CN106186082A - 一种Fe2O3相变合成的Fe3O4空心纳米粒子及其应用 - Google Patents

一种Fe2O3相变合成的Fe3O4空心纳米粒子及其应用 Download PDF

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CN106186082A
CN106186082A CN201610593930.1A CN201610593930A CN106186082A CN 106186082 A CN106186082 A CN 106186082A CN 201610593930 A CN201610593930 A CN 201610593930A CN 106186082 A CN106186082 A CN 106186082A
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洪振生
周凯强
真义超
黄志高
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Fujian Normal University
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    • C01G49/00—Compounds of iron
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    • C01G49/08—Ferroso-ferric oxide (Fe3O4)
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
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Abstract

本发明公开了一种Fe2O3相变合成的Fe3O4空心纳米粒子及其在钠离子电池中的应用。所述Fe3O4空心纳米粒子是将氯化铁和对苯二甲酸溶解到N,N‑二甲基甲酰胺中，然后滴入氢氧化钠搅拌混匀，再转移到反应釜中进行反应，经离心洗涤得到红色Fe2O3空心纳米粒子，最后在氩气氛围下经高温退火后相变制得。本发明通过溶剂热法一步合成Fe2O3空心纳米粒子前驱体，再经由热处理引起Fe2O3相变生成Fe3O4，所得Fe3O4空心纳米粒子表现出优异的储钠性能，可用作钠离子电池负极材料。

Description

一种Fe2O3相变合成的Fe3O4空心纳米粒子及其应用
技术领域
本发明属于电极材料技术领域，具体涉及一种Fe2O3相变合成的Fe3O4空心纳米粒子及其应用。
背景技术
锂离子电池（LIBs）由于具有高容量、高电压和循环寿命长等显著优点而被广泛应用于移动电子设备、国防工业、电动汽车等领域。但是随着锂离子电池的不断普及，锂（碳酸锂）的价格不断上升，而锂资源也存在地球中储量较少、分布不均、难以开采等问题。钠元素相比于锂而言，储量更丰富，价格低廉且来源广泛，因而钠离子电池近年来得到广泛的关注，未来在储能领域的大规模应用上具有比LIBs更好的应用前景。但钠离子电池因缺乏合适的负极材料而制约其实际应用，因此，开发性能优异的钠离子电池负极材料是当前该领域的研究热点和重点。
发明内容
本发明的目的在于提供一种Fe2O3相变合成的Fe3O4空心纳米粒子及其应用，所得Fe3O4空心纳米粒子表现出优异的储钠性能，可作为负极材料，用于制备钠离子电池。
为实现上述目的，本发明采用如下技术方案：
一种Fe2O3相变合成的Fe3O4空心纳米粒子，其是将0.1-0.4 g氯化铁和0.1-0.6 g对苯二甲酸溶解到8-10 mL N,N-二甲基甲酰胺中，搅拌混匀后滴入1-4 mL 0.1-0.5 mol/L氢氧化钠，继续搅拌10-20 min，然后于130-170℃反应釜中反应3-12h，反应物经离心洗涤得红色产物，即为Fe2O3空心纳米粒子；所得Fe2O3空心纳米粒子于氩气氛围下，经300-500℃退火后相变生成所述Fe3O4空心纳米粒子。
所得Fe3O4空心纳米粒子可作为负极材料，用于制备钠离子电池。
本发明的显著优点在于：
本方法巧妙应用参与反应的有机配体，与Fe3+配位结合形成过渡状态的金属有机复合物，然后，金属有机复合物经溶解再结晶的过程，形成Fe2O3空心纳米粒子前驱体，再在氩气氛围下还原得到Fe3O4空心纳米粒子。
本发明制备成本低，产品纯度高、性能优异，且可大量合成。所制备的Fe3O4空心纳米粒子在钠离子电池中表现出相对较高的比容量和良好的循环稳定性，为铁基电极材料的设计和应用提供了良好的方法和指导。
附图说明
图1为Fe2O3空心纳米粒子前驱体与Fe3O4空心纳米粒子的XRD图。
图2为Fe3O4空心纳米粒子的扫描电镜图（a）和透射电镜图（b）。
图3为Fe3O4空心纳米粒子的充放电曲线图。
图4为Fe3O4与Fe2O3空心纳米粒子的循环性能对比图。
具体实施方式
一种Fe2O3相变合成的Fe3O4空心纳米粒子，其是将0.1-0.4 g氯化铁和0.1-0.6 g对苯二甲酸溶解到8-10 mL N,N-二甲基甲酰胺中，搅拌混匀后滴入1-4 mL 0.1-0.5 mol/L氢氧化钠，继续搅拌10-20 min，然后于130-170℃反应釜中反应3-12h，反应物经离心洗涤得红色产物，即为Fe2O3空心纳米粒子；所得Fe2O3空心纳米粒子于氩气氛围下，经300-500℃退火后相变生成所述Fe3O4空心纳米粒子。
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
将0.1 g氯化铁和0.1 g对苯二甲酸溶解到8 mL N,N-二甲基甲酰胺中，搅拌混匀后滴入1 mL 0.1 mol/L氢氧化钠，继续搅拌10 min，然后于130℃反应釜中反应12h，反应物经离心洗涤得红色产物，即为Fe2O3空心纳米粒子；所得Fe2O3空心纳米粒子于氩气氛围下，经300℃退火后相变生成所述Fe3O4空心纳米粒子。
实施例2
将0.2 g氯化铁和0.3 g对苯二甲酸溶解到9 mL N,N-二甲基甲酰胺中，搅拌混匀后滴入2 mL 0.2 mol/L氢氧化钠，继续搅拌15 min，然后于150℃反应釜中反应8h，反应物经离心洗涤得红色产物，即为Fe2O3空心纳米粒子；所得Fe2O3空心纳米粒子于氩气氛围下，经400℃退火后相变生成所述Fe3O4空心纳米粒子。
实施例3
将0.4 g氯化铁和0.6 g对苯二甲酸溶解到10 mL N,N-二甲基甲酰胺中，搅拌混匀后滴入4 mL 0.5 mol/L氢氧化钠，继续搅拌20 min，然后于170℃反应釜中反应3h，反应物经离心洗涤得红色产物，即为Fe2O3空心纳米粒子；所得Fe2O3空心纳米粒子于氩气氛围下，经500℃退火后相变生成所述Fe3O4空心纳米粒子。
图1为Fe2O3空心纳米粒子前驱体与Fe3O4空心纳米粒子的XRD图。从图1中可以看出，所得Fe2O3空心纳米粒子前驱体为纯相斜方晶体，所得Fe3O4空心纳米粒子为纯相立方晶体。
图2为Fe3O4空心纳米粒子的扫描电镜图（a）和透射电镜图（b）。从图2中可以看出，所得Fe3O4纳米粒子的内部是空心结构，其整体粒径在100-200 nm之间，而且由许多尺寸大约为15-20 nm的小粒子组成。
用所制备的Fe3O4纳米粒子作为钠离子电池负极材料进行测定。钠离子电池组装：Fe3O4纳米粒子：聚偏氟乙烯：乙炔黑＝80-85：5-10：10-15混合研磨后均匀地涂在1.2 cm2的铜片上做负极，正极为金属钠，电解质是1M NaClO4的EC+DEC (EC/ DEC=1/1 v/v) 溶液。电池组装在氩气保护下手套箱里进行（氧气和水分含量均低于1ppm）。
图3为Fe3O4空心纳米粒子的充放电曲线图。从图3中可以看出，Fe3O4空心纳米粒子的充放电曲线是斜坡型的充放电曲线，无明显电压平台；在电流密度为100 mA/g的电流密度下，其首次放电容量达442 mAh/g，首次充电容量达221 mAh/g。
图4为Fe3O4与Fe2O3空心纳米粒子的循环性能对比图。从图4中可以看出，Fe2O3虽然具有较高的首次放电容量（686 mAh/g），但随后其容量迅速下降，经过60次循环后，其容量只有15 mAh/g；而Fe3O4经过60次循环之后，其可逆比容量仍稳定在150 mAh/g。
由此可见，与Fe2O3纳米粒子相比，Fe3O4纳米粒子具有相对较高的比容量和良好的循环稳定性，其更适合作为电极材料。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (2)

1. 一种Fe2O3相变合成的Fe3O4空心纳米粒子，其特征在于：将0.1-0.4 g氯化铁和0.1-0.6 g对苯二甲酸溶解到8-10 mL N,N-二甲基甲酰胺中，搅拌混匀后滴入1-4 mL 0.1-0.5mol/L氢氧化钠，继续搅拌10-20 min，然后于130-170℃中反应3-12h，反应物经离心洗涤得Fe2O3空心纳米粒子；所得Fe2O3空心纳米粒子于氩气氛围下，经300-500℃退火后相变生成所述Fe3O4空心纳米粒子。
2.一种如权利要求1所述Fe3O4空心纳米粒子在钠离子电池中的应用。
CN201610593930.1A 2016-07-27 2016-07-27 一种Fe2O3相变合成的Fe3O4空心纳米粒子及其应用 Expired - Fee Related CN106186082B (zh)

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CN110078130B (zh) * 2019-05-19 2021-11-26 东北电力大学 一种中空结构铁基化合物的制备方法及其作为超级电容器负极材料的应用

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