Preparation of polypyrrole coated with conductive carbon black/indium oxide composite and its application in lead-acid batteries
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摘要: 为了改善铅酸电池负极不可逆硫酸盐化及析氢问题，通过原位化学聚合的方法制备导电炭黑/氧化铟表面包覆聚吡咯[PPy@(C/In2O3)]复合材料，采用SEM、FTIR、BET和XRD等表征手段分别对复合材料的微观形貌和结构进行分析；通过循环伏安法(CV)和线性扫描法(LSV)测试了复合材料的电化学性能。最后，将PPy@(C/In2O3)复合材料添加到铅酸电池负极活性材料中，探究PPy@(C/In2O3)对铅酸电池高倍率部分荷电状态(HRPSoC)循环寿命及放电容量的影响。结果表明：PPy@(C/In2O3)保留了导电炭黑的基本结构特征，具有较大比表面积；同时具有较高析氢过电位及较大比容量。当将PPy@(C/In2O3)复合材料添加到铅酸电池负极活性材料中，不仅可以降低负极板内阻抑制电池的负极硫酸盐化问题，而且可以减弱电池负极析氢问题，在提高铅酸电池放电容量同时，显著提高了铅酸电池高倍率部分荷电状态循环寿命。最终，含有PPy@(C/In2O3)的负极板的铅酸电池显示出了优异的HRPSoC循环寿命，较空白组电池循环寿命提高了1.78倍。
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关键词:
- 聚吡咯包覆导电炭黑/氧化铟复合材料 /
- 硫酸盐化 /
- 析氢 /
- 高倍率部分荷电状态 /
- 铅酸电池
Abstract: In order to improve the irreversible sulfation and hydrogen evolution of the negative electrode of lead-acid batteries, in this study, the olypyrrole coated with conductive carbon black/indium oxide composite [PPy@(C/In2O3)] were prepared by in-situ oxidation polymerization on C/In2O3. The composite materials were characterized by SEM, FTIR, BET and XRD. The electrochemical performance of the composites was analyzed by CV and LSV. Finally, the PPy@(C/In2O3) composite materials were added in the negative active material of lead-acid batteries. The effect of composite materials on the high-rate partial-state-of-charge (HRPSoC) performance of lead-acid batteries was investigated. The results show that the PPy@(C/In2O3) retain the structural feature of C, and have larger specific surface area than PPy, and have higher hydrogen evolution over-potential and capacitance than C. When PPy@(C/In2O3) composite materials were added to the negative active material of the lead-acid batteries, it can not only reduce the internal resistance of the negative plate and inhibit the negative sulfation problem of the batteries, but also reduce the hydrogen evolution problem of the negative electrode of the batteries. At the same time, the discharge capacity significantly improves the cycle life of the lead-acid batteries under the HRPSoC operation. Finally, the lead-acid batteries containing the negative plate of PPy@(C/In2O3) show excellent HRPSoC cycle life which increased by 1.78 times compared with the cycle life of the blank battery. -
图 2 (a) 铅酸电池极板及超细玻璃纤维(AGM)隔膜；(b) 电池封装；(c) 待测电池
Figure 2. (a) Lead-acid battery plates and absorbent glass mat (AGM) separator; (b) Battery encapsulation; (c) Test battery
图 3 铅酸电池的高倍率部分荷电状态循环寿命性能测试程序
Figure 3. High-rate partial state-of-charge cycle life performance test program for lead-acid batteries
Ich—Constant current charging current; Id—Constant current discharge current; SoC—State-of-charge
图 4 C (a)、PPy (b) 及PPy@(C/In2O3) (c) 的SEM图像；PPy@(C/In2O3)的EDS映射分布： C元素 (d) 和In元素 (e)
Figure 4. SEM images of C (a), PPy (b) and PPy@(C/In2O3) (c); EDS mapping of the obtained PPy@(C/In2O3): C (d) and In (e)
图 5 PPy@(C/In2O3)、PPy和C的氮气吸附/脱附等温曲线
Figure 5. Nitrogen adsorption/desorption isothermal curves of PPy@(C/In2O3), PPy and C
图 6 (a) PPy@(C/In2O3)、PPy和C的FTIR图谱；(b) PPy@(C/In2O3)、PPy、C及In2O3的XRD图谱
Figure 6. (a) FTIR spectra of PPy@(C/In2O3), PPy and C; (b) XRD patterns of PPy@(C/In2O3), PPy, C and In2O3
图 7 10 mV/s扫速下−0.8~0.0 V电压范围内EC、EPPy@(C/In2O3)及EPPy的CV曲线
Figure 7. CV curves of EC, EPPy@(C/In2O3) and EPPy in the range of −0.8-0.0 V at a scanning rate of 10 mV/s
EPPy@(C/In2O3), EPPy and EC—Working electrode prepared by PPy@(C/In2O3), PPy and C additive
图 8 5 mV/s扫速下−1.6~−1.1 V电压范围内EC、EPPy@(C/In2O3)及EPPy的线性扫描伏安(LSV)曲线
Figure 8. Linear sweep voltammetry (LSV) curves of EC, EPPy@(C/In2O3) and EPPy from −1.6-−1.1 V at a scanning rate of 5 mV/s
图 9 分别添加C (a)、PPy (b) 及PPy@(C/In2O3) (c) 负极板活性物质微观结构
Figure 9. Microstructures of negative plate active material adding C (a), PPy (b) and PPy@(C/In2O3) (c), respectively
图 10
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $ 、LPPy及LC的Nyquist图Figure 10. Nyquist plots of test batteries of
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $ , LPPy and LC${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $, LPPy and LC—Lead-acid battery prepared by PPy@(C/In2O3), PPy and C additive
图 11
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $ 、LPPy及LC在0.1 A·s倍率下的放电容量曲线Figure 11. Discharge capacity curves of
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $ , LPPy and LC at 0.1 A·s
图 12
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $ 、LPPy及LC充放电电压在1 A·s条件下随高倍率部分荷电状态(HRPSoC)循环寿命的变化Figure 12. Change of end-of-charge/discharge voltage as a function of the high-rate partial-state-of-charge (HRPSoC) cycle life for
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $ , LPPy and LC at 1 A·s
图 13 LC (a)、LPPy (b) 及
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ (c) HRPSoC循环测试结束后负极板的SEM图像Figure 13. SEM images of negative plates after the HRPSoC cycle of LC (a), LPPy (b) and
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $ (c)
图 14
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $ 、LPPy及LC HRPSoC循环测试结束后负极板的XRD图谱Figure 14. XRD patterns of negative plates of
${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}} $ , LPPy and LC after the HRPSoC cycle -
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