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A New Intermetallic NiSn5 Phase: Induced Synthesis, Crystal Structure Resolving and Mechanism Investigation Hangjun Ying, Jianming Bai, Shi-Jun Li, Fengxia Xin, Guangjin Wang, Wen Wen, Xufeng Yan, Zhen Meng, and Wei-Qiang Han J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.9b00704 • Publication Date (Web): 03 May 2019 Downloaded from http://pubs.acs.org on May 3, 2019
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suggests the higher diffusion barrier of Ni into the J0 phase than that of Fe and Co.
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In order to further investigate the induction mechanism of Fe3+ in the formation of Ni0.62Sn5, we study the phase evolution of lithiation and delithiation processes using ex situ XRD technique in Shanghai Synchrotron Radiation Facility (SSRF). The different lithiation/delithiation stages are marked using “a-i” in the first voltage-capacity curve (Figure 4b). The corresponding ex situ XRD patterns of the electrode slices at selected lithiation/delithiation stages are displayed in Figure 4a. No obvious change are detected from the open circuit potential (a) to 0.7 V (d), suggesting that this lithiation process may be chiefly attributed to the formation of solid-electrolyte interface (SEI) film and the reduction of amorphous surface oxidation layer.20,30 When the potential shifts to 0.3 V (e), the Ni is crowded out from the NiSn5, and the Sn combines with Li to yield Li-Sn alloys. In contrast, the FeSn5 XRD remains unchanged but slightly shifts when discharged to 0.3 V, demonstrating the FeSn5 goes through a solutionizing process by forming LixMySn5 from 0.7 to 0.3 V (Supporting Information, Figure S9).20 This difference between NiSn5 and FeSn5 implies that the NiSn5 lattice structure is insecure and vulnerable to the insertion of Li+, which is in agreement with the above analysis. In the delithiation process, a weak hump centered at 30.8° may be ascribed to the formation of cubic phase U0 (Figure 4a, f-h).31 It is found that, both FeSn5 and CoSn5 show a complete reversibility during the initial lithiation/delithiation process, the MSn5 (M=Fe, Co) phases resurge when the electrodes are charged to 1.5 V (Supporting Information, Figure S9).20 However, the Li+ insertion/extraction has an irreversible impact on the structure of NiSn5, there are no diffraction peaks corresponding to MSn5 detected at the charging potential of 1.5 V (h). When the potential is further increased to 2.0 V (i), puny peaks centered at about 24.4° and 26.2° are observed, which is more likely to be corresponding to FeSn5 rather than NiSn5. As TEM test result shows, the NiSn5 generates agglomeration after initial cycle. No obvious lattice fringes are observed, suggesting the crystalline structure of NiSn5 is irreversibly destroyed after one charge-discharge cycle (Supporting Information, Figure S10). Although the crystal structure of NiSn5 is destroyed, the Sn and Ni elements are still uniformly distributed in the nanoparticles (Supporting Information, Figure S11). It proves that the Sn and Ni can’t alloy spontaneously to form NiSn5 even though they are uniformly mixed, further confirming the irreversibility of NiSn5. The failure of induction of FeSn5 in the cycled electrode may be due to the poor diffusion kinetic at room temperature. The lithiation/delithiation mechanism investigation result also agrees with the discussion above. In addition, the loosely stacked structure may also account for the inadequate electrochemical activity of Ni-Sn intermetallic.12 Although the cycling stability and the coulombic efficiency of NiSn5 are improved compared with J0 template (Supporting Information, Figure S12), the capacity still undergoes rapid decline in comparison to CoSn5.20 The irreversibility of NiSn5 during lithiation/delithiation is responsible for the relative poor cyclability. In summary, we synthesize a new tetragonal NiSn5 phase by an induction synthesis method. The NiSn5 phase can't be synthesized through the previous polyol method, by which we have prepared the FeSn5 and CoSn5 intermetallic alloys. By
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introducing a minute amount of Fe3+ or Co2+, we successfully induce the alloying reaction to form NiSn5 intermetallic alloy. Structure refinement reveals the existence of stoichiometric Ni atomic vacancies in NiSn5, yielding a defect structure of Ni0.62Sn5. Fe3+/Co2+ plays an important role in the formation of NiSn5, which probably works by forming FeSn5/CoSn5 seed crystal. The existence of FeSn5/CoSn5 may significantly reduces the alloying energy barrier between Ni and Sn to form NiSn5. The lithiation/delithiation investigation reveals the irreversibility of NiSn5 as anode for lithium ion batteries. This work provides a new enlightenment and methodology for the exploitation of metastable alloys which are difficult to obtain through the conventional methods. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website Experiment section, TEM images, XRD patterns, XPS spectrum, ICP analysis result, and cycling performance (Figures 7[ 76G (PDF) AUTHOR INFORMATION Corresponding Authors *E-mail:
[email protected]. Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS This work is financially supported by the research start-up fund from zhejiang university. REFERENCES (1) Wang, X.-L.; Han, W.-Q.; Chen, H.; Bai, J.; Tyson, T. A.; Yu, X.Q.; Wang, X.-J.; Yang, X.-Q. Amorphous hierarchical porous GeOx as high-capacity anodes for Li ion batteries with very long cycling life. J. Am. Chem. Soc. 2011, 133, 20692-20695. (2) Zhang, G.; Yu, L.; Wu, H. B.; Hoster, H. E.; Lou, X. W. D. Formation of ZnMn2O4 ball-in-ball hollow microspheres as a highperformance anode for lithium-Ion batteries. Adv. Mater. 2012, 24, 4609-4613. (3) Wang, Z.; Wang, Z.; Wu, H.; Lou, X. W. D. Mesoporous singlecrystal CoSn(OH)6 hollow structures with multilevel interiors. Sci. Rep. 2013, 3, 1391. (4) Gong, X.; Gu, Y.-Q.; Li, N.; Zhao, H.; Jia, C.-J.; Du, Y. Thermally stable hierarchical nanostructures of ultrathin MoS2 nanosheet-coated CeO2 hollow spheres as catalyst for ammonia decomposition. Inorg. Chem. 2016, 55, 3992-3999. (5) Wu, B.; Liu, D.; Mubeen, S.; Chuong, T. T.; Moskovits, M.; Stucky, G. D. Anisotropic growth of TiO2 onto gold nanorods for plasmonenhanced hydrogen production from water reduction. J. Am. Chem. Soc. 2016, 138, 1114-1117. (6) Sun, Z.; Liao, T.; Sheng, L.; Kou, L.; Kim, J. H.; Dou, S. X. Deliberate design of TiO2 nanostructures towards superior photovoltaic cells. Chem.-Eur. J. 2016, 22, 11357-11364. (7) Murray, C. B.; Kagan, C.; Bawendi, M. Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu. Rev. Mater. Sci. 2000, 30, 545-610. (8) Kodama, D.; Shinoda, K.; Sato, K.; Konno, Y.; Joseyphus, R. J.; Motomiya, K.; Takahashi, H.; Matsumoto, T.; Sato, Y.; Tohji, K.
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