LiFePO4/C复合材料制备过程中碳源及碳包覆方法的研究进展

LiFePO4以其价格低廉、稳定性好、循环性能好和无毒等优点,有望成为下一代锂离子电池的正极材料,但是LiFePO4电导率低和锂离子扩散系数小限制了它的实用化。碳包覆作为一种非常有效的导电改性方法,受到极大关注。在碳包覆中采用不同的碳源和不同的碳包覆方法,对LiFePO4的电化学性能影响不同。结合国内外的研究现状,综述了LiFePO4/C复合材料制备过程中不同碳源以及不同的碳包覆方法对其电化学性能影响的研究进展。     

用两种碳源制备高性能LiFePO4/C正极材料

为了提高LiFePO4材料的电化学性能,以碳溶胶和葡萄糖两种物质为碳源、采用高温固相法制备了LiFePO4/C复合正极材料.通过XRD、TEM、恒电流充放电等方法研究了材料的结构与电化学性能.XRD结果表明,两种碳源的添加对LiFePO4的晶体结构没有影响.从TEM图上可观测到颗粒外部明显的碳包覆层.电化学性能测试表明,在同样倍率下,以两种碳源制备的LiFePO4/C材料放电比容量高于以单一碳源制备的LiFePO4/C,且表现出优良倍率性能和循环稳定性:在0.1C下的放电比容量达162mAh/g,1C下放电比容量为157mAh/g,循环20次后容量没有任何衰减.     

高密度LiFePO4/C正极材料的合成其及电化学性能研究

以Li2CO3为锂源,葡萄糖为C源,与高密度前驱体FePO4混合,采用高温固相反应法合成高密度的锂离子电池正极材料LiFePO4/C复合材料.采用X射线衍射、电子扫描显微镜和恒电流充放电对制得的LiFPO4进行了研究.结果表明,合成材料结晶完整,为均一的橄榄石型结构.C的含量在很大程度上影响LiFePO4的密度,当C的含量为3.0%(质量分数)时,所制正极材料LiFePO4/C的振实密度可达到2.14g/cm3,0.1C放电容量为121.5mAh/g,体积比容量达到260.OmAh/V.     

LiFePO4/C正极材料的微波合成及性能研究

采用机械球磨结合微波辐射工艺合成C包覆锂离子电池正极材料LiFePO4/C.通过X射线衍射(XRD)、扫描电镜(SEM)和恒电流充放电测试研究了不同C源和掺C量对样品物相结构、形貌和电化学性能的影响.实验结果表明,微波法可以快速合成LiFePO4/C正极材料;以乙炔黑作为C源,掺杂8%(质量分数)所合成的样品具有最好的电化学性能,在室温下以20mA/g进行充放电测试,其首次放电容量为148.44mAh/g,10次循环后仍有144.74mAh/g,容量保持率为97.51%.     

锂离子电池正极材料LiFePO4的研究进展

LiFePO4因具有高的比容量、良好的循环性、环境友好等特点，成为目前最受关注的锂离子电池正极材料。概述了LiFePO4的结构和电化学性能，介绍了LiFePO4主要的几种制备方法，包括固相法、水热法、微波法。同时阐述了提高LiFePO4电化学性能所做的改性研究，并对该材料的发展方向进行了展望。     

焙烧温度对LiFePO4/C复合材料的影响

采用两步高温固相合成法制备锂离子电池正极复合材料LiFePO4/C复合材料。经300℃预培烧及后续高温培烧原材料,高温焙烧温度分别为600℃、650℃、700℃时,均得到了纳米尺寸的LiFePO4/C复合材料。在高温焙烧温度为650℃时,X射线衍射(XRD)结果表明,所得到的LiFePO4/C样品无杂质产生、峰型完好且结晶良好;扫描电镜(SEM)测试结果表明,所得材料的纯度较高、颗粒较小,无团聚现象。电化学性能测试结果表明培烧温度为650℃时,材料具有最好的电化学性能,电池的充放电循环性能最好。     

烧结方式对LiFePO4/C复合正极材料电化学性能的影响

对LiFePO4/C复合前驱体,分别采用静态氮气气氛,动态氮气气氛及静态真空三种烧结方式进行碳热还原合成LiFePO4/C复合正极材料.采用XRD、SEM、CV和充放电循环测试等方法分析和表征材料的结构、形貌和电化学性能.结果表明,烧结方式对所得材料的结晶度、晶粒大小、碳含量、合成温度以及电化学性能均有显著影响.真空烧结所得材料结晶度高,而动态气氛烧结对材料颗粒细化及均匀化都有积极影响,同时也能有效促进锂离子扩散动力学.动态气氛烧结可将材料的烧结温度降低到500℃,且所得材料表现出优异的电化学性能.0.5C倍率下循环首次放电比容量达到163.4 mAh/g,50次循环后容量保持率为99.02%.     

LiFePO4/C制备工艺的优化及其性能

用共沉淀法制备了球形NH4FePO4·H2O前驱体,再与Li2CO3和葡萄糖混合用固相焙烧法制备了LiFePO4/C正极材料.利用正交实验考察了焙烧温度、焙烧时间、球磨时间、x(Li):x(Fe)和葡萄糖用量等对材料首次放电比容量的影响,得到了最佳工艺条件.通过XRD、SEM、FTIR和恒流充放电测试仪等测试了材料的结构和电化学性能.所得材料在室温下电流密度为0.1、0.5和1C时首次放电比容量分别为147.6、136.7和122.3mAh/g,循环50次后容量分别为142.8、127.3和106.7mAh/g;在60℃下电流密度为0.5C时,其首次放电比容量为163.8mAh/g,循环性能良好.     

柠檬酸包覆合成LiFePO4/C工艺的优化

以柠檬酸为碳源,采用机械液相球磨与高温固相烧结相结合制备了LiFePO4/C复合材料,考察了烧结温度、烧结时间、柠檬酸用量、球磨时间等工艺条件对LiFePO4/C材料性能的影响.采用XRD、SEM和恒电流充放电等手段对该材料进行结构表征和电化学性能测试.结果表明,合成LiFePO4/C复合正极材料的适宜工艺为,球磨时间10h,烧结温度600℃,烧结时间18h,柠檬酸用量10%,气体流量0.6L/min.在优化工艺条件下制备的LiFePO4/C复合正极材料首次放电容量可达到146.2mAh/g.     

聚丙烯酰胺改性LiFePO4/C正极材料的研究

以聚丙烯酰胺(PAM)作为分散剂, 采用液相控制结晶-碳热还原法制备LiFePO₄/C正极材料, 考察了PAM对LiFePO₄/C正极材料性能的影响, 采用热化学分析、X射线衍射、扫描电镜、碳含量分析和充放电测试等分析测试手段对材料进行表征。结果表明, 将PAM溶于酸液中且添加量为1.5wt%时制备的LiFePO₄平均粒径约为100 nm, 颗粒分散较为均匀; 该材料在0.1C、1C、2C、5C和10C倍率下首次放电比容量分别为153.8、142.5、138.4、128.7和124.3 mAh/g, 1C倍率下循环100次后容量保持率仍在99%以上; 交流阻抗分析表明: 1.5wt%PAM改性后的材料的各种阻抗值均降低, 锂离子的导电速率提高了28倍。PAM改性后的LiFePO₄/C正极材料的离子及电子导电性提高了, 具有优良的倍率性能与循环性能, 有利于大规模推广应用。     

Electrospinning fabrication and electrochemical properties of LiFePO4/C composite nanofibers

LiFePO₄/C composite nanofibers were synthesized by calcination of the [LiOH + Fe(NO₃)₃ + H₃PO₄]/PVP electrospun nanofibers. Polyvinyl pyrrolidone (PVP) was used as the electrospinning template and carbon source. During the calcination [LiOH + Fe(NO₃)₃ + H₃PO₄] were transformed to LiFePO₄ and PVP was decomposed into carbon. The morphology and properties of the as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller (BET) specific surface area analysis, electrochemical impedance spectroscopy and galvanostatic charge–discharge measurements. The results indicate that the mean diameter of as-prepared LiFePO₄/C composite nanofibers is 179.08 ± 29.66 nm and the BET specific surface area is 66.59 m² g^?1. The addition of carbon does not affect the structure of LiFePO₄, but improves its electrochemical performances. At the current density of 0.2 C, the initial discharge capacity of LiFePO₄/C electrode is 133.6 mAh g^?1 and there is no obvious capacity fading after 100 cycles. The formation mechanism of the LiFePO₄/C composite nanofibers was also proposed.     

用碳热还原法制备LiFePO4/C复合正极材料

以Fe2O3为铁源,以葡萄糖为碳添加剂,利用碳热还原法成功地制备了LiFePO4/C复合材料.研究了不同焙烧温度对样品性能的影响.利用X射线衍射仪、扫描电镜和碳硫(质量分数)分析方法对所得样品的晶体结构、表面形貌、含碳量进行分析研究.研究结果表明,样品中碳含量(质量分数)为10%的LiFePO4/C复合材料为单一的橄榄石型晶体结构, 碳的加入使LiFePO4 颗粒粒径减小.碳分散于晶体颗粒之间,增强了颗粒之间的导电性.电化学性能测试结果表明,LiFePO4/C充放电性能和循环性能都得到显著改善.其中,碳含量为10%在700℃下焙烧8h合成出的样品电化学性能最佳,在0.1、0.5和1C倍率下放电,LiFePO4/C首次放电比容量达159.3、137.0、130.6mAh/g,充放电循环30次,容量只衰减了2.2%、5.3%、7.6%.其表现出良好的循环性能.     

Comparison of electrochemical performances of LiFePO4/C composite materials by two preparation routes

This study reports on the preparation of LiFePO₄/C composite materials prepared by the hydrothermal and sol–gel processes for comparison. The synthesis condition on the hydrothermal process was performed at 170 °C for 19 h. The polystyrene (PS) polymer was used as a carbon source; the PS was added at a range of 0–5 wt.%. The temperature of the post-thermal process was set at 750–850 °C. The citric acid (denoted as CA) was used as the reducing agent and the carbon source in the sol–gel process. The temperatures of the sintering process were set at a range of 650–850 °C. The optimal sintering temperature was at 850 °C for 12 h in the hydrothermal process; the optimal carbon residue content was approximately 3.20 wt.%. It was revealed that the highest discharge capacity of LiFePO₄/C composites by the hydrothermal process at 0.1 C is 163 mAh g^?1. The optimal sintering temperature was found to be at 750 °C for the sol–gel process. The highest carbon content was approximately 11.94 wt.% as the molar ratio of CA is 1.0. The highest discharge capacity of LiFePO₄/C composites by the sol–gel process at 0.1 C was approximately 130.35 mAh g^?1.     

Effects of particle size and carbon coating on electrochemical properties of LiFePO4/C prepared by hydrothermal method

In this study, well-crystallized phase pure LiFePO₄/C (LFP/C) powders were synthesized using the hydrothermal reaction method. To improve the electronic conductivity of the LFP/C powder after ball-milling, the LFP/C powders were double-coated with carbon. Scanning electron microscopy and transmission electron microscopy were employed to observe the micromorphology of the samples and the carbon coating, which was analyzed using Raman spectroscopy. Furthermore, the electrochemical properties were evaluated using cyclic voltammetry, electrochemical impedance spectra, and the charge–discharge cycling test. The ball-mill and the process for double-coating carbon decrease the particle size and increase the conductivity of the LFP/C, thereby reducing the Li-ion diffusion length and improving the reversibility of the Li-ion intercalation/de-intercalation in the LFP/C crystallites. The capacity of the small-particle LFP/C with the double-layer carbon coating was 133 mAh/g at 0.1 °C, and remained at 83 mAh/g as the charge–discharge rate increased to 10 °C. In addition, good cycle stability was observed, with a retention rate of 98 % after 50 cycles at 1 °C.     

改进固相法制备LiFePO4/C正极材料及其性能

采用改进的固相反应法制备了掺碳的磷酸铁锂正极材料,并用XRD,SEM,元素分析,红外光谱及激光粒度分布仪等对样品进行了测试分析.结果表明,样品具有单一的橄榄石结构和较好的放电平台(约3.4V),粒度较小粒径分布均匀,0.1C首次放电比容量为137.8mAh/g,循环20次后容量保持率为92.6%,以1C倍率首次放电比容量为129.6mAh/g,循环20次后容量下降10.8%.     

Coaxial electrospinning fabrication and electrochemical properties of LiFePO4/C/Ag composite hollow nanofibers

LiFePO₄/C/Ag composite hollow nanofibers were synthesized by calcination of the coaxial electrospun nanofibers with polyvinyl pyrrolidone (PVP) as core and [LiOH + Fe(NO₃)₃ + H₃PO₄]/PVP/AgNO₃ as shell. PVP was used as the electrospinning template and carbon source. During the calcination, LiFePO₄ precursor was transformed to LiFePO₄ while AgNO₃ and PVP were decomposed into silver and carbon. The morphology and properties of the as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, BET specific surface area analysis, electrochemical impedance spectroscopy and galvanostatic charge–discharge measurements. The results indicate that the mean diameter of as-prepared LiFePO₄/C/Ag composite hollow nanofibers is 154.5 ± 18.6 nm and the BET specific surface area is 119.14 m² g^?1. The addition of silver and carbon does not affect the structure of LiFePO₄, but improves its electrochemical performances. At the current density of 0.2 C, the initial discharge capacity of LiFePO₄/C/Ag hollow nanofibers electrode is 138.71 mAh g^?1, which is higher than that of LiFePO₄/C nanofibers electrode. The improved specific capacity may be attributed to increase electrode conductivity after the introduction of silver. The formation mechanism of the LiFePO₄/C/Ag composite hollow nanofibers was also proposed.     

Modifying the morphology and structure of graphene oxide provides high-performance LiFePO4/C/rGO composite cathode materials

In this study we synthesized LiFePO₄/carbon/reduced graphene oxide (LFP/C/rGO) composite cathode materials using a method involving sol–gel processing, spray-drying, and calcination. To improve the electrochemical performance of LFP/C, we tested graphene oxides (GOs) of various morphologies as conductive additives, including pristine GO, three-dimensional GO, and hydrothermal porous GO (HTGO). Among our samples, the cathode material prepared through spray-drying with the addition of 1 wt% of HTGO (denoted SP-LFP/C/1%rHTGO) displayed the best electrochemical performance; its discharge capacities at 0.1C, 1C, 5C, and 10C were 160.5, 151.8, 138.8, and 130.3 mA h g⁻¹, respectively. From measurements of its long-term cycling performance, the discharge capacity in the first cycle and the capacity retention after 30 cycles at 0.1C were 160.2 mA h g⁻¹ and 99.6%, respectively; at 10C, these values were 132.2 mA h g⁻¹ and 91.8%, respectively. The electronic conductivity of SP-LFP/C/1%rHTGO (6.58 × 10⁻⁵ S cm⁻¹) was higher than that of the pristine LFP/C (9.24 × 10⁻⁶ S cm⁻¹). The Li⁺ ion diffusivities (D_Li⁺) of the SP-LFP/C/1%HTGO cathode, measured using AC impedance (3.91 × 10⁻¹³ cm² s⁻¹) and cyclic voltammetry (6.66 × 10⁻¹⁰ cm² s⁻¹ for discharge), were superior to those of the LFP/C cathode (9.31 × 10⁻¹⁵ cm² s⁻¹ and 1.79 × 10⁻¹⁰ cm² s⁻¹ for discharge, respectively). Galvanostatic intermittent titration revealed that the value of D_Li⁺ was located in a reasonable range from 1 × 10⁻¹⁰ to 1 × 10⁻¹⁷ cm² s⁻¹; its value dropped to its lowest point when the state of charge was close to 50%. Thus, the use of spray-drying and the addition of conductive HTGO (having a 3D wrinkled morphology and interconnected pore structure) can enhance the electronic conductivity and Li⁺ ion diffusivity of LFP/C cathode materials, thereby improving the electrochemical performance significantly.     

Hydrothermal synthesis of spindle-shape and craggy-faced LiFePO4/C composite materials for high power Li-ion battery

The large surface area and excellent conductivity are two important factors for LiFePO₄ to achieve high power capability in Li-ion batteries. This paper presents a hydrothermal method to obtain large surface, spindle-shape and carbon-coated LiFePO₄ particles. Pyrogallic acid was added to serve as reducing agent, surface growth directing template and carbon source to synthesize craggy-faced LiFePO₄/C composite materials. It helps to control the morphology and implement carbon coating on the particles. The LiFePO₄/C particle synthesized with 8 wt.% pyrogallic acid demonstrates excellent electrochemical performance, cyclic ability and rate capability.     

不同锂源水热法合成LiFePO4的研究进展

LiFePO4具有较高的能量密度、较好电化学性能和热力学稳定性而成为最为热门、应用最为广泛的锂离子电池正极材料。其合成方法有很多,其中的水热法具有反应快、操作简单、产品形貌易于控制且颗粒粒径小等优点而备受关注。用不同的锂源合成出来的产品的形貌和性能也不一样。现分别以磷酸锂、碳酸锂、醋酸锂、氢氧化锂等化合物为锂源对水热法合成LiFePO4进行了一定探讨,并综述了各自利用水热法合成磷酸铁锂的研究进展情况。