Stable cycle-life properties of Ti-doped LiFePO4 compounds synthesized by co-precipitation and normal temperature reduction method

Submicron-sized LiFePO₄ and Ti-doped LiFePO₄ cathode materials were synthesized by a reformative co-precipitation and normal temperature reduction method, for which Ti ions were added in the process of preparing precursors to pursue a kind of sufficient and homogenous doping way. ICP and XRD analyses indicate that Ti ions were sufficiently doped in LiFePO₄ and did not alter its crystal structure. It is noted that higher Ti ions doping levels are conducive to electrochemical performance of LiFePO₄, especially on the aspect of stable cycle-life at higher C rates. The sample doped with 3 at% Ti shows the most impressive cycling performance, even after 100 cycles, discharge capacity of 133 mAh g⁻¹ was obtained (102.3% of its initial value) at 1C rate, and the discharge decreased little from 124 to 120 mAh g⁻¹ (96.8% of its initial value) at 2C rate.     

A novel method to synthesize LiVPO4F/C composite materials and its electrochemical Li-intercalation performances

Triclinic LiVPO₄F/C composite materials were prepared from a sucrose-containing precursor by one-step heat treatment. As-prepared composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurements. XRD studies showed that Li₃PO₄ impurity phase appeared in the sample synthesized at 600 °C and pure LiVPO₄F samples could be obtained when the sintered temperature was higher than 650 °C. The sample synthesized at 650 °C presents the highest initial discharge capacity of 132 mAh g⁻¹ at 0.2 C rate, and exhibited better cycling stability (124 mAh g⁻¹ at 50th cycle at 0.2 C rate) and better rate capability (100 mAh g⁻¹ at 50th cycle under 1 C rate) in the voltage range 3.0-4.4 V.     

The preparation and characterization of olivine LiFePO4/C doped with MoO3 by a solution method

Composite Li_0.99Mo_0.01FePO4/C cathode materials were prepared by an easy solution method followed by heat-treating at various temperatures. XRD, SEM, TGA/DTA, EA, CV, XPS and charge–discharge cycles were used to evaluate the Li_0.99Mo_0.01FePO₄/C composite powders. The results indicate that mix-doping method does not affect the olivine structure of the cathode but considerably improves its capacity delivery and cycle performance. Among the prepared cathode materials, the sample heat-treated at 700 °C for 12 h shows best electrochemical performances. It shows initial specific discharge capacities of 161 and 124 mAh g^− 1 with C rates of 0.2C and 2C, respectively, which is ascribed to the enhancement of the electronic conductivity by ion doping and carbon coating.     

Synthesis of spherical LiFePO4/C via Ni doping

Spherical LiFePO₄/C powders were synthesized by the conventional solid-state reaction method via Ni doping. Low-cost asphalt was used as both the reduction agent and the carbon source. An Ni-doped spherical LiFePO₄/C composite exhibited better electrochemical performances compared to an un-doped one. It presented an initial discharge capacity of 161 mAhg⁻¹ at 0.1 C rate (the theoretical capacity of LiFePO₄ with 5 wt% carbon is about 161 mAhg⁻¹). After 50 cycles at 0.5 C rate, its capacity remained 137 mAhg⁻¹ (100% of the initial capacity) compared to 115 mAhg⁻¹ (92% of the initial capacity) for an un-doped one. The electrochemical impedance spectroscopy analysis and cyclic voltammograms results revealed that Ni doping could decrease the resistance of LiFePO₄/C composite electrode drastically and improve its reversibility.     

A carbon–LiFePO<Subscript>4</Subscript> nanocomposite as high-performance cathode material for lithium-ion batteries

A cathode material of an electrically conducting carbon–LiFePO₄ nanocomposite is synthesized by wet ball milling and spray drying of precursor powders prior to a solid-state reaction. The structural characterization shows that the composite is composed of LiFePO₄ crystals and 4.8 wt.% amorphous carbon. Galvanostatic charge/discharge measurements indicate that the composite exhibits a superior high energy and high cycling stability. This composite delivers a discharge capacity of 159.1 mAh g⁻¹ at 0.1 C, 150.8 mAh g⁻¹ at 1 C, and 140.1 mAh g⁻¹ at 2 C rate. The capacity retention of 99% is achieved after 200 cycles at 2 C. The 18,650 cylindrical batteries are assembled using the composite as cathode materials and demonstrate the capacity of 1,400 mAh and the capacity retention of 97% after 100 cycles at 1 C. These results reveal that the as-prepared LiFePO₄–carbon composite is one of the promising cathode materials for high-performance, advanced lithium-ion batteries directed to the hybrid electric vehicle and pure electric vehicle markets.     

Organic acid assisted solid-state synthesis of Li1.2Ni0.16Co0.08Mn0.56O2 nanoparticles as lithium ion battery cathodes

Lithium-rich layered oxide Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ can be referred as a crystalline mixture of Li₂MnO₃ and LiNi_0.4Co_0.2Mn_0.4O₂ at equal molar ratio. In the paper, the solid state reaction of M(AC)₂·4H₂O (M = Mn, Co and Ni) and LiOH·H₂O has been performed to obtain nanocrystalline Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ using a small molecular organic acid (i.e., oxalic acid (OA), citric acid (CA) or tartaric acid (TA)) as additive. The introduction of organic acids can help to improve the layered structure and inhibit the particle growth of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂, and the different organic acids exert distinct influences on the structural and electrochemical properties of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂. In detail, the nanoparticles obtained in the presence of OA have the smallest average size of 50–150 nm, which correspondingly exhibit the highest initial discharge capacity of 267.52 mAh g⁻¹ at 0.1C and the best high-rate capability (e.g., 152.22 mAh g⁻¹, 5C) when applied as a lithium ion battery cathode. Furthermore, the active substance obtained from TA shows the best cycling stability and a discharge capacity of 202.42 mAh g⁻¹ can be retained after 50 cycles at 0.5C.     

Structural and electrochemical properties of LiFe1 − 3x/2Bi x PO4/C synthesized by sol–gel

In this study, LiFe_1???3x/2Bi _x PO₄/C cathode material was synthesized by sol–gel method. From XRD patterns, it was found that the Bi-doped LiFePO₄/C cathode material had the same olivine structure with LiFePO₄/C. SEM studies revealed that Bi doping can effectively decrease the particle sizes. It shortened Li⁺ diffusion distance between LiFePO₄ phase and FePO₄ phase. The LiFe_0.94Bi_0.04PO₄/C powder exhibited a specific initial discharge capacity of about 149.6 mAh g^?1 at 0.1 rate as compared to 123.5 mAh g^?1 of LiFePO₄/C. EIS results indicated that the charge-transfer resistance of LiFePO₄/C decreased greatly after Bi doping.     

Molten salt synthesis of Li1 + x (Ni0.5Mn0.5)1 − xO2 as cathode material for Li-ion batteries

Li_1 + x(Ni_0.5Mn_0.5)_1 − xO₂ cathode material for Li-ion batteries has been prepared by a molten salt method using Li₂CO₃ salt. The influences of synthetic temperature and time have been intensively investigated. It is easy to obtain materials with a hexagonal α-NaFeO₂ structure except broad peaks between 20° and 25°. Nickel in Li_1 + x(Ni_0.5Mn_0.5)_1 − xO₂ is oxidized to a trivalent state while manganese maintained a tetravalent state. It is found that the discharge capacities of all samples increase with cycling. The sample prepared at 850 °C for 5 h has a discharge capacity of 130 mAh g^− 1 between 2.5 and 4.5 V versus V_Li+/Li at a specific current of 0.13 mA cm^− 2 after 50 cycles at 25 °C.     

Facile synthesis of Nb2O5 nanorod array films and their electrochemical properties

Nb₂O₅ nanorod array films were synthesized by a facile hydrothermal process using niobium metal foil and NH₄F as precursors. The Nb₂O₅ nanorods stand on the niobium metal foil substrate and are less than 100 nm in diameter and about 1 μm in length. X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) characterizations indicate that these nanorods have orthorhombic structure and grew longitudinally along 〈0 0 1〉 direction. The nanorod growth mechanism was discussed. Thermal annealing at a temperature below 500 °C did not change the microstructure of nanorods but improve the crystallinity. The Nb₂O₅ nanorod array films have been tested as cathode material for lithium battery, which showed a good specific capacity up to 380 mAh g⁻¹ even after 50 charge/discharge cycles.     

Effects of nano-carbon webs on the electrochemical properties in LiFePO4/C composite

LiFePO₄/C composite is one of ways to surmount the lower electrical conductivity of LiFePO₄. In this paper, we suggest a new type of LiFePO₄/C composite in which amorphous nano-carbon webs are wrapping and connecting LiFePO₄ particles. This type of composite was obtained by adapting a new liquid-based powder preparation method, that is, all raw materials (LiFePO₄ and carbon precursor materials) were dissolved in liquid and solidified. This composite was very effective in enhancing the electrochemical properties such as capacity and rate capability. Even as high as at 400 m Ag⁻¹ current density, a capacity of about 105 m Ahg⁻¹ was obtained at 25 °C.     

A lithium ion battery using nanostructured Sn-C anode, LiFePO4 cathode and polyethylene oxide-based electrolyte

In this work we report a lithium ion battery based on a nanostructured Sn-C anode, an improved lithium iron phosphate, LiFePO₄, cathode and a polyethylene oxide-based electrolyte. The battery has a solid-like configuration, high safety and can operate at room temperature with a stable capacity of the order of 120 mAh g^− 1 at a voltage of 2.8 V. These properties candidate the battery as very appealing energy accumulation system suitable for environmentally friendly, safe, applications.     

Synthesis and electrochemical properties of nanostructured Li2FeSiO4/C cathode material for Li-ion batteries

Nanostructured Li₂FeSiO₄/C was synthesized by high-energy ball-milling and the amorphous citrate-assisted techniques. Similar redox behaviour is observed for samples prepared by the amorphous citrate-assisted route followed by a 4 h heat treatment: 0.3 V polarization and more sloping behaviour was observed when cycling between 2.0 V and 3.7 V at 60 °C; lower capacity fade is also observed compared to Li₂FeSiO₄/C prepared by the solid-state reaction technique. A discharge capacity of 102 mA h g^− 1 is obtained for samples prepared by the high-energy ball-milling method, while capacities decrease from 95 to 77 mA h g^− 1 using the amorphous citrate method for heat-treatment times increasing successively from 4 h to 18 h.     

LiFePO<Subscript>4</Subscript>/C with high capacity synthesized by carbothermal reduction method

The olivine-type LiFePO₄/C cathode materials were prepared via carbothermal reduction method using cheap Fe₂O₃ as raw material and different contents of glucose as the reducing agent and carbon source. Their structural and morphological properties were investigated by X-ray diffraction, scanning electron microscope, transmission electron microscope, and particle size distribution analysis. The results demonstrated that when the content of the carbon precursor of glucose was 16 wt.%, the synthesized powder had good crystalline and exhibited homogeneous and narrow particle size distribution. Even and thin coating carbon film was formed on the surface of LiFePO₄ particles during the pyrolysis of glucose, resulting in the enhancement of the electronic conductivity. Electrochemical tests showed that the discharge capacity first increased and then decreased with the increase of glucose content. The optimal sample synthesized using 16 wt.% glucose as carbon source exhibited the highest discharge capacity of 142 mAh g⁻¹ at 0.1C rate with the capacity retention rate of 90.4% and 118 mAh g⁻¹ at 0.5C rate.     

Electrochemical performance of Mo-doped LiFePO4/C composites prepared by two-step solid-state reaction

To improve the performance of LiFePO₄, LiFe_1?x Mo _x PO₄/C (x?=?0, 0.005, 0.010, 0.015, 0.020, 0.025) cathode materials were synthesized via two-step ball milling solid-state reaction. The prepared samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectra, and galvanostatic charge–discharge test. It is apparent from XRD analysis that Mo doping enlarges the interplanar distance of crystal plane parallel to [010] direction in LiFePO₄. In other words, it widens one-dimensional diffusion channels of Li⁺ along the [010] direction. The results of electrochemical test indicate that the LiFe_0.99Mo_0.01PO₄/C composite exhibits a discharge capacity of 144.8 mAh g^?1 at 1 C rate, a decreased charge transfer resistance of 162.4 Ω and better reversibility of electrode reactions. The present synthesis route is promising and practical for the preparation of LiFePO₄ materials.     

Study of a novel porous gel polymer electrolyte based on TPU/PVdF by electrospinning technique

Investigation on a new electrospun gel polymer electrolyte consisting of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride) (PVdF) has been made. Its characteristics were investigated by scanning electron microscopy, FT-IR, Differential Scanning Calorimeter (DSC) analysis. This kind of gel polymer electrolyte had a high ionic conductivity about 3.2 × 10^− 3 S cm^− 1 at room temperature, and exhibited a high electrochemical stability up to 5.0 V versus Li⁺/Li, good mechanical strength and stability to allow safe operation in rechargeable lithium-ion polymer batteries. A Li/GPE/LiFePO₄ cell delivered a high discharge capacity when it was evaluated at 0.1 °C—rate at 25 °C (167.8 mAh g^− 1). And a very stable cycle performance also existed under this low current density.     

Effect of Nd concentration on structural and optical properties of Nd:Y2O3 transparent ceramic

Y₂O₃ transparent ceramics with different Nd concentration (0.1-7.0at%) were fabricated using ZrO₂ as additive. All the samples exhibit high transparency over a broad spectral region. The elements (Y, O and Nd) are uniformly distributed in the ceramic body, and the average grain size increases with Nd content. Based on the absorption spectrum, the Judd-Ofelt intensity parameters are calculated (Ω₂=4.364×10⁻²⁰ cm², Ω₄=3.609×10⁻²⁰ cm² and Ω₆=2.919×10⁻²⁰ cm²). The absorption coefficients increase linearly with Nd³⁺ doping concentration. The absorption cross-section at 804 nm and stimulated emission cross-section at 1078 nm are calculated to be 1.54×10⁻²⁰ and 7.24×10⁻²⁰ cm², respectively. All the emission bands exhibit the highest emission intensities with 1.0at% Nd³⁺ ion content, while the lifetime decreases dramatically from 321.5 μs (0.1at% Nd) to 17.9 μs (7.0at% Nd). According to the emission spectra and measured lifetime, the optimum doping concentration of Nd³⁺ ion in Y₂O₃ transparent ceramic might be around 1.0at%.     

Electrochemical performance of LiFePO4/C synthesized by solid state reaction using different lithium and iron sources

LiFePO₄/C cathode materials were prepared from different lithium and iron sources, using glucose as the carbon source and the reducing agent, via a solid state reaction. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), galvanostatic charge-discharge test and cyclic voltammetry (CV). The results showed that the LiFePO₄/C is olivine-type phase, and composed of relatively large particles of about 400 nm and some nano-sized particles, which favor the electronic conductivity. The LiFePO₄/C cathode material synthesized from Li₂CO₃ and Fe₂O₃ had the smallest particles and the highest uniformity. It delivered the capacity of 145.8 mA h/g at 0.2 C, and had good reversibility and high capacity retention. The precursor of LiFePO₄/C was characterized by thermogravimetry (TG) to discuss the crystallization formation mechanism of LiFePO₄.     

Electrochemical properties of α-Fe2O3 /MWCNTs as anode materials for lithium-ion batteries

α-Fe₂O₃/MWCNTs composites were prepared by a simple hydrothermal process. The crystalline structure and the electrochemical performance of the as-synthesized samples were investigated. Results show that as anode materials for lithium-ion batteries, the α-Fe₂O₃/MWCNTs exhibit an initial discharge capacity of 1256 ± 5 mAh g⁻¹ and a stable specific discharge capacity of 430 ± 5 mAh g⁻¹ at ambient temperature, for up to 100 cycles with no noticeable capacity fading, while the initial discharge capacity of the bare Fe₂O₃ is 992.3 mAh g⁻¹, and the discharge capacity is 146.6 mAh g⁻¹ after 100 cycles. Moreover, the α-Fe₂O₃/MWCNTs composites also exhibit excellent rate performance.     

A PEG-assisted rheological phase reaction synthesis of 5LiFePO<Subscript>4</Subscript>⋅Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C as cathode material for lithium ion cells

5LiFePO₄⋅Li₃V₂(PO₄)₃/C composite cathode material is synthesized by a polyethylene glycol (PEG)-assisted rheological phase method. As a surfactant and dispersing agent, PEG can effectively inhabit the aggregation of colloidal particles during the formation of the gel. Meanwhile, PEG will coat on the particles to play the role of carbon source during the sintering. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy, and electrochemical methods. XRD results indicate that the 5LiFePO₄⋅Li₃V₂(PO₄)₃/C composites are well crystallized and contain olivine-type LiFePO₄ and monoclinic Li₃V₂(PO₄)₃ phases. The composite synthesized at 650 °C exhibits the initial discharge capacities of 134.8 and 129.9 mAh g⁻¹ and the capacity retentions of 96.2 and 97.1 % after 50 cycles at 1C and 2C rates, respectively.     

One-step synthesis and electrochemical behavior of LiMnO2 and its composite from MnO2 in the presence of glucose

LiMnO₂ and 0.23Li₂MnO₃·0.77LiMnO₂ were prepared by a convenient one-step solid-state reaction from MnO₂ using glucose as organic carbon resource. The crystal structure and morphology of the as-prepared materials was examined by X-ray powder diffraction and field emission scanning electron microscopy, respectively. The ration of Li to Mn was determined by means of atomic absorption spectrometry and the Li/Mn molar ratio in the products was 1.23. The electrochemical properties were investigated by charge-discharge test and electrochemical impedance measurements. The prepared composite material presented an initial discharge capacity of 45 mAh g^-1 and a good cycling performance with reversible capacity of 218 mAh g^-1 after 30 cycles. On the basis of the experimental results, the discharge efficiency of this composite material more than 100% was also discussed.