CN111574216B - 兼容金属锂负极的Li1.4Al0.4Ti1.6(PO4)3固态电解质及其制备方法 - Google Patents

兼容金属锂负极的Li1.4Al0.4Ti1.6(PO4)3固态电解质及其制备方法 Download PDF

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CN111574216B
CN111574216B CN202010473041.8A CN202010473041A CN111574216B CN 111574216 B CN111574216 B CN 111574216B CN 202010473041 A CN202010473041 A CN 202010473041A CN 111574216 B CN111574216 B CN 111574216B
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aao template
lithium
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白莹
郜蒙蒙
赵慧玲
郁彩艳
尹延锋
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Abstract

本发明提供了一种兼容金属锂负极的Li1.4Al0.4Ti1.6(PO4)3固态电解质及其制备方法及其使用该固态电解质的锂离子电池。双通AAO模板孔径中的LATP纳米线的一端与正极直接接触，另一端与锂金属负极直接存在的空气间隙，避免LATP和锂金属负极之间直接接触会引发的副反应，提高了LATP结构的稳定性，防止副反应产物在界面聚集导致的全固态锂离子电池界面离子电导率降低。

Description

兼容金属锂负极的Li1.4Al0.4Ti1.6(PO4)3固态电解质及其 制备方法
技术领域
本发明涉及一种兼容金属锂负极的Li1.4Al0.4Ti1.6(PO4)3 (LATP)固态电解质和制备方法及使用该固态电解质的全固态锂离子电池。
背景技术
随着锂离子电池向电动汽车、智能电网等领域的不断拓展，目前的商业化电池已经越来越难以满足人们对高能量密度的迫切需求，高能量密度带来的安全隐患也日益突出。因此，兼具高能量密度和高安全性能的全固态锂离子电池重新回归历史舞台，并引起了人们极大的研究兴趣。全固态电池采用不可燃、无腐蚀、不挥发、无漏液的固态电解质替代常规的可燃液态电解质，因此与热失控和电解质燃烧相关的安全问题将有望从根本上得以解决。此外，固态电解质一般具有较宽的电化学稳定窗口（5 V以上），便于匹配高电压正极和金属锂负极，实现电池的高质量能量密度；在工艺上，固态电解质具有柔性化发展前景，支持双极性堆叠电池，并可通过匹配更薄的集电器有效减少单体电池间的冗余空间，实现体积能量密度的提升。经过人们不断地探索和开发，目前一些固态电解质已经拥有了与液态电解质相比拟的离子电导率，但固态电池距离商业化仍有一段距离。研究者普遍认为，全固态电池进一步发展和应用的关键在于其中的界面问题。
作为一种典型的固态电解质，Li1.4Al0.4Ti1.6(PO4)3 (LATP)具有六方晶格结构，空间群为R3-c，Li、Al、Ti、P和O分别位于晶格中的6b、12c、18e和36f格点位，形成了TiO6/AlO6八面体和PO4四面体共同组成的共价Ti-Al-P-O骨架，锂离子在骨架中分布。该电解质不仅具有优越的离子传输能力（锂离子扩散系数接近10-3 S cm-1），而且其稳定的结构和廉价的成本吸引了众多研究者的关注。
作为典型的锂离子电池负极，金属锂的氧化还原电位很低（-3.04 V，相对标准氢电极），LATP和锂金属负极之间直接接触会产生严重的副反应，锂金属将LATP中的Ti4+还原为Ti3+，不仅破坏了LATP的结构稳定性，而且副反应产物在界面的聚集又降低了界面的离子电导率。
发明内容
为了解决LATP基全固态锂离子电池的上述技术问题，本发明提供了一种兼容金属锂负极的LATP固态电解质及其制备方法。
本发明的技术解决方案是：
一种兼容金属锂负极的Li1.4Al0.4Ti1.6(PO4)3固态电解质，其特征在于，正极和负极之间采用双通AAO模板作为固态电解质的结构骨架，在其中一端沿双通AAO模板的孔内壁向另一端致密生长连续均匀的LATP纳米颗粒，作为锂离子快速传导的路径。所述LATP纳米颗粒粒径均匀；所述LATP纳米颗粒未完全将双通AAO模板的孔径填充满，所述锂离子快速传导路径LATP的长度距另一端的具有一定的距离形成间隙；所述双通AAO模板具有间隙的一端与锂金属负极接触，另一端与正极直接接触，所述间隙能有效避免LATP与负极锂金属的直接接触而引起的不良副反应，又能够保证锂离子在电场作用下的有效输运。
具体的，所述LATP纳米颗粒粒径均匀，直径为20 – 30 nm。
具体的，所述锂离子快速传导路径LATP的长度距另一端的距离为10 – 50 nm。
一种兼容金属锂负极的LATP固态电解质的制备方法，包含以下步骤：
步骤1，制备一定浓度的LATP前驱体溶液；
步骤2，双通AAO模板预处理：在真空的状态下对双通AAO模板进行加热，以除掉其中的水分和杂质，然后保持负压冷却至室温。
步骤3，通过控制注入孔径的LATP与双通AAO模板的摩尔比，进而控制注入LATP固化后占据孔径的体积比。将适量的 LATP前驱体溶液在负压状态下喷注到经所述步骤2处理过的双通AAO模板上，由于毛细作用和负压、以及喷注压力的多重因素，LATP前驱体溶液会喷注进入到AAO模板的孔径内。优选地，AAO模板与LATP的摩尔比为1:5.00 – 4.99，其中AAO模板的孔隙率为50%-80%。
步骤4，对喷注了适量LATP前驱体溶液的AAO模板进行退火处理，获得一端具有空气间隙的兼容金属锂负极的LATP固态电解质。
优选地，空气间隙的长度为10 – 50 nm。
本发明的有益效果是：
提供了一种兼容金属锂负极的LATP固态电解质及其制备方法和使用该固态电解质的锂离子电池，避免了LATP和锂金属负极之间直接接触而引发的严重副反应对电池性能的损害。本发明通过控制AAO模板与LATP的摩尔比，在双通AAO模板孔中注入适量的LATP，以获得合适长度的空气间隙尺寸，较好的兼顾了LATP对锂离子良好的导通作用以及优越的界面稳定性。
附图说明
以下结合附图对本发明做进一步说明。
附图1为本发明中制备的LATP固态电解质的X射线衍射图谱。
附图2为AAO模板原始表面的SEM图。
附图3为采用了实施例1制备的LATP固态电解质的下表面SEM图。
附图4为采用实施例1制备的LATP固态电解质的上表面（具有空气间隙）SEM图。
附图5为采用实施例1制备的全固态锂离子电池的充放电测试图（正极材料和负极材料分别为磷酸铁锂和金属锂）。
具体实施方式
为了使本发明的目的、技术方案及优点更加清晰，下面通过实施例进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，但本发明的内容并非局限于此。
实施例1
一种兼容金属锂负极的Li1.4Al0.4Ti1.6(PO4)3固态电解质，其特征在于，正极和负极之间采用双通AAO模板作为固态电解质的结构骨架，在其中一端沿双通AAO模板的孔内壁向另一端致密生长连续均匀的LATP纳米颗粒，作为锂离子快速传导的路径。所述LATP纳米颗粒粒径均匀，直径为20nm；所述LATP纳米颗粒未完全将双通AAO模板的孔径填充满，所述锂离子快速传导路径LATP的长度距另一端的具有10 nm的距离形成空气间隙；所述双通AAO模板具有间隙的的一端与锂金属负极接触，另一端与正极直接接触，所述空气间隙能有效避免LATP与负极锂金属的直接接触而引起的不良副反应，又能够保证锂离子在电场作用下的有效输运。
一种兼容金属锂负极的LATP固态电解质的制备方法，包含以下步骤：
步骤1，制备LATP前驱体溶液：将0.27g硝酸锂、0.39g九水合硝酸铝、0.535ml磷酸分别溶于5 ml无水乙醇中，为防止九水合硝酸铝水解，滴加少量硝酸，搅拌30 min后，将硝酸锂滴加到九水合硝酸铝中，所得溶液记为溶液A。将1.305ml钛酸异丙酯溶于5 ml无水乙醇中，将溶液A缓慢滴加到钛酸异丙酯中，所得溶液记为溶液B。最后将磷酸滴入溶液B中，所得溶液即为LATP前驱体溶液。
步骤2，预处理双通AAO模板：将厚度为30μm、质量为25mg、孔隙率为60%的AAO模板放入玻璃瓶中，在200 °C加热状态下抽真空24 h，去除水蒸气和杂质，使AAO模板的孔径处于负压状态后自然冷却。
步骤3，取935μL的LATP前驱体溶液，在保持负压状态的前提下将前驱体溶液喷注入双通AAO模板的孔径中，静置24h，确保注入的LATP前驱体溶液位于双通AAO孔径的下端部，其中双通AAO与LATP的摩尔比为1：5.00，AAO模板的孔隙率为70%。
步骤4，将喷注过LATP前驱体溶液的AAO模板在空气氛围下进行煅烧（设定程序：先升温至500°C、保温5 h，再升温至750°C、保温15 h），以提高LATP纳米颗粒的均匀性，自然冷却后即可得到具有空气间隙（距离AAO模板孔道一端10 nm）且兼容金属锂负极的LATP固态电解质。制备后的LATP固态电解质的下表面SEM图如附图3所示，上表面（具有空气间隙）SEM图，如附图4所示。
步骤5，将所述步骤4制备的具有双通AAO模板的所述LATP固态电解质具有间隙的一端与锂金属负极接触，另一端与磷酸铁锂正极活性材料直接接触后获得全固态锂离子电池，充放电测试曲线如图5所示。
实施例2
一种兼容金属锂负极的LATP固态电解质的制备方法，包含以下步骤：
步骤1，制备Li1.4Al0.4Ti1.6(PO4)3前驱体溶液：将0.27g硝酸锂、0.39g九水合硝酸铝、0.535ml磷酸分别溶于5 ml无水乙醇中，为防止九水合硝酸铝水解，滴加少量硝酸，搅拌30 min后，将硝酸锂滴加到九水合硝酸铝中，所得溶液记为溶液A。将1.305ml钛酸异丙酯溶于5 ml无水乙醇中，将溶液A缓慢滴加到钛酸异丙酯中，所得溶液记为溶液B。最后将磷酸滴入溶液B中，所得溶液即为LATP前驱体溶液。
步骤2，预处理AAO模板：将厚度为30μm、质量为26 mg的AAO模板放入玻璃瓶中，在200 °C加热状态下真空抽滤24 h，去除水蒸气和杂质，使AAO模板的孔径处于负压状态后冷却。
步骤3，取195μl的LATP前驱体溶液，在不破坏保持负压状态的前提下将前驱体溶液喷注入双通AAO模板的孔径中，静置24h，其中AAO与LATP的摩尔比为1：4.99，AAO模板的孔隙率为70%。
步骤4，将喷注过LATP前驱体溶液的AAO模板在空气氛围下进行煅烧（设定程序：先升温至500 °C 、保温5 h，再升温至750 °C、保温15 h），以提高LATP纳米颗粒的均匀性，自然冷却后即可得到具有空气间隙（距离AAO模板孔道一端50 nm）且兼容金属锂负极的LATP固态电解质。

Claims (2)

1.一种兼容金属锂负极的Li1.4Al0.4Ti1.6(PO4)3固态电解质，其特征在于，正极和负极之间采用双通AAO模板作为固态电解质的结构骨架，在其中一端沿双通AAO模板的孔内壁向另一端致密生长连续均匀的LATP纳米颗粒，作为锂离子快速传导的路径，所述LATP纳米颗粒粒径均匀；所述LATP纳米颗粒未完全将双通AAO模板的孔径填充满，所述锂离子快速传导路径LATP的长度距另一端的具有一定的距离形成空闲间隙；所述双通AAO模板具有间隙的一端与锂金属负极接触，另一端与正极直接接触，所述间隙能有效避免LATP与负极锂金属的直接接触而引起的不良副反应，又能够保证锂离子在电场作用下的有效输运；
所述锂离子快速传导路径LATP的长度距另一端的距离为10 -50 nm；
所述LATP纳米颗粒的直径为20-30 nm；
所述兼容金属锂负极的LATP固态电解质的制备方法，包含以下步骤：
步骤1，制备一定浓度的LATP前驱体溶液；
步骤2，双通AAO模板预处理：在真空的状态下对双通AAO模板进行加热，以除掉其中的水分和杂质，然后保持负压冷却至室温；
步骤3，通过控制注入孔径的LATP与双通AAO模板的摩尔比，进而控制注入LATP固化后占据孔径的体积比；将适量的 LATP前驱体溶液在负压状态下喷注到经所述步骤2处理过的双通AAO模板上，由于毛细作用和负压、以及喷注压力的多重因素，LATP前驱体溶液会喷注进入到AAO模板的孔径内；AAO模板与LATP的摩尔比为1:5.00-4.99，其中AAO模板的孔隙率为50% - 80%；
步骤4，对喷注了适量LATP前驱体溶液的AAO模板进行退火处理，获得一端具有空气间隙的兼容金属锂负极的LATP固态电解质；
其中，AAO模板与LATP的摩尔比为1:5.00- 4.99，其中AAO模板的孔隙率为50% - 80%。
2.如权利要求1所述的兼容金属锂负极的Li1.4Al0.4Ti1.6(PO4)3 固态电解质，其特征在于，空气间隙的长度为10 - 50 nm。
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