Sodium Difluoro(oxalato)borate Additive-Induced Robust SEI and CEI Layers Enable Dendrite-Free and Long-Cycling Sodium-Ion Batteries,Advanced Functional Materials

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Sodium Difluoro(oxalato)borate Additive-Induced Robust SEI and CEI Layers Enable Dendrite-Free and Long-Cycling Sodium-Ion Batteries
Advanced Functional Materials ( IF 18.5 ) Pub Date : 2024-04-10 , DOI: 10.1002/adfm.202402310
Xiaohao Liu _{1,

2} , Jiahua Zhao ₂ , Huanhuan Dong ₂ , Lingling Zhang ₂ , Hang Zhang ₂ , Yun Gao ₂ , Xunzhu Zhou _{1,

2} , Longhai Zhang ₁ , Li Li _{2,

3} , Yang Liu ₃ , Shuchun Chou ₄ , Weihong Lai ₅ , Chaofeng Zhang ₁ , Shulei Chou ₂

Affiliation

Sodium-ion batteries (SIBs) are a promising candidate for large-scale energy storage due to the low cost and abundant sodium resources. However, the formation of sodium dendrites on the surface of hard carbon (HC) anodes is the most intractable challenge for full cells during charging, leading to severe performance degradation and safety hazards. Here, a robust additive-induced borate and fluoride-rich interphase is constructed by introducing sodium difluoro(oxalato)borate (NaDFOB) as additive in the ether-based electrolyte to relieve the performance deterioration for SIBs. NaDFOB can participate in the passivation process of electrolyte-electrode interfaces through preferential oxidation and reduction of DFOB⁻ to effectively restrain the growth of sodium dendrites. Moreover, the electrolyte decomposition and dissolution of transition metal ions are effectively inhibited. Benefiting from that, FeMn-based Prussian blue (FeMnHCF) || HC full cell with a negative/positive capacity ratio (N/P ratio) of 1.09 displays a capacity retention of 82.1%, especially with a low N/P ratio of 0.96 the cell still demonstrates a stable Coulombic efficiency of over 99.9% after 500 cycles via using NaDFOB as additive. As a practical demonstration, the designed 18650 full cells display enhanced cycling stability with NaDFOB additive. The findings provide insights into the additive-induced inorganic-rich interfacial layers for dendrite-free SIBs.

中文翻译：

二氟（草酸）硼酸钠添加剂诱导的稳健 SEI 和 CEI 层可实现无枝晶和长循环钠离子电池

由于成本低廉且钠资源丰富，钠离子电池（SIB）是大规模储能的有希望的候选者。然而，硬碳（HC）负极表面钠枝晶的形成是全电池在充电过程中最棘手的挑战，导致严重的性能下降和安全隐患。在这里，通过在醚基电解液中引入二氟草酸硼酸钠（NaDFOB）作为添加剂，构建了强大的添加剂诱导的硼酸盐和富含氟化物的界面，以缓解SIB的性能恶化。 NaDFOB可以通过DFOB ^-的优先氧化和还原参与电解质-电极界面的钝化过程，从而有效抑制钠枝晶的生长。而且，有效抑制电解液的分解和过渡金属离子的溶解。受益于此，铁锰基普鲁士蓝 (FeMnHCF) ||负/正容量比（N/P比）为1.09的HC全电池显示出82.1%的容量保持率，特别是在0.96的低N/P比下，电池在500次后仍表现出超过99.9%的稳定库伦效率通过使用NaDFOB作为添加剂进行循环。作为实际演示，设计的 18650 全电池显示出使用 NaDFOB 添加剂增强的循环稳定性。这些发现为无枝晶 SIB 的添加剂诱导的富含无机物的界面层提供了见解。

更新日期：2024-04-10

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