Na掺杂Li2-xNaxMnSiO4/C正极材料的微波辅助合成与电化学性能

doi:10.7503/cjcu20180694

摘要/Abstract

摘要：

采用溶胶-凝胶法并辅以微波热处理合成了Na掺杂改性的Li_2-_xNa_xMnSiO₄/C(x=0, 0.05, 0.09, 0.13)复合正极材料. 利用X射线衍射(XRD)、扫描电子显微镜(SEM)、恒电流充放电测试、循环伏安(CV)和交流阻抗(EIS)测试等对材料进行了表征. 结果表明, 经微波辐射后得到的电极材料具有Pmn2₁型空间结构, 其碳层分布均匀, 粒径细小均匀, 约为15~30 nm. 在微波辅助原位碳包覆和Na掺杂共同作用下, 复合材料的电荷转移电阻明显降低, Li⁺扩散速率增大, 展现出优良的电化学性能. 在0.1C倍率下Li_1.91Na_0.09MnSiO₄/C样品首次放电比容量为211 mA∙h/g, 50次循环后仍保持80 mA∙h/g的可逆容量; 0.5C和2.0C倍率下的放电比容量分别为106和53 mA∙h/g, 大电流下的可逆容量明显提高.

关键词: 正极材料, Li₂MnSiO₄, 微波辅助合成, 原位碳包覆, 钠掺杂

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

中图分类号:

O646

TrendMD:

马东玮, 田润赛, 刘振江, 冯源源, 丁泓宇, 冯季军. Na掺杂Li_2-_xNa_xMnSiO₄/C正极材料的微波辅助合成与电化学性能. 高等学校化学学报, 2019, 40(6): 1280.

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^†. Chem. J. Chinese Universities, 2019, 40(6): 1280.

图/表 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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Na掺杂Li_2-_xNa_xMnSiO₄/C正极材料的微波辅助合成与电化学性能

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

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