微波法制备LiFePO4及其电化学性能的研究

采用微波法合成锂离子电池正极材料LiFePO4,并通过X射线衍射(XRD)、电子扫描电镜(SEM)和恒电流充放电实验,研究了在一定微波功率下合成出的材料的性能。结果表明,当含碳量在5%时,采用0.1C进行充放电,材料比容量可达126mAh/g,循环50次后,比容量仅下降10%,循环稳定性好。     

Improvement of electrochemical properties of LiFePO4/C cathode materials by chlorine doping

The olivine-type cathode materials of LiFePO₄ were prepared via solid-state reaction under argon atmosphere and doped by chlorine to improve their electrochemical performances. The crystal structure, morphology, and electrochemical properties of the prepared samples were investigated using thermogravimetry–differential scanning calorimetry, X-ray diffraction, Fourier transform infrared, scanning electron microscopy, cyclic voltammetry, and charge–discharge cycle measurements. The result showed that the electrochemical performance of LiFePO₄ had been improved by chlorine doping, and the effect of chlorine in lattice was discussed. The heavily doped samples show better electrochemical performance in relative high rates.     

Enhanced high rate and low temperature electrochemical properties of LiFePO4/C composites by doping samarium ion

The olivine-type samarium-doped LiFe_{1 ? 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, LiFe_0.99Sm_0.01PO₄/C showed the best rate capacity, cycling stability, and low temperature performance. The LiFe_0.99Sm_0.01PO₄/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.     

Impact of carbon structure and morphology on the electrochemical performance of LiFePO4/C composites

The electrochemical performance of LiFePO₄/C composites in lithium cells is closely correlated to pressed pellet conductivities measured by AC impedance methods. These composite conductivities are a strong function not only of the amount of carbon but of its structure and distribution. Ideally, the amount of carbon in composites should be minimal (less than about 2 wt%) so as not to decrease the energy density unduly. This is particularly important for plug-in hybrid electric vehicle applications (PHEVs) where both high power and moderate energy density are required. Optimization of the carbon structure, particularly the sp²/sp³ and disordered/graphene (D/G) ratios, improves the electronic conductivity while minimizing the carbon amount. Manipulation of the carbon structure can be achieved via the use of synthetic additives including iron-containing graphitization catalysts. Additionally, combustion synthesis techniques allow co-synthesis of LiFePO₄ and carbon fibers or nanotubes, which can act as “nanowires” for the conduction of current during cell operation.     

新型碳热还原法制备复合正极材料LiFePO4/C

以FePO4为前驱体,采用碳热还原法合成了复合正极材料LiFePO4/C。考察了煅烧温度、煅烧时间,碳含量等因素对LiFePO4组成和电化学的影响,结果表明,600℃煅烧24 h,碳含量为10%时,LiFePO4具有最佳的电化学性能,其首次放电容量为146 mAh.g-1,循环15次后容量还维持在141 mAh.g-1。     

不同包碳方式对LiFePO4/C微观结构及电化学性能的影响

综合利用碳-硫测试、XRD、SEM、BET、拉曼光谱、EIS及扣式电池测试等分析技术手段,对LiFePO4/C制备过程中原位包碳与非原位包碳(分别记为LFP-1、LFP-2)的研究结果表明,在碳含量、相结构一致的前提下,LFP-1为10μm左右带孔的大颗粒,LFP-2为由100nm左右小颗粒组成的类球状颗粒,前者的电荷转移电阻(Rct)、倍率性能、循环性能优于后者,这归结于不同的包碳方式导致的LiFePO4/C微观结构的不同,从而使拉曼光谱结果中LFP-1的ID/IG和Asp3/Asp2低于LFP-2,即前者石墨化程度高于后者。从而表明,碳的包裹情况对改善LiFePO4/C的电化学性能有重要的影响。该结果对提高橄榄石类锂离子电池正极材料的综合性能有重要意义。     

Physical and electrochemical properties of La-doped LiFePO4/C composites as cathode materials for lithium-ion batteries

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 LiFe_0.99La_0.01PO₄/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 LiFe_0.99La_0.01PO₄/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 LiFe_0.99La_0.01PO₄/C composite developed here could be used as a cathode material for lithium-ion batteries.     

Synthesis and electrochemical properties of K-doped LiFePO4/C composite as cathode material for lithium-ion batteries

Li_1 − x K _x FePO₄/C (x = 0, 0.03, 0.05, and 0.07) composites were synthesized at 700 °C in an argon atmosphere by carbon thermal reduction method. Based on X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analysis, the composite was ultrafine sphere-like particles with 100–300 nm size, and the lattice structure of LiFePO₄ was not destroyed by K doping, while the lattice volume was enlarged. The electrochemical properties were investigated by four-point probe conductivity measurements, galvanostatic charge and discharge tests, cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the capacity performance at high rate and cyclic stability were improved by doping an appropriate amount of K, which might be ascribed to the fact that the doped K ion expands Li ion diffusion pathway. Among the doped materials, the Li_0.97K_0.03FePO₄/C samples exhibited the best electrochemical activity, with the initial discharge capacity of 153.7 mAh g⁻¹ at 0.1 C and the capacity retention rate of about 92% after 50 cycles at above 1 C, 11% higher than undoped sample. Remarkably, it still showed good cycle retention at a high current rate of 10 C.     

重量法测定碳包覆磷酸铁锂中磷的含量

采用重量法测定碳包覆磷酸铁锂中磷的含量。对比了灼烧除碳与过滤除碳前处理后以磷钼酸喹啉重量法测定碳包覆磷酸铁锂中的磷含量。优化的试验条件如下:1样品经过滤除碳预处理;2沉淀剂加入量为20mL;3加热温度为90℃。方法用于碳包覆磷酸铁锂样品的测定,加标回收率在98.9%~99.8%之间,测定值的相对标准偏差(n=9)在0.30%~0.43%之间。     

球磨法原位合成LiFePO_4/CNTs复合材料及电化学性能

采用简单、有效和可规模化的球磨工艺,原位合成了碳纳米管(CNTs)均匀分布且连接磷酸铁锂(Li FePO4)颗粒的Li Fe PO4/CNTs复合材料。该复合材料颗粒均匀,分散性好,粒径大约在200 nm~1μm之间,其分散和连接状态可由碳纳米管和粘结剂调控。当CNTs含量为4 wt%、PVDF含量为5 wt%时复合材料显示出最好的电化学性能。0.25C条件下首次放电容量达137 m Ah·g-1,50次循环后,容量仍保持在95%以上,,显示出良好的循环稳定性和可逆性。与没有添加CNTs的样品相比,CNTs网络结构极大地提高了活性物质的电导率,从而明显改善电化学性能。     

Enhancement of electrochemical properties of niobium‐doped LiFePO4/C synthesized by sol–gel method

LiFePO₄/C and LiFe_1–xNb _xPO₄/C composites were synthesized using a sol–gel method. The influence of niobium doping on the constitution, morphology, and electrochemical properties of the samples was studied in detail. X‐Ray diffraction patterns indicate that appropriate Nb doping does not alter seriously the structure of LiFePO₄. Electrochemical characterization of the electrodes showed that the Li‐ion batteries based on LiFe_1–xNb _xPO₄/C electrode exhibited better charge/discharge performance than those based on LiFePO₄/C. The LiFe_0.95Nb_0.05PO₄/C‐based cell had the specific capacity of 157, 121, and 85 mAh/g at 0.2, 2, and 5 C, respectively, in comparison with 126, 94, and 52 mAh/g for the LiFePO₄/C cell. The results show that the addition of niobium promotes the electrochemical performance of the materials especially at high charge/discharge rates of the battery.     

Effects of carbon sources and carbon contents on the electrochemical properties of LiFePO4/C cathode material

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.     

Site-dependent electrochemical performance of Mg doped LiFePO4

Exotic metal (EM) doping in LiFePO4 materials could mitigate their poor electronic conductivity and electrochemical performance. This effect is believed to be dependent on the EM dwelling site, which has yet been well clarified due to experimental difficulty. Herein, we report on Mg-doped LiFePO₄ samples with dopant in two distinct sites, namely the Li_1 − 2xMg_xFePO₄ and LiFe_1 − xMg_xPO₄, using a specially designed two-step reaction. The conductivity and electrochemical test results are a clear indication that the performance of the doped LiFePO₄ samples is highly Mg site dependent, consistent with theoretical analysis.     

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.     

Synthetic LiFePO4/C without using inert gas

LiFePO_4/C was synthesized by high temperature solid-state method with cheap Fe2O3, LiH2PO4 and glucose as raw materials in absence of inert gas. The sample had ordered olivine-type structure other impurities characterized by the test of X-ray diffraction (XRD). The charge-discharge test showed the sample could demonstrate 120.5 mAh/g at 0.2C rate with good cyclic capability. The powder microelectrode cyclic voltammetry test indicated that the redox process of the sample had good reversibility.     

Synthesis and electrochemical characterizations of nano-crystalline LiFePO4 and Mg-doped LiFePO4 cathode materials for rechargeable lithium-ion batteries

Nano-crystalline LiFePO₄ and LiMg_0.05Fe_0.95PO₄ cathode materials were synthesized by sol–gel method in argon atmosphere using succinic acid as a chelating agent. Physico-chemical characterizations were done by thermogravimetric and differential thermal analysis, X-ray diffraction, scanning electron microscopy, transmittance electron microscopy, and Raman spectroscopy. Electrochemical behavior of the cathode materials were analyzed using cyclic voltammetry, and galvanostatic charge/discharge cycling studies were employed to characterize the reaction of lithium-ion insertion into and extraction from virginal and magnesium-doped LiFePO₄, in the voltage range 2.5 to 4.5 V (Vs Li/Li⁺) using 1 M LiPF₆ with 1:1 ratio of ethylene carbonate and dimethyl carbonate as electrolytes. LiMg_0.05Fe_0.95PO₄ exhibits initial charge and discharge capacities of 159 and 141 mAh/g at 0.2 C rate respectively, as compared to 121 and 107 mAh/g of pristine LiFePO₄. Furthermore, LiMg_0.05Fe_0.95PO₄ has retained more than 89% of the capacity even after 60 cycles. Hence, LiMg_0.05Fe_0.95PO₄ is a promising cathode material for rechargeable lithium-ion batteries.     

Effects of heteroatoms on doped LiFePO4/C composites

A series of supervalent cation doped Li_1–x M_0.01Fe_0.99PO₄/C composites (M?=?Ti, Zr, V, Nb, and W) were synthesized by solid-state reaction. The effects of the heteroatoms were studied by X-ray diffraction, cyclic voltammetry, and electrochemical impedance measurement. After doping, the lattice structure of LiFePO₄ is not destroyed and the reversibility of lithium ion intercalation and deintercalation is improved. The diffusion coefficient of lithium ions depends on the radius of the heteroatoms. As the radius of the heteroatom is larger, the diffusion coefficient increases.     

Enhancing electrochemical performance of LiFePO4 by in situ reducing flexible graphene

Well-dispersed graphene materials reduced by Ac under hydrothermal condition were used as conductive additives to improve intrisic disadvantage of promising LiFePO₄ battery materials, which was synthesized at surface of graphene sheets. The as-prepared LiFePO₄/graphene composites were characterized by X-ray powder diffraction (XRD), scan electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge tests. The results show that, compared with conventional LiFePO₄ platelets, the composite deliver excellent electrochemical performances, due to flexible graphene-based porous conducting network. We believe that such a facile process will provide a new pathway for further enhancing its energy storage efficiency.     

Carboxylic acid-assisted solid-state synthesis of LiFePO4/C composites and their electrochemical properties as cathode materials for lithium-ion batteries

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.     

Physical and electrochemical characterizations of LiFePO4-incorporated Ag nanoparticles

Olivine-type LiFePO₄ composite materials for cathode material of the lithium-ion batteries were synthesized by using a sol-gel method and were coated by a chemical deposition of silver particles. As-obtained LiFePO₄/C-Ag (2.1 wt.%) composites were characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), conductivity measurements, cyclic voltammetry, as well as galvanostatic measurements. The results revealed that the discharge capacity of the LiFePO₄/C-Ag electrode is 136.6 mAh/g, which is 7.6% higher than that of uncoated LiFePO₄/C electrode (126.9 mAh/g). The LiFePO₄/C coated by silver nanoparticles enhances the electrode conductivity and specific capacity at high discharge rates. The improved capacity at high discharge rates may be attributed to increased electrode conductivity and the synergistic effect on electron and Li⁺ transport after silver incorporation.