Mo-doped Na3V2(PO4)3@C composites for high stable sodium ion battery cathode

doi:10.1007/s11706-018-0414-3

Front. Mater. Sci.

2018, Vol. 12

Issue (1) : 53-63 https://doi.org/10.1007/s11706-018-0414-3

RESEARCH ARTICLE

Mo-doped Na₃V₂(PO₄)₃@C composites for high stable sodium ion battery cathode

Xiaoxiao WANG¹, Wanwan WANG¹, Baichuan ZHU², Fangfang QIAN¹, Zhen FANG¹(

)

¹. College of Chemistry and Materials Science, The Key Laboratory of Functional Molecular Solids (Ministry of Education), Anhui Laboratory of Molecule-Based Materials, Center for Nano Science and Technology, Anhui Normal University, Wuhu 241000, China
². Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei 230026, China

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Abstract

NASICON-type Na₃V₂(PO₄)₃ (NVP) with superior electrochemical performance has attracted enormous attention with the development of sodium ion batteries. The structural aggregation as well as poor conductivity of NVP hinder its application in high rate perforamance cathode with long stablity. In this paper, Na₃V₂₋_xMo_x(PO₄)₃@C was successfully prepared through two steps method, including sol–gel and solid state thermal reduction. The optimal doping amount of Mo was defined by experiment. When x was 0.15, the Na₃V_1.85Mo_0.15(PO₄)₃@C sample has the best cycle performance and rate performance. The discharge capacity of Na₃V_1.85Mo_0.15(PO₄)₃@C could reach 117.26 mA·h·g⁻¹ at 0.1 C. The discharge capacity retention was found to be 94.5% after 600 cycles at 5 C.

Keywords energy storage materials doping electrochemical reactions Na ion battery

Corresponding Author(s): Zhen FANG

Online First Date: 26 February 2018 Issue Date: 07 March 2018

Cite this article:

Xiaoxiao WANG,Wanwan WANG,Baichuan ZHU, et al. Mo-doped Na₃V₂(PO₄)₃@C composites for high stable sodium ion battery cathode[J]. Front. Mater. Sci., 2018, 12(1): 53-63.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-018-0414-3
https://academic.hep.com.cn/foms/EN/Y2018/V12/I1/53

Fig.1 Rietveld refined XRD patterns of Na₃V_1.85Mo_0.15(PO₄)₃.

Fig.2 XPS spectra of (a) Mo 3d, (b) V 2p, (c) C 1s, and (d) P 2p.

Fig.3 EDS spectra of prepared Mo-NVP@C samples and atomic percentage of Mo in as-prepared Mo-NVP@C samples.

Fig.4 SEM images of as-prepared Na₃V₂₋_xMo_x(PO₄)₃@C samples in (a)(b)(c)(d)(e)(f) high magnification and (g)(h)(i)(j)(k)(l) low magnification.

Fig.5 (a) TEM image and (b)(c)(d) HRTEM images of as-prepared Mo-NVP@C sample (x = 0.15).

Fig.6 Raman spectra of as-prepared Mo-Na₃V₂₋_x(PO₄)₃@C samples with the x value of (a) 0, (b) 0.05, (c) 0.10, (d) 0.15, (e) 0.20 and (f) 0.25 (black lines: experimental curves; red lines: fitted curves; green line: deconvoluted curves).

Fig.7 (a) CV curves of as-prepared Mo-NVP@C samples with the potential window range of 2.2–3.8 V and the scan rate at 0.1 mV·s⁻¹. (b) Charge–discharge curves of as-prepared Mo-NVP@C samples at 0.2 C with the potential window range of 2.2–3.8 V.

Fig.8 Long cycle performance at the current rate of (a) 1 C for 200 cycles and (b) 5 C for 600 cycles of as-prepared Mo-NVP@C samples.

Tab.1 Capacity retention of as-prepared Mo-NVP@C samples at 1 and 5 C for 200 and 600 cycles

Fig.9 (a) Rate performance of as-prepared Mo-NVP@C samples between 2.2 and 3.8 V at the current rates of 0.5, 1, 2, 5, 10, 20, 40, 20, 10, 5, 2, 1 and 0.5 C. (b) Nyquist plots of as-prepared Mo-NVP@C samples for fresh cells.

Fig. S1&chsp;?(a) XRD spectra of as-prepared Mo-NVP@C samples. (b) High resolution diffraction peaks of the (113) plane of Mo-NVP@C samples.

Table S1&chsp;?Lattice parameters in the R-3c space group for Mo-NVP@C samples

Fig. S2&chsp;?Crystal structure of NASICON-type NVP.

Fig. S3&chsp;?Equivalent electrical circuit applied to the fitting of the EIS. R_s is the ohmic resistance of the electrolyte and electrode; R_ct is the charge transfer resistance; W_o is the Warburg impedance; CPE represents the double layer capacitance and passivation film capacitance.

Table S2&chsp;Fitting results of Nyquist plots for Mo-NVP@C samples

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