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1.
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.  相似文献   

2.
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.  相似文献   

3.
Carbon-coated LiFePO4 cathode materials were prepared by a solid-state method incorporating different sizes of polystyrene (PS) spheres as carbon sources. In scanning electron microscope images, small PS spheres appear more effective at preventing aggregation of LiFePO4 particles. From transmission electron microscopy images, it was found that the LiFePO4 particles were completely uniformly coated with 5-nm carbon layer when the carbon source was 0.22 μm PS spheres. When the size of PS sphere was increased to 2.75 μm, a network of carbon was formed and wrapped around the LiFePO4 to create a conductive web. Raman spectroscopy and four-point probe conductivity measurement showed that using larger sizes of PS spheres as carbon sources leads to greater conductivity of LiFePO4/C. The LiFePO4 precursor sintered with 0.22 μm PS spheres delivered an initial discharge capacity of 145 mAh g?1 at a 0.2 C rate, but it only sustained 289 cycles at 80% capacity. When the diameter of PS spheres was increased to 2.75 μm, the discharge capacity of LiFePO4/C decreased, but the cycle life reached 755 cycles, the highest number in this work probably due to the network formation of carbon wrapping around LiFePO4 particles.  相似文献   

4.
To enhance the capability of LiFePO4 materials, we attempted to coat carbon by incorporating various organic carboxylic acids as carbon sources. The purity of LiFePO4 was confirmed by XRD analysis. Galvanostatic cycling, cyclic voltammetry, electric impedance spectroscopy, and conductivity measurements were used to evaluate the material’s electrochemical performance. The best cell performance was delivered by the sample coated with 60 wt.% malonic acid. Its first-cycle discharge capacity was 149 mA h g?1 at a 0.2 C rate or 155 mA h g?1 at a 0.1 C rate. The presence of carbon in the composite was verified by total organic carbon and Raman spectral analysis. The actual carbon content of LiFePO4 was 1.90 wt.% with the addition of 60 wt.% malonic acid. The LiFePO4/C samples sintered with 60 wt.% various carboxylic acids were measured by Raman spectral analysis. The intense broad bands at 1,350 and 1,580 cm?1 are assigned to the D and G bands of residual carbon in LiFePO4/C composites, respectively. The peak intensity (I D/I G) ratio of the synthesized powders is from 0.907 to 0.935. Carbon coatings of LiFePO4 with low I D/I G ratios can be produced by incorporating carboxylic acid additives before the final calcining process. The use of carboxylic acid as a carbon source increases the overall conductivity (~10?4 S cm?1) of the material.  相似文献   

5.
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.  相似文献   

6.
不同碳源对多孔球形LiFePO4/C复合材料的影响   总被引:2,自引:0,他引:2  
采用喷雾干燥-碳热还原法(SDCTM),分别研究了无机和有机碳源对锂离子正极材料LiFePO4/C形貌、结构及其充放电性能的影响。结果表明:以无机碳源炭黑制备的LiFePO4/C呈不规则球形,一次颗粒粒径在800nm左右,比表面积为2m2·g-1,0.1C放电比容量为107.3mAh·g-1。而以有机碳源制备的LiFePO4/C,其形貌较为规则,呈多孔球形结构,具有较高的比表面积和放电比容量。其中,以柠檬酸为碳源制备的多孔球形LiFePO4/C复合材料,其孔径均在50nm左右,比表面积可达32m2·g-1;在室温下,0.1C和10C首次放电比容量分别为158.8和87.2mAh·g-1,具有优异的循环性能和高倍率充放电性能。  相似文献   

7.
Although LiFePO4 (LFP) is considered to be a potential cathode material for the lithium-ion batteries, its rate performance is significantly restricted by sluggish kinetics of electrons and lithium ions. Several attempts have been made so far to improve the performance of LiFePO4 by reducing the grain size, doping with aliovalent atoms, and coating conductive materials such as carbon or RuO2. We report here synthesis of LFP nanoplates by solvothermal method, tailoring the thickness as well as carbon coverage at surfaces to explore their influence on the storage performance. Due to the fact that Li+ ion diffuses along the b-axis, solvothermal method was aimed to control the thickness of nanoplates across the b-axis. We synthesized several nanoplates with various plate thicknesses along b-axis; among those, nanoplates of LFP with ~30-nm-thick b-axis having thin (2–5 nm) and uniform layer of carbon coating exhibits high storage capacity as well as high rate performances. Thus, a favorable morphology for LiFePO4 has been achieved via solvothermal method for fast insertion/extraction of Li+ as compared to spherical nanoparticles of carbon-coated LFP. Galvanostatic cycling shows a capacity of 164?±?5 mAh g?1 at 0.1 C rate, 100?±?5 mAh g?1 at 10 C rate, and 46?±?5 mAh g?1 at 30 C rate, with excellent capacity retention of up to 50 cycles. Further attempts have been made to synthesize LiMnPO4 (LMP) as well as Li(Fe1???x Mn x )PO4/C (x?=?0.5) nanoplates using solvothermal method. Although LiMnPO4 does not exhibit high storage behavior comparable with that of LiFePO4, the mixed systems have shown an impressive storage performance.  相似文献   

8.
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.  相似文献   

9.
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).  相似文献   

10.
Mesoporous LiFePO4/C composites containing 80 wt% of highly dispersed LiFePO4 nanoparticles (4–6 nm) were fabricated using bimodal mesoporous carbon (BMC) as continuous conductive networks. The unique pore structure of BMC not only promises good particle connectivity for LiFePO4, but also acts as a rigid nano-confinement support that controls the particle size. Furthermore, the capacities were investigated respectively based on the weight of LiFePO4 and the whole composite. When calculated based on the weight of the whole composite, it is 120 mAh·g?1 at 0.1 C of the high loading electrode and 42 mAh·g?1 at 10 C of the low loading electrode. The electrochemical performance shows that high LiFePO4 loading benefits large tap density and contributes to the energy storage at low rates, while the electrode with low content of LiFePO4 displays superior high rate performance, which can mainly be due to the small particle size, good dispersion and high utilization of the active material, thus leading to a fast ion and electron diffusion.  相似文献   

11.
Pure LiFePO4 and LiNi x Fe1?x PO4/C (x?=?0.00–0.20) nanocomposite cathode materials have been synthesized by cheap and convenient sol–gel-assisted carbothermal reduction method. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy, and inductively coupled plasma have been used to study the phase, morphology, and chemical composition of un-doped and Ni-doped materials. XRD patterns display the slight shrinkage in crystal lattice of LiFePO4 after Ni2+ doping. The SEM images have revealed that Ni-doped particles are not agglomerated and the particle sizes are practically homogeneously distributed. The particle size is found between 50 and 100 nm for LiNi0.20Fe0.80PO4/C sample. The discharge capacity at 0.2 C rate has increased up to 155 mAh g?1 for the LiNi0.05Fe0.95PO4/C sample and good capacity retention of 99.1 % over 100 cycles, while that of the unsubstituted LiFePO4/C and pure LiFePO4 has showed only 122 and 89 mAh g?1, respectively. Doping with Ni has a noticeable effect on improving its electrical conductivity. However, serious electrochemical declension will occur when its doping density is beyond 0.05 mol LiNi0.20Fe0.80PO4/C electrode shows only 118 mAh g?1, which is less than un-doped LiFePO4/C sample at 0.2 C. The cycling voltammogram demonstrates that Ni-doped LiNi0.05Fe0.95PO4/C electrode has more stable lattice structure, enhanced conductivity, and diffusion coefficient of Li+ ions, in which Ni2+ is regarded to act as a column in crystal lattice structure to prevent the collapse during cycling process.  相似文献   

12.
The olivine-type samarium-doped LiFe1 ? x Sm x PO4/C (x?=?0, 0.01, 0.02, 0.03, 0.04, and 0.05) composites were synthesized via liquid-phase precipitation reaction combined with the high-temperature solid-state method. The structure, morphology, and electrochemical performance of the samples were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscope, energy dispersive spectroscopy, galvanostatic charge–discharge, galvanostatic intermittent titration technique, and electrochemical impedance spectroscopy. The results showed that the small amount of Sm3+ ion-doped can keep the olivine microstructure of LiFePO4, modify the particle morphology, decrease polarization overpotential and charge transfer resistance, and enhance exchange current density, thus improve the electrochemical performance of the LiFePO4/C. However, the large doped content of Sm3+ ion can form more SmPO4, which can weaken the electrochemical performance of LiFePO4/C. Among all the doped samples, LiFe0.99Sm0.01PO4/C showed the best rate capacity, cycling stability, and low temperature performance. The LiFe0.99Sm0.01PO4/C sample exhibited the initial discharge capacity of 148.1, 133.4, 117.5, and 106.6 mAh g?1 at 1C, 2C, 5C, and 10C, respectively. In addition, the discharge capacity of the material was 94.8 mAh g?1 after 800 cycles at 10C. Moreover, the initial discharge capacity of 0.1C, 0.2C, 0.5C, and 1C were 104.4, 96.2, 53.9, and 50.8 mAh g?1 at ?20 °C.  相似文献   

13.
Olivine-type LiFePO4 is one of the most promising cathode materials for lithium-ion batteries, but its poor conductivity and low lithium-ion diffusion limit its practical application. The electronic conductivity of LiFePO4 can be improved by carbon coating and metal doping. A small amount of La-ion was added via ball milling by a solid-state reaction method. The samples were characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM)/mapping, differential scanning calorimetry (DSC), transmission electron microscopy (TEM)/energy dispersive X-ray spectroscopy (EDS), and total organic carbon (TOC). Their electrochemical properties were investigated by cyclic voltammetry, four-point probe conductivity measurements, and galvanostatic charge and discharge tests. The results indicate that these La-ion dopants do not affect the structure of the material but considerably improve its rate capacity performance and cyclic stability. Among the materials, the LiFe0.99La0.01PO4/C composite presents the best electrochemical behavior, with a discharge capacity of 156 mAh g?1 between 2.8 and 4.0 V at a 0.2 C-rate compared to 104 mAh g?1 for undoped LiFePO4. Its capacity retention is 80% after 497 cycles for LiFe0.99La0.01PO4/C samples. Such a significant improvement in electrochemical performance should be partly related to the enhanced electronic conductivities (from 5.88?×?10?6 to 2.82?×?10?3 S cm?1) and probably the mobility of Li+ ion in the doped samples. The LiFe0.99La0.01PO4/C composite developed here could be used as a cathode material for lithium-ion batteries.  相似文献   

14.
Storage stabilities of LiFePO4/C composite at different conditions are investigated in terms of structural and electrochemical evolutions. The results from different aging tests indicate that moisture and temperature are the key factors that have the most profound effects on the structure homogeneity which in turn influences the electrochemical performance of LiFePO4/C. Although the storage in a humid‐hot environment, such as saturated humidity air at 50°C, does not greatly influence the discharging capacity of LiFePO4/C, it does reduce the initial charging capacity, thus the amount of reversible Li+ ions in a practical LiFePO4/graphite cell decreases. This impact is explained by the lithium extraction during the storage, forming olivine FePO4 and associated Li3PO4. Elevated storage temperature also favors the delithiation process. The degree of delithiation increases from about 6% at 50°C to 18% at 80°C. It is also found that re‐calcination at 650°C effectively resolves the problem of the structural heterogeneity of the stored LiFePO4/C. Therefore both the initial charging capacity and coulombic efficiency of the stored sample in the first cycle revert to the original value of the fresh one.  相似文献   

15.
The highly crystalline LiFePO4 particles were hydrothermally fabricated by using different heating sources at 160°C for 60 min. The X-ray diffraction patterns of both sample presented a good fit with the pure phase without impurity phases. Rietveld refinement results reveal that the degree of Fe Li · , antisite defect could decrease with increasing heating rate. Morphologic studies and specific surface areas result show that the morphology and mean crystallite sizes of the obtained particles were strongly dependent on heating rate. Electrochemical data show that the hydrothermally synthesized LiFePO4 with nanorod structure prepared by microwaves heating source exhibited higher electrochemical activity during charge and discharge process.  相似文献   

16.
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.  相似文献   

17.
LiFePO4/C and LiYb0.02Fe0.98PO4/C composite cathode materials were synthesized by simple solution technique. The samples were characterized by X-ray diffraction, scanning electron microscope, and thermogravimetric–differential thermal analysis. Their electrochemical properties were investigated by cyclic voltammetry, four-point probe conductivity measurements, and galvanostatic charge and discharge tests. The carbon-coated and Yb3+-doped LiFePO4 sample exhibited an enhanced electronic conductivity of 1.9 × 10?3 Scm?1, and a specific discharge capacity of 146 mAhg?1 at 0.1 C. The results suggest that the improvement of the electrochemical performance can be attributed to the ytterbium doping, which facilitates the phase transformation between triphylite and heterosite during cycling, and the conductivity improvement by carbon coating.  相似文献   

18.
Cathode material LiFe0.7?V0.2PO4/C is successfully synthesized by multistep sintering through carbon thermal reaction including 650 °C for 10 h and 750 °C for 6 h. The crystal structure and surface morphology of the synthesized materials are characterized by X-ray diffractometer and scanning electron microscope, respectively. Cycle voltammetry, electrochemical impedance spectroscopy, and charge–discharge test are used to investigate the electrochemical performances of these samples. The results revealed that the synthesized LiFe0.7?V0.2PO4/C material simultaneously contains olivine structure LiFePO4 and monoclinic structure Li3V2(PO4)3. It shows improved conductivity, Li-ion diffusion coefficient, excellent charge/discharge performance, and reversibility due to both the incorporation of Li3V2(PO4)3 fast ion conductor and the employed multistep sintering. The initial discharge specific capacities of LiFe0.7?V0.2PO4/C by multistep sintering are 167.8, 154.7, and 140.8 mAh g?1 at 0.5, 1, and 2 C, respectively. After a total of 230 cycles at different rates, the sample still shows good performances. After 100 cycles at 2 C, the capacity retention is 99.1 %, and the capacity is 139.6 mAh g?1. The LiFe0.7?V0.2PO4/C material synthesized by this method can be used as a cathode material for advanced lithium-ion batteries.  相似文献   

19.
LiFePO4/C composites are prepared by using two types of carbon source: one using polymer (PAALi) and the other using sucrose. The physical characteristics of LiFePO4/C composites are investigated by X-ray diffraction), scanning electron microscopy, BET, laser particle analyzer, and Raman spectroscopy. Their electrochemical properties are characterized by cyclic voltammograms, constant current charge–discharge, and electrochemical impedance spectra. These analyses indicate that the carbon source and carbon content have a great effect on the physical and electrochemical performances of LiFePO4/C composites. An ideal carbon source and appropriate carbon content can effectively increase the lithium-ion diffusion coefficient and exchange current density, decrease the charge transfer resistance (R ct), and enhance the electrochemical performances of LiFePO4/C composite. The results show that PAALi is a better carbon source for the synthesis of LiFePO4/C composites. When the carbon content is 4.11 wt.% (the molar ratio of PAALi/Li2C2O4 was 2:1), as-prepared LiFePO4/C composite shows the best combination between electrochemical performances and tap density.  相似文献   

20.
Carbon-coated LiFeBO3 is prepared by sol-gel method, and polyethylene glycol 6000 (PEG-6000) is chosen as carbon source. Compared with conventional solid-state method, the LiFeBO3/C nano-particles were obtained at a relatively lower temperature (500 °C). It was demonstrated that the prepared LiFeBO3 is a highly pure monoclinic structure with space group of C2/c, the primary particle size of the carbon-coated LiFeBO3 is about 20–50 nm, and the thickness of carbon coating is about 6.2 nm. In comparison with the LiFeBO3/C with lower carbon content, the LiFeBO3/C with higher carbon content exhibits better electrochemical properties. The specific capacities of LiFeBO3/C are 206.9, 181.3, and 166.1 mAh g?1 after 50 cycles in the range of 5, 40, and 100 mA g?1 current density, respectively. Particularly, the LiFeBO3/C with higher carbon content is demonstrated to own great structural stability, which can maintain its original crystal structure and Li storage properties even after 6 months of air exposure at room temperature.  相似文献   

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