原位构建ZnO梯度缓冲层对Li|LATP界面稳定性的研究
Study on the Stability of Li|LATP Interface by In-Situ ZnO Gradient Buffer Layer
摘要: 钠超离子导体(NASICON)型Li1.3Al0.3Ti1.7(PO4)3 (LATP)由于其高的锂离子电导率、优异的空气稳定性和低成本而备受关注，被认为是下一代固态锂电池最有前途的固态电解质之一。然而，由于其与锂金属会发生强烈的副反应，存在着严重的界面问题。在此，提出了一种简单且方便的滴筑方法，通过构建PEO-ZnO梯度缓冲层，在LATP和锂金属阳极之间形成紧密而稳定的界面。缓冲层除了能够减缓副反应，减缓LATP的消耗分解之外，该缓冲层还能够抑制锂枝晶的生长和提高界面稳定性。与未引入氧化锌相比，引入1%和5%梯度缓冲层的扣式电池，在0.1 mA·cm−2单位面积电流稳定长时间循环(1000小时)，而纯PEO基对称电池在0.1 mA·cm−2电流密度下仅循环500小时。以LiFePO4构建的全电池在0.1 C倍率下首次放电比容量为154.99 mAh·g−1，循环150圈后容量下降至129.76%。同时具有较高的化学稳定性窗口(5 V vs. Li/Li+)以及抑制锂枝晶的能力。在动态电流测试模式下仍维持优异的循环特性。这种策略有效提高了LATP与电极界面的相容性，减缓了副反应的发生，为开发低成本、高稳定性固态锂金属电池铺平了新的道路。
Abstract: Sodium superionic conductor (NASICON) type Li1.3Al0.3Ti1.7(PO4)3 (LATP) has attracted much attention due to its high lithium-ion conductivity, excellent air stability, and low cost, and is considered to be one of the most promising solid-state electrolytes for next-generation solid-state lithium batteries. However, due to the strong side reaction with lithium metal, there are serious interface problems. Here, a simple and convenient drip construction method is proposed to form a tight and stable interface between LATP and lithium metal anode by constructing a PEO-ZnO gradient buffer layer. In addition to slowing down the side reaction and the dissipation decomposition of LATP, the buffer layer can also inhibit the growth of lithium dendrites and improve the interfacial stability. Compared with the non-introduction of zinc oxide, the button battery with 1% and 5% gradient buffer layer was stable for a long time cycle (1000 hours) at 0.1 mA·cm−2 unit area current, while the pure PEO-based symmetric battery was only cycled for 500 hours at 0.1 mA·cm−2 current density. The full battery built with LiFePO4 has a specific capacity of 154.99 mAh·g−1 at 0.1 C, and the capacity drops to 129.76% after 150 cycles. It also has a high chemical stability window (5 V vs. Li/Li+) and the ability to inhibit lithium dendrites. Excellent cycling characteristics are maintained in dynamic current test mode. This strategy effectively improves the compatibility between LATP and electrode interface, slows down the occurrence of side reactions, and paves a new way for the development of low-cost, high-stability solid-state lithium metal batteries.
文章引用：刘圣奇, 杨晨, 张真硕, 王积辉, 孙浩宁, 刘争. 原位构建ZnO梯度缓冲层对Li|LATP界面稳定性的研究[J]. 材料科学, 2025, 15(4): 816-824. https://doi.org/10.12677/ms.2025.154086

参考文献

[1] Green, F. (2018) The Logic of Fossil Fuel Bans. Nature Climate Change, 8, 449-451. [Google Scholar] [CrossRef] 
[2] Rahman, M.M., Sultana, N. and Velayutham, E. (2022) Renewable Energy, Energy Intensity and Carbon Reduction: Experience of Large Emerging Economies. Renewable Energy, 184, 252-265. [Google Scholar] [CrossRef] 
[3] Chen, R., Nolan, A.M., Lu, J., Wang, J., Yu, X., Mo, Y., et al. (2020) The Thermal Stability of Lithium Solid Electrolytes with Metallic Lithium. Joule, 4, 812-821. [Google Scholar] [CrossRef] 
[4] Wada, M. (2009) Research and Development of Electric Vehicles for Clean Transportation. Journal of Environmental Sciences, 21, 745-749. [Google Scholar] [CrossRef] [PubMed]
[5] Zou, C., Ma, F., Pan, S., Lin, M., Zhang, G., Xiong, B., et al. (2022) Earth Energy Evolution, Human Development and Carbon Neutral Strategy. Petroleum Exploration and Development, 49, 468-488. [Google Scholar] [CrossRef] 
[6] Scrosati, B. and Garche, J. (2010) Lithium Batteries: Status, Prospects and Future. Journal of Power Sources, 195, 2419-2430. [Google Scholar] [CrossRef] 
[7] Rai, K. and Kundu, S. (2020) Fabrication and Performances of High Lithium-Ion Conducting Solid Electrolytes Based on NASICON Li1.3Al0.3Ti1.7-XZrx(po4)3 (0≤X≤0.2). Ceramics International, 46, 23695-23705.
[8] Sen, S. and Richter, F.H. (2023) Typology of Battery Cells—From Liquid to Solid Electrolytes. Advanced Science, 10, Article 2303985. [Google Scholar] [CrossRef] [PubMed]
[9] Yu, Z., Cui, Y. and Bao, Z. (2020) Design Principles of Artificial Solid Electrolyte Interphases for Lithium-Metal Anodes. Cell Reports Physical Science, 1, Article 100119. [Google Scholar] [CrossRef] 
[10] Levit, O., Xu, P., Shvartsev, B., Avioz Cohen, G., Stanciu, L., Tsur, Y., et al. (2020) Interphases Formation and Analysis at the Lithium-Aluminum-Titanium-Phosphate (LATP) and Lithium-Manganese Oxide Spinel (LMO) Interface during High-Temperature Bonding. Energy Technology, 8, Article 2000634. [Google Scholar] [CrossRef] 
[11] Hao, X., Zhao, Q., Su, S., Zhang, S., Ma, J., Shen, L., et al. (2019) Constructing Multifunctional Interphase between Li1.4Al0.4Ti1.6(PO4)3 and Li Metal by Magnetron Sputtering for Highly Stable Solid-State Lithium Metal Batteries. Advanced Energy Materials, 9, Article 1901604. [Google Scholar] [CrossRef] 
[12] Huang, C., Huang, S., Wang, A., Liu, Z., Pei, D., Hong, J., et al. (2023) Correction: Stabilizing the Li1.4Al0.4Ti1.6(PO4)3/li Interface with an in Situ Constructed Multifunctional Interlayer for High Energy Density Batteries. Journal of Materials Chemistry A, 11, 17316-17317. [Google Scholar] [CrossRef] 

为你推荐