CN103022483A - Preparation method of power lithium ion battery anode material - Google Patents
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Abstract
本发明涉及一种动力锂离子电池正极材料的制备方法，其具体步骤为：首先配制氧化石墨溶液，然后制备FeF3纳米颗粒，再制备非支撑的FeF3/氧化石墨烯薄膜；将得到的非支撑的FeF3/氧化石墨烯薄膜进行光还原，得到动力锂离子电池正极材料—FeF3/石墨烯薄膜。本发明在有效的解决FeF3材料在电池循环过程中严重的极化现象的同时，创新性的利用最新的光还原法还原FeF3/氧化石墨烯，以克服传统高温还原法还原FeF3生成Fe以及纳米颗粒团聚的缺点，大大的提高了锂离子电池正极材料的比容量。本发明制备工艺简单、制备的FeF3/石墨烯薄膜可以直接用作锂离子电池正极材料，避免另外加入导电添加剂和粘结剂，而且材料具有很好的延展性和灵活的加工性能，适合工业化大规模生产。The invention relates to a preparation method of a positive electrode material for a power lithium-ion battery. The specific steps are as follows: first preparing a graphite oxide solution, then preparing FeF 3 nanoparticles, and then preparing an unsupported FeF 3 /graphene oxide film; The supported FeF 3 /graphene oxide film is photoreduced to obtain the positive electrode material of the power lithium ion battery—FeF 3 /graphene film. The present invention effectively solves the serious polarization phenomenon of FeF 3 materials in the battery cycle process, and innovatively utilizes the latest photoreduction method to reduce FeF 3 /graphene oxide, so as to overcome the traditional high-temperature reduction method to reduce FeF 3 to generate Fe And the shortcomings of nanoparticle agglomeration, greatly improving the specific capacity of lithium-ion battery cathode materials. The preparation process of the present invention is simple, and the prepared FeF 3 /graphene film can be directly used as the positive electrode material of lithium-ion batteries, avoiding the addition of conductive additives and binders, and the material has good ductility and flexible processing performance, and is suitable for industrialization Mass production.
Description
技术领域：Technical field:
本发明涉及动力锂离子电池正极材料的制备方法，尤其涉及一种动力锂离子电池正极材料三氟化铁-石墨烯复合材料的制备方法，属于高容量、高效率动力锂离子电池正极材料的制备方法。The invention relates to a method for preparing a positive electrode material of a power lithium ion battery, in particular to a method for preparing a positive electrode material of a power lithium ion battery, an iron trifluoride-graphene composite material, which belongs to the preparation of a high capacity, high efficiency power lithium ion battery positive electrode material method.
背景技术：Background technique:
随着石油、煤等能源的日益紧缩，人类社会正面临着越来越严重的能源危机。锂离子电池作为高性能的绿色储能装置，具有性能好，安全，成本低，环境友好等特点，成为纯电动车（EV）、混合电动车（HEV）和航空航天等大型动力电源领域的首选。锂离子电池正极材料是电池的重要组成部分，正极材料的性能制约着锂离子电池的功率与能量密度，随着大容量储能设备的发展对动力型锂离子电池正极材料提出了更高的要求。目前对动力锂离子电池正极材料的研究，主要为尖晶石锰酸锂（LiMn2O4）、磷酸亚铁锂（LiF4PO4）和镍钴锰三元系Li（Ni，Co，Mn）O2。虽然对这些材料的研究取得了重大的进展，但是这些材料存在最重要的缺陷是理论容量都过低，使其在大型动力电源领域的广泛应用受到很大的限制。所以探索高容量、高效率、循环性能好和新型环保的正极材料成为近几年研究的热点。With the increasing reduction of oil, coal and other energy sources, human society is facing an increasingly serious energy crisis. As a high-performance green energy storage device, lithium-ion batteries have the characteristics of good performance, safety, low cost, and environmental friendliness, and have become the first choice for large-scale power sources such as pure electric vehicles (EV), hybrid electric vehicles (HEV) and aerospace . Lithium-ion battery cathode material is an important part of the battery. The performance of the cathode material restricts the power and energy density of the lithium-ion battery. With the development of large-capacity energy storage equipment, higher requirements are put forward for the cathode material of the power lithium-ion battery. . At present, the research on positive electrode materials for power lithium-ion batteries is mainly spinel lithium manganese oxide (LiMn 2 O 4 ), lithium iron phosphate (LiF 4 PO 4 ) and nickel-cobalt-manganese ternary system Li (Ni, Co, Mn ) O 2 . Although significant progress has been made in the research of these materials, the most important defect of these materials is that the theoretical capacity is too low, which limits their wide application in the field of large-scale power supplies. Therefore, exploring high-capacity, high-efficiency, good cycle performance and new environmentally friendly cathode materials has become a research hotspot in recent years.
三氟化铁（FeF3）具有很高的理论比容量(712mA·h·g-1)，约为目前产品化氧化物材料的3~5倍。同时FeF3还原电位高，电化学可逆容量高，安全性能好等优势，是新一代动力锂离子电池正极材料的研究热点。但三氟化铁（FeF3）的导电性差，在锂离子的脱嵌过程中，伴随着严重的极化现象，导致在充放电过程中容量衰减严重，降低了电池的效率和循环性能。Iron trifluoride (FeF 3 ) has a very high theoretical specific capacity (712mA·h·g -1 ), which is about 3~5 times that of the currently commercialized oxide materials. At the same time, FeF 3 has the advantages of high reduction potential, high electrochemical reversible capacity, and good safety performance. It is a research hotspot for the anode material of a new generation of power lithium-ion batteries. However, the conductivity of iron trifluoride (FeF 3 ) is poor. In the process of lithium ion intercalation and deintercalation, it is accompanied by severe polarization phenomenon, which leads to serious capacity decay during charge and discharge, which reduces the efficiency and cycle performance of the battery.
石墨烯因具有特殊结构和性能，成为国际科学研究的热点。这种单层碳原子厚度的二维碳材料具有卓越的导热导电性、超大的比表面积、良好的化学稳定性、宽的电化学窗口、低热膨胀系数以及优异的力学性能，而且石墨烯本身具有储锂特性，可以同三氟化铁（FeF3）进行复合，有效克服FeF3应用过程中的导电性差和极化严重等缺点。因此，FeF3/石墨烯复合材料有望成为新一代高容量、高效率的动力锂离子电池正极材料。Graphene has become a hotspot of international scientific research because of its special structure and properties. This two-dimensional carbon material with a single-layer carbon atom thickness has excellent thermal conductivity, large specific surface area, good chemical stability, wide electrochemical window, low thermal expansion coefficient and excellent mechanical properties, and graphene itself has Lithium storage characteristics, can be combined with iron trifluoride (FeF 3 ), effectively overcome the shortcomings of poor conductivity and serious polarization in the application process of FeF 3 . Therefore, FeF 3 /graphene composites are expected to become a new generation of high-capacity, high-efficiency lithium-ion battery cathode materials.
发明内容：Invention content:
本发明的目的在于克服现有技术的不足，提供一种高容量、高效率的动力锂离子电池正极材料的制备方法。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a method for preparing a high-capacity, high-efficiency power lithium-ion battery cathode material.
本发明的技术方案为：首先得到纳米级的FeF3，增加活性材料与锂离子接触面积的同时，减少了活性材料的绝对体积的变化，提高了材料的比容量。其次是通过自组装方式使纳米FeF3与石墨烯“骨架”复合，并采用最新的光还原法还原FeF3/氧化石墨烯以克服传统高温还原法生成Fe的缺点。利用石墨烯具有极好的导电能力和卓越的柔韧性，能与正极材料复合，从而获得优良的电极整体电学性能，避免额外加入导电添加剂和粘合剂，也克服了纳米FeF3在充放电过程中严重的极化现象。The technical proposal of the present invention is: first obtain nanoscale FeF 3 , increase the contact area between the active material and lithium ions, reduce the change of the absolute volume of the active material, and increase the specific capacity of the material. The second is to combine nano- FeF3 with graphene "skeleton" by self-assembly, and use the latest photoreduction method to reduce FeF3 /graphene oxide to overcome the shortcomings of traditional high-temperature reduction methods to generate Fe. Graphene has excellent electrical conductivity and excellent flexibility, and can be combined with positive electrode materials to obtain excellent overall electrical properties of the electrode, avoiding additional conductive additives and binders, and also overcomes the problem of nano-FeF 3 in the charge and discharge process severe polarization.
本发明的具体技术方案为：一种动力锂离子电池正极材料的制备方法，其具体步骤如下：The specific technical scheme of the present invention is: a kind of preparation method of positive electrode material of power lithium ion battery, and its specific steps are as follows:
1）氧化石墨溶液的制备：1) Preparation of graphite oxide solution:
通过改性的Hummer法制备氧化石墨，然后配制浓度为0.25g/L-1g/L的氧化石墨溶液；Prepare graphite oxide by a modified Hummer method, and then prepare a graphite oxide solution with a concentration of 0.25g/L-1g/L;
2）FeF3纳米颗粒的制备：2) Preparation of FeF 3 nanoparticles:
分别配制物质的量浓度为1-2mol/L的NH4HF2水溶液和0.1-0.5mol/L的Fe(NO3)3的乙醇溶液，按NH4HF2和Fe(NO3)3的物质量比3-6：1，搅拌的情况下，将NH4HF2水溶液加入到Fe(NO3)3的乙醇溶液中，随后继续搅拌反应，反应结束后洗涤，离心收集沉淀，沉淀为(NH4)3FeF6前驱体，将前驱体并干燥；最后将干燥的样品放置在石英舟中，放置在气氛保护的管式炉中，保持一定的气体流速，在300-500℃下，煅烧1-3h，得到FeF3纳米颗粒；Prepare respectively NH 4 HF 2 aqueous solution and 0.1-0.5 mol/L Fe(NO 3 ) 3 ethanol solution with concentration of 1-2 mol/L, according to the content of NH 4 HF 2 and Fe(NO 3 ) 3 The mass ratio is 3-6:1, under the condition of stirring, add the NH 4 HF 2 aqueous solution to the ethanol solution of Fe(NO 3 ) 3 , then continue to stir the reaction, wash after the reaction, and collect the precipitate by centrifugation, the precipitate is (NH 4 ) 3 FeF 6 precursor, dry the precursor; finally place the dried sample in a quartz boat, place it in an atmosphere-protected tube furnace, maintain a certain gas flow rate, and calcinate at 300-500°C for 1 -3h, obtain FeF 3 nanoparticles;
3）FeF3/石墨烯薄膜的制备：3) Preparation of FeF 3 /graphene film:
按纳米FeF3的质量与水的体积比为0.005g/ml-0.05g/ml，将纳米FeF3超声分散在去离子水中，得FeF3分散液，然后按FeF3的质量与氧化石墨的质量比为1-2：1，将FeF3分散液与浓度为0.25g/L-1g/L的氧化石墨溶液混合，继续超声分散后，将混合液真空抽虑到滤膜上面；自然风干，从滤膜上面取下来；得到非支撑的FeF3/氧化石墨烯薄膜；将得到的非支撑的FeF3/氧化石墨烯薄膜进行光还原，得到动力锂离子电池正极材料—FeF3/石墨烯薄膜。According to the volume ratio of the mass of nano- FeF3 to water is 0.005g/ml-0.05g/ml, ultrasonically disperse the nano- FeF3 in deionized water to obtain a FeF3 dispersion, and then press the mass of FeF3 to the mass of graphite oxide The ratio is 1-2:1, mix the FeF 3 dispersion with the graphite oxide solution with a concentration of 0.25g/L-1g/L, continue to ultrasonically disperse, and vacuum the mixed solution onto the filter membrane; Remove the top of the filter membrane; obtain an unsupported FeF 3 /graphene oxide film; perform photoreduction on the obtained unsupported FeF 3 /graphene oxide film to obtain a positive electrode material for a power lithium ion battery—FeF 3 /graphene film.
氧化石墨的制备优选通过改性的Hummer法制备氧化石墨，具体方法参见本发明人申请专利《一种氧化还原制备石墨烯的方法》（申请(专利)号:CN201110372309.X）。通过XRD、Raman和FT-IR表征，制备的氧化石墨氧化程度高，在水溶液中分散性好。The preparation of graphite oxide is preferably prepared by the modified Hummer method. For the specific method, please refer to the patent application "A method for preparing graphene by redox" (application (patent) number: CN201110372309.X). Characterized by XRD, Raman and FT-IR, the prepared graphite oxide has a high degree of oxidation and good dispersion in aqueous solution.
优选步骤（2）中将NH4HF2水溶液加入到Fe(NO3)3的乙醇溶液中，随后继续搅拌反应时间为2-5h；所述的洗涤为反应结束后加入乙醇洗涤体系，其中加入乙醇的体积与Fe(NO3)3的物质量比为8L/mol-20L/mol；优选步骤（2）中所述的离心的转速为3000-10000rpm；所述的干燥为将前驱体在50-80℃下真空干燥12-24h；优选步骤（2）中所述的气体流速为10-90ml·min-1。优选步骤（2）中所述的管式炉反应管为石英管或刚玉管。Preferably, in step (2), the NH 4 HF 2 aqueous solution is added to the ethanol solution of Fe(NO 3 ) 3 , and then the stirring is continued for 2-5 hours; the washing is to add the ethanol washing system after the reaction, wherein the The mass ratio of the volume of ethanol to Fe(NO 3 ) 3 is 8L/mol-20L/mol; the centrifugation speed described in the preferred step (2) is 3000-10000rpm; the drying is the precursor at 50 Vacuum drying at -80°C for 12-24 hours; preferably, the gas flow rate in step (2) is 10-90ml·min -1 . Preferably, the tube furnace reaction tube described in step (2) is a quartz tube or a corundum tube.
优选步骤（3）中所述的超声分散的频率均为40-80Hz；制备FeF3分散液时超声分散的时间为5-60min；FeF3分散液与氧化石墨溶液混合，继续超声分散的时间为1-2h。优选步骤（3）所述的滤膜为纤维素滤膜、PVDF滤膜、阳极电镀铝氧化膜或Anodisc无机膜的一种。The frequency of the ultrasonic dispersion described in the preferred step (3) is 40-80Hz; the time for ultrasonic dispersion when preparing the FeF 3 dispersion is 5-60min; the time for the FeF 3 dispersion to be mixed with the graphite oxide solution and to continue the ultrasonic dispersion is 1-2h. Preferably, the filter membrane described in step (3) is one of cellulose filter membrane, PVDF filter membrane, anodized aluminum oxide membrane or Anodisc inorganic membrane.
优选所述的光还原为将非支撑的FeF3/氧化石墨烯纸，剪切成小的带状，暴露在窗口尺寸为10mm×20mm的数码照相机的闪光灯下，距离闪光灯的距离为0.5-2mm，打开闪光灯，闪光时间在1-2毫秒。Preferably, the light reduction is to cut the unsupported FeF 3 /graphene oxide paper into small strips, and expose it to the flashlight of a digital camera with a window size of 10mm×20mm, and the distance from the flashlight is 0.5-2mm , turn on the flash, and the flash time is 1-2 milliseconds.
有益效果：Beneficial effect:
本发明制备的FeF3/石墨烯复合材料克服了目前正极材料领域的存在的关键问题，将正极材料的容量提高到目前传统氧化物材料的3-5倍，同时大大的提高了锂离子电池效率、循环稳定性和安全性，同时工艺简单，制备效率高、成本低廉，易于工业的大规模生产。The FeF 3 /graphene composite material prepared by the present invention overcomes the key problems existing in the field of positive electrode materials, increases the capacity of positive electrode materials to 3-5 times that of traditional oxide materials, and greatly improves the efficiency of lithium-ion batteries , cycle stability and safety, simple process, high preparation efficiency, low cost, and easy industrial mass production.
本发明采用FeF3活性材料纳米化和石墨烯复合化的联合使用，利用石墨烯卓越的导热导电性、超大的比表面积、良好的化学稳定性、低热膨胀系数以及优异的力学性能，可以有效的解决FeF3材料在循环过程中严重的极化现象。同时创新性的利用最新的光还原法还原FeF3/氧化石墨烯，以克服传统高温还原法还原FeF3生成Fe的缺点。最后石墨烯卓越的导电性质，避免了另外加入导电添加剂和粘结剂，制备的FeF3/石墨烯纸可以直接用作电池的正极，不需要任何后期处理，简化了电池正极的制备工艺。The present invention adopts the joint use of FeF3 active material nanometerization and graphene compounding, and utilizes graphene's excellent thermal conductivity, super large specific surface area, good chemical stability, low thermal expansion coefficient and excellent mechanical properties, which can effectively Solve the serious polarization phenomenon of FeF 3 material in the cycle process. At the same time, innovatively use the latest photoreduction method to reduce FeF 3 /graphene oxide to overcome the shortcomings of traditional high-temperature reduction method to reduce FeF 3 to generate Fe. Finally, the excellent conductive properties of graphene avoid the addition of conductive additives and binders, and the prepared FeF 3 /graphene paper can be directly used as the positive electrode of the battery without any post-processing, which simplifies the preparation process of the positive electrode of the battery.
附图说明：Description of drawings:
图1为FeF3/石墨烯薄膜的合成示意图；Fig. 1 is the synthesizing schematic diagram of FeF 3 /graphene film;
图2为FeF3/氧化石墨烯薄膜和FeF3/石墨烯薄膜的实物图；Fig. 2 is the physical figure of FeF 3 / graphene oxide film and FeF 3 / graphene film;
图3为实施例1用的石墨、制备的石墨烯和氧化石墨的XRD图；Fig. 3 is the XRD figure of the graphite that embodiment 1 uses, the graphene of preparation and graphite oxide;
图4为实施例1制备的(NH4)3FeF6前驱体、FeF3和FeF3/石墨烯薄膜的XRD图；Fig. 4 is the XRD pattern of (NH 4 ) 3 FeF 6 precursor, FeF 3 and FeF 3 /graphene film prepared in embodiment 1;
图5为实施例1制备的FeF3/氧化石墨烯薄膜的表面扫描电镜照片（a）、实施例1制备的FeF3/石墨烯薄膜的TEM照片（b）、实施例子1用光还原制备的FeF3/石墨烯薄膜的断面扫描电镜照片（c），实施例子1制备的FeF3/氧化石墨烯薄膜的断面扫描电镜照片（d）Figure 5 is the surface scanning electron micrograph (a) of the FeF 3 /graphene oxide film prepared in Example 1, the TEM photo (b) of the FeF 3 /graphene film prepared in Example 1, and the photoreduction prepared in Example 1. Cross-sectional scanning electron micrograph of FeF 3 /graphene film (c), cross-sectional scanning electron micrograph of FeF 3 /graphene oxide film prepared in Example 1 (d)
图6实施例1制备的FeF3(黑色原点)和光还原(红色三角)FeF3-GO纳米复合材料在100mAg-1条件下充放电循环时比容量与库仑效率曲线。Fig. 6 The specific capacity and coulombic efficiency curves of FeF 3 (black origin) and photoreduced (red triangle) FeF 3 -GO nanocomposites prepared in Example 1 under the condition of 100 mAg -1 charge and discharge cycles.
具体实施方式：Detailed ways:
下面结合附图及实施例对本发明作进一步详细说明。以下实施例中氧化石墨的制备参见本发明人申请专利《一种氧化还原制备石墨烯的方法》（申请(专利)号:CN201110372309.X）。FeF3/石墨烯薄膜的合成示意图如图1所示。The present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments. For the preparation of graphite oxide in the following examples, refer to the inventor's patent application "A Method for Preparing Graphene by Redox" (application (patent) number: CN201110372309.X). The schematic diagram of the synthesis of FeF 3 /graphene film is shown in Figure 1.
实施例1：Example 1:
1）氧化石墨的制备：1) Preparation of graphite oxide:
取1g（8000目）天然鳞片石墨与47ml质量浓度为98%硫酸混合均匀后，加入1.7g硝酸钾，在7℃的水浴中快速加入5.2g高锰酸钾，混合均匀，加入高锰酸钾的过程保持体系温度0-20℃。然后将体系温度升高到50℃，反应1.5h，然后加入70ml水，同时将体系升温至90℃反应13min，再加入160ml蒸馏水终止反应，离心洗涤至pH为6，70℃真空干燥得到氧化石墨固体。XRD表征如图3，氧化石墨的层间距离为0.863nm，相比初始石墨的层间距0.34nm，有很大的增加，说明插层氧化石墨的效果非常好。Take 1g (8000 mesh) of natural flake graphite and 47ml of sulfuric acid with a mass concentration of 98% and mix evenly, then add 1.7g of potassium nitrate, quickly add 5.2g of potassium permanganate in a water bath at 7°C, mix well, and then add potassium permanganate The process maintains the system temperature at 0-20°C. Then raise the temperature of the system to 50°C, react for 1.5h, then add 70ml of water, and at the same time raise the temperature of the system to 90°C for 13min, then add 160ml of distilled water to terminate the reaction, centrifugally wash until the pH is 6, and vacuum dry at 70°C to obtain graphite oxide solid. The XRD characterization is shown in Figure 3. The interlayer distance of graphite oxide is 0.863nm, which is greatly increased compared with the initial graphite interlayer distance of 0.34nm, indicating that the effect of intercalated graphite oxide is very good.
2）FeF3纳米颗粒的制备：2) Preparation of FeF 3 nanoparticles:
配制物质的量浓度为1mol/L的NH4HF2水溶液和0.2mol/L的Fe(NO3)3的乙醇溶液，取10ml NH4HF2水溶液逐滴加入到10ml的Fe(NO3)3乙醇溶液中，加入过程保持搅拌，随后继续搅拌2h。反应结束后，加入16ml的乙醇洗涤体系，在5000rpm的转速下离心收集沉淀，将收集的样品在60℃下真空干燥24h。最后将干燥的样品放置在石英舟中，放置在气氛为纯Ar气的石英管式炉中，气体流速为90ml.min-1，在400℃下，煅烧2h，得到FeF3纳米颗粒。XRD表征如图4，可以清楚的看出合成了纯相的(NH4)3FeF6前驱体和FeF3，没有杂质峰出现。图5b为FeF3/石墨烯薄膜TEM图，可以清楚的看到单分散的纳米三氟化铁，尺寸在20-30nm左右。The concentration of the prepared substance is 1mol/L NH 4 HF 2 aqueous solution and 0.2 mol/L Fe(NO 3 ) 3 ethanol solution, take 10ml NH 4 HF 2 aqueous solution and add dropwise to 10ml Fe(NO 3 ) 3 In the ethanol solution, keep stirring during the addition process, and then continue to stir for 2h. After the reaction, 16 ml of ethanol was added to wash the system, the precipitate was collected by centrifugation at 5000 rpm, and the collected sample was vacuum-dried at 60° C. for 24 hours. Finally, the dried sample was placed in a quartz boat, placed in a quartz tube furnace with an atmosphere of pure Ar gas at a gas flow rate of 90ml.min -1 , and calcined at 400°C for 2h to obtain FeF 3 nanoparticles. The XRD characterization is shown in Figure 4. It can be clearly seen that the pure-phase (NH 4 ) 3 FeF 6 precursor and FeF 3 are synthesized, and no impurity peaks appear. Figure 5b is a TEM image of the FeF 3 /graphene film, and it can be clearly seen that the monodispersed nano-iron trifluoride has a size of about 20-30nm.
3）FeF3/石墨烯薄膜的制备：3) Preparation of FeF 3 /graphene film:
称取0.05g FeF3纳米粉，在80Hz频率下，超声5min分散在1ml去离子水中，然后将FeF3分散液同100ml的浓度为0.5g/L的氧化石墨溶液混合，继续超声1.5h，然后将混合液真空抽滤到纤维素滤膜上面。将上层为FeF3/氧化石墨烯薄膜的滤膜在空气中自然风干后，从滤膜上面取下来，得到非支撑的FeF3/氧化石墨烯薄膜。将薄膜剪切成小的带状，暴露在窗口尺寸为10mm×20mm的数码照相机的闪光灯下，距离闪光灯的距离为0.5mm，打开闪光灯，闪光时间在2毫秒，得到锂离子电池正极材料—FeF3/石墨烯薄膜。图2为FeF3/氧化石墨烯，可以看到材料显暗棕色。图5a为FeF3/氧化石墨烯薄膜的表面SEM照片，从10微米的尺度可以看到表面很平整，1微米的尺度可以清楚的看到，氧化石墨烯包裹着纳米FeF3颗粒的结构，复合效果良好。图5d为FeF3/氧化石墨烯薄膜SEM断面照片，可以清晰的看到薄膜的规整的片层结构，尺寸在8微米左右。XRD表征如图4，FeF3/石墨烯材料的石墨烯剥离效果很好，没有明显的石墨特征峰出现，说明石墨烯在材料中以无序的结构存在。图5b为，FeF3/石墨烯薄膜的TEM照片，可以清楚的看到均匀分布的纳米FeF3颗粒，进一步说明FeF3和石墨烯的复合效果良好。图5c为光还原后的FeF3/石墨烯薄膜的SEM断面图，与还原前相比，结构变的杂乱，尺寸由原来的8μm增加到现在的20μm左右，说明光还原的效率高，瞬间产生的能量和蒸汽扩大了石墨烯的片层之间的距离，形成了理想的FeF3/石墨烯复合结构。FeF3/氧化石墨烯薄膜和FeF3/石墨烯薄膜的实物图如图2所示。Weigh 0.05g of FeF 3 nanopowder, and disperse it in 1ml of deionized water by ultrasonication for 5min at a frequency of 80Hz, then mix the FeF 3 dispersion with 100ml of graphite oxide solution with a concentration of 0.5g/L, continue ultrasonication for 1.5h, and then The mixture was vacuum filtered onto a cellulose filter. After the filter membrane whose upper layer is the FeF 3 /graphene oxide film is naturally air-dried in the air, it is removed from the filter membrane to obtain an unsupported FeF 3 /graphene oxide film. Cut the film into small strips, expose it to the flashlight of a digital camera with a window size of 10mm×20mm, the distance from the flashlight is 0.5mm, turn on the flashlight, and the flash time is 2 milliseconds to obtain the lithium-ion battery cathode material—FeF 3 / Graphene film. Figure 2 is FeF 3 /graphene oxide, it can be seen that the material is dark brown. Figure 5a is the SEM photo of the surface of the FeF 3 /graphene oxide film. From the scale of 10 microns, it can be seen that the surface is very smooth, and it can be clearly seen from the scale of 1 micron. The structure of graphene oxide wrapped nano-FeF 3 particles, composite works well. Figure 5d is a SEM cross-sectional photo of the FeF 3 /graphene oxide film, and the regular lamellar structure of the film can be clearly seen, with a size of about 8 microns. The XRD characterization is shown in Figure 4. The graphene exfoliation effect of the FeF 3 /graphene material is very good, and no obvious graphite characteristic peaks appear, indicating that graphene exists in a disordered structure in the material. Figure 5b is a TEM photo of the FeF 3 /graphene film, and uniformly distributed nano-FeF 3 particles can be clearly seen, which further illustrates that the composite effect of FeF 3 and graphene is good. Figure 5c is the SEM cross-sectional view of the FeF 3 /graphene film after photoreduction. Compared with before reduction, the structure becomes disordered, and the size increases from the original 8 μm to the current 20 μm, indicating that the efficiency of photoreduction is high and instantaneous The energy and steam expand the distance between graphene sheets, forming an ideal FeF 3 /graphene composite structure. The physical pictures of FeF 3 /graphene oxide film and FeF 3 /graphene film are shown in Fig. 2 .
4）电池组装和测试：4) Battery assembly and testing:
将纳米FeF3、超导炭黑和PVDF按照质量比为50：35：15溶解在NMP溶剂中，均匀涂覆在铝箔上，制备纯的FeF3正极片。在充满氩气的手套箱中，以金属锂片为负极，组装成纽扣电池。在1-4.5V的电压范围内，室温下，以100mAh/g的电流进行充放电循环测试，循环100次。Nano-FeF 3 , superconducting carbon black and PVDF were dissolved in NMP solvent at a mass ratio of 50:35:15, and evenly coated on aluminum foil to prepare a pure FeF 3 positive electrode sheet. In a glove box filled with argon, a lithium metal sheet was used as the negative electrode to assemble a button battery. In the voltage range of 1-4.5V, at room temperature, the charge-discharge cycle test was performed with a current of 100mAh/g, and the cycle was repeated 100 times.
将FeF3/石墨烯纸放置在铝箔上制成正极片，在气氛保护的手套箱中，以金属锂片为负极，组装成纽扣电池。在1-4.5V的电压范围内，室温下，以50-100mAh/g的电流进行充放电循环测试，循环100次。图6为纯的纳米FeF3和FeF3/石墨烯薄膜组装的电池在100mAh/g条件下充放电循环曲线。纯的FeF3正极材料的首次放电容量为587mAh/g，循环10周后，容量小于100mAh/g，容量衰减严重。FeF3/石墨烯薄膜正极材料的首次放电容量为700mAh/g左右，循环10周后，保留容量为580mAh/g左右，50周后，保留容量为225mAh/g，100周后保留容量为200mAh/g。说明FeF3/石墨烯薄膜相比纯的纳米FeF3，容量有很大的提高，而且具有良好的循环性能。Place the FeF 3 /graphene paper on the aluminum foil to make a positive electrode sheet, and in an atmosphere-protected glove box, use a metal lithium sheet as the negative electrode to assemble a button battery. In the voltage range of 1-4.5V, at room temperature, the charge-discharge cycle test is performed with a current of 50-100mAh/g, and the cycle is 100 times. Fig. 6 is the charging and discharging cycle curves of batteries assembled with pure nano-FeF 3 and FeF 3 /graphene film under the condition of 100mAh/g. The initial discharge capacity of pure FeF 3 cathode material is 587mAh/g, and after 10 cycles, the capacity is less than 100mAh/g, and the capacity fades seriously. The initial discharge capacity of FeF 3 /graphene thin film cathode material is about 700mAh/g, after 10 cycles, the retention capacity is about 580mAh/g, after 50 weeks, the retention capacity is 225mAh/g, and after 100 cycles, the retention capacity is 200mAh/g. g. It shows that the capacity of FeF 3 /graphene film is greatly improved compared with pure nano-FeF 3 , and it has good cycle performance.
实施例2：Example 2:
1）氧化石墨的制备：1) Preparation of graphite oxide:
取1g（8000目）天然鳞片石墨与56ml质量浓度为92%硫酸混合均匀后，加入1.2g硝酸钾，在11℃的水浴中快速加入5.8g高锰酸钾，混合均匀，加入高锰酸钾的过程保持体系温度0-20℃。然后将体系温度升高到50℃，反应2h，然后加入60ml水，同时将体系升温至75℃反应25min，再加入200ml蒸馏水终止反应，离心洗涤至pH为5，65℃真空干燥得到氧化石墨固体。同实施例1表征结果一致，氧化石墨的层间距离为0.85nm，相比于初始石墨，层间距离有明显的增加，说明氧化石墨氧化效果很好。Take 1g (8000 mesh) of natural flake graphite and 56ml of sulfuric acid with a mass concentration of 92% and mix evenly, then add 1.2g of potassium nitrate, quickly add 5.8g of potassium permanganate in a water bath at 11°C, mix well, and then add potassium permanganate The process maintains the system temperature at 0-20°C. Then raise the temperature of the system to 50°C, react for 2 hours, then add 60ml of water, and at the same time raise the temperature of the system to 75°C for 25 minutes, then add 200ml of distilled water to terminate the reaction, centrifugally wash until the pH is 5, and vacuum dry at 65°C to obtain solid graphite oxide . Consistent with the characterization results of Example 1, the interlayer distance of graphite oxide is 0.85nm, which is significantly increased compared with the initial graphite, indicating that the oxidation effect of graphite oxide is very good.
2）FeF3纳米颗粒的制备：2) Preparation of FeF 3 nanoparticles:
配制物质的量浓度为1.5mol/L的NH4HF2水溶液和0.5mol/L的Fe(NO3)3的乙醇溶液，取10ml NH4HF2水溶液逐滴加入到10ml的Fe(NO3)3乙醇溶液中，加入过程保持搅拌，随后继续搅拌3h。反应结束后，加入50ml的乙醇洗涤体系，在6000rpm的转速下离心收集沉淀，将收集的样品在70℃下真空干燥18h。最后将干燥的样品放置在石英舟中，放置在气氛为纯Ar气的刚玉管式炉中，气体流速为88ml.min-1，在300℃下，煅烧3h，得到FeF3纳米颗粒。The concentration of the prepared substance is 1.5mol/L NH 4 HF 2 aqueous solution and 0.5 mol/L Fe(NO 3 ) 3 ethanol solution, take 10ml NH 4 HF 2 aqueous solution and add dropwise to 10ml Fe(NO 3 ) 3 ethanol solution, keep stirring during the addition process, then continue to stir for 3h. After the reaction was completed, 50 ml of ethanol was added to wash the system, the precipitate was collected by centrifugation at 6000 rpm, and the collected sample was vacuum-dried at 70° C. for 18 h. Finally, the dried sample was placed in a quartz boat, placed in a corundum tube furnace with an atmosphere of pure Ar gas, the gas flow rate was 88ml.min -1 , and calcined at 300°C for 3h to obtain FeF 3 nanoparticles.
3）FeF3/石墨烯薄膜的制备：3) Preparation of FeF 3 /graphene film:
取实施例1中的氧化石墨固体，配制浓度为0.25g/L的GO溶液称。称取0.025g FeF3纳米粉，在70Hz频率下，超声15min分散在5ml去离子水中，然后将FeF3分散液同80ml的浓度为0.25g/L的氧化石墨溶液混合，继续超声2h，然后将混合液真空抽滤到PVDF滤膜上面。在空气中自然风干，将上层为FeF3/氧化石墨烯薄膜的滤膜在空气中自然风干后，从滤膜上面取下来，得到非支撑的FeF3/氧化石墨烯薄膜。将薄膜剪切成小的带状，暴露在窗口尺寸为10mm×20mm的数码照相机的闪光灯下，距离闪光灯的距离为1mm，打开闪光灯，闪光时间在1.5毫秒，得到锂离子电池正极材料-FeF3/石墨烯薄膜。Get the graphite oxide solid in Example 1 and prepare a GO solution with a concentration of 0.25g/L. Weigh 0.025g of FeF 3 nanopowder, and disperse it in 5ml of deionized water by ultrasonication for 15min at a frequency of 70Hz, then mix the FeF 3 dispersion with 80ml of graphite oxide solution with a concentration of 0.25g/L, continue ultrasonication for 2h, and then The mixture was vacuum filtered onto the PVDF membrane. Naturally air-dry in the air, after the filter membrane with the upper layer being the FeF 3 /graphene oxide film is naturally air-dried in the air, remove it from the filter membrane to obtain an unsupported FeF 3 /graphene oxide film. Cut the film into small strips, expose it to the flashlight of a digital camera with a window size of 10mm×20mm, the distance from the flashlight is 1mm, turn on the flashlight, and the flash time is 1.5 milliseconds to obtain the lithium-ion battery cathode material-FeF 3 / graphene film.
4）电池组装和测试：4) Battery assembly and testing:
将FeF3/石墨烯薄膜放置在铝箔上制成正极片，在气氛保护的手套箱中，以金属锂片为负极，组装成纽扣电池。在1-4.5V的电压范围内，室温下，以100mAh/g的电流进行充放电循环测试，循环100次。薄膜材料的首次放电比容量为682mAh/g，循环100次后为保留容量为212mAh/g。Place the FeF 3 /graphene film on the aluminum foil to make a positive electrode sheet, and in an atmosphere-protected glove box, use a metal lithium sheet as the negative electrode to assemble a button battery. In the voltage range of 1-4.5V, at room temperature, the charge-discharge cycle test was performed with a current of 100mAh/g, and the cycle was repeated 100 times. The first discharge specific capacity of the film material is 682mAh/g, and the retention capacity after 100 cycles is 212mAh/g.
实施例3：Example 3:
1）氧化石墨的制备：1) Preparation of graphite oxide:
取1g（8000目）天然鳞片石墨与43ml质量浓度为96%硫酸混合均匀后，加入2g硝酸钾，在10℃的水浴中快速加入6g高锰酸钾，混合均匀，加入高锰酸钾的过程保持体系温度0-20℃。然后将体系温度升高到45℃，反应3h，然后加入60ml水，同时将体系升温至85℃反应20min，再加入120ml蒸馏水终止反应，离心洗涤至pH为7，50℃真空干燥得到氧化石墨固体。同实施例1表征结果一致，氧化石墨的层间距离为0.845nm，相比于初始石墨，层间距离有明显的增加，说明氧化石墨氧化效果很好。Take 1g (8000 mesh) of natural flake graphite and 43ml of sulfuric acid with a mass concentration of 96% and mix evenly, then add 2g of potassium nitrate, quickly add 6g of potassium permanganate in a water bath at 10°C, mix well, and add potassium permanganate Keep the system temperature at 0-20°C. Then raise the temperature of the system to 45°C, react for 3 hours, then add 60ml of water, and at the same time raise the temperature of the system to 85°C for 20 minutes, then add 120ml of distilled water to terminate the reaction, centrifugally wash until the pH is 7, and vacuum dry at 50°C to obtain solid graphite oxide . Consistent with the characterization results of Example 1, the interlayer distance of graphite oxide is 0.845nm, which is significantly increased compared with the initial graphite, indicating that the oxidation effect of graphite oxide is very good.
2）FeF3纳米颗粒的制备：2) Preparation of FeF 3 nanoparticles:
配制物质的量浓度为2mol/L的NH4HF2水溶液和0.1mol/L的Fe(NO3)3的乙醇溶液，取9ml NH4HF2水溶液逐滴加入到30ml的Fe(NO3)3乙醇溶液中，加入过程保持搅拌，随后继续搅拌5h。反应结束后，加入60ml的乙醇洗涤体系，在8000rpm的转速下离心收集沉淀，将收集的样品在75℃下真空干燥14h。最后将干燥的样品放置在石英舟中，放置在气氛为纯Ar气的石英管式炉中，气体流速为82ml.min-1，在500℃下，煅烧1h，得到FeF3纳米颗粒。The amount of prepared substance is 2mol/L NH 4 HF 2 aqueous solution and 0.1mol/L Fe(NO 3 ) 3 ethanol solution, take 9ml NH 4 HF 2 aqueous solution and add dropwise to 30ml Fe(NO 3 ) 3 In the ethanol solution, keep stirring during the addition process, and then continue to stir for 5h. After the reaction, 60 ml of ethanol was added to wash the system, the precipitate was collected by centrifugation at 8000 rpm, and the collected sample was vacuum-dried at 75° C. for 14 h. Finally, the dried sample was placed in a quartz boat, placed in a quartz tube furnace with an atmosphere of pure Ar gas at a gas flow rate of 82ml.min -1 , and calcined at 500°C for 1 hour to obtain FeF 3 nanoparticles.
3）FeF3/石墨烯薄膜的制备：3) Preparation of FeF 3 /graphene film:
取实施例1中的氧化石墨固体，配制浓度为1g/L的GO溶液称。取0.04g FeF3纳米粉，在60Hz频率下，超声60min分散在2ml去离子水中，然后将FeF3分散液同20ml的浓度为1g/L的氧化石墨烯溶液混合，继续超声2.5h，然后将混合液真空抽滤到Anodisc无机膜上面。在空气中自然风干，从滤膜上面取下来。将上层为FeF3/氧化石墨烯薄膜的滤膜在空气中自然风干后，从滤膜上面取下来，得到非支撑的FeF3/氧化石墨烯薄膜。将薄膜剪切成小的带状，暴露在窗口尺寸为10mm×20mm的数码照相机的闪光灯下，距离闪光灯的距离为0.8mm，打开闪光灯，闪光时间在1毫秒，得到锂离子电池正极材料-FeF3/石墨烯薄膜。Get the graphite oxide solid in Example 1 and prepare a GO solution with a concentration of 1g/L. Take 0.04g of FeF 3 nanopowder and disperse it in 2ml of deionized water by ultrasonication for 60min at a frequency of 60Hz, then mix the FeF 3 dispersion with 20ml of graphene oxide solution with a concentration of 1g/L, continue ultrasonication for 2.5h, and then The mixture was vacuum filtered onto the Anodisc inorganic membrane. Air dry naturally and remove from the filter. After the filter membrane whose upper layer is the FeF 3 /graphene oxide film is naturally air-dried in the air, it is removed from the filter membrane to obtain an unsupported FeF 3 /graphene oxide film. Cut the film into small strips, expose it to the flashlight of a digital camera with a window size of 10mm×20mm, the distance from the flashlight is 0.8mm, turn on the flashlight, and the flash time is 1 millisecond to obtain the lithium-ion battery cathode material-FeF 3 / Graphene film.
4）电池组装和测试：4) Battery assembly and testing:
将FeF3/石墨烯薄膜放置在铝箔衬底上，制成正极片，在气氛保护的手套箱中，以金属锂片为负极，组装成纽扣电池。在1-4.5V的电压范围内，室温下，以100mAh/g的电流进行充放电循环测试，循环100次。薄膜材料的首次放电比容量为652mAh/g，循环100次后保留容量为193mAh/g。Place the FeF 3 /graphene film on the aluminum foil substrate to make a positive electrode sheet, and in an atmosphere-protected glove box, use the metal lithium sheet as the negative electrode to assemble a button battery. In the voltage range of 1-4.5V, at room temperature, the charge-discharge cycle test was performed with a current of 100mAh/g, and the cycle was repeated 100 times. The first discharge specific capacity of the thin film material is 652mAh/g, and the retention capacity after 100 cycles is 193mAh/g.
实施例4：Example 4:
1）氧化石墨的制备：1) Preparation of graphite oxide:
取5g（8000目）天然鳞片石墨与210ml质量浓度为94%硫酸混合均匀后，加入5.5g硝酸钾，在8℃的水浴中快速加入29g高锰酸钾，混合均匀，加入高锰酸钾的过程保持体系温度0-20℃。然后将体系温度升高到55℃，反应3h，然后加入350ml水，同时将体系升温至95℃反应15min，再用300ml蒸馏水和30ml双氧水（30wt%）还原过量的高锰酸钾，离心洗涤至pH为6，60℃真空干燥得到氧化石墨固体。同实施例1表征结果一致，氧化石墨的层间距离为0.815nm，相比于初始石墨，层间距离有明显的增加，说明氧化石墨氧化效果很好。Take 5g (8000 mesh) of natural flake graphite and 210ml of sulfuric acid with a mass concentration of 94% and mix evenly, then add 5.5g of potassium nitrate, quickly add 29g of potassium permanganate in a water bath at 8°C, mix well, add potassium permanganate The process maintains the system temperature at 0-20°C. Then raise the temperature of the system to 55°C, react for 3 hours, then add 350ml of water, and at the same time raise the temperature of the system to 95°C for 15 minutes, then reduce the excess potassium permanganate with 300ml of distilled water and 30ml of hydrogen peroxide (30wt%), and centrifugally wash to The pH was 6, and the graphite oxide solid was obtained by vacuum drying at 60°C. Consistent with the characterization results of Example 1, the interlayer distance of graphite oxide is 0.815nm, which is significantly increased compared with the initial graphite, indicating that the graphite oxide has a good oxidation effect.
2）FeF3纳米颗粒的制备：2) Preparation of FeF 3 nanoparticles:
配制物质的量浓度为1.2mol/L的NH4HF2水溶液和0.5mol/L的Fe(NO3)3的乙醇溶液，取50ml NH4HF2水溶液逐滴加入到30ml的Fe(NO3)3乙醇溶液中，加入过程保持搅拌，随后继续搅拌4h。反应结束后，加入200ml的乙醇洗涤体系，在10000rpm的转速下离心收集沉淀，将收集的样品在80℃下真空干燥12h。最后将干燥的样品放置在石英舟中，放置在气氛为纯Ar气的刚玉管式炉中，气体流速为79ml.min-1，3500℃下，煅烧2.5h，就获得了FeF3纳米颗粒。The concentration of the prepared substance is 1.2mol/L NH 4 HF 2 aqueous solution and 0.5 mol/L Fe(NO 3 ) 3 ethanol solution, take 50ml NH 4 HF 2 aqueous solution and add dropwise to 30ml Fe(NO 3 ) 3 ethanol solution, keep stirring during the addition process, then continue to stir for 4h. After the reaction was completed, 200 ml of ethanol was added to wash the system, and the precipitate was collected by centrifugation at 10,000 rpm, and the collected sample was vacuum-dried at 80° C. for 12 hours. Finally, the dried sample was placed in a quartz boat, placed in a corundum tube furnace with pure Ar gas at a gas flow rate of 79ml.min -1 , and calcined at 3500°C for 2.5h to obtain FeF 3 nanoparticles.
3）FeF3/石墨烯薄膜的制备：3) Preparation of FeF 3 /graphene film:
取实施例1中的氧化石墨固体，配制浓度为0.35g/L的GO溶液称。取0.035gFeF3纳米粉，在40Hz频率下，超声30min分散在4ml去离子水中，然后将FeF3分散液同100ml的浓度为0.35g/L的氧化石墨烯溶液混合，继续超声1h，然后将混合液真空抽滤到阳极电镀铝氧化膜上面。将上层为FeF3/氧化石墨烯薄膜的滤膜在空气中自然风干后，从滤膜上面取下来，得到非支撑的FeF3/氧化石墨烯薄膜。将薄膜剪切成小的带状，暴露在窗口尺寸为10mm×20mm的数码照相机的闪光灯下，距离闪光灯的距离为2mm，打开闪光灯，闪光时间在1.5毫秒，得到锂离子电池正极材料-FeF3/石墨烯薄膜。Get the graphite oxide solid in Example 1 and prepare a GO solution with a concentration of 0.35g/L. Take 0.035g of FeF 3 nanopowder and disperse it in 4ml of deionized water by ultrasonication for 30min at a frequency of 40Hz, then mix the FeF 3 dispersion with 100ml of graphene oxide solution with a concentration of 0.35g/L, continue ultrasonication for 1h, and then mix The liquid is vacuum filtered onto the anodized aluminum oxide film. After the filter membrane whose upper layer is the FeF 3 /graphene oxide film is naturally air-dried in the air, it is removed from the filter membrane to obtain an unsupported FeF 3 /graphene oxide film. Cut the film into small strips, expose it to the flashlight of a digital camera with a window size of 10mm × 20mm, the distance from the flashlight is 2mm, turn on the flashlight, and the flash time is 1.5 milliseconds to obtain the lithium-ion battery cathode material-FeF 3 / graphene film.
4）电池组装和测试：4) Battery assembly and testing:
将FeF3/石墨烯薄膜放置在铝箔上制成正极片，在充满氩气的手套箱中，以金属锂片为负极，组装成纽扣电池。在1-4.5V的电压范围内，室温下，以100mAh/g的电流进行充放电循环测试，循环100次。薄膜材料的首次放电容量为667mAh/g，循环100次后保留容量为223mAh/g。Place the FeF 3 /graphene film on the aluminum foil to make a positive electrode sheet, and in a glove box filled with argon gas, use the metal lithium sheet as the negative electrode to assemble a button battery. In the voltage range of 1-4.5V, at room temperature, the charge-discharge cycle test was performed with a current of 100mAh/g, and the cycle was repeated 100 times. The initial discharge capacity of the thin film material is 667mAh/g, and the retention capacity after 100 cycles is 223mAh/g.
本发明通过结合FeF3活性材料的纳米化和石墨烯复合化工艺，利用具有卓越的导热导电性、超大的比表面积、良好的化学稳定性、宽的电化学窗口、低热膨胀系数以及优异的力学性能的石墨烯作为复合物，而且石墨烯本身具有储锂特性，在有效的解决FeF3材料在电池循环过程中严重的极化现象的同时，创新性的利用最新的光还原法还原FeF3/氧化石墨烯薄膜，以克服传统高温还原法还原FeF3生成Fe以及纳米颗粒团聚的缺点，大大的提高了锂离子电池正极材料的容量，约为目前主要研究热点正极材料的3-5倍。本发明制备工艺简单、制备的FeF3/石墨烯薄膜可以直接用作锂离子电池负极材料，避免另外加入导电添加剂和粘结剂，而且材料具有很好的延展性和灵活的加工性能，适合工业化大规模生产。In the present invention, by combining the nanometerization of FeF3 active material and graphene compounding process, it has excellent thermal conductivity, super large specific surface area, good chemical stability, wide electrochemical window, low thermal expansion coefficient and excellent mechanical properties. Graphene with high performance is used as a composite, and graphene itself has lithium storage characteristics. While effectively solving the serious polarization phenomenon of FeF 3 materials during battery cycling, innovatively use the latest photoreduction method to reduce FeF 3 / Graphene oxide film, to overcome the shortcomings of traditional high-temperature reduction method to reduce FeF3 to generate Fe and nanoparticle agglomeration, greatly improves the capacity of lithium-ion battery cathode materials, which is about 3-5 times that of the current main research hotspot cathode materials. The preparation process of the present invention is simple, and the prepared FeF 3 /graphene film can be directly used as the negative electrode material of lithium-ion batteries, avoiding the addition of conductive additives and binders, and the material has good ductility and flexible processing performance, and is suitable for industrialization Mass production.
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