In-situ observation of electrolyte-dependent interfacial change of the graphite anode in sodium-ion batteries by atomic force microscopy
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摘要: 石墨在碳酸酯基电解液中储钠活性很低，因此被认为不合适作为钠离子电池负极材料。而最近的研究表明，在以线性醚为溶剂的钠离子电解液中，石墨具有高的储钠容量和首圈库伦效率。因此，探索这种溶剂依赖型的石墨界面演绎过程具有重要的意义。本研究采用原位原子力显微镜（Atomic force microscopy，AFM）实时观测石墨在碳酸酯基和线性醚基电解液下的界面微观动态过程。结果表明：在线性醚溶剂下，石墨电极界面没有固体电解质界面膜（Solid electrolyte interphase，SEI）形成，且溶剂化钠离子可以在石墨层间进行可逆的插入和脱出，AFM结果从界面角度解释了其具有高初始库伦效率的内在原因。然而在碳酸酯溶剂中，可以观察到石墨电极表面出现明显的沉积物，对应SEI的生长；并且在充电过程中SEI逐渐减少，表明碳酸酯溶剂下形成的SEI不稳定，造成不可逆的容量损失和低库伦效率。此外，石墨表面未出现明显的台阶变化，反映了没有钠离子的脱嵌过程。上述研究结果为石墨负极界面反应动态过程提供了见解，从微观尺度揭示了溶剂依赖的石墨负极储钠行为及其界面反应机理，为高性能钠离子电池体系的设计与发展提供了理论依据。Abstract: Graphite has proved to be inactive for Na+ storage in ester-based electrolytes when used as the anode material. Recent studies have shown the feasibility of a graphite anode for Na+ storage with a large capacity and a high initial Coulombic efficiency (ICE) in linear ether-based electrolytes. Understanding such solvent-dependent electrochemical behavior at the nanometer scale is essential but has remained elusive, especially the direct visualization of the graphite/electrolyte interface. We report the in-situ observation by atomic force microscopy of a working battery that allowed us to monitor and visualize the changes of the graphite/electrolyte interface in both linear ether and ester-based electrolytes. Results indicate that there is no solid electrolyte interphase (SEI) formation in the linear ether-based electrolytes and the co-intercalation is reversible and stable in the following cycles, which are responsible for the relatively high ICE, large capacity and excellent stability. In the ester-based electrolytes, SEI deposition is obvious during the sodiation process, but not in the desodiation process, leading to a serious consumption of the electrolyte, and thus a low ICE and irreversible Na+ storage. Our findings provide insights into the dynamics of changes in the graphite/electrolyte interface and reveal the solvent-dependent Na+ storage at the nanometer scale, paving the way to develop high-performance Na+ batteries.
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Key words:
- Graphite anode /
- In situ atomic force microscopy /
- Sodium-ion batteries /
- Diglyme
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Figure 1. Galvanostatic discharge-charge curves of the graphite electrode in (a) carbonate and (b) diglyme electrolytes, at the current density of 100 mA g−1. (c) Long-term cycling performance and Coulombic efficiency of diglyme electrolyte at 100 mA g−1. (d) CV curves in diglyme electrolyte at 0.1 mV s−1.
Figure 2. (a) Schematic of the in situ AFM setup. (b-j) In situ AFM images of HOPG electrode in 1 mol L−1 diglyme electrolyte during the first discharging cycle from 1.84 to 0.51 V. The long white arrows indicate the scan directions.
Figure 3. (a-i) In situ AFM images of HOPG electrode in 1 mol L−1 diglyme electrolyte during the first charging cycle from 0.02 to 1.96 V.
Figure 4. (a) 3D AFM morphology images of HOPG surface in 1 mol L−1 diglyme electrolyte. (b) Schematic of the in situ Raman setup and in situ Raman spectra of graphite electrode in diglyme electrolyte during cycling.
Figure 5. (a-l) In situ AFM images of HOPG electrode in 1 mol L−1 diglyme electrolyte during the first discharging cycle from 0.80 to 0.16 V. Height cross-section profiles of cracke (h’) A and (i’) B.
Figure 6. In situ AFM images of HOPG electrode in 1 mol L−1 carbonate electrolyte (a) during the first discharging cycle from 2.54 to 0.09 V and (b) during the first charging cycle from 0.01 to 2.50 V.
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