期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 18, 期 29, 页码 19888-19893出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6cp03379b
关键词
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资金
- JSPS KAKENHI Grant [26790053]
- Grants-in-Aid for Scientific Research [26790053] Funding Source: KAKEN
Spinel lithium titanate (LTO; Li4Ti5O12) is one of the promising materials for negative electrodes of sodium-ion batteries (SIBs). The stable charge-discharge performance of SIB cells using LTO electrodes depends on the reversible Na insertion-extraction mechanism of LTO, where the spinel lattice is expanded with Na insertion, and two phases, Na-inserted LTO (Na-LTO) and Li-inserted LTO (Li-LTO) phases, are generated. These phases are confirmed using X-ray diffraction (XRD), while the mechanism of the two-phase coexistence with different lattice volumes is yet unclear. Here, we investigate the detailed morphology of the coexisting Na-LTO and Li-LTO phases using in situ XRD measurements and high-resolution transmission electron microscopy (TEM) observation. Na-LTO (a = 8.74 angstrom) and Li-LTO (a = 8.36 angstrom) phases are confirmed in both the electrochemically formed Na-inserted LTO electrode and the single-crystalline LTO thin specimen. We observed that the Na-LTO/Li-LTO interface is parallel to the (001) plane, and contains an inevitable lattice mismatch along the interface, while the expansion of the Na-LTO phase can be partially relaxed normal to the interface. We observed that the Na-LTO/ Li-LTO interface has interface layers of lattice disordering with a 1-2 nm width, relaxing the lattice mismatch, as opposed to results from the previous scanning TEM observation. How the different lattice volumes at the two-phase interface are relaxed should be the key issue in investigation of the mechanism of Na insertion and extraction in LTO electrodes.
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