CN109987607A - 介孔硅/二硅化钴复合微球材料及其制备方法和应用 - Google Patents
介孔硅/二硅化钴复合微球材料及其制备方法和应用 Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 42
- 239000010703 silicon Substances 0.000 title claims abstract description 42
- 239000010941 cobalt Substances 0.000 title claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 39
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 5
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- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明公开了一种介孔硅/二硅化钴复合微球材料及其制备方法和应用,该方法为:在搅拌条件下,向硝酸钴的乙醇溶液中依次加入氨水和正硅酸乙酯的乙醇溶液制备前驱体,然后采用镁热法还原所得前驱体,最后用盐酸清洗还原产物。所述介孔硅/二硅化钴复合微球用于锂离子电池负极材料时,其二硅化钴组分与介孔结构有利于抑制材料粉化、改善电极反应动力学,有效提高材料的实际容量、循环性能和高倍率性能。
Description
技术领域
本发明涉及锂离子电池电极材料领域,具体涉及一种介孔硅/二硅化钴复合微球材料及其制备方法和应用。
背景技术
锂离子电池因能量密度高、功率密度大及循环寿命长等优势,已在二次电池领域占据了主导地位,成功应用于便携式电子产品、电动汽车以及电池储能电站等领域。然而,传统的锂离子电池所用的石墨碳负极材料的性能已经达到一个难以突破的瓶颈,严重制约着新能源的发展。研发高比容量、高安全性的替代性负极材料并推动其实际应用已经成为当前研究的重点。
新型的硅基负极材料因其极高的理论容量和低廉的价格而表现出良好的应用前景。但是,硅基负极材料目前还存在实际容量低、循环性能差以及高倍率性能差等缺点。硅是一种导电性较差的半导体材料,它不具备石墨的层状结构,其储锂机理是基于硅与锂之间可逆的合金化/去合金化反应,伴随着300%以上的体积改变,一方面导致电极材料粉化与脱落,造成活性物质的减少,另一方面也导致SEI膜的破裂与再形成,造成锂离子和电解液的持续性消耗,同时也增大电极阻抗。因此,要实现硅基负极材料的实际应用,就必须克服这些缺点,增强电极反应的动力学,提高材料在充放电循环过程中的结构稳定性。
发明内容
本发明提出了一种介孔硅/二硅化钴复合微球材料及其制备方法和应用,所述材料具有比容量高、循环寿命好以及高倍率性能好等优点,所述制备方法简单,成本低廉。
所述介孔硅/二硅化钴复合微球材料的制备方法,其步骤如下:
(1) 在搅拌条件下,往0.05~0.2 mol/L的硝酸钴的乙醇溶液中依次加入4 mol/L的氨水和0.5 mol/L的正硅酸乙酯的乙醇溶液,硝酸钴溶液、氨水和正硅酸乙酯溶液的体积比为1:2:3,在25 oC下反应24~72 h后,离心分离所得沉淀物并用去离子水清洗,烘干后得到前驱体粉末;
(2) 将前驱体粉末与镁粉按1:1的质量比混合均匀,置于氩气气氛中,加热到700 oC使其反应并保温2~6 h,冷却后,将产物用2 mol/L的盐酸清洗,再用去离子水反复清洗,烘干后制得介孔硅/二硅化钴复合微球材料。
所述介孔硅/二硅化钴复合微球材料中,所含硅的质量分数为80%~95%,所含二硅化钴的质量分数为5%~20%,复合微球的直径为0.5~1.0 μm,由宽为40~60 nm的条状纳米颗粒组装而成,其中介孔的尺寸为20~50 nm。
本发明的有益效果在于:
(1) 所述介孔硅/二硅化钴复合微球具有网状介孔的三维结构,由条状纳米颗粒彼此相连组装而成。网状介孔结构可有效解决纳米颗粒团聚问题,有利于充分发挥纳米颗粒优势,增大电化学反应界面,缩短电荷传输距离,提高电化学反应速率;网状介孔结构还为硅与锂合金化过程中的体积膨胀提供了容纳空间,可有效缓冲材料内应力,抑制材料粉化。
(2) 所述介孔硅/二硅化钴复合微球中的二硅化钴组分具有良好的导电性,可有效减轻电极极化;二硅化钴与硅的复合,也有利于提高材料的结构强度。
所述介孔硅/二硅化钴复合微球的上述优势有利于稳定材料结构,增强材料参与电极反应的动力学,从而提升材料的实际可逆容量、循环性能和高倍率性能。
附图说明
为了更清楚地说明本发明实施的技术方案,下面将对实施例中所需要使用的附图作简单地介绍。
图1为实施例1中介孔硅/二硅化钴复合微球材料的X射线衍射(XRD)图谱;
图2为实施例1中介孔硅/二硅化钴复合微球材料的电镜照片,其中图2(a)是扫描电镜(SEM)照片,图2(b)是透射电镜(TEM)照片;
图3为实施例1中介孔硅/二硅化钴复合微球材料的循环性能曲线。
具体实施方式
下面通过具体实施例对本发明做出进一步的具体说明,但本发明并不局限于下述实例。
实施例1:
(1) 在搅拌条件下,往10 mL浓度为0.1 mol/L的硝酸钴的乙醇溶液中依次加入20 mL浓度为4 mol/L的氨水溶液和30 mL浓度为0.5 mol/L的正硅酸乙酯的乙醇溶液,在25 oC下反应36 h后,离心分离所得沉淀物并用去离子水清洗,烘干后得到前驱体粉末;
(2) 将前驱体粉末与镁粉按1:1的质量比混合均匀,置于氩气气氛中,加热到700 oC使其反应并保温3 h,冷却后,将产物用2 mol/L的盐酸清洗,再用去离子水反复清洗,烘干后制得介孔硅/二硅化钴复合微球材料。
所得介孔硅/二硅化钴复合微球材料中,硅的质量分数为88%,二硅化钴的质量分数为12%,其XRD图谱如图1所示。复合微球的直径为0.7 μm,由宽为40~60 nm的条状纳米颗粒组装而成,其中介孔的尺寸为20~50 nm,其电镜照片如图2所示。
将该介孔硅/二硅化钴复合微球材料与乙炔黑、聚偏二氟乙烯(PVDF)按80:10:10的质量比混合,再加入N-甲基吡咯烷酮(NMP),搅拌成均匀浆料,涂布在铜箔集流体上,真空烘干后制得工作电极,采用金属锂片为对电极,采用1 mol/L LiPF6的碳酸乙烯酯(EC)/碳酸二甲酯(DMC)/氟代碳酸乙烯酯(FEC)(EC与DMC的体积比为1:1,FEC质量分数为10%)溶液为电解液,采用Celgard2400聚丙烯膜为隔膜,在高纯氩气保护的手套箱中组装成CR2025扣式电池。在25 oC的环境下,在0.02~1.5 V的电压区间内,采用100 mA/g、500 mA/g及1000mA/g等不同电流密度对电池进行恒流充放电测试,测分析材料的可逆容量、循环稳定性和高倍率性能。
本实施例的介孔硅/二硅化钴复合微球材料,其实际容量高,循环稳定性和高倍率稳定性好。材料在100 mA/g电流密度下的首次可逆容量(充电容量)为2250 mAh/g,经100次循环后的容量保持率为77%,如图3所示;材料在500 mA/g和1000 mA/g电流密度下的首次可逆容量分别为,1860 mAh/g和1210 mAh/g。
实施例2:
(1) 在搅拌条件下,往10 mL浓度为0.05 mol/L的硝酸钴的乙醇溶液中依次加入20 mL浓度为4 mol/L的氨水溶液和30 mL浓度为0.5 mol/L的正硅酸乙酯的乙醇溶液,在25 oC下反应36 h后,离心分离所得沉淀物并用去离子水清洗,烘干后得到前驱体粉末;
(2) 将前驱体粉末与镁粉按1:1的质量比混合均匀,置于氩气气氛中,加热到700 oC使其反应并保温3 h,冷却后,将产物用2 mol/L的盐酸清洗,再用去离子水反复清洗,烘干后制得介孔硅/二硅化钴复合微球材料。
所得介孔硅/二硅化钴复合微球材料中,硅的质量分数为93%,二硅化钴的质量分数为7%,复合微球的直径为0.7 μm,由宽为40~60 nm的条状纳米颗粒组装而成,其中介孔的尺寸为20~50 nm。
将该介孔硅/二硅化钴复合微球材料与乙炔黑、聚偏二氟乙烯(PVDF)按80:10:10的质量比混合,再加入N-甲基吡咯烷酮(NMP),搅拌成均匀浆料,涂布在铜箔集流体上,真空烘干后制得工作电极,采用金属锂片为对电极,采用1 mol/L LiPF6的碳酸乙烯酯(EC)/碳酸二甲酯(DMC)/氟代碳酸乙烯酯(FEC)(EC与DMC的体积比为1:1,FEC质量分数为10%)溶液为电解液,采用Celgard2400聚丙烯膜为隔膜,在高纯氩气保护的手套箱中组装成CR2025扣式电池。在25 oC的环境下,在0.02~1.5 V的电压区间内,采用100 mA/g、500 mA/g及1000mA/g等不同电流密度对电池进行恒流充放电测试,测分析材料的可逆容量、循环稳定性和高倍率性能。
本实施例的介孔硅/二硅化钴复合微球材料,其实际容量高,循环稳定性和高倍率稳定性好。材料在100 mA/g电流密度下的首次可逆容量(充电容量)为2310 mAh/g,经100次循环后的容量保持率为72%;材料在500 mA/g和1000 mA/g电流密度下的首次可逆容量分别为,1890 mAh/g和1260 mAh/g。
实施例3:
(1) 在搅拌条件下,往10 mL浓度为0.2 mol/L的硝酸钴的乙醇溶液中依次加入20 mL浓度为4 mol/L的氨水溶液和30 mL浓度为0.5 mol/L的正硅酸乙酯的乙醇溶液,在25 oC下反应48 h后,离心分离所得沉淀物并用去离子水清洗,烘干后得到前驱体粉末;
(2) 将前驱体粉末与镁粉按1:1的质量比混合均匀,置于氩气气氛中,加热到700 oC使其反应并保温5 h,冷却后,将产物用2 mol/L的盐酸清洗,再用去离子水反复清洗,烘干后制得介孔硅/二硅化钴复合微球材料。
所得介孔硅/二硅化钴复合微球材料中,硅的质量分数为80%,二硅化钴的质量分数为20%,复合微球的直径为0.8 μm,由宽为40~60 nm的条状纳米颗粒组装而成,其中介孔的尺寸为20~50 nm。
将该介孔硅/二硅化钴复合微球材料与乙炔黑、聚偏二氟乙烯(PVDF)按80:10:10的质量比混合,再加入N-甲基吡咯烷酮(NMP),搅拌成均匀浆料,涂布在铜箔集流体上,真空烘干后制得工作电极,采用金属锂片为对电极,采用1 mol/L LiPF6的碳酸乙烯酯(EC)/碳酸二甲酯(DMC)/氟代碳酸乙烯酯(FEC)(EC与DMC的体积比为1:1,FEC质量分数为10%)溶液为电解液,采用Celgard2400聚丙烯膜为隔膜,在高纯氩气保护的手套箱中组装成CR2025扣式电池。在25 oC的环境下,在0.02~1.5 V的电压区间内,采用100 mA/g、500 mA/g及1000mA/g等不同电流密度对电池进行恒流充放电测试,测分析材料的可逆容量、循环稳定性和高倍率性能。
本实施例的介孔硅/二硅化钴复合微球材料,其实际容量高,循环稳定性和高倍率稳定性好。材料在100 mA/g电流密度下的首次可逆容量(充电容量)为1960 mAh/g,经100次循环后的容量保持率为70%;材料在500 mA/g和1000 mA/g电流密度下的首次可逆容量分别为,1710 mAh/g和1110 mAh/g。
Claims (3)
1.一种介孔硅/二硅化钴复合微球材料,其特征在于,复合微球中所含硅的质量分数为80%~95%,所含二硅化钴的质量分数为5%~20%,复合微球的直径为0.5~1.0 μm,由宽为40~60nm的条状纳米颗粒组装而成,其中介孔的尺寸为20~50 nm。
2.根据权利要求1所述的介孔硅/二硅化钴复合微球材料的制备方法,其特征在于包括以下步骤:(1) 在搅拌条件下,往0.05~0.2 mol/L的硝酸钴的乙醇溶液中依次加入4 mol/L的氨水和0.5 mol/L的正硅酸乙酯的乙醇溶液,硝酸钴溶液、氨水和正硅酸乙酯溶液的体积比为1:2:3,在25 oC下反应24~72 h后,离心分离所得沉淀物并用去离子水清洗,烘干后得到前驱体粉末;(2) 将前驱体粉末与镁粉按1:1的质量比混合均匀,置于氩气气氛中,加热到700 oC使其反应并保温2~6 h,冷却后,将产物用2 mol/L的盐酸清洗,再用去离子水反复清洗,烘干后制得介孔硅/二硅化钴复合微球材料。
3.根据权利要求1或2所述的介孔硅/二硅化钴复合微球材料在锂离子电池负极材料中的应用。
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