CN110444731B - 全固态锂电池负极界面修饰方法 - Google Patents

全固态锂电池负极界面修饰方法 Download PDF

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CN110444731B
CN110444731B CN201910803248.4A CN201910803248A CN110444731B CN 110444731 B CN110444731 B CN 110444731B CN 201910803248 A CN201910803248 A CN 201910803248A CN 110444731 B CN110444731 B CN 110444731B
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刘芳洋
赖延清
徐向群
汪齐
蒋良兴
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李劼
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Hunan Enjie Frontier New Material Technology Co ltd
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Abstract

本发明公开了一种全固态锂电池负极界面修饰方法，界面修饰层由1‑丁基‑2,3‑二甲基咪唑四氟硼酸盐、锂盐和添加剂按比例组成，厚度为10nm‑50μm，修饰层的制备步骤包括：按(69.9‑90)：(5‑30)：(0.1‑5)质量比例称取1‑丁基‑2,3‑二甲基咪唑四氟硼酸盐、锂盐和添加剂，将三者加热搅拌均匀；将搅拌得到的溶液涂在固态电解质层和/或负极上，静置凝固后得到修饰层。在本发明中，1‑丁基‑2,3‑二甲基咪唑四氟硼酸盐具有较高的离子电导率和宽的电化学窗口，通过加热熔化添加锂盐和添加剂能改善其电化学性能，用这种产物做界面层能避免锂负极和固态电解质的直接接触，改善固态电池的电化学性能。

Description

全固态锂电池负极界面修饰方法
技术领域
本发明涉及全固态锂电池领域，具体涉及一种全固态锂电池负极界面修饰方法。
背景技术
锂离子电池以其高能量密度和高功率密度等优点在储能领域中广泛的应用，现在锂离子电池已经成为了电动汽车有力的候选者之一。但是消费市场对锂离子电池的能量密度和安全性有进一步要求，特别是最近特斯拉汽车发生自燃事件，加大了对电池安全的的关注。使用固态电解质取代电解液能有效避免电解液所产生的泄露易燃等事故。由于固态电解质比电解液有更宽的电化学窗口，固态电池能使用高压插层正极，极大提升固态电池的能量密度，还可以避免液态电解液的封装工艺。
但是固态电池在循环过程中，固态电解质可能与锂负极发生氧化还原反应，会生成高阻抗的界面相积累在负极和固态电解质之间，影响锂离子传输；固态电解质和锂负极之间固固接触引发的不完整接触，会导致在循环过程局部电流密度过大；这些问题会严重影响固态电池的倍率性能。
发明内容
本发明主要在于提供一种全固态锂电池负极界面修饰方法，主要是解决现有固态电池中，锂负极和固态电解质之间生成界面相和润湿性差等问题。
为了实现上述目的，本发明提供的全固态锂电池负极界面修饰方法，所述全固态锂电池包括正极、固态电解质层、修饰层和负极；所述固态电解质层介于所述正极和所述修饰层之间；所述修饰层介于固态电解质层与负极之间，所述修饰层由1-丁基-2,3-二甲基咪唑四氟硼酸盐、锂盐和添加剂按比例组成，且厚度为10nm-50μm，所述修饰层的制备步骤包括：
步骤1：按(69.9-90)：(5-30)：(0.1-5)质量比例称取1-丁基-2,3-二甲基咪唑四氟硼酸盐、锂盐和添加剂，将三者加热搅拌均匀；
步骤2：将步骤1得到的溶液滴涂、喷涂或者旋涂在固态电解质层和/或负极上，静置凝固后得到修饰层。
优选地，步骤1中的加热温度为40-80℃，加热时间为1-36h。
优选地，所述锂盐包括无机锂盐、有机锂盐中的一种或两种，无机锂盐包括高氯酸锂、四氟硼酸锂、六氟磷酸锂、三氟甲磺酸锂中的一种，有机锂盐包括二(三氟甲基磺酰)亚胺锂、二草酸硼酸锂、二氟草酸硼酸锂、双腈胺锂中的一种。
优选地，所述添加剂为FEC、硝酸锂、亚硝酸锂和氟化铜的一种或几种。
本发明的技术构思如下：
离子液体具有很高的耐氧化能力，较高的稳定性和较高的锂盐溶解能力。但是大部分离子液体本身在常温下液态成膜性较差，通常采用离子液体与聚合物复合的方式来改善离子液体的成膜性的问题，而1-丁基-2,3-二甲基咪唑四氟硼酸盐本身的熔点是37℃，在常温下具备界面修饰层的作用。
在本发明的技术方案中，1-丁基-2,3-二甲基咪唑四氟硼酸盐这种离子液体具有较高的离子电导率和宽的电化学窗口，通过加热熔化添加锂盐和添加剂能极大地改善这种离子液体的电化学性能，用这种产物做界面层，能避免锂负极和固态电解质的直接接触，能显著改善固态电池的电化学性能。
和现有技术相比，本发明可以减少全固态电池的成本，适合产业化生产。本发明所采用的这种离子液体在充放电过程中可以缓冲电极体积变化所带来的应力变化。
附图说明
图1是实施例1得到的全固态电池的恒流放电性能曲线。
具体实施方式
下面通过实施例对本发明作进一步的说明，但不限于此。
实施例1
采用LiFeO4作为正极材料涂布成极片，Li1.3Al0.3Ti1.7(PO4)3作为电解质片，金属锂做负极。按89.9:10:0.1称取1-丁基-2,3-二甲基咪唑四氟硼酸盐、锂盐和硝酸锂在50℃下加热搅拌12小时，将产物滴涂在电解质片上，静置凝固后得到厚度为2μm的修饰层。按照正极-电解质-修饰层-负极的顺序组装成扣式电池进行测试。请参照图1，在25℃下测试，0.5C下恒流放电100圈后还能保持115mAh/g，表现出良好的循环稳定性。
实施例2
采用LiCo0.8 Ni0.1Al0.1O2作为正极材料涂布成极片，NASICON型的Li1.4Al0.4Ti1.6(PO4)3作为电解质片，金属锂做负极。按79.9:20:3称取1-丁基-2,3-二甲基咪唑四氟硼酸盐、锂盐和硝酸锂在60℃下加热搅拌24小时，将产物滴涂在电解质片上，静置凝固后得到厚度为20μm的修饰层。按照正极-电解质-修饰层-负极的顺序组装成扣式电池进行测试。在25℃下测试，0.5C下恒流放电100圈后还能保持123mAh/g，表现出良好的循环稳定性。

Claims (3)

1.一种全固态锂电池负极界面修饰方法，其特征在于，所述全固态锂电池包括正极、固态电解质层、修饰层和负极；所述固态电解质层介于所述正极和所述修饰层之间；所述修饰层介于固态电解质层与负极之间，所述修饰层由1-丁基-2,3-二甲基咪唑四氟硼酸盐、锂盐和添加剂按比例组成，且厚度为10 nm-50 µm，所述修饰层的制备步骤包括：
步骤1：按 (69.9-90)：(5-30)：(0.1-5)质量比例称取1-丁基-2,3-二甲基咪唑四氟硼酸盐、锂盐和添加剂，将三者加热搅拌均匀，其中，所述添加剂为FEC、硝酸锂、亚硝酸锂和氟化铜的一种或几种，加热温度为40-80 ℃；
步骤2：将步骤1得到的溶液滴涂、喷涂或者旋涂在固态电解质层和/或负极上，静置凝固后得到修饰层。
2.根据权利要求1所述的全固态锂电池负极界面修饰方法，其特征在于，步骤1中的加热时间为1-36 h。
3.根据权利要求1所述的全固态锂电池负极界面修饰方法，其特征在于，所述锂盐包括无机锂盐、有机锂盐中的一种或两种，无机锂盐包括高氯酸锂、四氟硼酸锂、六氟磷酸锂中的一种，有机锂盐包括二(三氟甲基磺酰)亚胺锂、二草酸硼酸锂、二氟草酸硼酸锂、双腈胺锂、三氟甲磺酸锂中的一种。
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