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Research Article | Open Access

Enhanced ionic conductivity of Ce-doped Na₃Zr₂Si₂PO₁₂ electrolyte for achieving superior performance of solid-state sodium batteries

Jiahui Liu, Zhaoyue Xia, Youli Chen, Daiwen Tao, Qilong Zhang()

School of Materials Science and Engineering, State Key Lab of Silicon and Advanced Semiconductor Materials, Zhejiang University, Hangzhou 310058, China

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Abstract

Solid-state sodium batteries (SSSBs) are gaining significant attention for their potential in electrochemical energy storage. However, the development of SSSBs is hindered by the low ionic conductivity of sodium-ion solid electrolytes (SSEs). Herein, Ce with a relatively large ionic radius is employed to replace Zr in Na₃Zr₂Si₂PO₁₂ (NZSP), aiming to increase the ionic conductivity of the SSEs. Through structural analysis and theoretical calculations, it is inferred that Ce doping is favorable for stabilizing phases with higher ionic conductivity, increasing the Na⁺ concentration via the substitution of Zr⁴⁺ with Ce³⁺, and facilitating the generation of a densified microscopic morphology. The Ce-doped NZSP achieves a high room-temperature conductivity of 2.08 mS·cm⁻¹ and good interfacial compatibility with Na metal. Furthermore, the assembled Na₃V₂(PO₄)₃ cell based on Ce-doped NZSP maintains a capacity of 111.18 mAh·g⁻¹ at 0.5 C after 200 cycles, with a high retention of 98.06%.

Keywords

solid electrolyte Na₃Zr₂Si₂PO₁₂ Ce doping ionic conductivity solid-state battery

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Journal of Advanced Ceramics

Volume 14 Issue 2,
February 2025

Article number: 9221023

DOI: 10.26599/JAC.2024.9221023

Cite this article:

Liu J, Xia Z, Chen Y, et al. Enhanced ionic conductivity of Ce-doped Na₃Zr₂Si₂PO₁₂ electrolyte for achieving superior performance of solid-state sodium batteries. Journal of Advanced Ceramics, 2025, 14(2): 9221023. https://doi.org/10.26599/JAC.2024.9221023

Fig. 1(a) XRD results of NZSP-xCe (x = 0–0.25). (b) Amplified diffraction peaks at 18.5°–20.5°, 27°–28.5°, and 33.5°–35°. (c) Relative phase contents of NZSP-xCe. Rietveld refinement results of (d) NZSP and (e) NZSP-0.2Ce. (f) DSC curves of NZSP-xCe (x = 0–0.25).
Fig. 2XPS scanning spectra of NZSP and NZSP-0.2Ce: (a) Zr 3d, (b) P 2p, and (c) Si 2p; (d) Ce 3d scanning spectra of raw materials and NZSP-0.2Ce. (e) Schematic illustration of rhombohedral structure, including a polyhedral view of T1 and T2 bottlenecks from Na1 to Na2 in NZSP and NZSP-0.2Ce.
Fig. 3SEM images of NZSP-xCe samples: (a) x = 0, (b) x = 0.1, (c) x = 0.15, (d) x = 0.20, and (e) x = 0.25. (f) EDS maps of Na, Zr, Si, P, and Ce in NZSP-0.2Ce pellet. Loading–unloading curves of electrolytes: (g) NZSP and (h) NZSP-0.2Ce. (i) Young’s modulus and hardness of NZSP and NZSP-0.2Ce.
Fig. 4(a) Impedance plots of NZSP-xCe at room temperature. (b) Arrhenius plot of NZSP-xCe with fitted curves. (c) Polarization current‒time curves of NZSP-xCe electrolytes with a constant voltage of 0.1 V (x = 0–0.25). (d) Cyclic voltammetry curves of stainless steel/NZSP-0.2Ce/Na.
Fig. 5(a) Contact angle test of molten metallic Na on NZSP and NZSP-0.2Ce surfaces. (b) Impedance comparison measured for symmetrical Na/NZSP/Na and Na/NZSP-0.2Ce/Na cells. Nyquist plots showing impedance evolution of (c) Na/NZSP/Na cell and (d) Na/NZSP-0.2Ce/Na cell after assembly. (e) Voltage response of symmetric Na/NZSP/Na and Na/NZSP-0.2Ce/Na cells at 0.1 mA·cm⁻². DRT calculated from EIS measurements of (f) Na/NZSP/Na and (g) Na/NZSP-0.2Ce/Na on different days.
Fig. 6(a) Cyclic voltammetry scans of NVP/NZSP-0.2Ce/Na cell obtained at 0.1 mV·s⁻¹. (b) Impedance curves. (c) Rate performance of NVP/NZSP/Na and NVP/NZSP-0.2Ce/Na cells. (d) Charge‒discharge curves of NVP/NZSP/Na and NVP/NZSP-0.2Ce/Na cells at the third cycle at a current rate of 0.2 C. (e) Cycling performance at 0.2 C. (f) Cycling performance at 0.5 C for NVP/NZSP-0.2Ce/Na.

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Table 1Dimensions of T1 and T2 triangular bottlenecks for NZSP and NZSP-0.2Ce

R3c	Na(1)–Na(2) T1 (Å²)	Na(1)–Na(2) T2 (Å²)
X = 0	5.577	5.715
X = 0.20	6.506	6.648

Table 2Bulk resistance (R_b), grain boundary resistance (R_gb), bulk conductivity (σ_b), specific grain boundary conductivity (σ_gb), total resistance (R_t), and σ_total of NZSP-xCe samples (x = 0–0.25)

Composition	R_b (Ω)	R_gb (Ω)	σ_b (mS·cm⁻¹)	σ_gb (mS·cm⁻¹)	R_total (Ω)	σ_total (mS·cm⁻¹)
X = 0	70.65	283.60	1.65	0.41	354.25	0.33
X = 0.10	54.43	61.80	2.22	1.95	116.23	1.04
X = 0.15	52.18	33.04	2.24	3.53	85.22	1.41
X = 0.20	46.09	11.92	2.61	10.11	58.01	2.08
X = 0.25	56.27	24.32	2.07	4.80	80.59	1.49

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