CN110783548B - 电化学活性材料及其制备方法 - Google Patents
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Abstract
一种电化学活性材料及其制备方法,属于电极材料技术领域。该电化学活性材料的制备方法,包括以下步骤:S1,制备表面包覆有纳米金晶的碳纳米管纸,再在充氩气手套箱中,于包覆有纳米金晶的碳纳米管纸表面辊轧金属锂箔;S2,加热至锂融化,使锂浸润到碳纳米管纸内部,得到锂‑金‑碳纳米管复合箔材;S3,在锂‑金‑碳纳米管复合箔材表面低温溅射一层纳米硅,得到电化学活性材料。本发明通过在碳纳米管表面设置纳米金晶层,避免了锂晶界对碳纳米管的排斥,使熔融锂很容易浸润碳纳米管,保证了碳纳米管在金属锂中的均匀分散。
Description
技术领域
本发明涉及的是一种电极材料领域的技术,具体是一种电化学活性材料及其制备方法。
背景技术
作为下一代锂金属电池关键负极材料之一,锂金属因其极大的比容量(3860mAh/g)受到了业界 越来越广泛的关注。在提供接近十倍于传统石墨负极的比容量的同时,锂金属负极的使用还可以显著 的拓展锂电池正极材料的选择,使得一些本身不含锂的正极材料,如硫,氧化钒等的应用成为可能。 但是由于锂金属十分活泼,导致其表面成分极其复杂,由此进一步导致了在电化学过程中的锂金属的 沉积和溶解具有明显的不均匀性,从而导致枝晶的过度生长。枝晶和电解液之间大量的副反应,在显 著拉低电池的库伦效率的同时,也极大的限制了锂电池的循环寿命和电池的安全性。
为了解决现有技术存在的上述问题,本发明由此而来。
发明内容
本发明针对现有技术存在的上述不足,提出了一种电化学活性材料及其制备方法,通过在碳纳 米管表面设置纳米金晶层,避免了锂晶界对碳纳米管的排斥,使熔融锂很容易浸润碳纳米管,保证了 碳纳米管在金属锂中的均匀分散。
本发明涉及一种电化学活性材料的制备方法,包括以下步骤:
S1,制备表面包覆有纳米金晶的碳纳米管纸,再在充氩气手套箱中,于包覆有纳米金晶的碳纳 米管纸表面辊轧金属锂箔;
S2,加热至锂融化,使锂浸润到碳纳米管纸内部,得到锂-金-碳纳米管复合箔材;
S3,在锂-金-碳纳米管复合箔材表面低温溅射一层纳米硅,得到电化学活性材料。
优选的,所述表面包覆有纳米金晶的碳纳米管纸通过在大孔隙率碳纳米管纸表面低压冷态溅射 金金属得到。
优选的,所述纳米金晶厚度为1~100nm,进一步优选为10~20nm。
优选的,所述锂箔厚度为0.1~100μm,进一步优选为1~20μm。
优选的,步骤S2中,加热温度为200℃~300℃。
优选的,所述辊轧金属锂箔及后续步骤均在充氩气手套箱中操作。
优选的,所述包覆纳米硅的厚度为100~300nm。
本发明涉及一种电化学活性材料,采用上述方法制备得到。
技术效果
与现有技术相比,本发明具有如下技术效果:
1)碳纳米管表面纳米金晶层的存在避免了锂晶界对碳纳米管的排斥,使熔融锂很容易浸润碳纳 米管,保证了碳纳米管在金属锂中的均匀分散;
2)碳纳米管的均匀加入解决了负极材料在充放电过程中巨大的体积膨胀问题,能够保证稳定的 SEI膜结构;
3)表面纳米硅层的存在,可有效避免电解液和活泼锂金属表面的直接接触,减少副反应的发生, 同时它还为锂金属和电解液之间构建了一层导离子过渡层,起到了很好的均匀离子通道的作用。
附图说明
图1为实施例1制备的电化学活性材料、锂箔分别与磷酸亚铁锂组装电池,测得的电池循环 性能对比图。
具体实施方式
下面结合附图及具体实施方式对本发明进行详细描述。
实施例1
本实施例涉及一种电化学活性材料的制备方法,包括以下步骤:
S1,裁取6cm*8cm的自制碳纳米管纸,将其固定于低压冷态溅射仪中,溅射功率14W,溅射 时间10s,使碳纳米管纸表面形成金金属层,金金属层厚度约15nm;
S2,在充氩气手套箱中,于金金属层表面辊轧相同大小的锂箔,然后置于加热板上加热至200℃, 锂完全融化后冷却得到Li/Au/CNTs复合箔材,备用;
S3,将冷却后的Li/Au/CNTs复合箔材固定于手套箱中的低压冷态溅射仪中,溅射功率14W, 溅射时间1min,使Li/Au/CNTs复合箔材表面形成纳米硅层,得到电化学活性材料Si/Li/Au/CNTs, 其中纳米硅层厚度约100nm。
将所制得的电化学活性材料用作负极与磷酸亚铁锂组装成电池Si/Li/Au/CNTs-LFP,作为对比, 以锂箔为负极与磷酸亚铁锂组装成电池Li-LFP。其0.1C相同倍率下循环性能对比曲线见附图1。由图 可见,以本发明实施例所制得的电化学活性材料为负极组成的电池循环性能明显优于以锂箔为负极的 电池。
实施例2
本实施例涉及一种电化学活性材料的制备方法,包括以下步骤:
S1,裁取6cm*8cm的自制碳纳米管纸,将其固定于低压冷态溅射仪中,溅射功率12W,溅射 时间15s,使碳纳米管纸表面形成金金属层,金金属层厚度约20nm;
S2,在充氩气手套箱中,于金金属层表面辊轧相同大小的锂箔,然后置于加热板上加热至220℃, 锂完全融化后冷却得到Li/Au/CNTs复合箔材,备用;
S3,将冷却后的Li/Au/CNTs复合箔材固定于手套箱中的低压冷态溅射仪中,溅射功率14W, 溅射时间1min,使Li/Au/CNTs复合箔材表面形成纳米硅层,得到电化学活性材料,其中纳米硅层厚 度约100nm。
需要强调的是:以上仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,凡是 依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方 案的范围内。
Claims (7)
1.一种电化学活性材料的制备方法,其特征在于,包括以下步骤:
S1,制备表面包覆有纳米金晶的碳纳米管纸,再在充氩气手套箱中,于包覆有纳米金晶的碳纳米管纸表面辊轧金属锂箔;
S2,加热,至锂融化,使锂浸润到碳纳米管纸内部,得到锂-金-碳纳米管复合箔材;
S3,在锂-金-碳纳米管复合箔材表面低温溅射一层纳米硅,得到电化学活性材料。
2.根据权利要求1所述电化学活性材料的制备方法,其特征是,所述表面包覆有纳米金晶的碳纳米管纸通过在大孔隙率碳纳米管纸表面低压冷态溅射金金属得到。
3.根据权利要求2所述电化学活性材料的制备方法,其特征是,所述纳米金晶厚度为1~100nm。
4.根据权利要求1所述电化学活性材料的制备方法,其特征是,所述锂箔厚度为0.1~100μm。
5.根据权利要求2所述电化学活性材料的制备方法,其特征是,步骤S2中,加热温度为200℃~300℃。
6.根据权利要求1所述电化学活性材料的制备方法,其特征是,所述纳米硅的厚度为100~300nm。
7.一种电化学活性材料,其特征在于,采用权利要求1-6任一项权利要求所述制备方法制成。
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