Effect of activator on lithium storage performance of porous carbon materials prepared from soybean hulls
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摘要: 生物质多孔碳材料因来源广泛、性价比高，被广泛应用在锂离子电池中，而制备过程中使用的活化剂对材料储锂性能影响较大。因此，以大豆壳为碳源，在不同工艺条件下制备多孔碳材料，通过结构表征和电化学性能测试，考察活化剂对多孔碳材料储锂性能的影响。研究表明：(1)当电流密度为185 mA·g−1，电压范围为0~3.0 V时，经CaCl2活化的多孔碳材料(DK-CaCl2)的首次放充电比容量为639.0/269.5 mA·h·g−1，而KOH活化的多孔碳(DK-KOH)的首次放充电比容量为986.7/307.5 mA·h·g−1；(2)大豆壳∶KOH的质量比分别为1∶2、1∶4和1∶8时，得到的多孔碳的首次放充电比容量为544.9/136.8、986.7/307.5和375.1/93.4 mA·h·g−1，200次循环后放电比容量分别为88.8、318.9和94.7 mA·h·g−1。这说明不同活化剂及不同活化比例制备的多孔碳材料储锂性能不同，这是由于材料的比表面积不同，导致了电化学性能的不同。Abstract: Biomass porous carbon materials are widely used in lithium ion batteries due to their wide sources and high cost performance, while activators used in the preparation process have a great influence on the lithium storage performance of materials. Therefore, using soybean shell as carbon source, porous carbon materials were prepared under different technological conditions, and the effect of activator on lithium storage performance of porous carbon materials was investigated through structural characterization and electrochemical performance tests. It may be shown as follows: (1) When the current density is 185 mA·g−1, the initial discharge and charge specific capacity of CaCl2-activated porous carbon (DK-CaCl2) is 639.0/269.5 mA·h·g−1, while that of KOH activated porous carbon (DK-KOH) is 986.7/307.5 mA·h·g−1; (2) When the mass ratios of soybean shell to KOH are 1∶2, 1∶4 and 1∶8, the first specific capacities of the obtained porous carbon are 544.9/136.8, 986.7/307.5 and 375.1/93.4 mA·h·g−1, after 200 cycles, their discharges retain 88.8, 318.9 and 94.7 mA·h·g−1, respectively. This indicates that the lithium storage performance of porous carbon materials prepared with different activators and activation ratios are different, which is due to the different specific surface area of materials, resulting in different electrochemical performance.
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Key words:
- activator /
- lithium ion battery /
- biomass porous carbon /
- CaCl2 /
- KOH
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图 1 以大豆壳为碳源通过水热法和高温碳化法制备多孔碳(DK)材料的流程示意图
Figure 1. Schematic diagram of preparation process of porous carbon (DK) materials by hydrothermal method and high temperature carbonization method using soybean shell as carbon source
图 2 DK-CaCl2和DK-KOH材料的XRD图谱(a)、FTIR 图谱(b)和拉曼图谱(c)
Figure 2. XRD patterns (a), FTIR spectra (b) and Raman spectra (c) of DK-CaCl2 and DK-KOH
ID/IG—Ratio of intensity of disordered carbon peak (D) to graphitized carbon peak (G)
图 3 DK-CaCl2和DK-KOH 材料的 SEM图像 ((a), (b)) 和TEM 图像 ((c), (d))
Figure 3. SEM images ((a), (b)) and TEM images ((c), (d)) of DK-CaCl2 and DK-KOH
图 4 DK-CaCl2和DK-KOH材料的N2吸附脱附曲线(a)和孔径分布曲线(b)
Figure 4. N2 adsorption and desorption curves (a) and pore size distribution curves (b) of DK-CaCl2 and DK-KOH
图 5 (a) 材料的首次充放电性能图；(b) 循环性能图；(c) DK-CaCl2的CV图；(d) DK-KOH的CV图；(e) EIS图；(f) 不同荷电状态下角频率平方根的倒数(ω−1/2)与Z'的关系
Figure 5. (a) Initial charge-discharge performance diagram; (b) Cyclic performance diagram; (c) CV diagram of DK-CaCl2; (d) CV diagram of DK-KOH; (e) EIS of DK-CaCl2 and DK-KOH materials; (f) Relationship between Z' and reciprocal of square root of angular frequency (ω−1/2) under different states of charge
图 6 DK-2KOH、DK-4KOH、DK-8KOH的XRD 图谱(a)和拉曼图谱(b)
Figure 6. XRD pattern (a) and Raman pattern (b) of DK-2KOH, DK-4KOH and DK-8KOH
DK-2KOH, DK-4KOH and DK-8KOH—Mass ratios of 1∶2, 1∶4 and 1∶8 of soybean husk∶KOH
图 7 DK-2KOH、DK-4KOH和DK-8KOH材料的SEM图像 ((a)~(c)) 和TEM图像 ((d)~(f))
Figure 7. SEM images ((a)-(c)) and TEM images ((d)-(f)) of DK-2KOH, DK-4KOH and DK-8KOH
图 8 (a)材料的首次充放电性能图；(b)循环性能图；(c) DK-2KOH的CV图；(d) DK-4KOH 的CV图；(e) DK-8KOH 的CV图；(f) EIS图；(g)不同荷电状态下角频率的平方根的倒数(ω−1/2)与Z'的关系
Figure 8. (a) Initial charge-discharge performance diagram; (b) Cyclic performance diagram; (c) CV diagram of DK-2KOH; (d) CV diagram of DK-4KOH; (e) CV diagram of DK-8KOH; (f) EIS diagram; (g) Relationship between Z' and reciprocal of square root of angular frequency (ω−1/2) under different states of charge
表 1 DK-CaCl2和 DK-KOH的拟合线性数据
Table 1. Fitting linear data of DK-CaCl2 and DK-KOH
Material Intercept Slope DK-CaCl2 67.37 21.75 DK-KOH 39.31 17.52 
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表 2 DK-2KOH、DK-4KOH和DK-8KOH的拟合线性数据
Table 2. Fitting linear data of DK-2KOH, DK-4KOH and DK-8KOH
Material Intercept Slope DK-2KOH 62.32 45.18 DK-4KOH 40.23 16.14 DK-8KOH 92.57 102.00
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