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Average and local structure analysis of Na/Li ion-exchanged Lix(Mn,Ni,Ti)O2 using synchrotron X-ray and neutron sources

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Abstract

Mn-rich layered Lix(Mn,Ni,Ti)O2 was synthesized by Na/Li ion exchange of a P3-Na0.7(Mn,Ni,Ti)O2 precursor. The combined chemical analysis with the ICP-AES, titration technique, and XANES indicated that their electroneutralities were satisfied in some vacancies of the transition metals (TMs). Average structure analyzed using synchrotron X-ray and neutron powder diffraction patterns confirmed a significant amount of vacancies at TM sites and further revealed the existence of a minor tetrahedral Li in the layered rock-salt type Lix(Mn,Ni,Ti)O2. Electrochemical properties of Li0.6Na0.02Mn0.71Ni0.13Ti0.12□0.04O2 exhibited high first discharge capacity of ca. 250 mAh g−1 and high cyclability of exceeding 200 mAh g−1 at the 50th cycle. PDF analysis achieved good fittings for the both total scatterings of synchrotron X-ray and neutron with additional tetrahedral Li and some TM vacancies. Each (Mn,Ni,Co)O6 octahedron in the refined local structure was calculated and expressed as 3D distributions, where the NiO6 and the host MnO6 octahedra were visually characterized as significantly less distorted and highly distorted octahedra, respectively. The co-substitution of Ni2+ ant Ti4+ played the role of stabilizing whole structure and preserving the transition metal vacancy to maintain the high capacity during cycles.

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Acknowledgements

The authors thank Dr. K. Osaka for technical support with the synchrotron XRD experiments at BL19B2, SPring-8 (Proposal Nos. 2016A1509, 2017A1578, and 2017B1807). The authors also thank Dr. T. Honma and Dr. H. Ofuchi for technical support with the XAFS experiments at BL14B2, SPring-8 (Proposal Nos. 2016B1852, 2017A1573, and 2017B1590). Synchrotron X-ray total scattering experiments at the BL04B2 beamline at SPring-8 were performed under Program No. 2015B1280 and we thank Dr. K. Ohara for supporting these experiments. The authors are grateful to Profs. T. Ishigaki and A. Hoshikawa at Ibaraki University for assistance with the neutron diffraction measurements with iMATERIA (BL20; Proposal Nos. 2017PM0006, 2017A0039, and 2016BM0010) at the Materials and Life Science Experimental Faculty of J-PARC. We acknowledge Profs. T. Otomo and K. Ikeda at KEK for their help on the neutron total scattering measurements with NOVA (BL21; Proposal No. 2018A0011) at J-PARC.

Funding

This work was supported by JSPS KAKENHI Grant Number 18K05302.

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Authors and Affiliations

  1. Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda-shi, Chiba, 278-8510, Japan

    Naoya Ishida, Kotaro Kawagoe, Naoto Kitamura & Yasushi Idemoto

  2. National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba-shi, Ibaraki, 305-8565, Japan

    Junji Akimoto

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  1. Naoya Ishida
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  2. Kotaro Kawagoe
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  3. Naoto Kitamura
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  4. Junji Akimoto
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  5. Yasushi Idemoto
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Correspondence to Naoya Ishida.

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Ishida, N., Kawagoe, K., Kitamura, N. et al. Average and local structure analysis of Na/Li ion-exchanged Lix(Mn,Ni,Ti)O2 using synchrotron X-ray and neutron sources. J Solid State Electrochem 25, 1319–1326 (2021). https://doi.org/10.1007/s10008-021-04909-x

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