Microstructure and electrochemical properties of 3D flower-like CoS anode materials used for lithium ion batteries synthesized by one-step hydrothermal method
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摘要: 以CoCl2·6H2O和硫脲(CH4N2S)为原料, 采用一步水热法, 通过改变钴硫摩尔比和添加表面活性剂制备出两种不同形貌(3D花状和球状)的硫化钴(CoS)锂离子电池负极材料。结果表明, 当钴硫摩尔比为1:1时, 在180℃下水热反应12 h可得到3D花状CoS负极材料, 其三维立体花状结构由纳米级层片组成; 当钴硫摩尔配比为1:1, 添加十六烷基三甲基溴化铵(CTAB), 在180℃下反应12 h可制得由小颗粒聚结成的球状CoS负极材料。在0.1C电流密度下, 3D花状CoS电池首次放电比容量为752 mAh·g-1, 并且具有良好的倍率性能; 在1C电流密度下, 经过200圈的循环测试后, 3D花状CoS电池仍有较高的放电比容量(185 mAh·g-1), 远高于球状CoS电池(118.6 mAh·g -1), 并且没有衰减的趋势。Abstract: Using CoCl2·6H2O and thiourea (CH4N2S) as the raw materials, the 3D flower-like and spherical cobalt sulfide (CoS) anode materials used for lithium ion batteries were synthesized by one-step hydrothermal method in this paper, through changing the molar ratio of Co to S and adding the surfactant. In the results, when the molar ratio of Co to S is 1:1 and the hydrothermal reaction is carried out at 180 fo℃ r 12 h, the obtained 3D flower-like CoS anode materials are composed of nano-scale layer structures. By adding the cetyl trimethyl ammonium bromide (CTAB) as surfactant, the globular cobalt sulfide anode materials formed by the agglomeration of small particles are obtained by hydrothermal reaction at 180 for 12 h℃ when the molar ratio of Co to S is 1:1. The first discharge capacity of 3D flower-like CoS anode materials is 752 mAh·g-1 at 0.1C, showing the good rate capability, and there is still high discharge capacity (185 mAh·g-1) after 200 cycles at 1C without the tendency of decay, which is much higher than that of the spherical CoS anode materials (118.6 mAh·g-1).
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图 1 花状和球状硫化钴试样X射线衍射图谱
Figure 1. XRD spectra of flower-like and spherical cobalt sulfide samples
图 2 花状和球状硫化钴试样显微形貌：（a）和（b）花状-1:1；（c）和（d）花状-1:2；（e）和（f）球状-1:1；（g）高倍率花状-1:1
Figure 2. SEM images of flower-like and spherical cobalt sulfide samples: (a) and (b) flower-like sample-1:1; (c) and (d) flower-like sample-1:2; (e) and (f) spherical sample-1:1; (g) higher magnification of flower-like sample-1:1
图 3 不同硫化钴样品的N2吸附‒脱附等温线（a）和孔径分布（b）
Figure 3. N2 desorption‒sorption isotherms (a) and pore distribution (b) of different cobalt sulfide samples
图 4 硫化钴电极材料倍率性能图
Figure 4. Specifc discharge capacities at various current rates of cobalt sulfide electrode materials
图 5 CoS负极材料循环伏安曲线：（a）0.5 mV·s‒1，CoS负极材料；（b）0.1~10 mV·s-1扫速，花状-1:1试样
Figure 5. CV curves of CoS electrode materials: (a) CoS electrode materials at 0.5 mV·s‒1; (b) flower-like sample-1:1 at the scan rates ranging from 0.1 to 10 mV·s‒1
图 6 CoS电极材料在0.1C的电流密度下首次充放电的电化学性能图
Figure 6. Electrochemical performance of initial charge–discharge curves at 0.1C of CoS electrode materials
图 7 CoS电极材料的交流阻抗图
Figure 7. Electrochemical impedance spectra of CoS electrode materials
图 8 CoS电极材料在1C的电流密度下从0.05~3.0 V循坏性能曲线
Figure 8. Cycling performance curves of CoS electrode materials at 1C from 0.05 V to 3.0 V
表 1 硫化钴样品的比表面积和孔体积数值
Table 1. Specific surface area and pore volume of cobalt sulfide samples
试样 比表面积/ (m2·g‒1) 孔体积/ (mL·g‒1) 花状-1:1 15.3611 0.0593 花状-1:2 6.2693 0.0364 球状-1:1 4.1639 0.0180 
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表 2 CoS电极材料阻抗参数
Table 2. Impedance parameters of CoS electrode materials
试样 欧姆电阻/ Ω 传荷电阻/ Ω 阻抗总和/ Ω 花状-1:1 1.75 175.12 176.87 球状-1:1 9.17 377.67 386.84 花状-1:2 1.82 242.73 244.55
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