CN104393272A - Lithium titanate cathode composite material and preparation method - Google Patents

Lithium titanate cathode composite material and preparation method Download PDF

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CN104393272A
CN104393272A CN201410569303.5A CN201410569303A CN104393272A CN 104393272 A CN104393272 A CN 104393272A CN 201410569303 A CN201410569303 A CN 201410569303A CN 104393272 A CN104393272 A CN 104393272A
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lithium titanate
lithium
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贾希来
魏飞
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China University of Petroleum Beijing
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Abstract

本发明提供了一种钛酸锂类负极复合材料及其制备方法，所述方法包括步骤：将纳米碳材料在溶剂中充分分散，制备出纳米碳的浆料；按照锂元素与钛元素摩尔比为3.5～4.5:5的比例分别称取含锂化合物与含钛化合物，将其加入到制得的纳米碳的浆料中，充分混合，得到前驱体浆料；将前驱体浆料进行喷雾干燥造粒，得到前驱体粉体；将前驱体粉体于800～900℃焙烧1～10小时，冷却后即得到所述钛酸锂类负极复合材料。本发明制备的钛酸锂/纳米碳复合材料能够增强高倍率钛酸锂活性材料的负载量，提高电极的能量密度。

The invention provides a lithium titanate negative electrode composite material and a preparation method thereof. The method comprises the steps of: fully dispersing the nano-carbon material in a solvent to prepare a nano-carbon slurry; according to the molar ratio of the lithium element to the titanium element Weigh the lithium-containing compound and the titanium-containing compound at a ratio of 3.5 to 4.5:5, add them to the prepared nano-carbon slurry, and mix thoroughly to obtain a precursor slurry; spray-dry the precursor slurry Granulating to obtain a precursor powder; roasting the precursor powder at 800-900° C. for 1-10 hours, and obtaining the lithium titanate negative electrode composite material after cooling. The lithium titanate/nano-carbon composite material prepared by the invention can enhance the loading capacity of the high-rate lithium titanate active material and improve the energy density of the electrode.

Description

一种钛酸锂类负极复合材料及制备方法A lithium titanate negative electrode composite material and preparation method thereof

技术领域technical field

本发明涉及一种钛酸锂类负极复合材料及制备方法，属于纳米和化工材料制备领域。The invention relates to a lithium titanate negative electrode composite material and a preparation method thereof, belonging to the field of preparation of nanometer and chemical materials.

背景技术Background technique

锂离子动力电池目前存在的主要问题为快速充电和安全性能较差。与石墨负极相比，钛酸锂负极能够明显提高锂离子动力电池的快速充电和安全性能，具有较大的应用前景。但是，钛酸锂材料电导率极低，使得钛酸锂导电性能很差，在一定程度上成为其应用的瓶颈之一。The current main problems of lithium-ion power batteries are fast charging and poor safety performance. Compared with graphite negative electrodes, lithium titanate negative electrodes can significantly improve the fast charging and safety performance of lithium-ion power batteries, and have great application prospects. However, the electrical conductivity of lithium titanate material is extremely low, which makes the conductivity of lithium titanate very poor, which has become one of the bottlenecks in its application to a certain extent.

为改善钛酸锂负极材料的导电性能，目前所采用的方法主要有三种：制备纳米钛酸锂，减小其粒径以缩短锂离子扩散路径，从而提高导电性；掺杂；碳包覆。其中，碳包覆技术主要是通过在钛酸锂颗粒表面包覆导电碳层，以提高材料的导电性能。In order to improve the conductivity of lithium titanate negative electrode materials, there are three main methods currently used: preparing nano-lithium titanate, reducing its particle size to shorten the diffusion path of lithium ions, thereby improving conductivity; doping; carbon coating. Among them, the carbon coating technology is mainly to improve the conductivity of the material by coating a conductive carbon layer on the surface of lithium titanate particles.

CN 102130324 A公开了一种钛酸锂/碳纳米管复合负极材料的制备方法，其中是将钛的化合物溶解在无水乙醇里为A液；将锂化合物溶解在去离子水中后加入纳米碳管并加入无水乙醇，为B液；搅拌后，在B液中加入适量有机酸，继续搅拌；在磁力搅拌下将B液缓慢加入A液中，老化1～12小时，为C液；在真空干燥箱中干燥C液使其变成干凝胶，再于氮气气氛下250～450℃预烧结1～4小时，再在600～1200℃烧结4～12小时，产物经研磨即得钛酸锂/碳纳米管复合负极材料。该材料在0.1C下第50周时的比容量可以达到171mAh·g-1。CN 102130324 A discloses a preparation method of lithium titanate/carbon nanotube composite negative electrode material, wherein the compound of titanium is dissolved in absolute ethanol to form A liquid; the lithium compound is dissolved in deionized water and then carbon nanotubes are added And add absolute ethanol to become liquid B; after stirring, add an appropriate amount of organic acid to liquid B and continue stirring; slowly add liquid B to liquid A under magnetic stirring, and age for 1 to 12 hours to become liquid C; Dry liquid C in a drying oven to make it into a xerogel, then pre-sinter at 250-450°C for 1-4 hours under a nitrogen atmosphere, and then sinter at 600-1200°C for 4-12 hours, and the product is ground to obtain lithium titanate / carbon nanotube composite anode material. The specific capacity of the material can reach 171mAh·g -1 at 0.1C at the 50th week.

CN 102496707 A公开了一种纳米碳包覆尖晶石钛酸锂电池负极材料的制备方法，其中是将二氧化钛和锂源放入到分散剂中，均匀混合后烘干；将烘干后的混合物在第一气氛下用400～800℃的温度预焙烧2～36小时，然后自然冷却至室温，获得中间产物；将所获得的中间产物与碳源放入到分散剂中，均匀混合后烘干；将烘干后的中间产物、碳源和分散剂的混合物在第二气氛下用700～950℃的温度二次焙烧2～36小时，自然冷却至室温，获得纳米碳包覆尖晶石钛酸锂。CN 102496707 A discloses a method for preparing a negative electrode material of a nano-carbon-coated spinel lithium titanate battery, wherein titanium dioxide and a lithium source are put into a dispersant, mixed uniformly and then dried; the dried mixture is Pre-calcined at 400-800°C for 2-36 hours in the first atmosphere, then naturally cooled to room temperature to obtain the intermediate product; put the obtained intermediate product and carbon source into the dispersant, mix evenly and then dry ; The mixture of the dried intermediate product, carbon source and dispersant is baked for 2-36 hours at a temperature of 700-950°C in a second atmosphere, and cooled naturally to room temperature to obtain nano-carbon-coated spinel titanium Lithium Oxide.

CN 102646810 A公开了一种三维多孔石墨烯掺杂与包覆钛酸锂复合负极材料的制备方法，其中是将三维多孔石墨烯溶于溶剂中配成1-12mg/mL溶液，在搅拌条件下加入锂源化合物、钛源化合物，控制Li原子与Ti原子的摩尔比为(0.7～0.9)：1，得到三维多孔石墨烯和钛酸锂前驱体溶胶凝胶，三维多孔石墨烯和钛酸锂前驱体溶胶凝胶在70～90℃条件下干燥除去溶剂，得到三维多孔石墨烯和钛酸锂前驱体粉末；在惰性气体保护下，将三维多孔石墨烯和钛酸锂前驱体粉末加热至700～950℃持续8～20小时，即得到三维多孔石墨烯掺杂与包覆钛酸锂复合材料，三维多孔石墨烯掺杂与包覆钛酸锂复合材料中三维多孔石墨烯的质量百分比为1～5wt％。CN 102646810 A discloses a preparation method of a three-dimensional porous graphene doped and coated lithium titanate composite negative electrode material, wherein the three-dimensional porous graphene is dissolved in a solvent to form a 1-12mg/mL solution, and the Add a lithium source compound and a titanium source compound, and control the molar ratio of Li atoms to Ti atoms to (0.7-0.9): 1 to obtain three-dimensional porous graphene and lithium titanate precursor sol-gel, three-dimensional porous graphene and lithium titanate The precursor sol-gel is dried at 70-90°C to remove the solvent to obtain three-dimensional porous graphene and lithium titanate precursor powder; under the protection of an inert gas, heat the three-dimensional porous graphene and lithium titanate precursor powder to 700 ~950°C for 8-20 hours, the three-dimensional porous graphene-doped and coated lithium titanate composite material is obtained, and the mass percentage of three-dimensional porous graphene in the three-dimensional porous graphene-doped and coated lithium titanate composite material is 1 ~5wt%.

上述制备碳包覆钛酸锂类负极材料的方法，工艺相对较为复杂，不利于大规模工业化生产。The above-mentioned method for preparing carbon-coated lithium titanate-based negative electrode materials has a relatively complicated process, which is not conducive to large-scale industrial production.

发明内容Contents of the invention

本发明的主要目的在于提供一种钛酸锂类负极复合材料的制备方法，通过简单易行的工艺，制备具有较小粒径尺寸、颗粒形貌均匀的钛酸锂负极复合材料，提高钛酸锂负极材料的导电性能，并适合于规模化生产。The main purpose of the present invention is to provide a preparation method of a lithium titanate negative electrode composite material, through a simple and easy process, to prepare a lithium titanate negative electrode composite material with a small particle size and a uniform particle shape, and to increase titanate The electrical conductivity of the lithium negative electrode material is suitable for large-scale production.

本发明的另一目的在于提供按照所述方法制备得到的钛酸锂类负极复合材料。Another object of the present invention is to provide the lithium titanate negative electrode composite material prepared according to the method.

为达上述目的，一方面，本发明提供了一种钛酸锂类负极复合材料的制备方法，该方法包括：In order to achieve the above object, on the one hand, the present invention provides a method for preparing a lithium titanate negative electrode composite material, the method comprising:

(1)将纳米碳材料在溶剂中充分分散，制备出纳米碳的浆料；(1) Fully dispersing the nano-carbon material in a solvent to prepare a nano-carbon slurry;

(2)按照锂元素与钛元素摩尔比为3.5～4.5:5的比例分别称取含锂化合物与含钛化合物，将其加入到步骤(1)制得的纳米碳的浆料中，充分混合，得到前驱体浆料；(2) Weigh the lithium-containing compound and the titanium-containing compound respectively according to the molar ratio of the lithium element to the titanium element being 3.5 to 4.5:5, add it to the nano-carbon slurry prepared in step (1), and mix thoroughly , to obtain the precursor slurry;

(3)将步骤(2)得到的前驱体浆料进行喷雾干燥造粒，得到前驱体粉体；(3) Spray drying and granulating the precursor slurry obtained in step (2) to obtain a precursor powder;

(4)将步骤(3)得到的前驱体粉体于800～900℃焙烧1～10小时，冷却后即得到所述钛酸锂类负极复合材料。(4) Calcining the precursor powder obtained in step (3) at 800-900° C. for 1-10 hours, and obtaining the lithium titanate-based negative electrode composite material after cooling.

根据本发明的具体实施方案，本发明的钛酸锂类负极复合材料的制备方法中，制备纳米碳的浆料时，所述溶剂为去离子水、氮甲基吡咯烷酮或异丙醇。According to a specific embodiment of the present invention, in the preparation method of the lithium titanate negative electrode composite material of the present invention, when preparing the nano-carbon slurry, the solvent is deionized water, nitrogen methyl pyrrolidone or isopropanol.

根据本发明的具体实施方案，本发明的钛酸锂类负极复合材料的制备方法中，所述纳米碳包括碳纳米纤维、碳纳米管、石墨烯和纳米炭黑(导电炭黑)中的一种或多种。这些纳米碳材料均具有较高导电性。According to a specific embodiment of the present invention, in the preparation method of the lithium titanate negative electrode composite material of the present invention, the nano-carbon includes one of carbon nanofibers, carbon nanotubes, graphene and nano-carbon black (conductive carbon black). one or more species. These nano-carbon materials all have high electrical conductivity.

根据本发明的具体实施方案，本发明的钛酸锂类负极复合材料的制备方法中，步骤(1)制得的纳米碳的浆料固含率为1～5％。According to a specific embodiment of the present invention, in the preparation method of the lithium titanate negative electrode composite material of the present invention, the solid content of the nano-carbon slurry prepared in step (1) is 1-5%.

根据本发明的具体实施方案，本发明的钛酸锂类负极复合材料的制备方法中，步骤(1)中对纳米碳的分散采用流体分散技术。优选地，本发明的流体分散技术是于5000-20000rpm转速下进行高速剪切分散。通常的剪切分散时间为5分钟到2小时。According to a specific embodiment of the present invention, in the preparation method of the lithium titanate negative electrode composite material of the present invention, the dispersion of nano-carbons in step (1) adopts fluid dispersion technology. Preferably, the fluid dispersion technology of the present invention is to perform high-speed shear dispersion at a rotational speed of 5000-20000 rpm. Typical shear dispersion times are from 5 minutes to 2 hours.

根据本发明的具体实施方案，本发明的钛酸锂类负极复合材料的制备方法中，所述含锂化合物包括氢氧化锂、碳酸锂和乙酸锂中的一种或多种；所述含钛化合物包括二氧化钛、氯化钛和正钛酸四丁酯中的一种或多种。According to a specific embodiment of the present invention, in the preparation method of the lithium titanate negative electrode composite material of the present invention, the lithium-containing compound includes one or more of lithium hydroxide, lithium carbonate and lithium acetate; the titanium-containing The compound includes one or more of titanium dioxide, titanium chloride and tetrabutyl orthotitanate.

根据本发明的具体实施方案，本发明的钛酸锂类负极复合材料的制备方法中，所述钛酸锂类负极复合材料中，钛酸锂的质量百分含量为40～94％，优选为80～94％。According to a specific embodiment of the present invention, in the preparation method of the lithium titanate-based negative electrode composite material of the present invention, in the lithium titanate-based negative electrode composite material, the mass percentage of lithium titanate is 40% to 94%, preferably 80-94%.

根据本发明的具体实施方案，本发明的钛酸锂类负极复合材料的制备方法中，将含锂化合物、含钛化合物与纳米碳的浆料充分混合的操作为进行搅拌。优选为在100～500rpm转速下搅拌10分钟到1小时。According to a specific embodiment of the present invention, in the preparation method of the lithium titanate negative electrode composite material of the present invention, the operation of fully mixing the slurry containing the lithium-containing compound, the titanium-containing compound and the nano-carbon is stirring. It is preferably stirred at 100-500 rpm for 10 minutes to 1 hour.

根据本发明的具体实施方案，本发明的钛酸锂类负极复合材料的制备方法中，步骤(3)中喷雾干燥造粒的温度为260～350℃。According to a specific embodiment of the present invention, in the preparation method of the lithium titanate-based negative electrode composite material of the present invention, the temperature for spray drying and granulation in step (3) is 260-350° C.

根据本发明的具体实施方案，本发明的钛酸锂类负极复合材料的制备方法中，前驱体粉体的焙烧时间为1～10小时，焙烧时间主要取决于所用用的钛源和锂源。According to a specific embodiment of the present invention, in the preparation method of the lithium titanate negative electrode composite material of the present invention, the calcination time of the precursor powder is 1 to 10 hours, and the calcination time mainly depends on the titanium source and lithium source used.

另一方面，本发明还提供了一种钛酸锂类负极复合材料，其是按照上述方法制备得到的。其具有较小粒径尺寸，颗粒形貌均匀。本发明的电极材料主要由钛酸锂和纳米碳组成。经过电化学测试，显示出优异的容量和倍率性能以及良好的循环稳定性能。On the other hand, the present invention also provides a lithium titanate negative electrode composite material, which is prepared according to the above method. It has a small particle size and uniform particle morphology. The electrode material of the invention is mainly composed of lithium titanate and nano carbon. After electrochemical tests, it shows excellent capacity and rate performance as well as good cycle stability.

综上所述，本发明提供了一种钛酸锂类负极复合材料及其制备方法，本发明通过将含有锂元素、钛元素的化合物和纳米碳材料按照特定比例直接混合，然后利用液相流体分散技术得到均匀的混合浆料，进行喷雾干燥得到前驱体粉末，将所得的粉末置于惰性气体中，煅烧制得钛酸锂/纳米碳复合材料，能够增强高倍率钛酸锂活性材料的负载量，提高电极的能量密度。In summary, the present invention provides a lithium titanate-based negative electrode composite material and a preparation method thereof. The present invention directly mixes compounds containing lithium and titanium elements and nano-carbon materials according to a specific ratio, and then utilizes liquid phase fluid to Dispersion technology obtains a uniform mixed slurry, which is spray-dried to obtain a precursor powder. The resulting powder is placed in an inert gas and calcined to obtain a lithium titanate/nano-carbon composite material, which can enhance the loading of high-rate lithium titanate active materials. increase the energy density of the electrode.

附图说明Description of drawings

图1为实施例1中钛酸锂复合材料的扫面电子显微镜下的形貌。FIG. 1 is the morphology of the lithium titanate composite material in Example 1 under a scanning electron microscope.

图2为实施例1中钛酸锂复合材料的X射线衍射图。FIG. 2 is an X-ray diffraction pattern of the lithium titanate composite material in Example 1.

图3为实施例1中钛酸锂复合材料在不同电流密度下的倍率性能。FIG. 3 shows the rate performance of the lithium titanate composite material in Example 1 at different current densities.

图4为实施例1中钛酸锂复合材料在10C的电流密度下的循环稳定性能。FIG. 4 is the cycle stability performance of the lithium titanate composite material in Example 1 at a current density of 10C.

具体实施方式Detailed ways

下面通过具体实施例进一步详细说明本发明的特点及所具有的技术效果，但本发明并不因此而受到任何限制。The characteristics and technical effects of the present invention will be further described in detail through specific examples below, but the present invention is not limited thereto.

实施例1Example 1

将碳纳米管添加到异丙醇溶剂中，利用高速流体分散仪10000rpm进行充分分散30分钟，制备固含率在1％的浆料。然后按照锂元素与钛元素摩尔比为4.2:5的比例分别称取一定量的乙酸锂与正钛酸四丁酯，使得钛酸锂在复合材料的质量百分含量在89％，然后将其加入到导电浆料中，200rpm转速下搅拌30分钟以充分混合得到均匀的前驱体反应料。将得到的混合料，输送至喷雾干燥器，在280℃下进行造粒，获得前驱体粉体。将得到的前驱体粉体粉末放入高温炉中焙烧，焙烧温度800℃，时间为10个小时，冷却后便得到改性的钛酸锂复合材料。对所得到的粉体材料进行形貌表征，如图1所示，在扫面电子显微镜下，可以看到粉末状颗粒材料，并且颗粒材料的上能够看到纤维状的碳纳米管。进一步对该粉体材料进行XRD结构表征，如图2所示，相关的衍射峰证实这种粉体材料为钛酸锂复合材料。The carbon nanotubes were added to the isopropanol solvent, and a high-speed fluid disperser was used at 10,000 rpm to fully disperse for 30 minutes to prepare a slurry with a solid content of 1%. Then weigh a certain amount of lithium acetate and tetrabutyl orthotitanate according to the ratio of lithium element and titanium element molar ratio of 4.2:5, so that the mass percentage of lithium titanate in the composite material is 89%, and then Add it into the conductive paste, and stir at 200rpm for 30 minutes to fully mix to obtain a uniform precursor reaction material. The obtained mixture was transported to a spray dryer and granulated at 280° C. to obtain a precursor powder. Put the obtained precursor powder into a high-temperature furnace and bake at a temperature of 800° C. for 10 hours. After cooling, a modified lithium titanate composite material is obtained. The morphology of the obtained powder material was characterized, as shown in Figure 1, under a scanning electron microscope, powdery granular material can be seen, and fibrous carbon nanotubes can be seen on the granular material. The powder material was further characterized by XRD structure, as shown in Figure 2, the relevant diffraction peaks confirmed that the powder material was a lithium titanate composite material.

将制得的钛酸锂复合材料与乙炔黑和粘结剂(PVDF)按80:10:10质量比加氮甲基吡咯烷酮(NMP)调匀，制得的电极片，并在真空烘箱中120℃下干燥12小时。以上述电极片作工作电极，以金属锂片为对电极，聚丙烯薄膜为隔膜，1mol/L LiPF6的EC+DEC(1:1，体积比)溶液作电解液，在氩气的手套箱中组装成扣式电池。于常温下在LAND电池测试***进行恒电流充放电循环测试，如图3的倍率性能结果表明本发明的这种钛酸锂负极在1C下的电化学容量达到170mAh g-1，在100C下容量能够到108mAh g-1。图4的循环稳定性测试结果表明，6000圈的循环稳定性保有率为98％，这体现了该复合材料优异的电化学性能。Mix the prepared lithium titanate composite material with acetylene black and binder (PVDF) according to the mass ratio of 80:10:10 and add nitrogen methyl pyrrolidone (NMP), and prepare the electrode sheet, and heat it in a vacuum oven at 120 °C Dry for 12 hours. With the above-mentioned electrode sheet as the working electrode, the metal lithium sheet as the counter electrode, the polypropylene film as the diaphragm, and the EC+DEC (1:1, volume ratio) solution of 1mol/L LiPF 6 as the electrolyte, in an argon glove box Assemble into a button battery. The constant current charge and discharge cycle test was carried out in the LAND battery test system at room temperature. The rate performance results shown in Figure 3 show that the lithium titanate negative electrode of the present invention has an electrochemical capacity of 170mAh g -1 at 1C, and a capacity of 100C at 100C. Capable to 108mAh g -1 . The cycle stability test results in Figure 4 show that the cycle stability retention rate of 6000 cycles is 98%, which reflects the excellent electrochemical performance of the composite material.

实施例2Example 2

将碳纳米纤维和导电炭黑按照质量百分比1:2，添加到氮甲基吡咯烷酮溶剂中，利用高速流体分散仪20000rpm进行充分分散5分钟，制备固含率在1％的浆料。然后按照锂元素与钛元素摩尔比为3.5:5的比例分别称取一定量的碳酸锂与二氧化钛，使得钛酸锂在复合材料的质量百分含量在90％，然后将其加入到导电浆料中，500rpm转速下搅拌10分钟以充分混合得到均匀的前驱体反应料。将得到的混合料，输送至喷雾干燥器，在280℃下进行造粒，获得前驱体粉体。将得到的前驱体粉体粉末放入高温炉中焙烧，焙烧温度800℃，时间为5个小时，冷却后便得到改性的钛酸锂复合材料。Carbon nanofibers and conductive carbon black were added to nitrogen methyl pyrrolidone solvent at a mass percentage of 1:2, and fully dispersed for 5 minutes using a high-speed fluid disperser at 20,000 rpm to prepare a slurry with a solid content of 1%. Then weigh a certain amount of lithium carbonate and titanium dioxide according to the ratio of lithium element and titanium element molar ratio of 3.5:5, so that the mass percentage of lithium titanate in the composite material is 90%, and then add it to the conductive paste , stirred at 500rpm for 10 minutes to fully mix to obtain a uniform precursor reaction material. The obtained mixture was transported to a spray dryer and granulated at 280° C. to obtain a precursor powder. Put the obtained precursor powder into a high-temperature furnace for calcination at a temperature of 800° C. for 5 hours, and obtain a modified lithium titanate composite material after cooling.

然后参照实施例1的电极制备方法制备出电极，经过恒电流充放电测试，结果表明本发明的这种钛酸锂负极在1C下的电化学容量达到158mAh g-1，在100C下容量能够到84mAh g-1，6000圈的循环稳定性保有率为99％。Then referring to the electrode preparation method of Example 1, an electrode was prepared, and after a constant current charge and discharge test, the results showed that the lithium titanate negative electrode of the present invention had an electrochemical capacity of 158mAh g -1 at 1C, and a capacity of 100C at 100C. 84mAh g -1 , 6000 cycle cycle stability retention rate is 99%.

实施例3Example 3

将石墨烯粉末和导电炭黑按照质量百分比1:2，添加到氮甲基吡咯烷酮溶剂中，利用高速流体分散仪8000rpm转速下进行充分分散30分钟，制备固含率在1％的浆料。然后按照锂元素与钛元素摩尔比为4.5:5的比例分别称取一定量的氢氧化锂与正钛酸四丁酯，使得钛酸锂在复合材料的质量百分含量在94％，然后将其加入到导电浆料中，200rpm转速下搅拌30分钟以充分混合得到均匀的前驱体反应料。将得到的混合料，输送至喷雾干燥器，在280℃下进行造粒，获得前驱体粉体。将得到的前驱体粉体粉末放入高温炉中焙烧，焙烧温度800℃，时间为5个小时，冷却后便得到改性的钛酸锂复合材料。Graphene powder and conductive carbon black were added to the nitrogen methyl pyrrolidone solvent at a mass percentage of 1:2, and fully dispersed for 30 minutes at a speed of 8000 rpm using a high-speed fluid disperser to prepare a slurry with a solid content of 1%. Then weigh a certain amount of lithium hydroxide and tetrabutyl orthotitanate according to the ratio of lithium element and titanium element molar ratio of 4.5:5, so that the mass percentage of lithium titanate in the composite material is 94%, and then It was added into the conductive paste, and stirred at 200 rpm for 30 minutes to fully mix to obtain a uniform precursor reaction material. The obtained mixture was transported to a spray dryer and granulated at 280° C. to obtain a precursor powder. Put the obtained precursor powder into a high-temperature furnace for calcination at a temperature of 800° C. for 5 hours, and obtain a modified lithium titanate composite material after cooling.

然后参照实施例1的电极制备方法制备出电极，经过恒电流充放电测试，结果表明本发明的这种钛酸锂负极在1C下的电化学容量达到165mAh g-1，在100C下容量能够到76mAh g-1，6000圈的循环稳定性保有率为98％。Then referring to the electrode preparation method in Example 1, an electrode was prepared, and after a constant current charge and discharge test, the results showed that the lithium titanate negative electrode of the present invention had an electrochemical capacity of 165mAh g -1 at 1C, and a capacity of 100C at 100C. 76mAh g -1 , 6000 cycle cycle stability retention rate is 98%.

实施例4Example 4

将碳纳米管和导电炭黑按照质量百分比1:2，添加到去离子水(H2O)溶剂，利用高速流体分散仪15000rpm进行充分分散30分钟，制备固含率在5％的浆料。然后按照锂元素与钛元素摩尔比为4:5的比例分别称取一定量的氢氧化锂与二氧化钛，使得钛酸锂在复合材料的质量百分含量在80％，然后将其加入到导电浆料中，150rpm转速下搅拌1小时以充分混合得到均匀的前驱体反应料。将得到的混合料，输送至喷雾干燥器，在280℃下进行造粒，获得前驱体粉体。将得到的前驱体粉体粉末放入高温炉中焙烧，焙烧温度900℃，时间为2个小时，冷却后便得到改性的钛酸锂复合材料。Carbon nanotubes and conductive carbon black were added to the deionized water (H 2 O) solvent at a mass percentage of 1:2, and fully dispersed for 30 minutes using a high-speed fluid disperser at 15,000 rpm to prepare a slurry with a solid content of 5%. Then weigh a certain amount of lithium hydroxide and titanium dioxide according to the molar ratio of lithium element and titanium element being 4:5, so that the mass percentage of lithium titanate in the composite material is 80%, and then add it to the conductive paste In the material, stir at 150 rpm for 1 hour to fully mix to obtain a uniform precursor reaction material. The obtained mixture was transported to a spray dryer and granulated at 280° C. to obtain a precursor powder. Put the obtained precursor powder into a high-temperature furnace for calcination at a temperature of 900° C. for 2 hours, and obtain a modified lithium titanate composite material after cooling.

然后参照实施例1的电极制备方法制备出电极，经过恒电流充放电测试，结果表明本发明的这种钛酸锂负极在1C下的电化学容量达到175mAh g-1，在100C下容量能够到110mAh g-1，6000圈的循环稳定性保有率为100％。Then referring to the electrode preparation method of Example 1, an electrode was prepared, and after a constant current charge and discharge test, the results showed that the lithium titanate negative electrode of the present invention had an electrochemical capacity of 175mAh g -1 at 1C, and a capacity of 100C at 100C. 110mAh g -1 , 6000 cycle cycle stability retention rate is 100%.

实施例5Example 5

将碳纳米纤维添加到氮甲基吡咯烷酮溶剂中，利用高速流体分散仪10000rpm进行充分分散20分钟，制备固含率在1％的浆料。然后按照锂元素与钛元素摩尔比为4:5的比例分别称取一定量的碳酸锂与正钛酸四丁酯，使得钛酸锂在复合材料的质量百分含量在89％，然后将其加入到导电浆料中，200rpm转速下搅拌30分钟以充分混合得到均匀的前驱体反应料。将得到的混合料，输送至喷雾干燥器，在280℃下进行造粒，获得前驱体粉体。将得到的前驱体粉体粉末放入高温炉中焙烧，焙烧温度900℃，时间为5个小时，冷却后便得到改性的钛酸锂复合材料。The carbon nanofibers are added to the nitrogen methyl pyrrolidone solvent, and the high-speed fluid disperser is used for 10000 rpm to fully disperse for 20 minutes to prepare a slurry with a solid content of 1%. Then weigh a certain amount of lithium carbonate and tetrabutyl orthotitanate according to the ratio of lithium element and titanium element molar ratio of 4:5, so that the mass percentage of lithium titanate in the composite material is 89%, and then Add it into the conductive paste, and stir at 200rpm for 30 minutes to fully mix to obtain a uniform precursor reaction material. The obtained mixture was transported to a spray dryer and granulated at 280° C. to obtain a precursor powder. Put the obtained precursor powder into a high-temperature furnace for calcination at a temperature of 900° C. for 5 hours, and obtain a modified lithium titanate composite material after cooling.

然后参照实施例1的电极制备方法制备出电极，经过恒电流充放电测试，结果表明本发明的这种钛酸锂负极在1C下的电化学容量达到168mAh g-1，在100C下容量能够到101mAh g-1，6000圈的循环稳定性保有率为94％。Then referring to the electrode preparation method of Example 1, an electrode was prepared, and after a constant current charge and discharge test, the results showed that the lithium titanate negative electrode of the present invention had an electrochemical capacity of 168mAh g -1 at 1C, and a capacity of 100C at 100C. 101mAh g -1 , 6000 cycle cycle stability retention rate is 94%.

Claims (9)

1. a preparation method for lithium titanate class anode material, the method comprising the steps of:
(1) nano-carbon material is fully disperseed in a solvent, prepare the slurry of nano-sized carbon;
(2) ratio being 3.5 ~ 4.5:5 according to elemental lithium and titanium elements mol ratio takes lithium-containing compound and titanium-containing compound respectively, is joined in the slurry of the obtained nano-sized carbon of step (1), fully mixes, obtain precursor pulp;
(3) precursor pulp that step (2) obtains is carried out spray drying granulation, obtain presoma powder;
(4) presoma powder step (3) obtained, in 800 ~ 900 DEG C of roastings 1 ~ 10 hour, namely obtains described lithium titanate class anode material after cooling.
2. the preparation method of lithium titanate class anode material according to claim 1, wherein, described nano-sized carbon comprise in carbon nano-fiber, carbon nano-tube, Graphene and nano carbon black one or more; Described solvent is deionized water, nitrogen methyl pyrrolidone or isopropyl alcohol.
3. the preparation method of lithium titanate class anode material according to claim 1, wherein, the slurry solid holdup of the nano-sized carbon that step (1) is obtained is 1 ~ 5%.
4. the preparation method of lithium titanate class anode material according to claim 1, wherein, adopts fluid dispersion technology to the dispersion of nano-sized carbon in step (1); Preferably, fluid dispersion technology carries out high speed shear dispersion under 5000 ~ 20000rpm rotating speed; Jitter time is between 5 minutes to 2 hours.
5. the preparation method of lithium titanate class anode material according to claim 1, wherein, described lithium-containing compound comprise in lithium hydroxide, lithium carbonate and lithium acetate one or more; Described titanium-containing compound comprise in titanium dioxide, titanium chloride and tetrabutyl titanate one or more.
6. the preparation method of lithium titanate class anode material according to claim 1, wherein, in described lithium titanate class anode material, the mass percentage of lithium titanate is 40 ~ 94%, is preferably 80 ~ 94%.
7. the preparation method of lithium titanate class anode material according to claim 1, wherein, stirs well-mixed for the slurry of lithium-containing compound, titanium-containing compound and nano-sized carbon being operating as.
8. the preparation method of lithium titanate class anode material according to claim 1, wherein, in step (3), the temperature of spray drying granulation is 260 ~ 350 DEG C.
9. a lithium titanate class anode material, it prepares according to the preparation method described in any one of claim 1 ~ 8.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104916843A (en) * 2015-04-20 2015-09-16 洛阳月星新能源科技有限公司 Natural graphite modification method for lithium ion battery negative electrode material
CN105529449A (en) * 2016-01-29 2016-04-27 珠海银隆新能源有限公司 Lithium titanate electrode material and preparation method thereof
WO2016090958A1 (en) * 2014-12-12 2016-06-16 宁波南车新能源科技有限公司 Preparation method for mixed capacitor negative electrode slurry
CN105702925A (en) * 2016-01-29 2016-06-22 珠海银隆新能源有限公司 Lithium titanate electrode material and preparation method therefor
CN106129394A (en) * 2016-08-26 2016-11-16 深圳博磊达新能源科技有限公司 A kind of lithium titanate anode material and lithium titanate battery
CN106299302A (en) * 2016-09-27 2017-01-04 深圳复兴新能源科技有限公司 A kind of preparation method of lithium titanate anode material
CN106848251A (en) * 2017-03-15 2017-06-13 北京朗盛特耐科技有限公司 A kind of preparation method of CNT lithium titanate composite anode material
WO2017132044A1 (en) * 2016-01-25 2017-08-03 Ford Cheer International Limited Lithium titanate electrode material, producing method and applications of same
CN107331869A (en) * 2017-01-21 2017-11-07 深圳市瑞能达科技有限公司 It is a kind of to lift the compound additive of lithium titanate electric material cryogenic property
CN109599536A (en) * 2017-09-30 2019-04-09 天津大学 Germanium hydrogen/redox graphene/conductive black nano composite lithium ion cell negative electrode material and preparation method thereof
CN110247026A (en) * 2018-03-08 2019-09-17 天津大学 A kind of GeCH3-RGO-SP nano composite lithium ion cell negative electrode material and preparation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102376945A (en) * 2010-08-20 2012-03-14 三星Sdi株式会社 Negative active material, method of preparing same, and rechargeable lithium battery including same
CN103181004A (en) * 2010-08-26 2013-06-26 宇部兴产株式会社 Lithium-titanium composite oxide electrode material compounded with fine carbon fibers
CN103840146A (en) * 2012-11-27 2014-06-04 西安物华新能源科技有限公司 Preparation method of high-tap-density lithium titanate material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102376945A (en) * 2010-08-20 2012-03-14 三星Sdi株式会社 Negative active material, method of preparing same, and rechargeable lithium battery including same
CN103181004A (en) * 2010-08-26 2013-06-26 宇部兴产株式会社 Lithium-titanium composite oxide electrode material compounded with fine carbon fibers
CN103840146A (en) * 2012-11-27 2014-06-04 西安物华新能源科技有限公司 Preparation method of high-tap-density lithium titanate material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TAO YUAN等: "One-Pot Spray-Dried Graphene Sheets-Encapsulated Nano-Li4Ti5O12 Microspheres for a Hybrid BatCap System", 《IND.ENG.CHEM.RES》 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016090958A1 (en) * 2014-12-12 2016-06-16 宁波南车新能源科技有限公司 Preparation method for mixed capacitor negative electrode slurry
CN104916843A (en) * 2015-04-20 2015-09-16 洛阳月星新能源科技有限公司 Natural graphite modification method for lithium ion battery negative electrode material
CN104916843B (en) * 2015-04-20 2017-04-12 洛阳月星新能源科技有限公司 Natural graphite modification method for lithium ion battery negative electrode material
CN108886135A (en) * 2016-01-25 2018-11-23 丰捷国际有限公司 Lithium titanate electrode material, manufacturing method and its application
EP3408882A4 (en) * 2016-01-25 2019-07-17 Ford Cheer International Limited Lithium titanate electrode material, producing method and applications of same
JP2019508867A (en) * 2016-01-25 2019-03-28 フォード・チア・インターナショナル・リミテッド Lithium titanate electrode material, method for producing the same and use thereof
WO2017132044A1 (en) * 2016-01-25 2017-08-03 Ford Cheer International Limited Lithium titanate electrode material, producing method and applications of same
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CN105702925A (en) * 2016-01-29 2016-06-22 珠海银隆新能源有限公司 Lithium titanate electrode material and preparation method therefor
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CN106129394B (en) * 2016-08-26 2019-08-23 深圳博磊达新能源科技有限公司 A kind of lithium titanate anode material and lithium titanate battery
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Application publication date: 20150304