CN107845787B - 石榴状Fe3O4@N-C锂电池负极材料制备方法 - Google Patents

石榴状Fe3O4@N-C锂电池负极材料制备方法 Download PDF

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CN107845787B
CN107845787B CN201710897213.2A CN201710897213A CN107845787B CN 107845787 B CN107845787 B CN 107845787B CN 201710897213 A CN201710897213 A CN 201710897213A CN 107845787 B CN107845787 B CN 107845787B
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李鹿
王春刚
苏忠民
谢海明
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Abstract

本发明公开了石榴状Fe3O4@N‑C纳米粒子，它是将40~50 mg聚丙烯酸、100~200μL氨水和20~35 mL去离子水依次加入容器中，搅拌混合均匀后，将80~120 mL异丙醇滴加到溶液中，滴加完毕后，再向溶液中加入50~100 mg四水合氯化亚铁，室温下搅拌反应；离心，沉淀烘干，通过在惰性气体保护下500~600℃煅烧后获得的；该纳米粒子是由许多超小的氮掺杂碳包覆四氧化三铁二级单元组装而成，二级单元粒径小于5 nm，大大减小了锂离子的传输距离。具有超高的循环稳定性和倍率性能。以其为活性材料制备的锂电池；实验表明具有超高的循环性能和快速充放电能力。

Description

石榴状Fe3O4@N-C锂电池负极材料制备方法
技术领域
本发明属于纳米复合材料及其应用技术领域，具体涉及一种石榴状氮掺杂碳包覆四氧化三铁（Fe3O4@N-C）高性能锂电池负极材料的制备方法。
背景技术
过渡金属氧化物MxOy（M = Fe、Co、Cu、Ni等）作为锂离子电池负极材料的研究始于2000年，Tarascon课题组首次报道了纳米尺度的过渡金属氧化物负极材料，并表现出优异的电化学性能，同时他还提出了这类材料作为锂离子电池负极材料的储锂机理与传统的嵌锂机理不同。在放电过程中，过渡金属氧化物MxOy与锂发生完全可逆的氧化还原反应，具有较高的理论可逆容量（500-1000 mAh g-1），普遍高于传统碳材料（理论容量为374 mAh g-1）。且过渡金属氧化物的放电平台高于石墨类，有利于避免充放电过程中锂枝晶的形成。因此，有利于新一代大容量锂离子电池的发展。而在众多的过渡金属氧化物中，铁的氧化物（如Fe2O3、Fe3O4等）在自然界中资源丰富、无毒、易于制备，且价格低廉，对其潜在的应用具有重要的实际意义，很快受到广大科研工作者的关注，被认为是最有希望的负极材料。
Fe3O4负极材料虽然具有很高的理论容量，但其本身在脱嵌锂过程中，会伴随着明显的体积膨胀/收缩的现象，极易导致电极材料团聚粉化脱落，很难和初始状态保持一致，表现出较差的循环稳定性及倍率性能。为了解决这一问题，起初人们大多采用碳包覆来解决稳定性问题，并取得了很好的效果（Yang C R, Wang Y Y, Wan C C. Compositionanalysis of the passive film on the carbon electrode of a lithium-ion batterywith an EC-based electrolyte. J. Power Sources, 1998, 72, 66-70；Claye A S,Fischer J E, Huffman C B, et a1. Solid-State Electrochemistry of the LiSingle Wall Carbon Nanotube System. J. Electrochem. Soc., 2000, 147, 2845-2852；Wu G T, Wang C S, Zhang X B, el a1. Structure and Lithium InsertionProperties of Carbon Nanotubes. J. Electrochem. Soc., 1999, 146, 1696-1701.）。碳包覆虽能有效缓解 Fe3O4的体积变化，起到是起到保护电极提高循环稳定性的作用，但对提升电极材料容量及倍率性能的能力有限。为了获得更高容量和倍率性能的电极材料，目前的研究重点侧重于制备具有特殊形貌的纳米材料。特殊纳米结构除可抑制充放电过程中的体积效应，改善电极材料的循环稳定性（Chen Y, Xia H, Lu L, et al. Synthesis ofporous hollow Fe3O4 beads and their applications in lithium ion batteries.Journal of Materials Chemistry, 2012, 22, 5006-5012. Wang J Z, Zhong C,Wexler D, et al. Graphene-Encapsulated Fe3O4 Nanoparticles with 3D LaminatedStructure as Superior Anode in Lithium Ion Batteries. Chemistry-A EuropeanJournal, 2011, 17, 661-667. Zhu F Q, Fan D, Zhu X, et al. Ultrahigh-DensityArrays of Ferromagnetic Nanorings on Macroscopic Areas. Adv. Mater., 2004,16, 2155-2159. Zhai Y M, Zhai J F, Dong S J. Temperature-dependent synthesisof CoPt hollow nanoparticles: from “nanochain” to “nanoring”. Chem. Commun.,2010, 46, 1500-1502. Cao H Q, Xu Z, Sang H, et al. Template Synthesis andMagnetic Behavior of an Array of Cobalt Nanowires Encapsulated in PolyanilineNanotubules. Adv. Mater., 2001, 13, 121-123.）。还具备比表面积大、Li+扩散路径短等优点，有利于提高电池的循环稳定性和高倍率性能。如空心球、片层、多孔球和超细颗粒等形貌（Kwon K-A, Lim H-S, Sun Y-K, et al. α-Fe2O3 Submicron Spheres withHollow and Macroporous Structures as High-Performance Anode Materials forLithium Ion Batteries. J. Phys. Chem. C, 2014, 118, 2897-2907. Wang B, Chen JS, Wu H B, et al. Quasiemulsion-Templated Formation of α-Fe2O3 Hollow Sphereswith Enhanced Lithium Storage Properties. J. Am. Chem. Soc., 2011, 133,17146-17148. Xu X, Cao R, Jeong S, et al. Spindle-like Mesoporous α-Fe2O3Anode Material Prepared from MOF Template for High-Rate Lithium Batteries.Nano Letters, 2012, 12, 4988-4991. Chen J, Xu L, Li W, et al. α-Fe2O3Nanotubes in Gas Sensor and Lithium-Ion Battery Applications. Adv. Mater.,2005, 17, 582-586. NuLi Y, Zhang P, Guo Z, et al. Preparation of α-Fe2O3submicro-flowers by a hydrothermal approach and their electrochemicalperformance in lithium-ion batteries. Electrochimica. Acta, 2008, 53, 4213-4218. Etacheri V, Seisenbaeva G A, Caruthers J, et al. Ordered Network ofInterconnected SnO2 Nanoparticles for Excellent Lithium-Ion Storage. AdvancedEnergy Materials, 2015, 5, 1401289. Wu Y, Wei Y, Wang J, et al. ConformalFe3O4 Sheath on Aligned Carbon Nanotube Scaffolds as High-Performance Anodesfor Lithium Ion Batteries. Nano Letters, 2013, 13, 818-823.），特别是超细纳米颗粒（＜10 nm）因其超小的粒径，赋予了其超凡的性能，成为近年来的研究热点。但超小粒子本身稳定性差，易聚集、难于大规模合成，严重制约了其发展。如何将碳包覆与超细纳米颗粒结合起来，寻找一种简单可控的方法，大规模合成稳定的超细纳米结构电极材料是一个巨大挑战。
发明内容
本发明的目的是提供一种具有分散性好、比容量大、循环性能好、使用寿命长的石榴状氮掺杂碳包覆四氧化三铁（Fe3O4@N-C）高性能锂电池负极材料。
石榴状Fe3O4@N-C纳米粒子，它是采用下述方法制备，包括：
1)、将40 ~ 50 mg聚丙烯酸、100 ~ 200 μL氨水和20 ~ 35 mL去离子水依次加入到容器中，搅拌混合均匀后，将80 ~ 120 mL异丙醇滴加至溶液中，滴加完毕后再向溶液中加入50 ~ 100 mg四水合氯化亚铁，室温下搅拌反应3 ~ 5 h；
2）、将步骤1）得到的混合溶液进行离心分离，沉淀在烘箱中烘干8 ~ 10 h；置于管式炉中，在惰性气体保护下500 ~ 600 ℃煅烧5 ~ 10 h，得到石榴状Fe3O4@N-C高性能锂电池负极材料；
所述的烘干温度为50℃；
所述的聚丙烯酸40 mg、氨水100 μL和去离子水20 mL；所述的异丙醇80 mL ；所述的四水合氯化亚铁50 mg；
所述的聚丙烯酸50 mg、氨水130 μL和去离子水23 mL；所述的异丙醇100 mL ；所述的四水合氯化亚铁60 mg；
所述的聚丙烯酸43 mg、氨水150 μL和去离子水30mL；所述的异丙醇100 mL ；所述的四水合氯化亚铁100 mg。
一种锂电池负极片的制备方法：用上述的石榴状Fe3O4@N-C纳米粒子为活性物质，乙炔黑为导电剂，聚偏氟乙烯为粘结剂，氮甲基吡咯烷酮为溶剂；混合后，研磨成浆；120 oC真空干重，压片，干燥；
所述的活性物质、导电剂、粘结剂的重量比为：78:10:10。
本发明提供了石榴状Fe3O4@N-C纳米粒子，它是将40 ~ 50 mg聚丙烯酸、100 ~200 μL氨水和20 ~ 35 mL去离子水依次加入容器中，搅拌混合均匀后，将80 ~ 120 mL异丙醇滴加到溶液中，滴加完毕后，再向溶液中加入50 ~ 100 mg四水合氯化亚铁，室温下搅拌反应；离心，沉淀烘干，通过在惰性气体保护下500 ~ 600 ℃煅烧后获得的；该纳米粒子是由许多超小的氮掺杂碳包覆四氧化三铁二级单元组装而成，二级单元粒径小于5 nm，大大减小了锂离子的传输距离，对电化学性能的提升有很大益处。具有超高的循环稳定性和倍率性能。以其为活性材料制备的锂电池；实验表明具有超高的循环性能和快速充放电能力。
附图说明
图1 石榴状Fe3O4@N-C纳米粒子的透射电镜图片；
图2 单个石榴状Fe3O4@N-C纳米粒子的透射电镜图片；
图3 石榴状Fe3O4@N-C纳米粒子的扫描电镜图片；
图4单个石榴状Fe3O4@N-C纳米粒子的透射电镜图片；
图5石榴状Fe3O4@N-C纳米粒子的面扫描电镜图片；
图6石榴状Fe3O4@N-C纳米粒子在不同电流密度下的充放电循环曲线。
具体实施方式
实施例1 Fe3O4@N-C纳米粒子的负极材料的制备
依次将40 mg聚丙烯酸、100 μL氨水和20 mL去离子水加入到100 mL圆底烧瓶中，搅拌混合均匀后将80 mL异丙醇缓慢滴加入溶液中，滴加完毕后再向溶液中加入50 mg四水合氯化亚铁，室温下搅拌反应3 h。将上述溶液进行离心分离，沉淀在50 oC烘箱中烘干8 h。随后，将固体置于管式炉中，在氩气保护下500 oC煅烧5 h得到石榴状Fe3O4@N-C高性能锂电池负极材料。
实施例2 Fe3O4@N-C高性能锂电池负极材料的制备
依次将50 mg聚丙烯酸、130 μL氨水和23 mL去离子水加入到100 mL圆底烧瓶中，搅拌混合均匀后将100 mL异丙醇缓慢滴加入溶液中，滴加完毕后再向溶液中加入60 mg四水合氯化亚铁，室温下搅拌反应4 h。将上述溶液进行离心分离，沉淀在50 oC烘箱中烘干10h。随后，将固体置于管式炉中，在氩气保护下600 oC煅烧10 h，得到石榴状Fe3O4@N-C高性能锂电池负极材料。
实施例3 Fe3O4@N-C纳米粒子的负极材料的制备
依次将43 mg聚丙烯酸、150 μL氨水和30 mL去离子水加入到100 mL圆底烧瓶中，搅拌混合均匀后将100 mL异丙醇缓慢滴加入溶液中，滴加完毕后再向溶液中加入100 mg四水合氯化亚铁，室温下搅拌反应5 h。将上述溶液进行离心分离，沉淀在50 oC烘箱中烘干10h。随后，将固体置于管式炉中，在氩气保护下550 oC煅烧8 h，得到石榴状Fe3O4@N-C高性能锂电池负极材料。
实施例4 Fe3O4@N-C纳米粒子电池的制备
制备出的石榴状Fe3O4@N-C纳米材料用于锂离子电池。以合成的石榴状Fe3O4@N-C纳米材料为活性物质，乙炔黑为导电剂，聚偏氟乙烯(PVDF)为粘结剂，氮甲基吡咯烷酮(NMP)为溶剂。电池的组装过程为：将活性物质、导电剂、聚偏氟乙烯按78:10:10的重量比准确称量，然后放入玛瑙研钵中充分混合、研磨均匀，然后加入几滴NMP，继续研磨至均匀浆状。将浆料均匀涂于已称量过的铜箔上。然后在真空干燥箱中于120 oC真空干燥12 h至恒重，30 MPa下压片，再继续干燥至少2 h，降到室温后取出称重。
实验半电池来测试合成材料的电化学性能，模拟电池的组装在无水无氧、充有氩气的手套箱中完成。将烘干的极片、电池壳和隔膜放入手套箱。以金属锂片为对电极，Celgard240聚丙烯多孔膜做隔膜，1.0 mol/L LiPF6的EC-DMC(体积比1:1)溶液做电解液，组装成扣式CR2032模拟电池，进行充放电测试。
实验表明所制备的石榴状Fe3O4@N-C锂离子电池负极材料具有超高的循环性能和快速充放电能力。如图6所示，在1 A g-1、10 A g-1和20 A g-1倍率下充放电，1000次充放电循环后容量分别为1063.0 mA h g-1、606.0 mA h g-1和417.1 mA h g-1。

Claims (7)

1.石榴状Fe3O4@N-C纳米粒子，它是采用下述方法制备，包括：
1)、将40 ~ 50 mg聚丙烯酸、100 ~ 200 μL氨水和20 ~ 35 mL去离子水依次加入到容器中，搅拌混合均匀后，将80 ~ 120 mL异丙醇滴加至溶液中，滴加完毕后再向溶液中加入50 ~ 100 mg四水合氯化亚铁，室温下搅拌反应3 ~ 5 h；
2）、将步骤1）得到的混合溶液进行离心分离，沉淀在烘箱中烘干8 ~ 10 h；置于管式炉中，在惰性气体保护下500 ~ 600 ℃煅烧5 ~ 10 h，得到石榴状Fe3O4@N-C高性能锂电池负极材料。
2.根据权利要求1所述的石榴状Fe3O4@N-C纳米粒子，其特征在于：所述的烘干温度为50℃。
3.根据权利要求1或2所述的石榴状Fe3O4@N-C纳米粒子，其特征在于：所述的聚丙烯酸40 mg、氨水100 μL和去离子水20 mL；所述的异丙醇80 mL ；所述的四水合氯化亚铁50 mg。
4.根据权利要求1或2所述的石榴状Fe3O4@N-C纳米粒子，其特征在于：所述的聚丙烯酸50 mg、氨水130 μL和去离子水23 mL；所述的异丙醇100 mL ；所述的四水合氯化亚铁60mg。
5.根据权利要求1或2所述的石榴状Fe3O4@N-C纳米粒子，其特征在于：所述的聚丙烯酸43 mg、氨水150 μL和去离子水30mL；所述的异丙醇100 mL ；所述的四水合氯化亚铁100mg。
6. 一种锂电池负极片的制备方法：用权利要求1所述的石榴状Fe3O4@N-C纳米粒子为活性物质，乙炔黑为导电剂，聚偏氟乙烯为粘结剂，氮甲基吡咯烷酮为溶剂；混合后，研磨成浆；120 ℃真空干重，压片，干燥。
7.根据权利要求6所述的一种锂电池负极片的制备方法，其特征在于：所述的活性物质、导电剂、粘结剂的重量比为：78:10:10。
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CN105185994A (zh) * 2015-08-31 2015-12-23 中原工学院 一种掺杂石墨烯的多孔碳/四氧化三铁纳米纤维锂电池负极材料及其制备方法

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