Microwave-assisted Synthesis and Electrochemical Performance of Na-Doped Cathode Materials Li2-xNaxMnSiO4/C†

doi:10.7503/cjcu20180694

Abstract

Abstract:

Li_2-_xNa_xMnSiO₄/C(x=0, 0.05, 0.09, 0.13) composite cathode materials were synthesized with microwave assisted sol-gel method. The crystal structure, morphology and electrochemical performance were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), galvanostatic charge-discharge test, cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS). The results indicate that the as-prepared materials can be well indexed to Pmn2₁ space group. The particles are fine with carbon layer coated uniformity and their size are evenly distributed in the range of 15—30 nm. With the synergistic effects of Na⁺ doping and microwave assisted in-situ carbon coating, the charge transfer resistance is reduced while the diffusion of Li⁺ is enhanced significantly, leading to excellent electrochemical performance. The Li_1.91Na_0.09MnSiO₄/C exhibits an initial discharge capacity as high as 211 mA∙h/g at 0.1C and retained 80 mA∙h/g after 50 cycles. The reversible capacities at high rate currents are also improved obviously, with discharge capacities of 106 mA∙h/g and 53 mA∙h/g at 0.5C and 2.0C separately.

Key words: Cathode material, Li₂MnSiO₄, Microwave assisted synthesis, in-situ carbon coating, Na-doping

CLC Number:

O646

TrendMD:

MA Dongwei,TIAN Runsai,LIU Zhenjiang,FENG Yuanyuan,DING Hongyu,FENG Jijun. Microwave-assisted Synthesis and Electrochemical Performance of Na-Doped Cathode Materials Li_2-_xNa_xMnSiO₄/C^†[J]. Chem. J. Chinese Universities, 2019, 40(6): 1280.

Figures/Tables 10

Scheme 1 Schematic diagram of sample synthesis process

Fig.1 XRD patterns of CN0(a), CN5(b), CN9(c) and CN13(d) samples

Fig.2 Refinement results of CN0(A) and CN9(B) samples Rp: profile factor; Rwp: weighted profile factor.

Table 1 Cell parameters of CN0 and CN9 samples

Sample	a/nm	b/nm	c/nm	V/nm³
CN0	0.63037	0.53828	0.49806	0.16900
CN9	0.63080	0.53825	0.49942	0.16956

Fig.3 SEM images of CN0(A) and CN9(B) samples

Fig.4 TEM(A) and HRTEM(B) images of CN9 sample

Fig.5 SEM image(A), elemental distribution mapping(B—E) and energy spectrum(F) of CN9 sample (B) Na; (C) Mn; (D) Si; (E) O.

Fig.6 Initial charge-discharge curves(A), rate performances(B) and cycle performances(C) of CN0, CN5, CN9, CN13 samples and CV curves of CN0 and CN9 samples scanned at 0.1 mV/s after five cycles(D)

Fig.7 Nyquist plots and equivalent circuit(inset)(A) and relationship between Z’ and ω-1/2 in low-frequency region(B—D) of CN0 and CN9 at room temperature The solid line represents the fitted results. (B) First cycle; (C) after 5 cycles; (D) after 30 cycles.

Table 2 EIS fitting results of CN0 and CN9 samples

Sample	R_e/W			R_ct/W			σ_w/(cm²·s^-1/2)			10¹³ $D L i +$ /(cm²·s^-1)
Sample	First cycle	After 5 cycls	After 30 cycls	First cycle	After 5 cycls	After 30 cycls	First cycle	After 5 cycls	After 30 cycls	First cycle	After 5 cycls	After 30 cycls
CN0	2.12	2.70	13.99	111.60	269.00	489.00	21.17	63.36	124.32	3.37	0.38	0.10
CN9	2.60	4.24	3.07	79.00	165.10	400.20	19.79	25.73	101.39	3.82	2.28	0.15

Table 2 EIS fitting results of CN0 and CN9 samples

Sample	R_e/W			R_ct/W			σ_w/(cm²·s^-1/2)			10¹³ $D L i +$ /(cm²·s^-1)
Sample	First cycle	After 5 cycls	After 30 cycls	First cycle	After 5 cycls	After 30 cycls	First cycle	After 5 cycls	After 30 cycls	First cycle	After 5 cycls	After 30 cycls
CN0	2.12	2.70	13.99	111.60	269.00	489.00	21.17	63.36	124.32	3.37	0.38	0.10
CN9	2.60	4.24	3.07	79.00	165.10	400.20	19.79	25.73	101.39	3.82	2.28	0.15

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Microwave-assisted Synthesis and Electrochemical Performance of Na-Doped Cathode Materials Li_2-_xNa_xMnSiO₄/C^†

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