技术领域technical field
本发明属于新能源材料制备与应用领域，具体涉及一种基于溶剂热方法合成高可逆性和高库伦效率的菊花形状纳米氧化钛的制备方法。The invention belongs to the field of preparation and application of new energy materials, and specifically relates to a method for preparing chrysanthemum-shaped nano-titanium oxide with high reversibility and high Coulombic efficiency based on a solvothermal method.
背景技术Background technique
锂离子电池作为新一代的清洁能源,是众多新型能源中的佼佼者,它被誉为“21世纪绿色二次电池”，因其能量密度高，循环寿命长，环境污染小，自放电小、无“记忆效应”等优点被广泛应用于通信设备、便携电子设备、静态储能系统以及电动汽车市场领域，其电化学性能主要取决于正负极电极材料。目前，碳材料是商业化最常用的锂离子电池负极材料，但由于操作电压与金属锂电极电位接近，在充放电过程中，可能会在碳电极表面析出金属锂，而形成的支晶会造成短路，尤其是在高倍率充放电过程中，会引发很大的安全问题。此外，首次充放电过程中，碳材料与电解液发生反应表面形成一层电子绝缘的固体电解质界面膜(SEI膜)，导致电解液消耗和较低的首轮库伦效率。因此，开发新型具有良好的循环稳定性和安全性的负极材料具有重要意义。As a new generation of clean energy, lithium-ion battery is the leader among many new energy sources. It is known as "21st century green secondary battery" because of its high energy density, long cycle life, low environmental pollution, small self-discharge, The advantages of no "memory effect" are widely used in communication equipment, portable electronic equipment, static energy storage systems and electric vehicle markets, and its electrochemical performance mainly depends on the positive and negative electrode materials. At present, carbon materials are the most commonly used anode materials for commercial lithium-ion batteries, but because the operating voltage is close to the potential of metal lithium electrodes, metal lithium may be precipitated on the surface of carbon electrodes during charge and discharge, and the formed dendrites will cause Short circuit, especially during high rate charge and discharge, will cause great safety problems. In addition, during the first charge and discharge process, the surface of the carbon material reacts with the electrolyte to form an electronically insulating solid electrolyte interfacial film (SEI film), resulting in electrolyte consumption and lower first-round Coulombic efficiency. Therefore, it is of great significance to develop new anode materials with good cycle stability and safety.
二氧化钛作为一种“零应变”材料，充放电过程中结构几乎不发生变化，具有高安全性、循环性能稳定、资源丰富、价格低廉、环境友好等优点，使其成为锂离子电池极具发展前景的负极材料。然而，二氧化钛电导率低(～10-13S cm-1)，导致倍率性能较差，尤其应用于电动汽车、大型储能电池领域受到极大的限制。因而，提高二氧化钛电极材料的导电性，进而提高倍率性能是其在锂离子电池应用领域亟待解决的问题。通常改善二氧化钛电极材料的导电性有两种方法，第一，复合高导电相物质，包括：金属、金属氧化物、碳基材料等；第二，合成纳米/微米分级结构，以此来提高二氧化钛的电极性能。然而，复合高导电相物质通常需要复杂的工艺过程，不适合大规模生产，因此合成纳米/微米分级结构被广泛认为是最佳的选择之一。纳米结构材料缩短了锂离子在固相中的扩散长度，同时增加电极和电解质之间的接触面积进而增加反应活性区域，导致每单位面积的电流密度减少，进而增加充放电速率。分级结构缩短了电子与锂离子的扩散长度，加强了锂离子在重复的嵌入与脱出过程中应力-应变释放。Wei等(J.Mater.Chem.A，2014，2：1102)合成分级结构的二氧化钛微球应用于锂离子电池，电流密度为1C时，100次充放电循环后容量仅为160.4mAh g-1，当电流密度提高到5C和10C时，容量分别降低到128.4和105.6mAh g-1。很多研究工作虽然致力于开发分级结构的二氧化钛，但应用于锂离子电池尚未获得满意的容量与稳定的循环性能，而且有些研究工作为了得到分级结构需要引入表面活性剂，这大大限制了大规模生产与应用。Titanium dioxide, as a "zero strain" material, hardly changes its structure during charging and discharging. It has the advantages of high safety, stable cycle performance, abundant resources, low price, and environmental friendliness, making it a promising development prospect for lithium-ion batteries. negative electrode material. However, the low conductivity of titanium dioxide (~10-13 S cm-1 ) leads to poor rate performance, which limits its application in the fields of electric vehicles and large energy storage batteries. Therefore, improving the conductivity of titanium dioxide electrode materials, and then improving the rate performance is an urgent problem to be solved in the field of lithium-ion battery applications. Generally, there are two ways to improve the conductivity of titanium dioxide electrode materials. First, compound high-conductivity phase materials, including: metals, metal oxides, carbon-based materials, etc.; second, synthesize nano/micro hierarchical structures to improve titanium dioxide. electrode performance. However, complex high-conductivity phase materials usually require complex processes and are not suitable for large-scale production, so the synthesis of nano/micro hierarchical structures is widely considered to be one of the best options. Nanostructured materials shorten the diffusion length of lithium ions in the solid phase, while increasing the contact area between the electrode and the electrolyte to increase the reactive area, resulting in a decrease in the current density per unit area, thereby increasing the charge-discharge rate. The hierarchical structure shortens the diffusion length of electrons and lithium ions, and strengthens the stress-strain release of lithium ions during repeated intercalation and extraction. Wei et al. (J.Mater.Chem.A, 2014, 2:1102) synthesized titanium dioxide microspheres with hierarchical structure and applied them to lithium-ion batteries. When the current density was 1C, the capacity after 100 charge-discharge cycles was only 160.4mAh g-1 , when the current density increased to 5C and 10C, the capacity decreased to 128.4 and 105.6mAh g-1 , respectively. Although a lot of research work is dedicated to the development of titanium dioxide with hierarchical structure, it has not yet obtained satisfactory capacity and stable cycle performance when applied to lithium-ion batteries, and some research work requires the introduction of surfactants in order to obtain a hierarchical structure, which greatly limits large-scale production. with application.
发明内容Contents of the invention
本发明的目的就是为了克服上述现有技术存在的缺陷，提供一种简单、环境友好的制备锂离子电池负极材料菊花形状纳米二氧化钛的方法，该方法通过合成出分级结构，缩短锂离子与电子扩散距离，增大比表面积以增加电极和电解质之间的接触面积，从而提高大倍率放电性能与高的库伦效率，以满足当前对锂离子电池的需求。The purpose of the present invention is to overcome the above-mentioned defects in the prior art, and provide a simple and environmentally friendly method for preparing lithium-ion battery anode material chrysanthemum-shaped nano-titanium dioxide, which shortens the diffusion of lithium ions and electrons by synthesizing a hierarchical structure Increase the specific surface area to increase the contact area between the electrode and the electrolyte, thereby improving the high-rate discharge performance and high Coulombic efficiency to meet the current demand for lithium-ion batteries.
本发明的目的可以通过以下技术方案来实现：The purpose of the present invention can be achieved through the following technical solutions:
一种锂离子电池负极材料菊花形状的纳米二氧化钛制备方法，包括下列步骤：A preparation method of nano-titanium dioxide in a chrysanthemum-shaped lithium-ion battery negative electrode material, comprising the following steps:
(1)将一定量的钛源化合物(1.2～6g)溶于短链的单元醇中，磁力搅拌10～15分钟形成澄清溶液，然后按照短链单元醇与多元醇体积比为(3～8):1加入多元醇，继续搅拌15～20分钟形成澄清溶液。(1) Dissolve a certain amount of titanium source compound (1.2-6g) in short-chain monoalcohols, stir magnetically for 10-15 minutes to form a clear solution, and then according to the volume ratio of short-chain monoalcohols to polyols (3-8 ): 1 Add polyol and continue to stir for 15-20 minutes to form a clear solution.
(2)将上述溶液转移至高压反应釜中，在一定温度下(120～230℃)进行水热反应10～36小时，待反应结束后，自然冷却至室温，离心洗涤分离干燥后得二氧化钛前驱体纳米材料。(2) Transfer the above solution to a high-pressure reactor, and carry out a hydrothermal reaction at a certain temperature (120-230°C) for 10-36 hours. After the reaction is completed, naturally cool to room temperature, centrifugally wash, separate and dry to obtain a titanium dioxide precursor bulk nanomaterials.
(3)将上步得到的二氧化钛前驱体纳米材料放入高温炉中400～600℃热处理4～8小时后，自然冷却至室温后便得到菊花形状纳米二氧化钛。(3) Put the titanium dioxide precursor nanomaterial obtained in the previous step into a high-temperature furnace for heat treatment at 400-600° C. for 4-8 hours, and then naturally cool to room temperature to obtain chrysanthemum-shaped nano-titanium dioxide.
以上所述的钛源化合物为：钛酸四丁酯，钛酸异丙酯，钛酸乙酯，四氯化钛中的一种或几种；短链单元醇为：乙醇，异丙醇，正丙醇，正丁醇，异丁醇中的一种或几种混合溶剂；多元醇为：乙二醇，丙三醇中的一种或两种混合溶剂。The titanium source compounds mentioned above are: one or more of tetrabutyl titanate, isopropyl titanate, ethyl titanate, and titanium tetrachloride; the short-chain unit alcohols are: ethanol, isopropanol, One or more mixed solvents of n-propanol, n-butanol, and isobutanol; polyols: one or two mixed solvents of ethylene glycol and glycerol.
(4)将上步合成的材料用于锂离子电池负极材料，以导电炭黑为导电剂，聚偏二氟乙烯(PVDF)为粘结剂制成锂离子电池负极片，以金属锂为对电极，聚丙烯微孔膜为隔膜，以体积比为1:1:1的碳酸乙烯酯(EC)/碳酸二甲酯(DMC)/碳酸二乙酯(DEC)的1M LiPF6为电解液，在氩气手套箱中组装成2025型扣式电池。采用LAND CT-2001A测试仪在室温下进行电化学性能测试。(4) Use the material synthesized in the previous step for the negative electrode material of lithium ion battery, use conductive carbon black as the conductive agent, polyvinylidene fluoride (PVDF) as the binder to make the negative electrode sheet of lithium ion battery, and use metal lithium as the opposite Electrode, polypropylene microporous membrane as separator, 1M LiPF6 of ethylene carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) with a volume ratio of 1:1:1 as electrolyte, Assemble into a 2025-type coin cell in an argon glove box. The electrochemical performance test was carried out at room temperature using a LAND CT-2001A tester.
根据本发明制备得到的菊花形状的纳米二氧化钛形貌均一，分散度好，没有团聚现象出现，结晶度好、具有丰富的介孔结构，是一种电化学性能优良的锂离子电池负极材料。The chrysanthemum-shaped nano-titanium dioxide prepared according to the invention has uniform appearance, good dispersion, no agglomeration phenomenon, good crystallinity and rich mesoporous structure, and is a lithium ion battery negative electrode material with excellent electrochemical performance.
本发明基于使用钛源化合物与多元醇形成前驱体络合物，其中多元醇起到模板剂与导向剂作用，短链单元醇作为分散溶剂，控制钛源化合物水解速度，进而形成菊花形状二氧化钛前驱体，通过煅烧得到产物。本发明制备方法具有产量高、工艺简单、易操作、原料易得、成本低廉、环境友好等优点，整个反应过程不需要特殊设备，利于工业化生产。最终得到产物质量较高，用作锂离子电池负极材料表现出良好的电化学性能，具有高的可逆性、高的库 伦效率与稳定的循环性能。The present invention is based on the use of titanium source compounds and polyols to form precursor complexes, wherein polyols act as templates and directing agents, and short-chain monoalcohols are used as dispersion solvents to control the hydrolysis rate of titanium source compounds, thereby forming a chrysanthemum-shaped titanium dioxide precursor body, and the product was obtained by calcination. The preparation method of the present invention has the advantages of high yield, simple process, easy operation, readily available raw materials, low cost, and environmental friendliness. The whole reaction process does not require special equipment, which is beneficial to industrial production. The quality of the final product is high, and it can be used as a negative electrode material for lithium-ion batteries, showing good electrochemical performance, high reversibility, high Coulombic efficiency and stable cycle performance.
附图说明Description of drawings
图1为实施例1所制备的菊花形状纳米二氧化钛的X-射线衍射图谱；Fig. 1 is the X-ray diffraction collection of patterns of the chrysanthemum shape nano-titanium dioxide prepared by embodiment 1;
图2为实施例1所制备的菊花形状纳米二氧化钛的扫描电子显微镜图；Fig. 2 is the scanning electron micrograph of the chrysanthemum shape nano-titanium dioxide prepared by embodiment 1;
图3为实施例4所制备的菊花形状纳米二氧化钛在电流密度为5C时充放电循环性能图；Fig. 3 is the chrysanthemum shape nano-titanium dioxide prepared by embodiment 4 when the current density is 5C, the charge-discharge cycle performance figure;
图4为实施例6所制备的菊花形状纳米二氧化钛在电流密度为10C时充放电循环性能图；Fig. 4 is the chrysanthemum shape nano-titanium dioxide prepared by embodiment 6 when the current density is 10C charge-discharge cycle performance figure;
图5为实施例7所制备的菊花形状纳米二氧化钛的倍率性能图。FIG. 5 is a graph of the rate performance of the chrysanthemum-shaped nano-titanium dioxide prepared in Example 7. FIG.
具体实施方式detailed description
以下结合附图对本发明作详细描述，有助于理解本发明，但本发明并不仅局限于以下实施例。The present invention will be described in detail below in conjunction with the accompanying drawings, which is helpful for understanding the present invention, but the present invention is not limited to the following embodiments.
实施例1Example 1
(1)将2.3g的钛酸四丁酯溶于一定体积异丙醇溶剂中，磁力搅拌15分钟后形成澄清溶液，然后按照异丙醇与丙三醇的体积比为4:1加入一定量的丙三醇试剂，继续搅拌20分钟形成澄清溶液。(1) Dissolve 2.3g of tetrabutyl titanate in a certain volume of isopropanol solvent, stir magnetically for 15 minutes to form a clear solution, and then add a certain amount of of the glycerol reagent and continued stirring for 20 minutes to form a clear solution.
(2)将上述溶液转移至高压反应釜中，在180℃进行水热反应14小时，待反应结束后，自然冷却至室温，离心洗涤分离干燥后得二氧化钛前驱体纳米材料。(2) The above solution was transferred to a high-pressure reactor, and hydrothermal reaction was carried out at 180° C. for 14 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifugally washed, separated and dried to obtain titanium dioxide precursor nanomaterials.
(3)将上步得到的二氧化钛前驱体纳米材料放入高温炉中500℃热处理5小时后，自然冷却至室温后便得到菊花形状纳米二氧化钛。(3) Put the titanium dioxide precursor nanomaterial obtained in the previous step into a high-temperature furnace for heat treatment at 500° C. for 5 hours, and then naturally cool to room temperature to obtain chrysanthemum-shaped nano-titanium dioxide.
(4)将上步合成的材料用于锂离子电池负极材料，以导电炭黑为导电剂，聚偏二氟乙烯(PVDF)为粘结剂制成锂离子电池负极片，以金属锂为对电极，聚丙烯微孔膜为隔膜，以体积比为1:1:1的碳酸乙烯酯(EC)/碳酸二甲酯(DMC)/碳酸二乙酯(DEC)的1M LiPF6为电解液，在氩气手套箱中组装成2025型扣式电池。采用LAND CT-2001A测试仪在室温下进行电化学性能测试，测试电压范围为1.0-3.0V。组装电池在0.59C(100mA g-1)电流密度下首次放电比容量305.4mAh g-1。(4) Use the material synthesized in the previous step for the negative electrode material of lithium ion battery, use conductive carbon black as the conductive agent, polyvinylidene fluoride (PVDF) as the binder to make the negative electrode sheet of lithium ion battery, and use metal lithium as the opposite Electrode, polypropylene microporous membrane as separator, 1M LiPF6 of ethylene carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) with a volume ratio of 1:1:1 as electrolyte, Assemble into a 2025-type coin cell in an argon glove box. The electrochemical performance test was carried out at room temperature with a LAND CT-2001A tester, and the test voltage range was 1.0-3.0V. The assembled battery has a specific capacity of 305.4mAh g-1 for the first discharge at a current density of 0.59C (100mA g-1 ).
图1为本实施例所制得的菊花形状纳米二氧化钛的X射线衍射图谱，从图中可以看出所获得的材料为纯锐钛矿相，没有其它相与其它杂质出现，并且材料的结晶良好。图2是菊花形状纳米二氧化钛的扫描电子显微镜图片，从图中可见，二氧化钛形貌与尺寸较均匀，均为类菊花形状。Fig. 1 is the X-ray diffraction spectrum of the chrysanthemum-shaped nano-titanium dioxide prepared in this embodiment, as can be seen from the figure that the obtained material is a pure anatase phase, no other phases and other impurities appear, and the crystallization of the material is good. Figure 2 is a scanning electron microscope picture of chrysanthemum-shaped nano-titanium dioxide. It can be seen from the figure that the shape and size of titanium dioxide are relatively uniform, and they are all in the shape of a chrysanthemum.
实施例2Example 2
(1)将1.2g的钛酸异丙酯溶于一定体积的正丙醇溶剂中，磁力搅拌10分钟后形成澄清溶液，然后按照正丙醇与丙三醇的体积比为3:1加入一定量的丙三醇试剂，继续搅拌15分钟形成澄清溶液。(1) Dissolve 1.2 g of isopropyl titanate in a certain volume of n-propanol solvent, stir magnetically for 10 minutes to form a clear solution, and then add a certain amount of amount of glycerol reagent and continue to stir for 15 minutes to form a clear solution.
(2)将上述溶液转移至高压反应釜中，在120℃进行水热反应36小时，待反应结束后，自然冷却至室温，离心洗涤分离干燥后得二氧化钛前驱体纳米材料。(2) The above solution was transferred to a high-pressure reactor, and hydrothermal reaction was carried out at 120°C for 36 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifuged, washed, separated and dried to obtain titanium dioxide precursor nanomaterials.
(3)将上步得到的二氧化钛前驱体纳米材料放入高温炉中450℃热处理8小时后，自然冷却至室温后便得到菊花形状纳米二氧化钛。(3) Put the titanium dioxide precursor nanomaterial obtained in the previous step into a high-temperature furnace for heat treatment at 450° C. for 8 hours, and then naturally cool to room temperature to obtain chrysanthemum-shaped nano-titanium dioxide.
(4)按照实施例一方法组装成电池后，在5C(850mA g-1)电流密度下测试首次放电比容量195.8mAh g-1，100次循环后放电比容量保持在178.9mAh g-1。(4) After the battery was assembled according to the method of Example 1, the first discharge specific capacity was tested at 5C (850 mA g-1 ) current density to be 195.8 mAh g-1 , and the discharge specific capacity remained at 178.9 mAh g-1 after 100 cycles.
实施例3Example 3
(1)将3.5g的四氯化钛溶于一定体积正丁醇溶剂中，磁力搅拌15分钟后形成澄清溶液，然后按照正丁醇与乙二醇和丙三醇混合溶剂的体积比为7：1加入一定量的乙二醇与丙三醇混合试剂，继续搅拌20分钟形成澄清溶液。(1) Dissolve 3.5g of titanium tetrachloride in a certain volume of n-butanol solvent, form a clear solution after magnetic stirring for 15 minutes, then be 7 according to the volume ratio of n-butanol, ethylene glycol and glycerol mixed solvent: 1 Add a certain amount of ethylene glycol and glycerol mixed reagent, and continue to stir for 20 minutes to form a clear solution.
(2)将上述溶液转移至高压反应釜中，在230℃进行水热反应10小时，待反应结束后，自然冷却至室温，离心洗涤分离干燥后得二氧化钛前驱体纳米材料。(2) The above solution was transferred to a high-pressure reactor, and hydrothermal reaction was carried out at 230°C for 10 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifugally washed, separated and dried to obtain titanium dioxide precursor nanomaterials.
(3)将上步得到的二氧化钛前驱体纳米材料放入高温炉中600℃热处理5小时后，自然冷却至室温后便得到菊花形状纳米二氧化钛。(3) Put the titanium dioxide precursor nanomaterial obtained in the previous step into a high-temperature furnace for heat treatment at 600° C. for 5 hours, and then naturally cool to room temperature to obtain chrysanthemum-shaped nano-titanium dioxide.
(4)按照实施例一方法组装成电池后，在5C电流密度下测试首次放电比容量187.5mAhg-1，100次循环后放电比容量保持在176.2mAh g-1。(4) After the battery was assembled according to the method of Example 1, the first discharge specific capacity was tested at a current density of 5C to be 187.5mAhg-1 , and the discharge specific capacity remained at 176.2mAh g-1 after 100 cycles.
实施例4Example 4
(1)将4.3g的钛酸乙酯溶于一定体积乙醇与异丙醇的混合溶剂中，磁力搅拌10分钟后形成澄清溶液，然后按照乙醇与异丙醇的混合溶剂总体积与丙三醇的体积比为6:1加入一定量的丙三醇试剂，继续搅拌15分钟形成澄清溶液。(1) Dissolve 4.3 g of ethyl titanate in a mixed solvent of a certain volume of ethanol and isopropanol, and form a clear solution after magnetic stirring for 10 minutes. Add a certain amount of glycerol reagent at a volume ratio of 6:1, and continue stirring for 15 minutes to form a clear solution.
(2)将上述溶液转移至高压反应釜中，在200℃进行水热反应12小时，待反应结束后，自然冷却至室温，离心洗涤分离干燥后得二氧化钛前驱体纳米材料。(2) The above solution was transferred to a high-pressure reactor, and the hydrothermal reaction was carried out at 200°C for 12 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifuged, washed, separated and dried to obtain titanium dioxide precursor nanomaterials.
(3)将上步得到的二氧化钛前驱体纳米材料放入高温炉中450℃热处理7小时后，自然冷却至室温后便得到菊花形状纳米二氧化钛。(3) Put the titanium dioxide precursor nanomaterial obtained in the previous step into a high-temperature furnace for heat treatment at 450° C. for 7 hours, and then naturally cool to room temperature to obtain chrysanthemum-shaped nano-titanium dioxide.
(4)按照实施例一方法组装成电池后，在5C电流密度下测试，结果如图3所示。(4) After the battery is assembled according to the method of Example 1, it is tested at a current density of 5C, and the results are shown in FIG. 3 .
图3为所制备的类菊花形状纳米二氧化钛的在5C电流密度下的充放电循环性能图，首 次放电比容量215.6mAh g-1，100次循环后放电比容量保持在198.3mAh g-1，容量保持率为92％，库伦效率接近100％，显示该材料具有优异的电化学性能。Figure 3 is the charge-discharge cycle performance diagram of the prepared chrysanthemum- like nano- titanium dioxide at 5C current density. The retention rate is 92%, and the Coulombic efficiency is close to 100%, showing that the material has excellent electrochemical performance.
实施例5Example 5
(1)将5.5g的钛酸乙酯溶于一定体积异丁醇的混合溶剂中，磁力搅拌10分钟后形成澄清溶液，然后按照异丁醇与丙三醇的体积比为8：1加入一定量的丙三醇试剂，继续搅拌15分钟形成澄清溶液。(1) Dissolve 5.5g of ethyl titanate in a mixed solvent of a certain volume of isobutanol, stir it magnetically for 10 minutes to form a clear solution, and then add a certain amount of amount of glycerol reagent and continue to stir for 15 minutes to form a clear solution.
(2)将上述溶液转移至高压反应釜中，在170℃进行水热反应15小时，待反应结束后，自然冷却至室温，离心洗涤分离干燥后得二氧化钛前驱体纳米材料。(2) The above solution was transferred to a high-pressure reactor, and hydrothermal reaction was carried out at 170° C. for 15 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifugally washed, separated and dried to obtain titanium dioxide precursor nanomaterials.
(3)将上步得到的二氧化钛前驱体纳米材料放入高温炉中450℃热处理6小时后，自然冷却至室温后便得到菊花形状纳米二氧化钛。(3) Put the titanium dioxide precursor nanomaterial obtained in the previous step into a high-temperature furnace for heat treatment at 450° C. for 6 hours, and then naturally cool to room temperature to obtain chrysanthemum-shaped nano-titanium dioxide.
(4)按照实施例一方法组装成电池后，在5C电流密度下测试首次放电比容量191.9mAhg-1，100次循环后放电比容量保持在180.2mAh g-1。(4) After the battery was assembled according to the method of Example 1, the first discharge specific capacity was tested at a current density of 5C to be 191.9mAhg-1 , and the discharge specific capacity remained at 180.2mAh g-1 after 100 cycles.
实施例6Example 6
(1)将6g的钛酸四丁酯溶于一定体积异丙醇的溶剂中，磁力搅拌10分钟后形成澄清溶液，然后按照异丙醇与丙三醇的体积比为5：1加入一定量的丙三醇试剂，继续搅拌15分钟形成澄清溶液。(1) Dissolve 6g of tetrabutyl titanate in a certain volume of isopropanol solvent, stir magnetically for 10 minutes to form a clear solution, and then add a certain amount of of the glycerol reagent and continued stirring for 15 minutes to form a clear solution.
(2)将上述溶液转移至高压反应釜中，在150℃进行水热反应24小时，待反应结束后，自然冷却至室温，离心洗涤分离干燥后得二氧化钛前驱体纳米材料。(2) The above solution was transferred to a high-pressure reactor, and hydrothermal reaction was carried out at 150°C for 24 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifugally washed, separated and dried to obtain titanium dioxide precursor nanomaterials.
(3)将上步得到的二氧化钛前驱体纳米材料放入高温炉中400℃热处理8小时后，自然冷却至室温后便得到菊花形状纳米二氧化钛。(3) Put the titanium dioxide precursor nanomaterial obtained in the previous step into a high-temperature furnace for heat treatment at 400° C. for 8 hours, and then naturally cool to room temperature to obtain chrysanthemum-shaped nano-titanium dioxide.
(4)按照实施例一方法组装成电池后，在5C电流密度下测试首次放电比容量195.4mAhg-1，100次循环后放电比容量保持在181.5mAh g-1。(4) After the battery was assembled according to the method of Example 1, the first discharge specific capacity was tested at a current density of 5C to be 195.4mAhg-1 , and the discharge specific capacity remained at 181.5mAh g-1 after 100 cycles.
图4为所制备的类菊花形状纳米二氧化钛在10C电流密度下的充放电循环性能图，首次放电比容量146.8mAh g-1，200次循环后放电比容量保持在134.6mAh g-1，容量保持率为91.7％，库伦效率接近100％，显示该材料具有优良的电化学性能，表明通过合成纳米/微米分级结构能够实现大电流放电，并且保持长期的循环稳定性与高的首轮库伦效率。Figure 4 is the graph of the charge-discharge cycle performance of the prepared chrysanthemum- like nano- titanium dioxide at a current density of 10C. The rate is 91.7%, and the coulombic efficiency is close to 100%, showing that the material has excellent electrochemical performance, indicating that the synthesis of nano/micro hierarchical structures can achieve high-current discharge, and maintain long-term cycle stability and high first-round coulombic efficiency.
实施例7Example 7
(1)将4.5g的钛酸异丙酯溶于一定体积乙醇溶剂中，磁力搅拌10分钟后形成澄清溶液，然后按照乙醇体积与丙三醇的体积比为4.5：1加入一定量的丙三醇试剂，继续搅拌15分钟形成澄清溶液。(1) Dissolve 4.5g of isopropyl titanate in a certain volume of ethanol solvent, stir it magnetically for 10 minutes to form a clear solution, and then add a certain amount of glycerin according to the volume ratio of ethanol to glycerol of 4.5:1 Alcohol reagent, stirring was continued for 15 minutes to form a clear solution.
(2)将上述溶液转移至高压反应釜中，在160℃进行水热反应18小时，待反应结束后，自然冷却至室温，离心洗涤分离干燥后得二氧化钛前驱体纳米材料。(2) The above solution was transferred to a high-pressure reactor, and the hydrothermal reaction was carried out at 160°C for 18 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifuged, washed, separated and dried to obtain titanium dioxide precursor nanomaterials.
(3)将上步得到的二氧化钛前驱体纳米材料放入高温炉中550℃热处理4小时后，自然冷却至室温后便得到菊花形状纳米二氧化钛。(3) Put the titanium dioxide precursor nanomaterial obtained in the previous step into a high-temperature furnace for heat treatment at 550° C. for 4 hours, and then naturally cool to room temperature to obtain chrysanthemum-shaped nano-titanium dioxide.
(4)按照实施例一方法组装成电池后，在5C电流密度下测试首次放电比容量200.5mAhg-1，100次循环后放电比容量保持在195mAh g-1。(4) After the battery was assembled according to the method of Example 1, the first discharge specific capacity was tested at a current density of 5C to 200.5mAhg-1 , and the discharge specific capacity remained at 195mAh g-1 after 100 cycles.
图5为所制备的类菊花形状纳米二氧化钛倍率性能图，表现出了优异的倍率性能，同时展现了高的首轮库伦效率，适宜实际应用。Figure 5 is a graph of the rate performance of the prepared chrysanthemum-like nano-titanium dioxide, which shows excellent rate performance and high first-round Coulombic efficiency, which is suitable for practical applications.
综上所述，本发明的一种锂离子电池负极材料菊花形状纳米二氧化钛的制备方法，该方法通过合成出纳米/微米分级结构，可以同时实现缩短离子传输距离和提高材料的导电性、材料的离子扩散速率，使得制备的材料具有优异的比容量、稳定的循环性能与高的库伦效率。To sum up, the preparation method of a lithium-ion battery negative electrode material chrysanthemum-shaped nano-titanium dioxide of the present invention, the method can simultaneously shorten the ion transmission distance and improve the conductivity of the material, the material's The ion diffusion rate makes the prepared material have excellent specific capacity, stable cycle performance and high Coulombic efficiency.
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