹ (C/10 rate). In the case of the full graphite |1 M LiPF₆ + TMS + VC 10 wt% |LiFePO₄ cell, both charging and discharging capacity (referred to cathode mass) stabilized at a value of ca. 120 mAh g⁻¹. Exchange current density for Li⁺ reduction on metallic lithium, estimated from electrochemical impedance spectroscopy (EIS) experiments, was j_o(Li/Li⁺) = 8.15 × 10⁻⁴ A cm⁻². Moreover, EIS suggests formation of the solid electrolyte interface (SEI) on lithium, lithiated graphite and LiFePO₄ electrodes, protecting them from further corrosion in contact with the liquid electrolyte. Scanning electron microscopy (SEM) images of pristine electrodes and those taken after electrochemical cycling showed changes which may be interpreted as a result of SEI formation. No graphite exfoliation was observed. The main decomposition peak of the LiPF₆ + TMS + VC electrolyte (TG/DTA experiment) was present at ca. 275 °C. The LiFePO₄(solid) + 1 M LiPF₆ + TMS + 10 wt% VC system shows a flash point of ca. 150 °C. This was much higher in comparison to that characteristic of a classical LiFePO₄ (solid) + 1 M LiPF₆ + 50 wt% EC + 50 wt% DMC system (T_f ≈ 37 °C).     

LiFePO4 cathode power with high energy density synthesized by water quenching treatment

A water quenching (WQ) method was developed to synthesize LiFePO₄ and C-LiFePO₄. Our results indicate that this synthesis method ensures improved electrochemical activity and small crystal grain size. The synthetic conditions were optimized using orthogonal experiments. The LiFePO₄ sample prepared at the optimized condition showed a maximum discharge capacity of 149.8 mAh g⁻¹ at a C/10 rate. C-LiFePO₄ with a low carbon content of 0.93% and a high discharge specific capacity of 163.8 mAh g⁻¹ has also been obtained using this method. Water quenching treatment shows outstanding improvement of the electrochemical performance of LiFePO₄.     

1-Alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids as highly safe electrolyte for Li/LiFePO4 battery

Several 1-alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids (alkyl-DMimTFSI) were prepared by changing carbon chain lengths and configuration of the alkyl group, and their electrochemical properties and compatibility with Li/LiFePO₄ battery electrodes were investigated in detail. Experiments indicated the type of ionic liquid has a wide electrochemical window (−0.16 to 5.2 V vs. Li⁺/Li) and are theoretically feasible as an electrolyte for batteries with metallic lithium as anode. Addition of vinylene carbonate (VC) improves the compatibility of alkyl-DMimTFSI-based electrolytes towards lithium anode and LiFePO₄ cathode, and enhanced the formation of solid electrolyte interface to protect lithium anodes from corrosion. The electrochemical properties of the ionic liquids obviously depend on carbon chain length and configuration of the alkyl, including ionic conductivity, viscosity, and charge/discharge capacity etc. Among five alkyl-DMimTFSI-LiTFSI-VC electrolytes, Li/LiFePO₄ battery with the electrolyte-based on amyl-DMimTFSI shows best charge/discharge capacity and reversibility due to relatively high conductivity and low viscosity, its initial discharge capacity is about 152.6 mAh g⁻¹, which the value is near to theoretical specific capacity (170 mAh g⁻¹). Although the battery with electrolyte-based isooctyl-DMimTFSI has lowest initial discharge capacity (8.1 mAh g⁻¹) due to relatively poor conductivity and high viscosity, the value will be dramatically added to 129.6 mAh g⁻¹ when 10% propylene carbonate was introduced into the ternary electrolyte as diluent. These results clearly indicates this type of ionic liquids have fine application prospect for lithium batteries as highly safety electrolytes in the future.     

Emulsion drying synthesis of olivine LiFePO4/C composite and its electrochemical properties as lithium intercalation material

The electroactive LiFePO₄/C nano-composite has been synthesized by an emulsion drying method. During burning-out the oily emulsion precipitates in an air-limited atmosphere at 300 °C, amorphous or low crystalline carbon was generated along with releasing carbon oxide gases, and trivalent iron as a cheap starting material was immediately reduced to the divalent one at this stage as confirmed by X-ray photoelectron spectroscopy, leading to a low crystalline LiFePO₄/C composite. Heat-treatment of the low crystalline LiFePO₄/C in an Ar atmosphere resulted in a well-ordered olivine structure, as refined by Rietveld refinement of the X-ray diffraction pattern. From secondary electron microscopic and scanning transmission electron microscopic observations with the corresponding elemental mapping images of iron and phosphorous, it was found that the LiFePO₄ powders are modified by fine carbon. The in situ formation of the nano-sized carbon during crystallization of LiFePO₄ brought about two advantages: (i) an optimized particle size of LiFePO₄, and (ii) a uniform distribution of fine carbon in the product. These effects of the fine carbon on LiFePO₄/C composite led to high capacity retention upon cycling at 25 and 50 °C and high rate capability, resulting from a great enhancement of electric conductivity as high as 10⁻⁴ S cm⁻¹. That is, the obtained capacity was higher than 90 mAh (g-phosphate)⁻¹ by applying a higher current density of about 1000 mA g⁻¹ (11 C) at 50 °C.     

Preparation and characterization of nano-particle LiFePO4 and LiFePO4/C by spray-drying and post-annealing method

Pure, nano-sized LiFePO₄ and LiFePO₄/C cathode materials are synthesized by spray-drying and post-annealing method. The influence of the sintering temperature and carbon coating on the structure, particle size, morphology and electrochemical performance of LiFePO₄ cathode material is investigated. The optimum processing conditions are found to be thermal treatment for 10 h at 600 °C. Compared with LiFePO₄, LiFePO₄/C particles are smaller in size due to the inhibition of crystal growth to a great extent by the presence of carbon in the reaction mixture. And that the LiFePO₄/C composite coated with 3.81 wt.% carbon exhibits the best electrode properties with discharge capacities of 139.4, 137.2, 133.5 and 127.3 mAh g⁻¹ at C/5, 1C, 5C and 10C rates, respectively. In addition, it shows excellent cycle stability at different current densities. Even after 50 cycles at the high current density of 10C, a discharge capacity of 117.7 mAh g⁻¹ is obtained (92.4% of its initial value) with only a low capacity fading of 0.15% per cycle.     

Effects of Na and Cl co-doping on electrochemical performance in LiFePO4/C

Na⁺ and Cl⁻ co-doped LiFePO₄/C composites were prepared via a simple solid state reaction. The structure, valence state and electrochemical performance were carefully investigated. Rietveld refinement on X-ray diffractions reveals that Na⁺ and Cl⁻ have successfully been introduced into the lattice of LiFePO₄. X-ray photoelectron spectroscopy proves that the co-doping of Na⁺ and Cl⁻ does not change the chemical state of Fe(II). Experimental results further show that the co-doping contributes to induce the lattice distortion, modify the particle morphology, and increase the electronic conductivity. Considerably enhanced capacity, coulombic efficiency and rate capability were obtained in the co-doped LiFePO₄. The specific capacities are 157 mAh g⁻¹ at 0.2 C, 115 mAh g⁻¹ at 10 C and 98 mAh g⁻¹ at 20 C for the (Na⁺, Cl⁻) co-doped LiFePO₄/C cathode material. The improvement can be ascribed to the enhanced electronic conductivity and electrode kinetics due to the micro-structural modification promoted by co-doping.     

Rheological phase reaction synthesis and electrochemical performance of Li3V2(PO4)3/carbon cathode for lithium ion batteries

Monoclinic lithium vanadium phosphate/carbon (Li₃V₂(PO₄)₃/C) cathode has been synthesized for applications in lithium ion batteries, via a rheological phase reaction (RPR) method. The sample is characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). This material exhibits high initial discharge capacity of 189 and 177 mAh g⁻¹ at 0.1 and 0.2 C between 3.0 and 4.8 V, respectively. Moreover, it displays good fast rate performance, which discharge capacities of 140, 133, 129 and 124 mAh g⁻¹ can be delivered after 100 cycles between 3.0 and 4.8 V vs. Li at a different rate of 0.5, 1, 2 and 5 C, respectively. The electrochemical impedance spectroscopy (EIS) is also investigated.     

One-step microwave synthesis and characterization of carbon-modified nanocrystalline LiFePO4

The precursors of LiFePO₄ were prepared by a sol-gel method using lithium acetate dihydrate, ferrous sulfate, phosphoric acid, citric acid and polyethylene glycol as raw materials, and then the carbon-modified nanocrystalline LiFePO₄ (LiFePO₄/C) cathode material was synthesized by a one-step microwave method with the domestic microwave oven. The effect of microwave time and carbon content on the performance of the resulting LiFePO₄/C material was investigated. Structural characterization by X-ray diffraction and scanning electron microscopy proved that the olivine phase LiFePO₄ was synthesized and the grain size of the samples was several hundred nanometers. Under the optimal conditions of microwave time and carbon content, the charge-discharge performance indicated that the nanosized LiFePO₄/C had a high electrochemical capacity at 0.2 C (152 mAh g⁻¹) and improved capacity retention; the exchange current density was 1.6977 mA cm⁻². Furthermore, the rate capability was improved effectively after LiFePO₄ was modified with carbon, with 59 mAh g⁻¹ being obtained at 20 C.     

Hydrothermal synthesis of carbon-coated lithium vanadium phosphate

A novel hydrothermal synthesis was developed to prepare carbon-coated lithium vanadium phosphate (Li₃V₂(PO₄)₃) powders to be used as cathode material for Li-ion batteries. The structural, morphological and electrochemical properties were investigated by means of X-ray powder diffraction (XRD), thermogravimetry (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and constant current charge-discharge cycling. This material exhibits high initial discharge capacity of 178, 173 and 172 mAh g⁻¹ at 0.1, 0.2 and 0.5 C between 3.0 and 4.8 V, respectively. Moreover, it displays good fast rate performance, which discharge capacities of 136, 132 and 127 mAh g⁻¹ can be delivered after 100 cycles between 3.0 and 4.8 V versus Li at a different rate of 1, 2 and 5 C, respectively. For comparison, the electrochemical properties of carbon-coated lithium vanadium phosphate prepared by traditional solid-state reaction (SSR) method are also studied.     

An optimized Ni doped LiFePO4/C nanocomposite with excellent rate performance

Both Ni doping and carbon coating are adopted to synthesize a nano-sized LiFePO₄ cathode material through a simple solid-state reaction. It is found that the Ni²⁺ has been successfully doped into LiFePO₄ without affecting the phospho-olivine structure from the XRD result. The images of SEM and TEM show that the size of particles is distributed in the range of 20-60 nm, and all the particles are coated with carbon completely. The results of XPS show the valence state of Fe and Ni in the LiFePO₄. The electronic conductivity of the material is as high as 2.1 × 10⁻¹ S cm⁻¹, which should be ascribed to the coefficient of the conductive carbon network and Ni doping. As a cathode material for lithium-ion batteries, the Ni doped LiFePO₄/C nanocomposite delivers a discharge capacity of 170 mAh g⁻¹ at 0.2 C, approaching the theoretical value. Moreover, the material shows excellent high-rate charge and discharge capability and long-term cyclability. At the high rates of 10 and 15 C, this material exhibits high capacities of 150 and 130 mAh g⁻¹, retaining 95% after 5500 cycles and 93% after 7200 cycles, respectively. Therefore, the as-prepared material is capable of such large-scale applications as electric vehicles and plug-in hybrid electric vehicles.