CN113003581A - 用于锂离子电池的SiOx-C复合负极材料的制备方法 - Google Patents

用于锂离子电池的SiOx-C复合负极材料的制备方法 Download PDF

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CN113003581A
CN113003581A CN202110157810.8A CN202110157810A CN113003581A CN 113003581 A CN113003581 A CN 113003581A CN 202110157810 A CN202110157810 A CN 202110157810A CN 113003581 A CN113003581 A CN 113003581A
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siox
lithium ion
ion battery
negative electrode
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潘二壮
郭卫疆
杨志国
徐妥夫
康程
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CNCEC Hualu New Materials Co Ltd
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    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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Abstract

本发明公开了一种用于锂离子电池的SiOx‑C复合负极材料的备方法，所述复合材料是在制备二氧化硅水凝胶的同时，直接加入前驱体，再经过高温碳化制备而成的。对SiOx进行碳复合，一方可以提高材料的电子电导率，改善其倍率性能；另一方面碳材料的引入可以缓冲SiOx颗粒在充放电过程中的体积变化，从而提升材料循环寿命；更重要的是本发明所涉及的制备方法更加简便且成本低。

Description

用于锂离子电池的SiOx-C复合负极材料的制备方法
技术领域
本发明属于锂离子电池负极材料技术领域，具体涉及一种锂离子电池SiOx-C的制备方法。
背景技术
锂离子电池凭借能量密度高、循环寿命长等优点被作为储能材料广泛用于便携式电子设备、电动汽车和电子存储系统等领域。目前商用的石墨负极材料因其理论容量(372mAh g-1)较低，而无法满足高比能锂离子电池的要求。硅材料的理论容量(4200mAh g-1)远远高于石墨，成为最有前景的锂离子电池负极材料之一。然而，硅材料的成本较高，且充放电过程中体积膨胀大，表现出较差的循环性能和倍率性能，严重限制了该材料的应用。目前，硅碳材料循环寿命得到了明显的改善，然而仍然存在成本和比容量的问题。
发明内容
针对现有技术中存在的问题，本发明的目的是提供一种用于锂离子电池的SiOx-C复合负极材料的制备方法，该SiOx-C复合材料是通过在制备二氧化硅水凝胶的同时，直接加入碳前驱体，再经过高温煅烧法制备而成的。该材料具有高的比容量、优异的循环性能和倍率性能。
本发明的目的是通过以下技术方案实现的。
一种用于锂离子电池的SiOx-C复合负极材料的制备方法，其特征在于：将正硅酸乙酯TEOS加入至乙醇中均匀溶解，再滴加稀盐酸搅拌后，直接加入碳前驱体，搅拌使其溶解充分后，再加入稀氨水调节，老化后通过常压干燥并研磨均匀，在惰性气氛下以一定的升温速度升温至800～1000℃并进行热处理保温，制得SiOx-C复合负极材料。
优选地，所述碳前驱体选自葡萄糖、明胶、酚醛树脂、线型酚醛树脂中任何一种或它们的混合物。
优选地，升温速度为1-10℃/min，热处理保温时间为1-5h。
优选地，所述高温处理所需的惰性气氛为氮气、氩气、氢氩混合气体或氢氮混合气体。
本发明所述复合负极材料是在制备二氧化硅水凝胶的同时，直接加入碳前驱体，再经过高温碳化制备而成的。对SiOx进行碳复合，一方面可以提高材料的电子电导率，改善其倍率性能；另一方面碳材料的引入可以缓冲SiOx颗粒在充放电过程中的体积变化，从而提升材料的循环寿命；更重要的是本发明所涉及的制备方法更加简便且成本低廉。
附图说明
图1a是采用实施例1制备的SiOx-C复合材料的扫描电子显微镜图；图1b是组装的锂离子电池的循环性能图。
图2a是采用实施例2制备的SiOx-C复合材料的扫描电子显微镜图；图2b是组装的锂离子电池的循环性能图。
具体实施方式
为了使本发明的目的、技术方案和优点更加清楚，下面将对本发明的技术方案进行详细描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明的实施例，本领域普通技术人员在没有付出创造性劳动的前提下所得到的所有其他实施方式，都属于本发明所保护的范围。
实施例1
将9mL TEOS加入至乙醇中均匀溶解，再滴加稀盐酸搅拌1小时后加入15g葡萄糖，搅拌1小时使其溶解充分后再加入稀氨水调节pH至7左右，使其形成葡萄糖-二氧化硅原位复合凝胶，老化12小时后通过常压干燥并研磨均匀形成粉末原料；将粉末原料在氮气氛下以10℃/min升温至1000℃并保温2小时。其形貌如图1a所示。按照锂离子电池负极材料在纽扣电池组装，材料在50mA/g的电流密度下的首次充电容量为514.2mAh/g测试结果见图1b。
实施例2
将9mL TEOS加入至乙醇中均匀溶解，再滴加稀盐酸搅拌1小时后加入10g线性酚醛树脂粉末，搅拌1小时使其溶解充分后再加入稀氨水调节pH至7左右，使其形成线性酚醛树脂-二氧化硅原位复合凝胶，老化12小时后通过常压干燥并研磨均匀形成粉末原料；将粉末原料在氮气氛下以10℃/min升温至1000℃并保温2小时。其形貌如图2a所示。按照锂离子电池负极材料在纽扣电池组装，材料在50mA/g的电流密度下的首次充电容量为503.9mAh/g测试结果见图2b。
锂离子电池的组装步骤如下：将实施例中制备的SiOx-C复合负极材料、导电剂Super P、粘结剂PVDF(聚偏氟乙烯)按照8:1:1的质量比混合均匀，再用NMP(N-甲基吡咯烷酮)为溶剂将混合物调浆涂于铜箔之上，经干燥裁片后作为工作电极；以1M LiFP6 EC/DEC(1:1)为电解液、锂金属为对电极和参比电极、组装成CR2025型纽扣半电池。

Claims (4)

1.一种用于锂离子电池的SiOx-C复合负极材料的制备方法，其特征在于：将正硅酸乙酯TEOS加入至乙醇中均匀溶解，再滴加稀盐酸搅拌后，直接加入碳前驱体，搅拌使其溶解充分后，再加入稀氨水调节，老化后通过常压干燥并研磨均匀，在惰性气氛下以一定的升温速度升温至800～1000℃并进行热处理保温，制得SiOx-C复合负极材料。
2.如权利要求1所述的用于锂离子电池的SiOx-C复合负极材料的制备方法，其特征在于：所述碳前驱体选自葡萄糖、明胶、酚醛树脂、线型酚醛树脂中任何一种或它们的混合物。
3.如权利要求1所述的用于锂离子电池的SiOx-C复合负极材料的制备方法，其特征在于：升温速度为1-10℃/min，热处理保温时间为1-5h。
4.如权利要求1所述的用于锂离子电池的SiOx-C复合负极材料的制备方法，其特征在于：所述高温处理所需的惰性气氛为氮气、氩气、氢氩混合气体或氢氮混合气体。
CN202110157810.8A 2021-02-05 2021-02-05 用于锂离子电池的SiOx-C复合负极材料的制备方法 Withdrawn CN113003581A (zh)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2023155333A1 (zh) * 2022-02-15 2023-08-24 常州大学 一种基于压电效应制备高性能锂离子硅基负极材料的方法及其应用

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CN103236534A (zh) * 2013-04-24 2013-08-07 北京科技大学 一种锂离子电池氧化硅/碳复合负极材料的制备方法

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CN103236534A (zh) * 2013-04-24 2013-08-07 北京科技大学 一种锂离子电池氧化硅/碳复合负极材料的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023155333A1 (zh) * 2022-02-15 2023-08-24 常州大学 一种基于压电效应制备高性能锂离子硅基负极材料的方法及其应用

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Application publication date: 20210622