CN108649264B - 一种添加缓冲层的薄膜固态电解质的制备方法 - Google Patents

一种添加缓冲层的薄膜固态电解质的制备方法 Download PDF

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CN108649264B
CN108649264B CN201810461744.1A CN201810461744A CN108649264B CN 108649264 B CN108649264 B CN 108649264B CN 201810461744 A CN201810461744 A CN 201810461744A CN 108649264 B CN108649264 B CN 108649264B
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薛文东
白立雄
王兴宇
王玉田
胡凯
戎马屹飞
李勇
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Abstract

本发明属于锂离子电池领域，涉及到一种添加缓冲层的新型薄膜固态电解质的制备方法。其特征是在LiPON薄膜表面添加缓冲层来改善LiPON薄膜的界面性能。LiPON薄膜的制备是利用磁控溅射设备，靶材选择为Li3PO4(纯度为99.9％)靶材；打开磁控溅射设备，安装靶材与基片，关闭溅射室，将其抽至7×10‑4Pa的高真空，然后通入氮气，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为10h。LiSiPON缓冲层的制备是选择Li3PO4‑Li3SiO3(纯度为99.9％)靶材，将溅射室抽至7×10‑4Pa的高真空，然后通入工作气体，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为1h。本发明可以改善LiPON固态电解质的水解还原问题，得到具有稳定界面结构的固态薄膜电解质。

Description

一种添加缓冲层的薄膜固态电解质的制备方法
技术领域
本发明涉及锂离子电池领域，尤其涉及全固态电池的制备，特别是一种快离子导体无机固态薄膜电解质的制备。
背景技术
电池的更新换代过程中，其性能在不断提升，但是电解液泄露、电池体积过大以及电池容量不够高等问题仍然存在。1992年，美国橡树岭国家实验室通过射频磁控溅射方式制备得到LiPON固态电解质薄膜，这使得固态电解质代替液体电解质成为可能。
全固态锂离子电池的优势在于体型小、安全性高、循环性能好、稳定性高且易于制作在不同基底上。
目前，关于全固态锂离子电池的研究主要集中在新的成膜技术研究、新的电池结构研究、新型阴阳极薄膜研究以及新型高离子电导率固态电解质的研究等诸多方面。现有方法获得薄膜制备效率低下、界面性能较难控制，严重阻碍了薄膜锂离子电池的发展。所以，改进LiPON电解质膜的制备技术，开发新型固态电解质薄膜是固态薄膜锂电池领域的重要课题。
发明内容
本发明主要针对现有LiPON薄膜在潮湿环境中容易水化问题，影响离子电导率，以及电池容量问题。提供在薄膜电解质表面添加缓冲层的解决方法。
本发明的基本构思主要是以Li3PO4和Li3PO4-Li2SiO3作为靶材，采用磁控溅射的办法溅射制备具有缓冲层的LiPON固态电解质薄膜，改善薄膜水化问题，提高薄膜电解质的离子电导率。
一种添加缓冲层的薄膜固态电解质的制备方法，其特征在于在LiPON薄膜表面添加缓冲层来改善LiPON薄膜的界面性能，制备步骤如下：
(1)LiPON薄膜的制备：利用磁控溅射设备，靶材选择为Li3PO4(纯度为99.9％)靶材；打开磁控溅射设备，安装靶材与基片，关闭溅射室，将其抽至7×10-4Pa的高真空，然后通入氮气，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为10h；
(2)LiSiPON缓冲层的制备：选择Li3PO4-Li3SiO3(纯度为99.9％)靶材，将溅射室抽至7×10-4Pa的高真空，然后通入工作气体，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为1h。
进一步地，所述靶材的厚度为3mm，直径为76.2mm。
进一步地，步骤(1)中所述氮气气体流量设置为80sccm。
进一步地，步骤(1)中所述制备的LiPON薄膜的厚度为1-2μm。
进一步地，步骤(2)中所述缓冲层的溅射过程中工作气体流量设置为40sccm。
进一步地，步骤(2)中缓冲层的溅射过程中通入工作气体为氮气和氩气的混合气体，其比例分别为4-1:0-3。
进一步地，步骤(2)中所述制备的LiSiPON缓冲层的厚度为0.1-0.3μm。
根据上述方法制备的全固态薄膜电解质与现有薄膜相比具有以下优点：
硅掺杂可以有效改善薄膜电解质的潮湿环境中的水解还原问题，利用硅掺杂的LiSiPON薄膜作为缓冲层，可以有效改善电解质薄膜的界面性能，稳定全固态薄膜电池结构。
具体实施方式
实施例一
1)第一步磁控溅射LiPON薄膜，靶材选择为Li3PO4靶材。打开磁控溅射设备，安装靶材与基片，关闭溅射室，将其抽至7×10-4Pa的高真空，然后通入氮气，气体流量设置为80sccm，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为10h.
2)第二步磁控溅射LiSiPON缓冲层，选择Li3PO4-Li3SiO3靶材，将溅射室抽至7×10-4Pa的高真空，然后通入工作气体，比例为4：0的氮氩混合气体，气体流量设置为40sccm，工作压强调整为1.5Pa，溅射功率设置为180W。溅射时间为1-3h。
实施例二
1)第一步磁控溅射LiPON薄膜，靶材选择为Li3PO4靶材。打开磁控溅射设备，安装靶材与基片，关闭溅射室，将其抽至7×10-4Pa的高真空，然后通入氮气，气体流量设置为80sccm，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为10h.
2)第二步磁控溅射LiSiPON缓冲层，选择Li3PO4-Li2SiO3靶材，将溅射室抽至7×10-4Pa的高真空，然后通入工作气体，比例为3：1的氮氩混合气体，气体流量设置为40sccm，工作压强调整为1.5Pa，溅射功率设置为180W。溅射时间为1-3h。
实施例三
1)第一步磁控溅射LiPON薄膜，靶材选择为Li3PO4靶材。打开磁控溅射设备，安装靶材与基片，关闭溅射室，将其抽至7×10-4Pa的高真空，然后通入氮气，气体流量设置为80sccm，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为10h.
2)第二步磁控溅射LiSiPON缓冲层，选择Li3PO4-Li2SiO3靶材，将溅射室抽至7×10-4Pa的高真空，然后通入工作气体，比例为2：2的氮氩混合气体，气体流量设置为40sccm，工作压强调整为1.5Pa，溅射功率设置为180W。溅射时间为1-3h。
实施例四
1)第一步磁控溅射LiPON薄膜，靶材选择为Li3PO4靶材。打开磁控溅射设备，安装靶材与基片，关闭溅射室，将其抽至7×10-4Pa的高真空，然后通入氮气，气体流量设置为80sccm，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为10h.
2)第二步磁控溅射LiSiPON缓冲层，选择Li3PO4-Li2SiO3靶材，将溅射室抽至7×10-4Pa的高真空，然后通入工作气体，比例为1：3的氮氩混合气体，气体流量设置为40sccm，工作压强调整为1.5Pa，溅射功率设置为180W。溅射时间为1-3h。
本具体实施例仅仅是对本发明的解释，并不是对本发明的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本发明的权利要求范围内都本发明的保护范围。

Claims (5)

1.一种添加缓冲层的薄膜固态电解质的制备方法，其特征在于在LiPON薄膜表面添加缓冲层来改善LiPON薄膜的界面性能，制备步骤如下：
(1)LiPON薄膜的制备：利用磁控溅射设备，靶材选择为纯度为99.9％的Li3PO4靶材；打开磁控溅射设备，安装靶材与基片，关闭溅射室，将其抽至7×10-4Pa的高真空，然后通入氮气，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为10h；
(2)LiSiPON缓冲层的制备：选择纯度为99.9％的Li3PO4-Li3SiO3靶材，将溅射室抽至7×10-4Pa的高真空，然后通入工作气体，工作压强调整为1.5Pa，溅射功率设置为180W，溅射时间为1h；
步骤(1)中所述制备的LiPON薄膜的厚度为1-2μm；
步骤(2)中所述制备的LiSiPON缓冲层的厚度为0.1-0.3μm。
2.根据权利要求1所述的添加缓冲层的薄膜固态电解质的制备方法，其特征在于所述靶材的厚度为3mm，直径为76.2mm。
3.根据权利要求1所述的添加缓冲层的薄膜固态电解质的制备方法，其特征在于步骤(1)中所述氮气气体流量设置为80sccm。
4.根据权利要求1所述的添加缓冲层的薄膜固态电解质的制备方法，其特征在于步骤(2)中所述缓冲层的溅射过程中工作气体流量设置为40sccm。
5.根据权利要求1所述的添加缓冲层的薄膜固态电解质的制备方法，其特征在于步骤(2)中缓冲层的溅射过程中通入工作气体为氮气和氩气的混合气体，其比例分别为4-1:0-3。
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