Li<Subscript>0.99</Subscript>Ti<Subscript>0.01</Subscript>FePO<Subscript>4</Subscript>/C composite as cathode material for lithium ion battery

Three kinds of LiFePO₄ materials, mixed with carbon (as LiFePO₄/C), doped with Ti (as Li_0.99Ti_0.01FePO₄), and treated both ways (as Li_0.99Ti_0.01FePO₄/C composite), were synthesized via ball milling by solid-state reaction method. The crystal structure and electrochemical behavior of the materials were investigated using X-ray diffraction, SEM, TEM, cyclic voltammetry, and charge/discharge cycle measurements. It was found that the electrochemical behavior of LiFePO₄ could be increased by carbon coating and Ti-doping methods. Among the materials, Li_0.99Ti_0.01FePO₄/C composite presents the best electrochemical behavior, with an initial discharge capacity of 154.5 mAh/g at a discharge rate of 0.2 C, and long charge/discharge cycle life. After 120 cycles, its capacity remains at 92% of the initial capacity. The Li_0.99Ti_0.01FePO₄/C composite developed here can be used as the cathode material for lithium ion batteries.     

Electrochemical and magnetic characterization of LiFePO<Subscript>4</Subscript> and Li<Subscript>0.95</Subscript>Mg<Subscript>0.05</Subscript>FePO<Subscript>4</Subscript> cathode materials

A series of lithium iron phosphates was synthesized via the sol–gel route. Iron phosphides, which are electronic conductors, were formed when sintered at 850°C. Magnetic susceptibility measurements on the samples show antiferromagnetic behaviour with T _N=50±2 K for LiFePO₄ and Li_0.95Mg_0.05PO₄ sintered at temperatures below 850°C. The LiFePO₄ and Li_0.95Mg_0.05FePO4 cathodes show a stable electrochemical capacity in the range of 150–160 mA h/g on cycling. The cyclability deteriorates with increasing sample sintering temperature due to the increased crystal size and impurities.     

Study of LiFePO4 synthesized using a molten method with varying stoichiometries

The synthesis of LiFePO₄ from a melt cast of Li₂CO₃, FePO₄, and carbon precursors at 1,000 °C was recently reported. The results indicate that it could be a competitive technique for the large-scale production of LiFePO₄. This paper focuses on particle size reduction and non-stoichiometric synthesis of LiFePO₄. The particles size was reduced using a planetary mill that is available in most research laboratories where the milling time and milling media were varied to obtain the best electrochemical results. In addition, the electrochemical performance of LiFePO₄ products synthesized from FePO₄ + x/2 Li₂CO₃ + C {\hbox{FeP}}{{\hbox{O}}_4} + x{/2}\,{\hbox{L}}{{\hbox{i}}_2}{\hbox{C}}{{\hbox{O}}_3} + {\hbox{C}} (sequentially varying the amount of x) at 1,000 °C has also been measured. The stoichiometric LiFePO₄ product shows the best capacity, while the off-stoichiometric material demonstrates different levels of impurities that have an effect on the performance of the material. The results indicate that adequate capacity at low discharge rates can be obtained using standard milling techniques, but, in order to obtain material from a melt cast synthesis that provides higher performance at faster discharge rates, a further particle size reduction will be required.     

Electrochemical properties of single-phase LiFePO4 synthesized using LiF as Li precursor and hydrogen and carbon gel as reducing agents

LiFePO₄ samples have been synthesized by mixing stoichiometric amounts of (NH₄)₂HPO₄, FeC₂O₄·2H₂O, and LiF. During synthesis, carbon gel was used as the carbon source. Single-phase LiFePO₄ can be formed when the heating temperature ranges from 650 to 800 °C and it is decomposed into Li₄P₂O₇, Li₃PO₄, Fe₂P, and Li₃P₇ when the temperature comes to 850 °C. We find that the ratio of the lattice parameter (a/c) decreases with the increasing temperature, thereby increasing the Li⁺ diffusion channel length. Both the decrease of a/c and the abrupt crystal growth are expected to contribute to the monotonic decrease of the initial capacity of the samples. The sample heated at 650 °C with a smaller uniform particle size and relative higher specific surface area (8.2 m²/g) shows an excellent electrochemical performance. The initial specific capacity of 156.7(3) mAh/g is obtained at the rate of C/10.     

Moisture driven aging mechanism of LiFePO4 subjected to air exposure

The impact of air exposure on LiFePO₄–C nanocomposites has been investigated at moderate temperature. We show here that the storage in 120 °C hot air for 30 days leads not only to the material delithiation but also to the formation of an amorphous ferric phosphate side-phase, accounting for 38% of the total iron. The formed phase is found to be partially hydrated, suggesting a water-driven aging mechanism and a proposed hypothetic formula: Li_xFePO₄(OH)_x. The side-phase displays new electrochemical activity but poor cyclability and the overall battery performance is thus deteriorated. The regeneration of pristine structure, together with the performance recovery can be achieved by a simple thermal treatment under inert atmosphere.     

Preparation and characterization of electrospun LiFePO4/carbon complex improving rate performance at high C-rate

LiFePO₄/carbon complexes were prepared by electrospinning to improve rate performance at high C-rate and their electrochemical properties were investigated to be used as a cathode active material for lithium ion battery. The LiFePO₄/carbon complexes were prepared by the electrospinning method. The prepared samples were characterized by SEM, EDS, XRD, TGA, electrometer, and electrochemical analysis. The LiFePO₄/carbon complexes prepared have a continuous structure with carbon-coated LiFePO₄ and the LiFePO₄ in LiFePO₄/carbon complex has improved thermal stability from carbon coating. The conductivity of LiFePO₄/carbon complex heat-treated at 800 °C is measured as 2.23 × 10^?2 S cm^?1, which is about 10⁶–10⁷ times more than that of raw LiFePO₄. The capacity ratio of coin cell manufactured from raw LiFePO₄ is 40%, whereas the capacity ratio of coin cell manufactured from LiFePO₄/carbon complex heat-treated at 800 °C is 61% (10 C/0.1 C). The improved rate performance of LiFePO₄/carbon complex heat-treated at 800 °C is due to the carbon coating and good electrical connection.     

采用复合锂源制备的LiFePO4/C材料及其碳含量优化

采用Li_2CO_3与Li OH·H_2O为复合锂源制备LiFePO_4/C材料,同时优化了材料中的碳含量。由于氢氧化锂的熔点低于碳酸锂,在同样的烧结温度下,采用复合锂源可以获得更佳的熔融状态,在高温合成过程中使锂离子具有更高的扩散性,能够更顺利地得到高纯度的LiFePO_4晶相。通过优化碳包覆量达到提高导电性与控制晶粒尺寸的目的,使材料晶相结构完整,纯度高,表现出优秀的加工性能与电化学性能。所制得的LiFePO_4/C材料放电克容量达到158.2 m Ah·g~(-1),在全电池中经过100 d存储后容量保持率仍然高于94.0%,具有优异的长期可靠性。     

Improving the rate and low-temperature performance of LiFePO<Subscript>4</Subscript> by tailoring the form of carbon coating from amorphous to graphene-like

A solid-state reaction process with poly(vinyl alcohol) as the carbon source is developed to synthesize LiFePO₄-based active powders with or without modification assistance of a small amount of Li₃V₂(PO₄)₃. The samples are analyzed by X-ray diffraction, scanning/transmission electron microscopy, and Raman spectroscopy. It is found that, in addition to the minor effect of a lattice doping in LiFePO₄ by substituting a tiny fraction of Fe²⁺ ions with V³⁺ ions, the change in the form of carbon coating on the surface of LiFePO₄ plays a more important role to improve the electrochemical properties. The carbon changes partially from sp³ to sp² hybridization and thus causes the significant rise in electronic conductivity in the Li₃V₂(PO₄)₃-modified LiFePO₄ samples. Compared with the carbon-coated baseline LiFePO₄, the composite material 0.9LiFePO₄·0.1Li₃V₂(PO₄)₃ shows totally different carbon morphology and much better electrochemical properties. It delivers specific capacities of 143.6 mAh g^?1 at 10 C rate and 119.2 mAh g^?1 at 20 C rate, respectively. Even at the low temperature of ?20 °C, it delivers a specific capacity of 118.4 mAh g^?1 at 0.2 C.     

Enhanced electrochemical performance of LiFePO<Subscript>4</Subscript>/C nanocomposites due to in situ formation of Fe<Subscript>2</Subscript>P impurities

We have studied LiFePO₄/C nanocomposites prepared by sol-gel method using lauric acid as a surfactant and calcined at different temperatures between 600 and 900 °C. In addition to the major LiFePO₄ phase, all the samples show a varying amount of in situ Fe₂P impurity phase characterized by x-ray diffraction, magnetic measurements, and Mössbauer spectroscopy. The amount of Fe₂P impurity phase increases with increasing calcination temperature. Of all the samples studied, the LiFePO₄/C sample calcined at 700 °C which contains ～15 wt% Fe₂P shows the least charge transfer resistance and a better electrochemical performance with a discharge capacity of 136 mA h g^?1 at a rate of 1 C, 121 mA h g^?1 at 10 C (～70 % of the theoretical capacity of LiFePO₄), and excellent cycleability. Although further increase in the amount of Fe₂P reduces the overall capacity, frequency-dependent Warburg impedance analyses show that all samples calcined at temperatures ≥700 °C have an order of magnitude higher Li⁺ diffusion coefficient (～1.3?×?10^?13 cm² s^?1) compared to the one calcined at 600 °C, as well as the values reported in literature. This work suggests that controlling the reduction environment and the temperature during the synthesis process can be used to optimize the amount of conducting Fe₂P for obtaining the best capacity for the high power batteries.     

Optimization of preparing LiFePO<Subscript>4</Subscript> for lithium-ion batteries via carbothermal reduction route

Lithium iron phosphate olivines (LiFePO₄) have been considered as very promising cathode for lithium-ion batteries due to their energy storage capacity combined with electrochemical and thermal stability. A key issue in synthesizing this materials is to optimize the synthetic conditions for obtain materials with excellent electrochemical properties. Here, we report full studies that investigate the synthesis of the LiFePO₄ by promising carbothermal reduction methods to prepare LiFePO₄ coated with pyrolytic carbon. Variation of the synthesis parameters showed that the materials synthesized at 700°C for 12 h have appropriate particles size and electronically conductive carbon. This makes it have better performances than others prepared at different temperature.     

Superior high-rate cycling performance of LiFePO4/C-PPy composite at 55 °C

A facile chemical polymerization method was applied to prepare LiFePO₄/C-PPy composite using Fe(III)tosylate as oxidant. The as-prepared LiFePO₄/C-PPy sample with PPy content of approximately 4 wt% showed great rate capability with a discharge capacity of 115 mAh/g at 20C. High temperate cycling performance of the LiFePO₄/C-PPy sample was compared with bare LiFePO₄/C at 5C charge–discharge rate at 55 °C. The LiFePO₄/C-PPy cathode showed superior cycling stability with an initial capacity of 155 mAh/g. Ninety percentage of this initial capacity was retained after 300 cycles, compared to 40% of that of bare LiFePO₄/C. The LiFePO₄/C-PPy electrode showed stable discharge plateau voltage of 3.35–3.25 V vs. Li⁺/Li during long term cycling. The superior performance of the LiFePO₄/C-PPy electrode was due to the enhanced electrical conductivity, negligible iron dissolution and alleviated electrode cracking contributed by PPy coating.     

Mechanism studies and electrochemical performance optimization on xLiFePO4·(1 ? x)Li3V2(PO4)3 hybrid materials

Hybrid materials xLiFePO₄·(1 − x)Li₃V₂(PO₄)₃ were synthesized by sol–gel method, with phenolic resin as carbon source and chelating agent, methylglycol as surfactant. The crystal structure, morphology and electrochemical performance of the prepared samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammetry (CV), galvanostatic charge–discharge test and particle size analysis. The results show that LiFePO₄ and Li₃V₂(PO₄)₃ co-exist in hybrid materials, but react in single phase. Compared with individual LiFePO₄ and Li₃V₂(PO₄)₃ samples, hybrid materials have smaller particle size and more uniform grain distribution. This structure can facilitate Li ions extraction and insertion, which greatly improves the electrochemical properties. The sample 0.7LiFePO₄·0.3Li₃V₂(PO₄)₃ retains the advantages of LiFePO₄ and Li₃V₂(PO₄)₃, obtaining an initial discharge capacity of 166 mA h/g at 0.1 C rate and 109 mA h/g at 20 C rate, with a capacity retention rate of 73.3% and an excellent cycle stability.     

LiFePO4/C composites from carbothermal reduction method

Using the cheap raw materials lithium carbonate, iron phosphate, and carbon, LiFePO₄/C composite can be obtained from the carbothermal reduction method. X-ray diffraction (XRD) and scanning electronic microscope (SEM) observations were used to investigate the structure and morphology of LiFePO₄/C. The LiFePO₄ particles were coated by smaller carbon particles. LiFePO₄/C obtained at 750 °C presents good electrochemical performance with an initial discharge capacity of 133 mAh/g, capacity retention of 128 mAh/g after 20 cycles, and a diffusion coefficient of lithium ions in the LiFePO₄/C of 8.80?×?10^?13 cm²/s, which is just a little lower than that of LiFePO₄/C obtained from the solid-state reaction (9.20?×?10^?13 cm²/s) by using FeC₂O₄ as a precursor.     

两种方法制备的磷酸铁锂/石墨烯复合材料的性能对比

以FeSO₄·7H₂O、NH₄H₂PO₄、H₂O₂、Li₂CO₃、C₆H₁₂O₆和自制的氧化石墨烯(GO)为原料,分别采用原位包覆法和非原位包覆法制备了石墨烯磷酸铁锂样品:LiFePO₄/C/G-1和LiFePO₄/C/G-2。用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、交流阻抗(EIS)和充放电测试研究了两种包覆方法制备的样品的晶体结构、形貌和电化学性能。结果表明原位法包覆所得复合材料LiFePO₄/C/G-1具有更优秀的电性能:在2.5~4.1V充放电,0.1C和1C首次放电比容量分别为158.15和150.5mAh·g^-1,在1C倍率下循环500次后容量保持率达到98.3%。     

Improved electrochemical performance of nano-crystalline Li2FeSiO4/C cathode material prepared by the optimization of sintering temperature

Li₂FeSiO₄/C cathode materials have been prepared using the conventional solid-state method by varying the sintering temperature (650 °C, 700 °C and 750 °C), and the structure and electrochemical performance of Li₂FeSiO₄/C materials are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic charge–discharge tests, respectively. The results show that Li₂FeSiO₄ nano-crystals with a diameter of about 6–8 nm are inbedded in the amorphous carbon, and the Li₂FeSiO₄/C material obtained at 700 °C exhibits an initial discharge capacity of 195 mA?h g^?1 at 1/16 C in the potential range of 1.5–4.8 V. The excellent electrochemical performance of Li₂FeSiO₄/C attributes to the improvement of conductivity and reduction of impurity by the optimization of the sintering temperature.     

Preparation and characterization of high-rate and long-cycle LiFePO4/C nanocomposite as cathode material for lithium-ion battery

Olivine LiFePO₄/C nanocomposite cathode materials with small-sized particles and a unique electrochemical performance were successfully prepared by a simple solid-state reaction using oxalic acid and citric acid as the chelating reagent and carbon source. The structure and electrochemical properties of the samples were investigated. The results show that LiFePO₄/C nanocomposite with oxalic acid (oxalic acid: Fe²⁺= 0.75:1) and a small quantity of citric acid are single phase and deliver initial discharge capacity of 122.1 mAh/g at 1 C with little capacity loss up to 500 cycles at room temperature. The rate capability and cyclability are also outstanding at elevated temperature. When charged/discharged at 60 °C, this materials present excellent initial discharge capacity of 148.8 mAh/g at 1 C, 128.6 mAh/g at 5 C, and 115.0 mAh/g at 10 C, respectively. The extraordinarily high performance of LiFePO₄/C cathode materials can be exploited suitably for practical lithium-ion batteries.     

NMR investigations on the lithiation and delithiation of nanosilicon-based anodes for Li-ion batteries

Lithiation and delithiation of nanosilicon anodes of 100–200 nm diameter have been probed by ex situ solid-state high-resolution ⁷Li nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM) methods. Samples were charged within pouch cells up to capacities of 1,500 mAh/g at 0.1 C, and subsequently discharged at the same rate. The NMR spectra reveal important quantitative information on the local lithium environments during the various stages of the charging/discharging process. The TEM experiments show that the electrochemical lithiation of nanosilicon particles results in core-shell materials, consisting of Li_xSi shells surrounding a core of residual silicon. The NMR spectra yield approximate Li/Si ratios of the lithium silicides present in the shells, based on the distinct local environments of the various types of ⁷Li nuclei present. The combination of NMR with TEM gives important quantitative conclusions about the nature of the electrochemical lithiation process: Following the initial formation of the solid electrolyte interphase layer, which accounts for an irreversible capacity of 240 mAh/g, lithium silicide environments with intermediate Li concentrations (Li₁₂Si₇, Li₇Si₃, and Li₁₃Si₄) are formed at the 500 to 1,000 mAh/g range during the charging process. At a certain penetration depth, further lithiation does not progress any further toward the interior of the silicon particles but rather leads to the formation of increasing amounts of the lithium-richest silicide, Li₁₅Si₄-type environments. Delithiation does not result in the reappearance of the intermediate-stage phases but rather only changes the amount of Li₁₅Si₄ present, indicating no microscopic reversibility. Based on these results, a detailed quantitative model of nanophase composition versus penetration depth has been developed. The results indicate the power and potential of solid-state NMR spectroscopy for elucidating the charging/discharging mechanism of nano-Si anodes.     

Surfactant assisted solvothermal synthesis of LiFePO_4 nanorods for lithium-ion batteries

Well-shaped and uniformly dispersed LiFePO_4 nanorods with a length of 400–500 nm and a diameter of about 100 nm, are obtained with participation of a proper amount of anion surfactant sodium dodecyl sulfonate(SDS) without any further heating as a post-treatment. The surfactant acts as a self-assembling supermolecular template, which stimulated the crystallization of LiFePO_4 and directed the nanoparticles growing into nanorods between bilayers of surfactant(BOS). LiFePO_4 nanorods with the reducing crystal size along the b axis shorten the diffusion distance of Li~+ extraction/insertion, and thus improve the electrochemical properties of LiFePO_4 nanorods. Such prepared LiFePO_4 nanorods exhibited excellent specific capacity and high rate capability with discharge capacity of 151 mAh/g, 122 mAh/g and 95 mAh/g at 0.1C, 1 C and 5 C, respectively. Such excellent performance of LiFePO_4 nanorods is supposed to be ascribed to the fast Li~+ diffusion velocity from reduced crystal size along the b axis and the well electrochemical conductivity. The structure, morphology and electrochemical performance of the samples were characterized by XRD, FE-SEM, HRTEM, charge/discharge tests, and EIS(electrochemical impedance spectra).     

A new charging mode of Li-ion batteries with LiFePO<Subscript>4</Subscript>/C composites under low temperature

Li-ion batteries with LiFePO₄/C composites are difficult to be charged at low temperatures. In order to improve the low temperature performance of LiFePO₄/C power batteries, the charge–discharge characteristics were studied at different temperatures, and a new charging mode under low temperature was proposed. In the new charging mode, the batteries were excited by current pulses with the charge rates between 0.75 C and 2 C, while the discharge rates between 3 and 4 C before the conventional charging (CC–CV). Results showed that the surface temperature of Li-ion battery ascended to 3 °C at the end of pulse cycling when the environment temperature was −10 °C. Comparing with the conventional charging, the whole charge time was cut by 36 min (23.4%) and the capacity was 7.1% more at the same discharge rate, respectively.     

LiFePO<Subscript>4</Subscript>/CA cathode nanocomposite with 3D conductive network structure for Li-ion battery

A novel LiFePO₄/Carbon aerogel (LFP/CA) nanocomposite with 3D conductive network structure was synthesized by using carbon aerogels as both template and conductive framework, and subsequently wet impregnating LiFePO₄ precursor inside. The LFP/CA nanocomposite was characterized by X-ray diffraction (XRD), TG, SEM, TEM, nitrogen sorption, electrochemical impedance spectra and charge/discharge test. It was found that the LFP/CA featured a 3D conductive network structure with LiFePO₄ nanoparticles ca. 10–30 nm coated on the inside wall of the pore of CA. The LFP/CA electrodes delivered discharge capacity for LiFePO₄ of 157.4, 147.2, 139.7, 116.3 and 91.8 mA h g⁻¹ at 1 °C, 5 °C, 10 °C, 20 °C and 40 °C, respectively. In addition, the LFP/CA electrode exhibited good cycling performance, which lost less than 1% of discharge capacity over 100 cycles at a rate of 10 °C. The good high rate performances of LiFePO₄ were attributed to the unique 3D conductive network structure of the nanocomposite.