Synthesis of magnesium vanadate-sodium vanadate composite nanowires by cation exchange as electrode materials for lithium ion batteries
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摘要: 为了满足对锂离子电池性能更好和更多样化的要求,研究了用于改善电池性能的电极材料,在众多电极材料中,钒基材料的价态变化丰富和种类繁多等优点使其适用于锂离子电池电极材料。以钒酸钠纳米线阵列为前驱体,采用离子交换法合成了钛箔上的钒酸镁(MgV2O6)-钒酸钠(NaV6O15)复合材料。后续在空气中煅烧,温度分别为300℃和500℃,随着煅烧温度的升高,纳米线的直径变大。对所制备样品的晶体结构、化学成分和微观形貌进行了详细的表征。其中,300℃煅烧制备的钒酸镁-钒酸钠复合材料的电化学储锂性能较好,在电流密度为50 mA·g−1下首次放电容量为1144 mA·h·g−1,经过100次循环后的放电比容量仍有837 mA·h·g−1,表现出良好的循环稳定性,较钒酸钠前驱体的储锂性能有大幅提升,为镁离子合成碱土金属钒酸盐应用于电化学储能领域的研究提供了新思路。Abstract: In order to meet the requirements for better and more diversified performance of lithium-ion batteries, electrode materials for improving battery performance were studied. Among many electrode materials, vanadium-based materials are suitable for lithium-ion battery electrode materials due to their rich valence changes and various types. Magnesium vanadate (MgV2O6)-sodium vanadate (NaV6O15) composites on titanium foil were synthesized by ion exchange method using sodium vanadate nanowar arrays as precursors. After calcination in air, the temperature was 300℃ and 500℃, respectively. With the increase of the calcination temperature, the diameter of the nanowires became larger. The crystal structure, chemical composition and microstructure of the prepared samples were characterized in detail. Among them, the magnesium vanadate and sodium vanadate composite prepared by calcination at 300℃ had better electrochemical lithium storage performance. The first discharge capacity was 1144 mA·h·g−1 at the current density of 50 mA·g−1, and the specific discharge capacity was still 837 mA·h·g−1 after 100 cycles, showing good cycling stability. Compared with sodium vanadate precursor, the lithium storage performance was significantly improved. It provides a new idea for the application of alkaline earth vanadate synthesized by magnesium ions in the field of electrochemical energy storage.
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Key words:
- cation exchange /
- hydrothermal method /
- magnesium vanadate /
- sodium vanadate /
- lithium ion battery
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图 3 原始制备的Na5V12O32 ((a), (b)) 和MgV2O6-NaV6O15复合物纳米线 ((c), (d))、MgV2O6-NaV6O15-300 ((e), (f)) 和MgV2O6-NaV6O15-500 ((g), (h)) 复合材料的SEM图像
Figure 3. SEM images of pristine Na5V12O32 ((a), (b)) and MgV2O6-NaV6O15 nanowires ((c), (d)), MgV2O6-NaV6O15-300 ((e), (f)) and MgV2O6-NaV6O15-500 ((g), (h)) composites
图 5 MgV2O6-NaV6O15-300复合材料的TEM图像 ((a), (b))、EDS (c) 和HRTEM图像 ((d), (e)) 及傅里叶变换图(FFT) ((d1), (d2)) 和反傅里叶变换图(IFFT) ((e1), (e2))
Figure 5. TEM images ((a), (b)), EDS images (c), HRTEM images ((d), (e)) of MgV2O6-NaV6O15-300 composite; Regions reveal the existence of MgV2O6 and V2O5 by fast fourier transform (FFT) ((d1), (d2)) and inverse fast fourier transform (IFFT) ((e1), (e2)) methods, respectively
图 7 电极在0.01~3 V电位范围内的动力学分析:(a) MgV2O6-NaV6O15-300电极前3圈CV曲线(0.1 mV·s−1);(b) 钒酸钠前驱体前3圈CV曲线(扫速: 0.1 mV·s−1); (c) MgV2O6-NaV6O15-300电极不同扫描速率下的CV曲线(0.2~1.0 mV·s−1);(d) MgV2O6-NaV6O15-300电极每个氧化还原峰的lgi和lgv图
i—Peak current; v—Sweep rate
Figure 7. Kinetic analysis electrode within the potential range of 0.01-3 V: (a) CV curves of the first three turns of MgV2O6-NaV6O15-300 electrode (0.1 mV·s−1); (b) CV curves of the first three turns of Na5V12O32 electrode (0.1 mV· s−1); (c) CV curves in different scan rates of MgV2O6-NaV6O15-300 electrode (0.2-1.0 mV·s−1); (c) lgi vs lgv plots at each redox peak of MgV2O6-NaV6O15-300 electrode
图 8 电化学性能:(a) 充放电;(b) 长周期;(c) 速率能力;(d) 电化学阻抗谱(EIS);(e) Na5V12O32和MgV2O6-NaV6O15-300电极Warburg阻抗的线性拟合
Rs—Ohmic resistance of the electrolyte and electrode; Rct—Charge-transfer resistance; Zw—Warburg impedance; Cdl—Double layer capacitor; ω—Angular frequency
Figure 8. Electrochemical performance: (a) Charge-discharge; (b) Long cycle; (c) Rate capability; (d) Electrochemical impedance spectra (EIS); (e) Linear fitting of the Warburg impedance for Na5V12O32 and MgV2O6-NaV6O15-300 electrodes
表 1 不同温度处理的MgV2O6-NaV6O15电极材料
Table 1. MgV2O6-NaV6O15 electrode materials treated at different temperatures
Sample Treated temperature/℃ MgV2O6-NaV6O15-300 300 MgV2O6-NaV6O15-500 500 -
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