CN103779545B - 一种Sn-Co-介孔碳复合物及其制备方法和应用 - Google Patents

一种Sn-Co-介孔碳复合物及其制备方法和应用 Download PDF

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CN103779545B
CN103779545B CN201410011801.8A CN201410011801A CN103779545B CN 103779545 B CN103779545 B CN 103779545B CN 201410011801 A CN201410011801 A CN 201410011801A CN 103779545 B CN103779545 B CN 103779545B
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CN103779545A (zh
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魏明灯
邓翠林
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Abstract

本发明公开了一种Sn-Co-介孔碳复合物及其制备方法和应用，采用纳米浇注和氢气还原法在较低温度下合成Sn-Co-介孔碳复合物，Sn-Co-介孔碳复合物是一种良好的锂电池负极材料，本发明工艺简单，成本廉价，能耗低，重现性好，可大量生产，符合环境要求。

Description

一种Sn-Co-介孔碳复合物及其制备方法和应用
技术领域
本发明属于锂电池负极材料制备领域，具体涉及一种Sn-Co-介孔碳复合物及其制备方法和应用。
背景技术
自上世纪锂电池开发成功以来，锂电池已经得到了广泛的应用，但是要得到循环性能好，比容量高，大电流充放电性能好的锂电池负极材料一直以来是科学家的研究重点。现在工业上常用的负极材料有金属锂、碳材料、Li4Ti5O12等。他们的容量都不高，且具有一定缺陷，如金属锂SEI膜严重，碳材料容量低因素，Li4Ti5O12胀气现象。随着介孔复合材料的兴起，介孔碳复合材料被认为是一种很有前景的负极材料，据已有文献报道，他们的比容量一般都在500-800mAhg-1之间，目前还未有制备Sn-Co-介孔碳复合物的相关专利报道。
发明内容
本发明的目的在于提供一种Sn-Co-介孔碳复合物及其制备方法和应用，工艺简单，成本廉价，能耗低，重现性好，可大量生产，符合环境要求。
为实现上述目的，本发明采用如下技术方案：
采用纳米浇注和氢气还原法在较低温度下合成Sn-Co-介孔碳复合物。包括以下步骤：
（1）将介孔碳用浓硝酸在70℃下回流2小时；
（2）将四氯化钴与二氯化亚锡按摩尔比为1：5加入反应器，加入无水乙醇，用磁力搅拌器搅拌30分钟后，再加入步骤（1）中酸处理过的介孔碳，超声15分钟，60℃烘干6小时；
（3）所得粉末在95%Ar/5%H2气氛管式炉中550℃煅烧4小时，即得到Sn-Co-介孔碳复合物。
所述的Sn-Co-介孔碳复合物作为锂电池负极。锂电池组装：按质量比：Sn-Co-介孔碳复合物：聚四氟乙烯：乙炔黑＝80：10：10混合研磨后，均匀地涂在铜网上做负极，参比电极和对电极均为金属锂，电解质由1MLiClO4的EC+DMC溶液，所有组装均在手套箱里进行，所述的EC+DMC溶液中EC和DMC的体积比为1：1。
本发明的显著优点在于：本发明工艺简单，成本廉价，能耗低，重现性好，可大量生产，符合环境要求。用此Sn-Co-介孔碳复合物作锂电池负极得到的锂电池具有很高的比容量，在电流密度为0.1Ag-1时充放电循环60圈容量稳定在562mAhg-1，同时表现出优异的倍率放电性能，即使在电流密度为1Ag-1时充放电容量稳定在351mAhg-1。
附图说明
图1是Sn-Co-介孔碳复合物的X射线衍射（XRD）图。
图2是Sn-Co-介孔碳复合物在电压范围为0.01-3V、电流密度为100mAhg-1下的循环性能图。
图3是Sn-Co-介孔碳复合物在电压范围为0.01-3V下的倍率放电性能图。
图4是Sn-Co-介孔碳复合物在电流密度为100mAhg-1下的前三圈充放电曲线图。
具体实施方式
本发明用纳米浇注和氢气还原法在较低温度下合成出Sn-Co-介孔碳复合物。用此Sn-Co-介孔碳复合物作锂电池负极得到的锂电池具有很高的比容量，在电流密度为0.1Ag-1时充放电循环60圈比容量稳定在562mAhg-1.同时表现出优异的倍率放电性能，即使在电流密度为1Ag-1时充放电容量稳定在351mAhg-1。
高性能Sn-Co-介孔碳复合物的制备方法是先将介孔碳用浓硝酸在70℃下回流2小时。将四氯化钴粉末与二氯化亚锡粉末按1:5摩尔比加入反应器，加入适量无水乙醇，用磁力搅拌器搅拌30分钟后，再加入酸处理过的介孔碳，超声15分钟，搅拌直至干燥，60℃烘干6小时。然后把所得粉末在95%Ar/5%H2气氛管式炉中550℃煅烧4小时，即得到Sn-Co-介孔碳复合物。
锂电池组装：按质量比Sn-Co-介孔碳复合物：聚四氟乙烯：乙炔黑＝80：10：10混合研磨后均匀地涂在铜网上做负极，参比电极和对电极均为金属锂，电解质由1MLiClO4的EC+DMC(EC/DMC=1/1v/v)溶液。所有组装均在手套箱里进行。
从图1可以看出，本方法合成的Sn-Co-介孔碳复合物由SnCo、CoSn2和SnO2组成，由峰强度知复合物晶相较好；从图2可以看出，合成的Sn-Co-介孔碳复合物在电压范围为0.01-3V、电流密度为100mAhg-1的条件下，循环60圈后比容量仍有562mAhg-1，展示了良好的循环稳定性；从图3可以看出，合成的Sn-Co-介孔碳复合物在电压范围为0.01-3V、大倍率1Ag-1条件下，充放电10圈后比容量稳定在351mAhg-1，表现出优异的倍率放电性能。从图4可以看出，电池的库伦效率为55.9%，这高于大部分文献报道的。第一圈放电曲线中，1V左右的电压平台对应SEI膜的形成或者部分氧化物的分解，接下来的2圈充放电曲线出现一对电压平台，分别为放电平台的0.2V左右、充电平台的0.5V左右，分别对应Sn-Co合金的嵌锂和脱锂反应。
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 (1)

1.一种Sn-Co-介孔碳复合物的制备方法，其特征在于：采用纳米浇注和氢气还原法合成Sn-Co-介孔碳复合物；包括以下步骤：
（1）将介孔碳用浓硝酸在70℃下回流2小时；
（2）将四氯化钴与二氯化亚锡按摩尔比为1：5加入反应器，加入无水乙醇，用磁力搅拌器搅拌30分钟后，再加入步骤（1）中酸处理过的介孔碳，超声15分钟，60℃烘干6小时；
（3）所得粉末在95%Ar+5%H2气氛管式炉中550℃煅烧4小时，即得到Sn-Co-介孔碳复合物。
CN201410011801.8A 2014-01-11 2014-01-11 一种Sn-Co-介孔碳复合物及其制备方法和应用 Expired - Fee Related CN103779545B (zh)

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CN102386380A (zh) * 2011-10-21 2012-03-21 福州大学 高性能ZnV2O4/介孔碳复合材料的制备方法和应用
CN103000863A (zh) * 2012-10-16 2013-03-27 华南师范大学 一种锂离子电池Sn-Co/C合金负极材料及其制备方法

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