CN110137465A - A kind of carbon@Fe2O3@carbosphere composite material and its application - Google Patents

A kind of carbon@Fe2O3@carbosphere composite material and its application Download PDF

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CN110137465A
CN110137465A CN201910394308.1A CN201910394308A CN110137465A CN 110137465 A CN110137465 A CN 110137465A CN 201910394308 A CN201910394308 A CN 201910394308A CN 110137465 A CN110137465 A CN 110137465A
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CN110137465B (en
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王震康
杨宏训
刘永闵
曹宗林
张翔
王伟
袁爱华
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Jiangsu University of Science and Technology
Marine Equipment and Technology Institute Jiangsu University of Science and Technology
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Abstract

本发明涉及一种碳@Fe2O3@碳微球复合材料及其应用，所述碳@Fe2O3@碳微球复合材料由正硅酸四乙酯，氨水，间苯二酚，甲醛，铁盐和多巴胺制备而成，制备出的碳@Fe2O3@碳微球直径为200～300 nm，所述微球碳内壳厚度约为15～30nm，所述的Fe2O3中间层厚度为30～60nm，所述碳外壳的厚度为3～7nm；所述碳@Fe2O3@碳微球纳米复合材料用作锂离子电池的负极材料。本发明的优点在于：本发明的碳@Fe2O3@碳微球材料应用于锂离子电池，极大改善了锂电池得容量保持率，而且工艺简单、重现性好、易于实施。

The present invention relates to a carbon@Fe 2 O 3 @carbon microsphere composite material and its application. The carbon@Fe 2 O 3 @carbon microsphere composite material is composed of tetraethyl orthosilicate, ammonia water, resorcinol, Prepared from formaldehyde, iron salt and dopamine, the prepared carbon@Fe2O3@carbon microspheres have a diameter of 200-300 nm, the thickness of the carbon inner shell of the microspheres is about 15-30 nm, and the Fe 2 O 3 middle layer The thickness is 30-60nm, and the thickness of the carbon shell is 3-7nm; the carbon @Fe 2 O 3 @carbon microsphere nanocomposite material is used as the negative electrode material of the lithium ion battery. The advantage of the present invention is that: the carbon @Fe 2 O 3 @carbon microsphere material of the present invention is applied to lithium ion batteries, greatly improving the capacity retention rate of lithium batteries, and the process is simple, reproducible and easy to implement.

Description

一种碳@Fe2O3@碳微球复合材料及其应用A carbon@Fe2O3@carbon microsphere composite material and its application

技术领域technical field

本发明属于锂离子电池负极材料技术领域，特别涉及一种碳@Fe2O3@碳微球复合材料及其应用。The invention belongs to the technical field of negative electrode materials for lithium ion batteries, and in particular relates to a carbon@ Fe2O3 @carbon microsphere composite material and its application.

背景技术Background technique

锂离子电池具有高电压、高容量、体积小、质量轻、无记忆效应、自放电小和循环寿命长等优点，使其成为21世纪极具潜力的新型化学电源。目前商业化锂电池中负极材料石墨的理论容量只有372 mAh/g，不能满足高性能电池的应用需求。因此，开发具有更高容量、长循环寿命和高倍率性能的负极材料成为国内外研究者追逐的目标。Lithium-ion batteries have the advantages of high voltage, high capacity, small size, light weight, no memory effect, small self-discharge and long cycle life, making them a new chemical power source with great potential in the 21st century. At present, the theoretical capacity of the negative electrode material graphite in commercial lithium batteries is only 372 mAh/g, which cannot meet the application requirements of high-performance batteries. Therefore, the development of anode materials with higher capacity, long cycle life and high rate performance has become the goal pursued by researchers at home and abroad.

为了提高Fe2O3 的电化学性能，主要从以下方面进行考虑：（1）制备纳米级Fe2O3空心纳米材料, 中空结构的存在一方面有利于电解质的渗透和锂离子的传输，另一方面可以缓解充放电过程中的材料体积的变化；（2）将Fe2O3 与碳进行复合，碳的存在不仅可以改善氧化铁固有的低电导率特性，亦能够作为缓冲层来缓解Fe2O3 在充放电过程中的体积变化所产生的应力；结合上述设计可以显著改善三氧化二铁作为负极材料的电化学性能，本发明利用简单的低温无机沉淀及后续煅烧退火等处理方法制备了碳@Fe2O3@碳微球复合材料。这种分级复合结构具有其独特的结构优势，一方面其具有由内部碳球形成的大中空结构与氧化铁内部的小中空结构可以显著增强该材料对于体积变化应力的承受度；另一方面，内外碳层的同时存在不仅能够更好的作为缓冲层缓解氧化铁的体积变化，也能够极大的增加该电极材料的电导率，从而增加其倍率性能。该碳@Fe2O3@碳微球负极材料应用于锂电池，能显著提高锂电池的循环寿命（在0.2 C的电流密度下循环100次后，取得了约1163 mAh/g的充电容量，并且库伦效率为98.06 %），该材料国内外目前还未见相关报道。In order to improve the electrochemical performance of Fe 2 O 3 , the main considerations are as follows: (1) Preparation of nanoscale Fe 2 O 3 hollow nanomaterials. On the one hand, it can alleviate the change of material volume during the charging and discharging process; (2) Compositing Fe 2 O 3 with carbon, the presence of carbon can not only improve the inherent low conductivity characteristics of iron oxide, but also act as a buffer layer to relieve Fe The stress generated by the volume change of 2 O 3 during charging and discharging; combined with the above design, the electrochemical performance of ferric oxide as a negative electrode material can be significantly improved. The present invention uses simple low-temperature inorganic precipitation and subsequent calcination annealing and other processing methods to prepare Carbon@Fe 2 O 3 @carbon microsphere composites. This hierarchical composite structure has its unique structural advantages. On the one hand, it has a large hollow structure formed by internal carbon spheres and a small hollow structure inside iron oxide, which can significantly enhance the material's tolerance to volume change stress; on the other hand, The simultaneous presence of inner and outer carbon layers can not only better serve as a buffer layer to alleviate the volume change of iron oxide, but also greatly increase the electrical conductivity of the electrode material, thereby increasing its rate performance. The carbon @Fe 2 O 3 @carbon microsphere anode material is applied to lithium batteries, which can significantly improve the cycle life of lithium batteries (after 100 cycles at a current density of 0.2 C, a charge capacity of about 1163 mAh/g was obtained, And the Coulombic efficiency is 98.06%), there is no relevant report on this material at home and abroad.

发明内容Contents of the invention

本发明要解决的技术问题是提供一种碳@Fe2O3@碳微球复合材料The technical problem to be solved by the present invention is to provide a carbon@Fe 2 O 3 @carbon microsphere composite material

及其应用，以解决现有的三氧化二铁作为锂离子电池负极材料循环寿命差的技术问题。and its application to solve the technical problem of poor cycle life of the existing ferric oxide as the negative electrode material of the lithium ion battery.

为解决上述技术问题，本发明的技术方案为：一种碳@Fe2O3@碳微球复合材料，其创新点在于：所述碳@Fe2O3@碳微球复合材料由正硅酸四乙酯，氨水，间苯二酚，甲醛，铁盐和多巴胺制备而成，制备出的碳@Fe2O3@碳微球直径为200～300 nm，所述微球碳内壳厚度约为15～30nm，所述的Fe2O3 中间层厚度为30～60nm，所述碳外壳的厚度为3～7nm；In order to solve the above-mentioned technical problems, the technical solution of the present invention is: a carbon @Fe 2 O 3 @carbon microsphere composite material, and its innovative point is that the carbon @Fe 2 O 3 @carbon microsphere composite material is composed of orthosilicon Tetraethyl ester, ammonia water, resorcinol, formaldehyde, iron salt and dopamine, the prepared carbon@Fe2O3@carbon microspheres have a diameter of 200-300 nm, and the thickness of the carbon inner shell of the microspheres is about 15 ~30nm, the thickness of the Fe 2 O 3 middle layer is 30~60nm, and the thickness of the carbon shell is 3~7nm;

所述碳@Fe2O3@碳微球复合材料，具体是通过以下步骤制备而成的：The carbon@Fe 2 O 3 @carbon microsphere composite material is specifically prepared through the following steps:

步骤1：二氧化硅@酚醛树脂微球的制备：将正硅酸四乙酯与氨水加入乙醇/水溶液中，搅拌1～2h后加入间苯二酚与甲醛并持续搅拌12～24 h；所述的乙醇/水溶液体系中，乙醇的体积分数为72～85 %，每升反应液中含TEOs为50～80 ml， 氨水浓度为120～180 ml，间苯二酚12～18 g，甲醛18～25 ml；随后将反应溶液移入高压反应釜并水热反应12～24 h；待自然冷却到室温后，离心洗涤收集产物，得二氧化硅@酚醛树脂微球；Step 1: Preparation of silica@phenolic resin microspheres: Add tetraethyl orthosilicate and ammonia water to ethanol/water solution, stir for 1-2 hours, then add resorcinol and formaldehyde and continue stirring for 12-24 hours; In the ethanol/water solution system described above, the volume fraction of ethanol is 72-85%, the content of TEOs per liter of reaction solution is 50-80 ml, the concentration of ammonia water is 120-180 ml, resorcinol 12-18 g, formaldehyde 18 ~25 ml; then transfer the reaction solution into an autoclave and conduct a hydrothermal reaction for 12-24 h; after naturally cooling to room temperature, centrifuge and wash to collect the product to obtain silica@phenolic resin microspheres;

步骤2：官能团化的中空碳球的制备：将二氧化硅@酚醛树脂置于管式炉中，在氮气或氩气或任意比的氮氩混合气氛围下以4～6 ℃/min 的速率升温至400～500 ℃，随后以1～2.5 ℃/min的速率升温到550～750 ℃以防止材料结构破碎，并保持2～4小时，使酚醛树脂充分碳化，之后自然冷却至室温，得到SiO2@碳微球材料；再将SiO2@碳微球置于15～25 wt%的氢氟酸溶液中浸泡12～24 h，然后离心分离，用去离子水清洗，得到中空碳球；随后将所得中空碳球首先置于25～35℃，质量分数为60～70 %的浓硝酸中搅2 h使其充分浸润并初步官能化，随后将温度升至50～80 ℃并继续搅拌8～10h进行官能化；然后水洗，干燥，得到官能团化的中空碳球；Step 2: Preparation of functionalized hollow carbon spheres: Put silica@phenolic resin in a tube furnace at a rate of 4-6 °C/min in an atmosphere of nitrogen or argon or a mixture of nitrogen and argon at any ratio Raise the temperature to 400-500 °C, then raise the temperature to 550-750 °C at a rate of 1-2.5 °C/min to prevent the material structure from breaking, and keep it for 2-4 hours to fully carbonize the phenolic resin, then naturally cool to room temperature to obtain SiO 2 @carbon microsphere material; then soak SiO 2 @carbon microspheres in 15-25 wt% hydrofluoric acid solution for 12-24 h, then centrifuge and wash with deionized water to obtain hollow carbon spheres; then The obtained hollow carbon spheres were first placed in concentrated nitric acid with a mass fraction of 60-70% at 25-35 °C and stirred for 2 h to fully infiltrate and initially functionalize, then the temperature was raised to 50-80 °C and continued to stir for 8-80 °C. 10h for functionalization; then washing with water and drying to obtain functionalized hollow carbon spheres;

步骤3：碳@Fe2O3 微球材料的制备：将步骤2所得的官能团化的中空碳球加入到去离子水中，得到中空碳球分散液；然后再向中空碳球分散液中加入铁盐，在60～80 ℃条件下以600～900 rpm/min的速度搅拌4～6 h，得到碳@FeOOH；所述的中空碳球分散液浓度为0.5～1 g/L，所述的铁盐的浓度为0.2～1 mol/L；通过离心收集产物，并用去离子水洗涤2～3次，得到羟基氧化铁包裹的中空碳微球复合材料碳@FeOOH；然后将碳@FeOOH 置于管式炉中，在氮气或氩气或任意比的氮氩混合气氛围下以1～6 ℃/min的速率升温到350～450 ℃并保持2～6 h，之后自然冷却至室温，得到碳@Fe2O3 微球纳米材料；Step 3: Preparation of carbon@Fe 2 O 3 microsphere material: Add the functionalized hollow carbon spheres obtained in step 2 into deionized water to obtain a hollow carbon sphere dispersion; then add iron to the hollow carbon sphere dispersion salt, stirred at a speed of 600-900 rpm/min for 4-6 h at 60-80 °C to obtain carbon@FeOOH; the concentration of the hollow carbon sphere dispersion is 0.5-1 g/L, and the iron The concentration of the salt is 0.2-1 mol/L; the product is collected by centrifugation and washed 2-3 times with deionized water to obtain the hollow carbon microsphere composite material carbon@FeOOH wrapped in iron oxyhydroxide; then the carbon@FeOOH is placed in the tube In a conventional furnace, the temperature was raised to 350-450 °C at a rate of 1-6 °C/min in the atmosphere of nitrogen or argon or any ratio of nitrogen-argon gas and kept for 2-6 h, and then naturally cooled to room temperature to obtain carbon@ Fe 2 O 3 microsphere nanomaterials;

步骤4：将步骤3中的碳@Fe2O3 微球纳米材料分散于三羟甲基氨基甲烷溶液中，并加入多巴胺后在常温下搅拌4～6 h；所述的碳@Fe2O3 微球纳米材料的分散浓度为0.5～1 g/L；所述的多巴胺浓度为0.4～1 g/L；所述的三羟甲基氨基甲烷的浓度为1～1.2 g/L；反应完成后通过离心收集产物，并用去离子水对产物洗涤2～3次；将干燥后的产物置于管式炉中，在氮气或氩气或任意比的氮氩混合气氛围下以2～4 ℃/min的速率升温到250～300 ℃并保持0.5～1 h，然后以0.5～1 ℃/min的速率升温到350～450 ℃以稳定材料结构，并保持2～4 h碳化多巴胺层，然后自然冷却至室温，得到碳@Fe2O3@碳微球复合材料。Step 4: Disperse the carbon@Fe 2 O 3 microsphere nanomaterial in step 3 in the tris hydroxymethylaminomethane solution, add dopamine and stir at room temperature for 4-6 h; the carbon @Fe 2 O 3. The dispersion concentration of microsphere nanomaterials is 0.5-1 g/L; the concentration of dopamine is 0.4-1 g/L; the concentration of tris is 1-1.2 g/L; the reaction is completed Afterwards, the product was collected by centrifugation, and the product was washed 2 to 3 times with deionized water; the dried product was placed in a tube furnace, and heated at 2 to 4 °C under the atmosphere of nitrogen or argon or a mixture of nitrogen and argon in any ratio. The temperature was raised to 250-300 ℃ at a rate of 0.5-1 ℃/min and maintained for 0.5-1 h, then the temperature was raised to 350-450 ℃ at a rate of 0.5-1 ℃/min to stabilize the material structure, and the dopamine layer was kept for 2-4 h to carbonize the dopamine layer, and then Cool to room temperature to obtain carbon@Fe 2 O 3 @carbon microsphere composite.

进一步地，所述铁盐为氯化铁、硝酸铁或者硫酸铁中的任意一种。Further, the iron salt is any one of ferric chloride, ferric nitrate or ferric sulfate.

一种上述的碳@Fe2O3@碳微球复合材料的应用，其创新点在于：所述碳@Fe2O3@碳微球纳米复合材料用作锂离子电池的负极材料。An application of the above-mentioned carbon @Fe 2 O 3 @carbon microsphere composite material is innovative in that the carbon @Fe 2 O 3 @carbon microsphere nanocomposite material is used as a negative electrode material for a lithium-ion battery.

进一步地，所述碳@Fe2O3@碳微球纳米复合材料应用于CR2032扣式锂离子电池，具体步骤如下：Further, the carbon @Fe 2 O 3 @carbon microsphere nanocomposite material is applied to a CR2032 button lithium ion battery, and the specific steps are as follows:

步骤A：按照70:20:10的质量比将碳@Fe2O3@碳微球纳米复合材料：导电剂Super P：粘结剂羧甲基纤维素钠混合均匀，得到固体混合物；Step A: According to the mass ratio of 70:20:10, carbon @Fe 2 O 3 @carbon microsphere nanocomposite material: conductive agent Super P: binder sodium carboxymethyl cellulose were mixed uniformly to obtain a solid mixture;

步骤B ：将步骤A得到的固体混合物与超纯水按照质量比为18：82～25：75进行混合，搅拌均匀，制得浆料；Step B: Mix the solid mixture obtained in Step A with ultrapure water at a mass ratio of 18:82 to 25:75, and stir evenly to prepare a slurry;

步骤C：将步骤B得到的浆料涂覆在铜箔上，经干燥、辊压后制得厚度为13～23 µm的锂离子电池电极片；Step C: Coating the slurry obtained in Step B on a copper foil, drying and rolling to prepare a lithium-ion battery electrode sheet with a thickness of 13-23 µm;

步骤D：将步骤C得到的锂离子电池电极片作为电池负极片，采用微孔聚丙烯膜为隔膜，采用溶剂1 mol/L LiPF6为电解液，溶剂为等体积的碳酸二甲酯和碳酸二丙酯，在充满氩气的手套箱中装配成CR2032扣式锂离子电池。Step D: use the lithium-ion battery electrode sheet obtained in step C as the negative electrode sheet of the battery, use a microporous polypropylene film as the diaphragm, and use a solvent of 1 mol/L LiPF 6 as the electrolyte, and the solvent is equal volumes of dimethyl carbonate and carbonic acid Dipropyl ester, assembled into a CR2032 coin lithium-ion battery in an argon-filled glove box.

本发明的优点在于：The advantages of the present invention are:

（1）本发明碳@Fe2O3@碳微球复合材料，该分级中空结构的存在一方面可以缓解三氧化二铁在充放电过程中的体积变化，另一方面还有利于电解质的渗透和锂离子的传输，这样能显著改善其循环寿命；而碳层的存在一方面能够改善三氧化二铁的低电导率的特性，也能够同时作为一个缓冲层缓解其在充放电过程中体积的变化，从而有效改善其循环稳定性；(1) The carbon@Fe 2 O 3 @carbon microsphere composite material of the present invention, the existence of the hierarchical hollow structure can alleviate the volume change of ferric oxide during charging and discharging on the one hand, and on the other hand, it is also conducive to the penetration of electrolyte and the transmission of lithium ions, which can significantly improve its cycle life; on the one hand, the existence of the carbon layer can improve the low conductivity characteristics of ferric oxide, and can also serve as a buffer layer to relieve its volume loss during charge and discharge. changes, thereby effectively improving its cycle stability;

（2）本发明碳@Fe2O3@碳微球复合材料的制备方法，其中，采用阶段梯度升温对SiO2@酚醛树脂进行碳化，后续中空碳球的官能化阶段预先使用浓硝酸对其进行浸润等步骤既保持了材料结构的完整性，亦取得了理想的官能化效果；随后通过无机沉淀→退火相转变→聚合物包裹→阶段升温碳化等一系列步骤，最终合成了结构完整的具有分级中空结构的碳@Fe2O3@碳微球材料；(2) The preparation method of the carbon@Fe 2 O 3 @carbon microsphere composite material of the present invention, wherein the SiO2@phenolic resin is carbonized by stepwise gradient heating, and concentrated nitric acid is used in the subsequent functionalization stage of the hollow carbon spheres. Steps such as infiltration not only maintain the integrity of the material structure, but also achieve the ideal functionalization effect; then through a series of steps such as inorganic precipitation → annealing phase transformation → polymer encapsulation → staged heating and carbonization, finally synthesized a hierarchical Carbon @Fe 2 O 3 @carbon microsphere material with hollow structure;

（3）本发明碳@Fe2O3@碳微球复合材料，可作为性能优良的锂离子电池负极材料，容量高且其能够显著提升锂电池的循环寿命，（0.2 C下循环100次后，取得了1163 mAh/g的充电容量，1 C下循环1000次后放电容量仍高达758.8 mAh/g），而且工艺简单、重现性好、易于实施，适合大规模生产。(3) The carbon @Fe 2 O 3 @carbon microsphere composite material of the present invention can be used as an anode material for lithium-ion batteries with excellent performance. It has high capacity and can significantly improve the cycle life of lithium batteries. (After 100 cycles at 0.2 C , achieved a charge capacity of 1163 mAh/g, and the discharge capacity was still as high as 758.8 mAh/g after 1000 cycles at 1 C), and the process is simple, reproducible, easy to implement, and suitable for mass production.

附图说明Description of drawings

下面结合附图和具体实施方式对本发明作进一步详细的说明。The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

图1是本发明实施例1制备的中空碳球扫描电镜图。Figure 1 is a scanning electron micrograph of hollow carbon spheres prepared in Example 1 of the present invention.

图2是本发明实施例1制备的碳@Fe2O3@碳微球的X射线衍射结果图。Fig. 2 is an X-ray diffraction diagram of carbon @Fe 2 O 3 @carbon microspheres prepared in Example 1 of the present invention.

图3是本发明实施例1制备的碳@Fe2O3@碳微球TEM图。Fig. 3 is a TEM image of carbon @Fe 2 O 3 @ carbon microspheres prepared in Example 1 of the present invention.

图4是本发明实施例1制备的碳@Fe2O3@碳微球高倍TEM图。Fig. 4 is a high magnification TEM image of carbon @Fe 2 O 3 @ carbon microspheres prepared in Example 1 of the present invention.

图5是本发明实施例1制备的碳@Fe2O3@碳微球作为负极材料的锂离子电池在0.2 C下的循环性能曲线。Fig. 5 is a cycle performance curve at 0.2 C of a lithium-ion battery using carbon @Fe 2 O 3 @ carbon microspheres prepared in Example 1 of the present invention as the negative electrode material.

图6是本发明实施例1制备的碳@Fe2O3@碳微球作为负极材料的锂离子电池在1C下的循环性能曲线。Fig. 6 is a cycle performance curve at 1C of a lithium-ion battery using carbon @Fe 2 O 3 @carbon microspheres prepared in Example 1 of the present invention as the negative electrode material.

具体实施方式Detailed ways

下面的实施例可以使本专业的技术人员更全面地理解本发明，但并不因此将本发明限制在所述的实施例范围之中。The following examples can enable those skilled in the art to understand the present invention more comprehensively, but the present invention is not limited to the scope of the described examples.

实施例1Example 1

（1）将1.7 ml TEOS，4 ml氨水同时加入由15 ml乙醇与6 ml水组成的混合溶液中搅拌1h。随后加入0.4 g间苯二酚与0.56 ml甲醛，继续搅拌24 h。随后将反应溶液于100 ℃水热反应24 h，离心收集产物并用乙醇洗涤4次。得SiO2@酚醛树脂。(1) Add 1.7 ml TEOS and 4 ml ammonia water to the mixed solution consisting of 15 ml ethanol and 6 ml water and stir for 1 hour. Subsequently, 0.4 g of resorcinol and 0.56 ml of formaldehyde were added, and stirring was continued for 24 h. Then, the reaction solution was hydrothermally reacted at 100 °C for 24 h, and the product was collected by centrifugation and washed four times with ethanol. Get SiO 2 @phenolic resin.

（2）将步骤(1)干燥后的SiO2@酚醛树脂置于管式炉中，以0.5 L/min的进气量通入氮气保护气体，先以6 ℃/min 的速率升温至400℃并保持半小时，随后以1 ℃/min的速率升温到700 ℃并保持2小时，得到SiO2@碳微球，再将SiO2@碳置于15 wt% 氢氟酸溶液中浸泡12 h后离心收集产物，并用水洗涤至中性，得到中空碳球。(2) Put the SiO 2 @phenolic resin dried in step (1) in a tube furnace, feed nitrogen protective gas at an air flow rate of 0.5 L/min, and first raise the temperature to 400°C at a rate of 6°C/min And keep it for half an hour, then raise the temperature to 700 ℃ at a rate of 1 ℃/min and keep it for 2 hours to get SiO 2 @ carbon microspheres, and then put SiO 2 @ carbon in 15 wt% hydrofluoric acid solution for 12 h The product was collected by centrifugation and washed with water until neutral to obtain hollow carbon spheres.

（3）将300 mg的中空碳球超声分散于20 ml浓硝酸(68 wt%)中，在室温下搅拌1h后升温至80 ℃并回流搅拌10 h，反应完成后以8000 r/min的转速离心收集产物并用超纯水洗涤5次，得到官能化得中空碳球。(3) Ultrasonic disperse 300 mg of hollow carbon spheres in 20 ml of concentrated nitric acid (68 wt%), stir at room temperature for 1 h, then raise the temperature to 80 °C and reflux for 10 h. The product was collected by centrifugation and washed 5 times with ultrapure water to obtain functionalized hollow carbon spheres.

（4）将50 mg的中空碳球超声40 min，使其均匀分散于100 ml去离子水中，并加入0.541 g 六水合氯化铁，在75 ℃下水浴搅拌5 h，反应完成后以8000 r/min的转速离心收集产物并用超纯水洗涤4次，得碳@FeOOH。(4) Sonicate 50 mg of hollow carbon spheres for 40 min to uniformly disperse them in 100 ml of deionized water, add 0.541 g of ferric chloride hexahydrate, and stir in a water bath at 75 °C for 5 h. The product was collected by centrifugation at a speed of 1/min and washed 4 times with ultrapure water to obtain carbon@FeOOH.

（5）将步骤(4)干燥后的碳@FeOOH 置于管式炉中，以0.5 L/min的进气量通入氮气，升温速率为2 ℃ / min，升温到350 ℃并煅烧2 h后自然冷却至室温，得到碳@Fe2O3 微球纳米复合材料。(5) Put the carbon @FeOOH dried in step (4) into a tube furnace, feed nitrogen gas at an air flow rate of 0.5 L/min, and heat up to 350 °C at a heating rate of 2 °C/min for 2 h. After natural cooling to room temperature, the carbon @Fe 2 O 3 microsphere nanocomposite was obtained.

（6）将150 mg的碳@Fe2O3 微球复合材料超声20 min，使其均匀分散于250 ml去离子水中，并加入0.1 g多巴胺和1 g三羟甲基氨基甲烷。室温下搅拌4 h。反应完成后以5000r/min的转速离心收集产物并用超纯水洗涤4次，将所得样品于60 ℃隔夜干燥；将干燥后的样品置于管式炉中，以4℃/min的速率升温到300 ℃并保持0.5 h，然后以1 ℃/min的速率升温到450 ℃并保持2 h彻底碳化多巴胺层，最终得到碳@Fe2O3@碳微球纳米复合材料。(6) 150 mg of carbon@Fe 2 O 3 microsphere composite was ultrasonically dispersed for 20 min to uniformly disperse it in 250 ml of deionized water, and 0.1 g of dopamine and 1 g of tris were added. Stir at room temperature for 4 h. After the reaction was completed, the product was collected by centrifugation at a speed of 5000r/min and washed 4 times with ultrapure water, and the obtained sample was dried overnight at 60°C; the dried sample was placed in a tube furnace and heated at a rate of 4°C/min to 300 ℃ and kept for 0.5 h, then raised to 450 ℃ at a rate of 1 ℃/min and kept for 2 h to completely carbonize the dopamine layer, and finally obtained carbon @Fe 2 O 3 @carbon microsphere nanocomposites.

（7）锂离子电池的组装和性能测试: 按照质量比70:20:10将碳@Fe2O3@碳微球、导电剂Super P及粘结剂羧甲基纤维素钠混合均匀；再按照质量比20：80将混合均匀后的固体混合物与超纯水进行混合并搅拌均匀制成浆料；之后将浆料涂覆在铜箔上，经干燥、辊压后制得锂离子电池电极片。随后以锂片作为电极正极片，微孔聚丙烯膜为隔膜，1 mol/LLiPF6 (溶剂为等体积的碳酸二甲酯和碳酸二丙酯)为电解液，与此电极片在充满氩气的手套箱中装配成CR2032扣式锂离子电池。将锂离子电池静置24小时后，分别在0.2C和1C电流密度下进行充放电测试，充放电压为0.01～3.0 V之间。(7) Assembly and performance testing of lithium-ion batteries: Mix carbon @Fe 2 O 3 @carbon microspheres, conductive agent Super P, and binder sodium carboxymethyl cellulose according to the mass ratio of 70:20:10; According to the mass ratio of 20:80, the uniformly mixed solid mixture is mixed with ultrapure water and stirred evenly to make a slurry; then the slurry is coated on a copper foil, dried and rolled to prepare a lithium-ion battery electrode piece. Then, the lithium sheet was used as the electrode positive sheet, the microporous polypropylene membrane was used as the diaphragm, and 1 mol/LLiPF 6 (solvent was equal volumes of dimethyl carbonate and dipropyl carbonate) was used as the electrolyte, and the electrode sheet was filled with argon gas. A CR2032 button lithium-ion battery is assembled in the glove box. After the lithium-ion battery was left to stand for 24 hours, charge and discharge tests were performed at 0.2C and 1C current densities, respectively, and the charge and discharge voltage was between 0.01 and 3.0 V.

本实施例的结果如图1至图5所示；由图1可以看出，其具有均匀的球形形貌，从个别破损处可以看出其具有中空结构，其直径大小约为220 nm；由图2可以看出，峰分别对应于三氧化二铁（JCPDS卡：33-0664）的峰，其中22 °附近的宽峰归因于材料中碳元素的峰；由图3可以看出，碳@Fe2O3@碳微球具有均匀的形貌分布，Fe2O3外包裹有碳层，厚度约为5 nm，此外Fe2O3纳米棒亦具有中空结构；由图4可以看出， Fe2O3外包裹有碳层，厚度约为5 nm；Fe2O3呈现棒状且具有中空结构。The results of this embodiment are shown in Figures 1 to 5; as can be seen from Figure 1, it has a uniform spherical shape, and it can be seen from individual damage that it has a hollow structure with a diameter of about 220 nm; It can be seen from Figure 2 that the peaks correspond to the peaks of ferric oxide (JCPDS card: 33-0664), and the broad peak near 22 ° is attributed to the peak of carbon in the material; it can be seen from Figure 3 that carbon @Fe 2 O 3 @carbon microspheres have a uniform shape distribution, and Fe 2 O 3 is wrapped with a carbon layer with a thickness of about 5 nm. In addition, Fe 2 O 3 nanorods also have a hollow structure; it can be seen from Figure 4 , Fe 2 O 3 is wrapped with a carbon layer with a thickness of about 5 nm; Fe 2 O 3 is rod-shaped and has a hollow structure.

实施例2Example 2

（1）将2.2 ml TEOS，4 ml氨水同时加入由19 ml乙醇与8 ml水组成的混合溶液中搅拌1h。随后加入0.4 g间苯二酚与0.56 ml甲醛，继续搅拌24 h。随后将反应溶液于100 ℃水热反应24 h，离心收集产物并用乙醇洗涤4次。得SiO2@酚醛树脂。(1) Add 2.2 ml TEOS and 4 ml ammonia water to the mixed solution consisting of 19 ml ethanol and 8 ml water and stir for 1 hour. Subsequently, 0.4 g of resorcinol and 0.56 ml of formaldehyde were added, and stirring was continued for 24 h. Then, the reaction solution was hydrothermally reacted at 100 °C for 24 h, and the product was collected by centrifugation and washed four times with ethanol. Get SiO 2 @phenolic resin.

（2）将步骤(1)干燥后的SiO2@酚醛树脂置于管式炉中，以0.5 L/min的进气量通入氮气保护气体，先以6 ℃/min 的速率升温至400℃并保持半小时，随后以1 ℃/min的速率升温到700 ℃并保持2小时，得到SiO2@碳微球，再将SiO2@碳置于15 wt% 氢氟酸溶液中浸泡12 h后离心收集产物，并用水洗涤至中性，得到中空碳球。(2) Put the SiO 2 @phenolic resin dried in step (1) in a tube furnace, feed nitrogen protective gas at an air flow rate of 0.5 L/min, and first raise the temperature to 400°C at a rate of 6°C/min And keep it for half an hour, then raise the temperature to 700 ℃ at a rate of 1 ℃/min and keep it for 2 hours to get SiO 2 @ carbon microspheres, and then put SiO 2 @ carbon in 15 wt% hydrofluoric acid solution for 12 h The product was collected by centrifugation and washed with water until neutral to obtain hollow carbon spheres.

（3）将300 mg的中空碳球超声分散于20 ml浓硝酸(68 wt%)中，在室温下搅拌1h后升温至80 ℃并回流搅拌10 h，反应完成后以8000 r/min的转速离心收集产物并用超纯水洗涤5次，得到官能化得中空碳球。(3) Ultrasonic disperse 300 mg of hollow carbon spheres in 20 ml of concentrated nitric acid (68 wt%), stir at room temperature for 1 h, then raise the temperature to 80 °C and reflux for 10 h. The product was collected by centrifugation and washed 5 times with ultrapure water to obtain functionalized hollow carbon spheres.

（4）将100 mg的中空碳球超声40 min，使其均匀分散于100 ml去离子水中，并加入0.829 g 硝酸铁，在75 ℃水浴搅拌5 h，反应完成后以8000 r/min的转速离心收集产物并用超纯水洗涤4次，得碳@FeOOH。(4) Sonicate 100 mg of hollow carbon spheres for 40 min to uniformly disperse them in 100 ml of deionized water, add 0.829 g of ferric nitrate, and stir in a water bath at 75 °C for 5 h. The product was collected by centrifugation and washed four times with ultrapure water to obtain carbon@FeOOH.

其他步骤与实施例1相同。Other steps are identical with embodiment 1.

实施例3Example 3

（1）将1.3 ml TEOS，4 ml氨水同时加入由12 ml乙醇与4 ml水组成的混合溶液中搅拌1h。随后加入0.4 g间苯二酚与0.56 ml甲醛，继续搅拌24 h。随后将反应溶液于100 ℃水热反应24 h，离心收集产物并用乙醇洗涤4次。得SiO2@酚醛树脂。(1) Add 1.3 ml TEOS and 4 ml ammonia water to the mixed solution consisting of 12 ml ethanol and 4 ml water and stir for 1 hour. Subsequently, 0.4 g of resorcinol and 0.56 ml of formaldehyde were added, and stirring was continued for 24 h. Then, the reaction solution was hydrothermally reacted at 100 °C for 24 h, and the product was collected by centrifugation and washed four times with ethanol. Get SiO 2 @phenolic resin.

（2）将步骤(1)干燥后的SiO2@酚醛树脂置于管式炉中，以0.5 L/min的进气量通入氮气保护气体，先以6 ℃/min 的速率升温至400℃并保持半小时，随后以1 ℃/min的速率升温到700 ℃并保持2小时，得到SiO2@碳微球，再将SiO2@碳置于15 wt% 氢氟酸溶液中浸泡12 h后离心收集产物，并用水洗涤至中性，得到中空碳球。(2) Put the SiO 2 @phenolic resin dried in step (1) in a tube furnace, feed nitrogen protective gas at an air flow rate of 0.5 L/min, and first raise the temperature to 400°C at a rate of 6°C/min And keep it for half an hour, then raise the temperature to 700 ℃ at a rate of 1 ℃/min and keep it for 2 hours to get SiO 2 @ carbon microspheres, and then put SiO 2 @ carbon in 15 wt% hydrofluoric acid solution for 12 h The product was collected by centrifugation and washed with water until neutral to obtain hollow carbon spheres.

（3）将300 mg的中空碳球超声分散于20 ml浓硝酸(68 wt%)中，在室温下搅拌1h后升温至80 ℃并回流搅拌10 h，反应完成后以8000 r/min的转速离心收集产物并用超纯水洗涤5次，得到官能化得中空碳球。(3) Ultrasonic disperse 300 mg of hollow carbon spheres in 20 ml of concentrated nitric acid (68 wt%), stir at room temperature for 1 h, then raise the temperature to 80 °C and reflux for 10 h. The product was collected by centrifugation and washed 5 times with ultrapure water to obtain functionalized hollow carbon spheres.

（4）将100 mg的中空碳球超声40 min，使其均匀分散于100 ml去离子水中，并加入1.021 g 硫酸铁，在75 ℃水浴搅拌5 h，反应完成后以8000 r/min的转速离心收集产物并用超纯水洗涤4次，得碳@FeOOH。(4) Sonicate 100 mg of hollow carbon spheres for 40 min to uniformly disperse them in 100 ml of deionized water, add 1.021 g of ferric sulfate, and stir in a water bath at 75 °C for 5 h. The product was collected by centrifugation and washed four times with ultrapure water to obtain carbon@FeOOH.

其他步骤与实施例1相同。Other steps are identical with embodiment 1.

实施例1-3的锂电性能结果如表1和表2所示。The lithium battery performance results of Examples 1-3 are shown in Table 1 and Table 2.

表1为实施例1～3的锂离子电池在0.2C电流下进行充放电测试第一圈和第100圈所获得的容量。Table 1 shows the capacities obtained in the first cycle and the 100th cycle of the charge-discharge test of the lithium-ion batteries of Examples 1-3 at a current of 0.2C.

表1Table 1

从表1可以看出，采用本发明的碳@Fe2O3@碳微球作为电极材料，应用于锂离子电池，在循环100圈后充电容量在1000 mAh/g以上，容量保持率在70 %以上，具有很好的循环性能，仍远高于当前商业化的石墨负极材料。It can be seen from Table 1 that the carbon @Fe 2 O 3 @carbon microspheres of the present invention are used as electrode materials and applied to lithium-ion batteries. After 100 cycles, the charging capacity is above 1000 mAh/g, and the capacity retention rate is 70 More than %, it has good cycle performance, which is still much higher than the current commercial graphite anode materials.

表2为实施例1～3的锂离子电池在1C电流下进行充放电测试第一圈和第1000圈所获得的容量。Table 2 shows the capacities obtained in the first cycle and the 1000th cycle of the charge and discharge test of the lithium ion batteries of Examples 1-3 at a current of 1C.

表2Table 2

从表2可以看出，采用本发明的碳@Fe2O3@碳微微球作为电极材料，应用于锂离子电池，在循环1000圈后充电容量在723 mAh/g以上，容量保持率在64.8 %以上，具有很好的循环性能，仍远高于当前商业化的石墨负极材料。It can be seen from Table 2 that the carbon @Fe 2 O 3 @carbon microspheres of the present invention are used as electrode materials and applied to lithium-ion batteries. After 1000 cycles, the charging capacity is above 723 mAh/g, and the capacity retention rate is 64.8 More than %, it has good cycle performance, which is still much higher than the current commercial graphite anode materials.

以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。The basic principles and main features of the present invention and the advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the present invention is not limited by the above-mentioned embodiments. What are described in the above-mentioned embodiments and the description only illustrate the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will also have Variations and improvements are possible, which fall within the scope of the claimed invention. The protection scope of the present invention is defined by the appended claims and their equivalents.

Claims (4)

1. a kind of carbon@Fe2O3@carbosphere composite material, it is characterised in that: the carbon@Fe2O3@carbosphere composite material is by positive silicon Sour tetra-ethyl ester, ammonium hydroxide, resorcinol, formaldehyde, molysite and dopamine are prepared, the carbon@Fe2O3@carbosphere diameter prepared For 200~300 nm, thickness of the shell is about 15~30nm in the microballoon carbon, the Fe2O3 Intermediate layer thickness is 30~60nm, The carbon shell with a thickness of 3~7nm；
The carbon@Fe2O3@carbosphere composite material, is prepared particular by following steps:
Step 1: the preparation of silica@phenolic resin microspheres: tetraethyl orthosilicate and ammonium hydroxide are added in ethanol/water solution, Resorcinol and formaldehyde are added after 1~2h of stirring and continues 12~24 h of stirring；In the ethanol/water solution system, ethyl alcohol Volume fraction be 72~85 %, containing TEOs be 50~80 ml in every liter of reaction solution, ammonia concn is 120~180 ml, 12~18 g of benzenediol, 18~25 ml of formaldehyde；Reaction solution is then moved into autoclave and 12~24 h of hydro-thermal reaction； After naturally cooling to room temperature, centrifuge washing collects product, obtains silica@phenolic resin microspheres；
Step 2: the preparation of the hollow carbon balls of function dough: silica phenolic resin is placed in tube furnace, in nitrogen or argon Be warming up to 400~500 DEG C under the argon-mixed atmosphere of nitrogen of gas or any ratio with the rate of 4~6 DEG C/min, then with 1~ The rate of 2.5 DEG C/min is warming up to 550~750 DEG C to prevent material structure broken, and is kept for 2~4 hours, makes phenolic resin Sufficiently carbonization, cooled to room temperature, obtains SiO later2@carbosphere material；Again by SiO2@carbosphere is placed in 15~25 wt% Hydrofluoric acid solution in impregnate 12~24 h, be then centrifuged for separating, be cleaned with deionized water, obtain hollow carbon balls；Then by institute It obtains hollow carbon balls and is initially positioned at 25~35 DEG C, 2 h are stirred in the concentrated nitric acid that mass fraction is 60~70 % infiltrates it sufficiently simultaneously just Step functionalization, temperature then rises to 50~80 DEG C and continues 8~10h of stirring be functionalized；Then it washes, it is dry, it obtains The hollow carbon balls of function dough；
Step 3: carbon@Fe2O3The preparation of micro-sphere material: the hollow carbon balls of the resulting function dough of step 2 are added to deionization In water, hollow carbon balls dispersion liquid is obtained；Then molysite is added into hollow carbon balls dispersion liquid again, under the conditions of 60~80 DEG C with The speed of 600~900 rpm/min stirs 4~6 h, obtains carbon@FeOOH；The hollow carbon balls dispersion liquid concentration be 0.5~ 1 g/L, the concentration of the molysite are 0.2~1 mol/L；By the way that product is collected by centrifugation, and it is washed with deionized 2~3 times, Obtain the hollow carbosphere composite material carbon FeOOH of FeOOH package；Then carbon@FeOOH is placed in tube furnace, 350~450 DEG C are warming up to the rate of 1~6 DEG C/min under the argon-mixed atmosphere of nitrogen of nitrogen or argon gas or any ratio and are protected 2~6 h are held, later cooled to room temperature, obtains carbon@Fe2O3Microsphere nano material；
Step 4: by the carbon@Fe in step 32O3Microsphere nano material is scattered in tris solution, and is added 4~6 h are stirred after dopamine at normal temperature；The carbon@Fe2O3 The dispersion concentration of microsphere nano material is 0.5~1 g/L； The dopamine concentration is 0.4~1 g/L；The concentration of the trishydroxymethylaminomethane is 1~1.2 g/L；It has reacted Product is washed 2~3 times by the way that product is collected by centrifugation, and with deionized water at rear；Product after drying is placed in tube furnace, 250~300 DEG C are warming up to simultaneously under the argon-mixed atmosphere of nitrogen of nitrogen or argon gas or any ratio with the rate of 2~4 DEG C/min 0.5~1 h is kept, is then warming up to 350~450 DEG C with the rate of 0.5~1 DEG C/min with stabilizing material structure, and keep 2 ~4 h Carbidopa amine layer, then cooled to room temperature, obtains carbon@Fe2O3@carbosphere composite material.
2. carbon@Fe according to claim 12O3@carbosphere composite material, it is characterised in that: the molysite be iron chloride, Any one in ferric nitrate or ferric sulfate.
3. a kind of carbon@Fe described in claim 12O3The application of@carbosphere composite material, it is characterised in that: the carbon@Fe2O3@ Carbosphere nanocomposite is used as the negative electrode material of lithium ion battery.
4. carbon@Fe according to claim 32O3The application of@carbosphere composite material, it is characterised in that: the carbon@Fe2O3@ Carbosphere nanocomposite applications are in CR2032 fastening lithium ionic cell, the specific steps are as follows:
Step A: according to the mass ratio of 70:20:10 by carbon@Fe2O3@carbosphere nanocomposite: conductive agent Super P: bonding Agent carboxymethyl sodium cellulosate is uniformly mixed, and obtains solid mixture；
Step B: the solid mixture that step A is obtained is mixed with ultrapure water according to mass ratio for 18:82~25:75, is stirred It mixes uniformly, slurry is made；
Step C: the slurry that step B is obtained is coated on copper foil, and the lithium with a thickness of 13~23 μm is made after drying, roll-in Ion battery electrode piece；
Step D: the lithium ion cell electrode piece that step C is obtained uses microporous polypropylene membrane for diaphragm as battery cathode sheet, Using 1 mol/L LiPF of solvent6For electrolyte, solvent is isometric dimethyl carbonate and dipropyl carbonate, is being full of argon gas Glove box in be assembled into CR2032 fastening lithium ionic cell.
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