CN110783547A - 锂-金-碳纳米管复合箔材的制备方法 - Google Patents
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Abstract
一种锂‑金‑碳纳米管复合箔材的制备方法,属于电化学活性材料技术领域。该锂‑金‑碳纳米管复合箔材的制备方法包括以下步骤:S1,制备大孔隙率的碳纳米管纸,通过低压冷态溅射工艺在碳纳米管纸表面形成具有均匀纳米金晶层的碳纳米管纸;S2,将包覆有纳米金晶层的碳纳米管纸放入充氩气的手套箱中,于其表面辊轧锂箔;S3,加热金属锂箔至金属锂融化,使金属锂浸润到碳纳米管纸内部,从而形成锂‑金‑碳纳米管复合箔材。本发明既可解决金属锂在无锂负极表面随机成核和生长,以及锂枝晶产生等问题,又可解决充放电过程中负极的体积巨大膨胀问题。
Description
技术领域
本发明涉及的是一种电化学材料领域的技术,具体是一种锂-金-碳纳米管复合箔材的制备方法。
背景技术
金属锂的比容量为3860mAh/g,电化学势为-3.04V(vs标准氢电极),是一种非常理想的锂电池负极材料。但在以金属锂为负极的电池充放电过程中,Li离子在金属锂负极表面分布不均匀造成锂枝晶生长一直是困扰金属锂负极的主要问题。对于负极锂而言影响其循环性能的另一大问题就是充放电过程中巨大的体积膨胀。为了尽可能的减少金属锂负极的体积变化,人们开始寻找能够储存金属锂的载体材料。在一项研究中人们利用Li辅助还原氧化石墨烯,制备了层状还原氧化石墨烯,将该材料的边缘与熔融的金属Li接触,Li就会在毛细作用下进入到材料之中。该Li/还原氧化石墨烯复合材料可以将负极的体积变化控制在20%以内,提高了电池的循环性能,降低了电池的极化,并成功抑制了锂枝晶的产生。但制备还原氧化石墨烯亦存在工艺复杂、环保等问题。
在Li-LMO、Li-LFP等电池中,锂被存储在正极材料之中,理论上负极在电池组装的时候可以不含锂,但是无锂负极面对着一个巨大挑战:金属锂在负极表面随机成核和生长,会导致负极镀锂不均匀,以及锂枝晶产生等问题。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,提出了一种锂-金-碳纳米管复合箔材的制备方法,既可解决金属锂在无锂负极表面随机成核和生长,以及锂枝晶产生等问题,又可解决充放电过程中负极的体积巨大膨胀问题。
本发明包括以下步骤:
S1,制备大孔隙率的碳纳米管纸,通过低压冷态溅射工艺在碳纳米管纸表面形成具有均匀纳米金晶层的碳纳米管纸;
S2,将包覆有纳米金晶层的碳纳米管纸放入充氩气的手套箱中,于其表面辊轧锂箔;
S3,加热金属锂箔至金属锂融化,使金属锂浸润到碳纳米管纸内部,从而形成锂-金-碳纳米管复合箔材。
优选的,所述纳米金晶层厚度为5nm~100nm,进一步优选为10~20nm。
优选的,所述锂箔厚度为0.1μm~100μm,进一步优选为1~20μm。
优选的,步骤S3中加热温度不低于180℃,不高于600℃,进一步优选为200℃≤T≤300℃。
技术效果
与现有技术相比,本发明具有如下技术效果:
1)实现了锂、金与碳纳米管材料的紧密均匀复合;
2)以本发明复合箔材为负极的锂离子电池在充放电过程中,可有效避免Li离子在负极表面分布不均匀的情况,成功抑制锂枝晶的生成;且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。
附图说明
图1为实施例1中包覆有纳米金晶层的碳纳米管纸的SEM照片;
图2为实施例1所制备复合箔材用作负极材料和以锂箔为负极分别组装电池,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
本实施例涉及一种金属包覆碳纳米管的制备方法,包括以下步骤:
S1,裁取6cm*8cm的自制碳纳米管纸,将其固定于小型的低压冷态溅射仪中,溅射功率14W,溅射时间10s,得到具有均匀纳米金晶层包覆的碳纳米管纸,纳米金晶层厚度约15nm,其SEM照片如图1所示;
S2,在充氩气手套箱中于纳米金晶层包覆的碳纳米管纸表面辊轧相同大小的锂箔,然后将其置于加热板上加热并保持在200℃直至锂完全融化,之后冷却得到锂-金-碳纳米管复合箔材。
将所制得的锂-金-碳纳米管复合箔材作为负极与磷酸亚铁锂组装成电池,作为对比,以锂箔为负极与磷酸亚铁锂组装成电池,进行测试。得到图2所示0.1C相同倍率下电池循环性能曲线对比图。由图可见,以锂-金-碳纳米管复合箔材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
本实施例涉及一种金属包覆碳纳米管的制备方法,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,得到具有均匀纳米金晶层包覆的碳纳米管纸,纳米金晶层厚度约20nm;
S2,在充氩气手套箱中于纳米金晶层包覆的碳纳米管纸表面辊轧相同大小的锂箔,然后将其置于加热板上加热并保持在220℃直至锂完全融化,之后冷却得到锂-金-碳纳米管复合箔材。
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 (4)
1.一种锂-金-碳纳米管复合箔材的制备方法,其特征在于,包括以下步骤:
S1,制备大孔隙率的碳纳米管纸,通过低压冷态溅射工艺在碳纳米管纸表面形成具有均匀纳米金晶层的碳纳米管纸;
S2,将包覆有纳米金晶层的碳纳米管纸放入充氩气的手套箱中,于其表面辊轧锂箔;
S3,加热金属锂箔至金属锂融化,使金属锂浸润到碳纳米管纸内部,从而形成锂-金-碳纳米管复合箔材。
2.根据权利要求1所述锂-金-碳纳米管复合箔材的制备方法,其特征是,所述纳米金晶层厚度为5nm~100nm。
3.根据权利要求1所述锂-金-碳纳米管复合箔材的制备方法,其特征是,所述锂箔厚度为0.1μm~100μm。
4.根据权利要求1所述锂-金-碳纳米管复合箔材的制备方法,其特征是,步骤S3中加热温度不低于180℃,不高于600℃。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113823795A (zh) * | 2021-08-25 | 2021-12-21 | 常州大学 | 抑制锂枝晶生长的复合电极材料的制备方法及其应用 |
CN117174914A (zh) * | 2023-09-20 | 2023-12-05 | 中能鑫储(北京)科技有限公司 | 一种应用于铝离子电池的三维集流体及其制备方法 |
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CN113823795A (zh) * | 2021-08-25 | 2021-12-21 | 常州大学 | 抑制锂枝晶生长的复合电极材料的制备方法及其应用 |
CN117174914A (zh) * | 2023-09-20 | 2023-12-05 | 中能鑫储(北京)科技有限公司 | 一种应用于铝离子电池的三维集流体及其制备方法 |
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