Characterization of Na2M2TeO6 (M = Ni, Zn) for Oxide-Based All-Solid-State Sodium-Ion Batteries
Authors: Yamamoto Kazuki , Ono Yuki , Inada Ryoji 
Published: July 2022

All-solid-state sodium (Na) ion batteries (SiBs) are promising high-safety and low cost alternatives to current lithium (Li) ion batteries (LiBs), particularly suitable for the application to large-scale electrical energy storage systems. Development of inorganic solid Na-ion conducting materials used for solid electrolyte is most critical issue to realize all-solid-state SiBs. The solid electrolyte materials should have not only high Na-ion conductivity at room temperature but also chemical and electrochemical stabilities against both cathode and anode active materials. Oxide based solid electrolytes have lower conductivity and poorer deformability than sulfide based one, but they have other advantages such as their chemical stability in air and easiness for handling.
Na2M2TeO6 (M = Zn, Mg, Ni, Co, etc.) with a P2-type honeycomb layered structure has been reported as a fast Na-ion conducting oxide [1]. Particularly, Na2Zn2TeO6 (NZTO) is an attractive candidate for a solid electrolyte material because of the high ionic conductivity well above 10-4 S cm-1 at room temperature, wide electrochemical potential window and lower densification temperature than other oxide-based Na-ion conductors such as NASICON and Na-β alumina [2–4]. On the other hand, Na2Ni2TeO6 (NNTO) has been investigated as a cathode active material for SiB operating at 3–4 V vs Na/Na+ [5,6]. Because of the similarity in their crystal structure and constituent elements, NNTO cathode and NZTO as solid electrolyte may be co-sintered without forming undesired secondary phases to fabricate all-solid-state SiBs.
In this work, we investigated firstly the reactivity between NNTO and NZTO powders at annealing temperature between 500 ºC and 800 ºC in air. From XRD measurements, it was found that the reaction between NNTO and NZTO is negligible at annealing temperature below 700 ºC while when annealed at 800 ºC, they forms a solid-solution phase without forming any secondary phases. Based on this result, we fabricated NNTO-NZTO laminate via co-sintering NNTO and NZTO pellets at 700 ºC in air. Thicknesses of NNTO and NZTO layers in the laminate were set to 1 mm.
From impedance measurements, apparent ionic conductivity of the NNTO-NZTO laminate was estimated to be approximately 0.1 mS cm-1 at 27 ºC, which is close to the prediction with taking into account only the conductivity of individually sintered NNTO (= 0.04 mS cm-1) and NZTO (= 0.36 mS cm-1) at 700 ºC. This indicates that the interfacial resistance between NNTO and NZTO layers is not so large. In addition, using the NNTO-NZTO laminate with NNTO layer thickness of 80 µm, electrochemical Na extraction reaction from NNTO layer through NZTO solid electrolyte was demonstrated via galvanostatic testing at room temperature. Obtained results are very fundamental but can be applied to fabricate all-solid-state SiBs with NNTO cathode and NZTO solid electrolyte via simple co-sintering process in future.

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