CN104617284A - 一种多孔四方片状TiO2及其制备方法和应用 - Google Patents

一种多孔四方片状TiO2及其制备方法和应用 Download PDF

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CN104617284A
CN104617284A CN201510060099.9A CN201510060099A CN104617284A CN 104617284 A CN104617284 A CN 104617284A CN 201510060099 A CN201510060099 A CN 201510060099A CN 104617284 A CN104617284 A CN 104617284A
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洪振生
周凯强
洪家兴
黄志高
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Abstract

本发明公开了一种多孔四方片状TiO2及其制备方法和在钠离子电池中的应用，将1.2-1.8g十六烷基磺酸钠分散于35-60mL1.5-2.5mol/L盐酸溶液中，然后滴加1.2-2mL钛酸异丙酯，在70-85℃下反应12-24小时，再经离心洗涤、干燥，经300-390℃退火得到所述的多孔四方片状TiO2，粒径为30-50nm，由4-7nm的纳米晶构筑形成的四方片状，且具有多孔的形貌。操作简便、成本低、纯度高、性能优异，可以大量合成。此产品还能推广至其他能源和催化等领域的应用。

Description

一种多孔四方片状TiO2及其制备方法和应用
技术领域
本发明属于钠离子电池负极材料制备领域，具体涉及一种多孔四方片状TiO2及其制备方法和在钠离子电池中的应用。
背景技术
近年来，锂离子电池具有高电压、高容量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，且锂的资源在地球中的储量也较少。钠元素在地球上的储量比锂要丰富得多，金属钠来源广泛且廉价，因而钠离子电池近年来得到广泛的关注。当前，钠离子电池因缺乏合适的负极材料而制约其应用，开发性能优异的钠离子电池负极材料是当然该领域的研究重点和热点。目前没有高性能多孔四方片状TiO2基钠离子电池的相关报道。
发明内容
本发明的目的在于提供一种多孔四方片状TiO2及其制备方法和在钠离子电池中的应用，操作简便、成本低、纯度高、性能优异，可以大量合成。此产品还能推广至其他能源和催化等领域的应用。
为实现上述目的，本发明采用如下技术方案：
一种多孔四方片状TiO2，其粒径为30-50 nm，由4-7 nm的纳米晶构筑形成的四方片状，且具有多孔的形貌。
制备方法：将1.2-1.8 g十六烷基磺酸钠分散于35-60 mL 1.5-2.5 mol/L盐酸溶液中，然后滴加1.2-2 mL钛酸异丙酯，在70-85 ℃下反应12-24 小时，再经离心洗涤、干燥，经300-390℃退火得到所述的多孔四方片状TiO2。
所述的多孔四方片状TiO2作为钠离子电池负极材料。钠离子电池组装：按四方片状TiO2、聚偏氟乙烯和乙炔黑的质量比为70-75：5-10：15-20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溶液；所述的EC+DEC溶液中EC和DEC的体积比为1:1；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。
本发明的显著优点在于：本发明首次提供了一种高性能多孔四方片状TiO2钠离子电池负极材料的制备方法，操作简便、成本低、纯度高(95%以上)、性能优异，可以大量合成。此多孔四方片状TiO2作为钠离子电池负极材料，结果表明其具有较高的比容量、优异的倍率充放电性能和良好的循环稳定性。电流密度为0.5 C的情况下，其可逆比容量高达270 mAhg-1，经过10次循环后，其比容量仍可达220 mAhg-1。该电极材料的具有斜坡型充放电曲线的特点，这有助于其在实际全电池中的使用。此产品还能推广至其他能源和催化等领域的应用。
附图说明
图1是多孔四方片状TiO2的XRD图。
图2是多孔四方片状TiO2的扫描电镜分析图（插图为电子衍射图）。
图3是钠电池的充电曲线图。
具体实施方式
实施例1
将1.2 g十六烷基磺酸钠分散于35 mL 1.5mol/L盐酸溶液中，然后滴加1.2mL钛酸异丙酯，在70℃下反应12小时，再经离心洗涤、干燥，经300℃退火得到所述的多孔四方片状TiO2，纯度为95%，粒径为30nm，由4nm的纳米晶构筑形成的四方片状，且具有多孔的形貌。
所述的多孔四方片状TiO2作为钠离子电池负极材料。钠离子电池组装：按四方片状TiO2、聚偏氟乙烯和乙炔黑的质量比为70：10：20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溶液；所述的EC+DEC溶液中EC和DEC的体积比为1:1；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。
电流密度为0.5 C的情况下，其可逆比容量高达270 mAhg-1，经过10次循环后，其比容量仍可达220 mAhg-1。
实施例2
将1.8 g十六烷基磺酸钠分散于60 mL 2.5 mol/L盐酸溶液中，然后滴加2 mL钛酸异丙酯，在85 ℃下反应24 小时，再经离心洗涤、干燥，经390℃退火得到所述的多孔四方片状TiO2，纯度为98%，粒径为50 nm，由7 nm的纳米晶构筑形成的四方片状，且具有多孔的形貌。
所述的多孔四方片状TiO2作为钠离子电池负极材料。钠离子电池组装：按四方片状TiO2、聚偏氟乙烯和乙炔黑的质量比为75：10：15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溶液；所述的EC+DEC溶液中EC和DEC的体积比为1:1；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。
电流密度为0.5 C的情况下，其可逆比容量高达270 mAhg-1，经过10次循环后，其比容量仍可达220 mAhg-1。
实施例3
将1.5 g十六烷基磺酸钠分散于50mL 2.0 mol/L盐酸溶液中，然后滴加1.6mL钛酸异丙酯，在80 ℃下反应18小时，再经离心洗涤、干燥，经350℃退火得到所述的多孔四方片状TiO2，纯度为99%，粒径为40 nm，由6nm的纳米晶构筑形成的四方片状，且具有多孔的形貌。
所述的多孔四方片状TiO2作为钠离子电池负极材料。钠离子电池组装：按四方片状TiO2、聚偏氟乙烯和乙炔黑的质量比为72：9：19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溶液；所述的EC+DEC溶液中EC和DEC的体积比为1:1；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。
电流密度为0.5 C的情况下，其可逆比容量高达270 mAhg-1，经过10次循环后，其比容量仍可达220 mAhg-1。
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 (4)

1.一种多孔四方片状TiO2，其特征在于：粒径为30-50 nm，由4-7 nm的纳米晶构筑形成的四方片状，且具有多孔的形貌。
2.一种制备如权利要求1所述的多孔四方片状TiO2的方法，其特征在于：将1.2-1.8 g十六烷基磺酸钠分散于35-60 mL 1.5-2.5 mol/L盐酸溶液中，然后滴加1.2-2 mL钛酸异丙酯，在70-85 ℃下反应12-24 小时，再经离心洗涤、干燥，经300-390℃退火得到所述的多孔四方片状TiO2。
3.一种如权利要求1所述的多孔四方片状TiO2的应用，其特征在于：所述的多孔四方片状TiO2作为钠离子电池负极材料。
4.根据权利要求3所述的应用，其特征在于：钠离子电池组装：按四方片状TiO2、聚偏氟乙烯和乙炔黑的质量比为70-75：5-10：15-20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溶液；所述的EC+DEC溶液中EC和DEC的体积比为1:1；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。
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CN107681148A (zh) * 2017-09-26 2018-02-09 福建师范大学 一种多孔无定形二氧化钛基钠离子电池及其制备方法
CN107681148B (zh) * 2017-09-26 2020-10-23 福建师范大学 一种多孔无定形二氧化钛基钠离子电池及其制备方法

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