聚吡咯包覆导电炭黑/氧化铟复合材料的制备及其在铅酸电池中的应用

刘飞; 陈远强; 刘永川; 陈素晶; 张易宁

doi:10.13801/j.cnki.fhclxb.20211231.001

聚吡咯包覆导电炭黑/氧化铟复合材料的制备及其在铅酸电池中的应用

刘飞^{1, 2,},
陈远强¹,
刘永川¹,
陈素晶¹,
张易宁^{1, 2, ,}

1.
中国科学院福建物质结构研究所　光电材料化学与物理院重点实验室，福州 350002
2.
中国科学院大学，北京 100049

基金项目: 中科院STS区域重点项目(KFJ-STS-QYZD-2021-09-001)；福建省STS计划配套项目(2021T3036；2020T3004；2019T3017；2020T3030)；福建省引导性项目(2020H0040)；泉州市科技项目(2020G17)

详细信息

通讯作者:
张易宁，博士，研究员，博士生导师，研究方向为储能材料与器件　E-mail: ynzhang@fjirsm.ac.cn

中图分类号: TB3333；TQ152
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出版历程
- 收稿日期: 2021-10-07
- 修回日期: 2021-11-25
- 录用日期: 2021-12-03
- 网络出版日期: 2022-01-03
- 刊出日期: 2022-11-30

Preparation of polypyrrole coated with conductive carbon black/indium oxide composite and its application in lead-acid batteries

1.
Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

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摘要

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。
- 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.
- polypyrrole coated with conductive carbon black/indium oxide composite /
- sulfation /
- hydrogen evolution /
- high-rate partial-state-of-charge /
- lead-acid battery

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碳化钨颗粒增强钢铁基(WC_P/Fe)复合材料因兼顾金属基体的良好韧性与陶瓷增强颗粒的高强度、高硬度、高模量而广泛应用于机械制造、能源开发、交通运输等领域，但基体与增强颗粒间热物理性能差异过大使复合材料在激冷激热环境下服役时产生热应力，诱发界面处裂纹的萌生与扩展^[1-4]。而将WC充分溶解，W在熔体中均匀扩散形成合金化复合层能有效解决该问题，故研究WC/Fe复合材料中W扩散均匀性十分必要^[5-7]。

蜂窝结构因形状连续、比强度高等特性而对复合材料的综合性能产生重要影响^[8-10]。Magotteaux公司发明X-win蜂窝结构ZTA_P/Fe复合材料技术，制造的磨辊使用寿命提高两倍以上^[11]；WU等^[12]从模拟与实验角度出发，揭示预制体孔径与孔距作为蜂窝结构重要参数对复合材料力学性能的影响；SONG等^[13]成功制备蜂窝结构还原氧化石墨烯增强环氧树脂(rGH/EP)复合材料，电磁屏蔽效能与导电性明显提升。但对蜂窝预制体结构与元素扩散均匀性间的关联机制仍研究较少。

本文采用真空消失模铸渗(V-EPC)工艺制备WC/Fe复合材料^[14-15]，选取孔径孔距比相同孔径不同的蜂窝预制体，并将W质量分数最高与最低的预制体原孔壁与原孔心处W质量分数作为W扩散均匀性的判断条件^[16-17]。表征复合层的显微组织、物相组成、元素分布，并检测预制体原孔壁与原孔心处W质量分数、硬度及复合层耐磨性，揭示其孔径对W质量分数分布的影响规律。通过求解非稳态扩散方程得解析解，对预制体孔内熔体凝固时的热物理场进行有限元模拟，并通过二次开发程序对其原孔内W质量分数分布进行数值模拟，揭示其孔径对W扩散均匀性的影响机制；提出W扩散均匀性与复合层耐磨性间的关联机制，为工程应用提供理论依据。

1. 实验材料与方法

为避免铸渗时W粉因粒径过小而大量烧损，选取铸造WC颗粒(WC/W₂C_P)为合金化提供W；表1为WC/Fe复合材料中预制体的成分组成，配置预制体粉末300 g，与5wt%水玻璃粘结剂均匀混合；表2为WC/Fe复合材料中预制体的结构参数，填充到预制体孔径孔距比相同孔径不同的蜂窝模具内，其轮廓为50 mm×100 mm×6 mm；采用CO₂硬化与微波烧结方法，得最终预制体。

表3为WC/Fe复合材料中基体的成分组成。配置基体并采用中频感应炉熔炼20 kg。图1为WC/Fe复合材料的制备过程，采用V-EPC工艺成型，浇注温度为1 500℃，型腔负压为0.05 MPa。

表 1 WC/Fe复合材料中预制体的成分

Table 1. Composition of preform in WC/Fe composites

Composition	Mass fraction/wt%	Size/μm
WC	40	150-200
Ni₆₀	30	60-90
FeCr₅₅C_6.0	30	150-200

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表 2 WC/Fe复合材料中预制体的结构参数

Table 2. Structure parameters of preform in WC/Fe composites

Diameter R/mm	Distance d/mm	Number n
3	6	63
6	12	16
9	18	7

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表 3 WC/Fe复合材料中基体的成分

Table 3. Composition of matrix in WC/Fe composites

Composition	C	Cr	Mn	Si	Fe
Mass fraction/wt%	1.2-1.3	18.0-20.0	0.4-0.6	1.0-1.2	Balance

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图 1 WC/Fe复合材料的制备过程

Figure 1. Preparation process of WC/Fe composites ((a)V-EPC (Vacuum-expendable pattern casting); (b)Honeycomb preform; (c)Transformation between preform and layer)

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采用尼康MA200型OM表征复合层显微组织，并统计预制体原孔壁与原孔心处平均晶粒尺寸分布。采用岛津7000S/L型XRD、牛津仪器Ultim Extreme型EDS面扫描表征复合层物相组成、元素分布。采用牛津仪器Ultim Extreme型EDS点扫描、上海光学仪器厂HX1000型显微硬度计表征复合层预制体原孔壁与原孔心处元素质量分数、硬度。采用广州试验仪器厂MS-5E型三体磨料磨损机表征复合层耐磨性，载荷为2 kg、转速为40 r/min、预磨时间为30 min、磨粒粒径为200~550 μm，并采用蔡司EVO18型SEM表征预制体原孔心处磨损形貌。采用COMSOL Multiphysics 5.4有限元模拟预制体孔内熔体凝固时的热物理场。采用MATLAB R2015b通过二次开发程序数值模拟预制体原孔内W质量分数分布。

2. 结果与分析

2.1 WC/Fe复合材料复合层的显微组织与元素分布

图2为不同预制体孔径下WC/Fe复合材料复合层的显微组织。熔体填充预制体孔洞，WC高温下分解，W由其孔壁扩散至孔心处，形成复合层。图3为不同预制体孔径下WC/Fe复合材料复合层原孔内的平均晶粒尺寸分布，随预制体孔径增加，其原孔壁处晶粒尺寸基本不变，而在其原孔心处先减小后增大。

图 3 不同预制体孔径下WC/Fe复合材料复合层原孔内的平均晶粒尺寸分布

Figure 3. Average grain size distribution into initial hole of layer in WC/Fe composites with different hole diameters of preform

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图4为不同预制体孔径下WC/Fe复合材料复合层原孔内的平均晶粒尺寸分布。表明复合层中均形成W₂C、WC、Ni₁₇W₃、Fe₃W₃C、(Fe,Cr)₃C。根据W-C相图，WC/W₂C_P中WC分解形成W₂C、C，而C扩散到熔体中使(Fe,Cr)₃C增多；根据Fe-W-C相图，熔体与W₂C发生包晶反应形成Fe₃W₃C；WC、Ni₆₀分解使W、Ni质量分数增加，形成镍钨化合物Ni₁₇W₃。

图 2 不同预制体孔径下WC/Fe复合材料复合层的显微组织

Figure 2. Microstructure of layer in WC/Fe composites with different hole diameters of preform

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图 4 不同预制体孔径下WC/Fe复合材料复合层的物相组成

Figure 4. Phase composition of layer in WC/Fe composites with different hole diameters of preform

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根据Fe-Cr-C相图^[18-19]，推测熔体(Cr：18.0wt%~20.0wt%，C：1.2wt%~1.3wt%)为典型亚共晶成分合金(Cr：11.0wt%~30.0wt%，C：<2.8wt%)，凝固时先析出一次奥氏体枝晶，待温度降至共晶点发生共晶转变形成共晶奥氏体与二次碳化物的混合共晶组织，而复合层为网状形貌的M₃C型碳化物^[7,20]。图5为不同预制体孔径下WC/Fe复合材料复合层的元素分布。Cr分布在共晶奥氏体与二次碳化物中，W、Ni弥散分布在一次奥氏体枝晶内。

图 5 不同预制体孔径下WC/Fe复合材料复合层的元素分布

Figure 5. Element distribution of layer in WC/Fe composites with different hole diameters of preform

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图6为不同预制体孔径下WC/Fe复合材料复合层原孔内的W质量分数分布。其原孔壁处W质量分数较高，而在其原孔心处较低。与晶粒尺寸的变化相反，随预制体孔径增加，其原孔壁处W质量分数基本不变，而在其原孔心处先增大后减小。为进一步表征W扩散均匀性，通过计算得不同预制体孔径下W扩散均匀性分别为84.1%、88.7%、86.9%，表明W扩散均匀性随其孔径增加而先增大后减小，W扩散均匀性的表达式为

图 6 不同预制体孔径下WC/Fe复合材料复合层原孔内的W质量分数分布

Figure 6. W mass fraction distribution into initial hole of layer in WC/Fe composites with different hole diameters of preform

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$\delta = 1 - \frac{{2\sqrt 3 }}{{{\rm{{\text{π}} }}{R^2}}}\frac{{C\left( {0,{t_{\max }}} \right) - C\left( {{R / 2},{t_{\max }}} \right)}}{{C\left( {0,0} \right)}}$

(1)

式中：δ为W扩散均匀性；C(0,t_max)、C(R/2,t_max)分别为预制体原孔壁、原孔心处W质量分数。

2.2 WC/Fe复合材料复合层的硬度分布与耐磨性

图7为不同预制体孔径下WC/Fe复合材料复合层原孔内的硬度分布。其原孔壁处硬度较高，而在其原孔心处较低。与W质量分数的变化相同，随预制体孔径增加，其原孔壁处硬度基本不变，而在其原孔心处先增大后减小。图8为不同预制体孔径下WC/Fe复合材料复合层原孔心处的磨损形貌。R=3 mm时其原孔心处犁沟最明显，R=9 mm时次之，R=6 mm时最不明显。图9为不同预制体孔径下WC/Fe复合材料复合层的磨损量。表明复合层耐磨性随其孔径增加而先增大后减小。

图 7 不同预制体孔径下WC/Fe复合材料复合层原孔内的硬度分布

Figure 7. Hardness distribution into initial hole of layer in WC/Fe composites with different hole diameters of preform

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图 8 不同预制体孔径下WC/Fe复合材料复合层原孔心处的磨损形貌

Figure 8. Wear morphologies at initial hole center of layer in WC/Fe composites with different hole diameters of preform

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图 9 不同预制体孔径下WC/Fe复合材料复合层的磨损量

Figure 9. Wear amount of layer in WC/Fe composites with different hole diameters of preform

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2.3 WC/Fe复合材料复合层的W扩散均匀性机制

为进一步探究影响W扩散均匀性的因素，对预制体原孔内W质量分数分布进行数值模拟。将W扩散区看作受固液界面移动驱动的半无限大物体，且扩散时间近似为预制体孔内熔体凝固时间^[21-22]。下式为W扩散区边界条件的表达式：

$\left\{ \begin{array}{l} C\left( {x,t} \right) = {C_{{\rm{SL}}}},x = x\left( t \right) \\ C\left( {x,t} \right) = {C_{{\rm{LS}}}},x < x\left( t \right) \end{array}\right.$

(2)

式中，C_SL、C_LS分别为固液界面固、液相侧W质量分数。根据Arrhenius方程，W质量分数分布为

$\left\{ \begin{array}{l} C\left( {x,t} \right) = \dfrac{{{C_{{\rm{SL}}}}}}{{{\rm{erf}}\left( k \right) - 1}}\left( {{\rm{erf}}\left( {\dfrac{x}{{2\sqrt {Dt} }}} \right) + 1} \right) \\ D = {D_0}{\rm{exp}}\left( { - \dfrac{{{E_{\rm{A}}}}}{{{k_{\rm{B}}}T}}} \right) \end{array} \right.$

(3)

式中：x为W扩散距离；t为W扩散时间；T为W扩散温度；D为W扩散系数；k为常数；E_A为W元素扩散激活能；k_B为玻尔兹曼常数^[22]。W扩散总时间为

${t_{{\rm{max}}}} = \frac{{{R^2}}}{{64{k^2}D}}$

(4)

通过解析解得W扩散过程同时受温度与固液界面移动影响。故先采用有限元模拟软件COMSOL Multiphysics 5.4模拟预制体孔内熔体凝固时的温度场与相场，表4为预制体孔内熔体凝固时热物理场模拟的参数设置。图10为预制体孔内熔体凝固时热物理场的有限元模拟。发现固液界面明显存在，且其左侧温度较高，熔体为液相，而其右侧温度较低，熔体为固相，即其孔壁处熔体先凝固，且固液界面移动驱动W扩散。此外，随预制体孔径增加，其孔内熔体高温区增多，使其平均温度增高，W扩散系数受W扩散温度影响，扩散温度越高扩散系数越大，其原孔内W质量分数分布曲线斜率绝对值越大；图11为不同预制体孔径下WC/Fe复合材料复合层原孔内W质量分数分布的数值模拟。再将该有限元模拟结果代入数学分析软件MATLAB R2015b的二次开发程序中进行数值模拟，最终得其原孔内W质量分数分布曲线，发现其原孔内W质量分数为W扩散距离的单调递减函数。因预制体孔径孔距比相同且W扩散区为受固液界面移动驱动的半无限大物体，故设置W初始质量分数相同。随预制体孔径增加，其原孔内W质量分数分布曲线斜率绝对值增大，故R=3 mm时其原孔心处W质量分数较R=6 mm时低，但R=6 mm时W扩散距离较R=9 mm时短，故其原孔心处W质量分数R=6 mm时最高，R=9 mm时次之，R=3 mm时最低，即该数值模拟与实验结果相符。

表 4 预制体孔内熔体凝固时热物理场模拟的参数设置

Table 4. Parameters setting of thermal physical field simulation when internal matrix of preform solidifies

Phase	Density/(kg·m⁻³)	Thermal conductivity/(W·m⁻¹·K⁻¹)	Heat capacity/(J·kg⁻¹·K⁻¹)
Fe(s)	8 500	200	400
Fe(l)	7 800	450	550
Inlet temperature/°C	Melting temperature/°C	Temperature transition half width/K	Surface emissivity
1 500	1 100	50	0.8
Specific heat/(J·kg⁻¹·K⁻¹)		Solidification latent heat/(kJ·kg⁻¹)	Heat transfer coefficient/(W·m⁻²·K⁻¹)
60		200	800

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图 10 不同预制体孔径下孔内熔体凝固时热物理场的有限元模拟

Figure 10. Finite element simulation of thermal physical field when internal matrix solidifies with different hole diameters of preform

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图 11 不同预制体孔径下WC/Fe复合材料复合层原孔内W质量分数分布的数值模拟

Figure 11. Numerical simulation of W mass fraction distribution in initial hole in WC/Fe composites with different hole diameters of preform

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预制体孔径较大时，其孔内熔体较多，温度也较高。一方面扩散时间较长，有利于W扩散；另一方面扩散距离较长，不利于W扩散均匀，使预制体原孔心处W质量分数降低。同理，预制体孔径较小时，扩散距离虽短，但扩散时间较短，使W扩散不充分，其原孔心处W质量分数较低，故W扩散均匀性也较低；故预制体孔径适中时，因兼顾扩散距离与扩散时间而使W扩散均匀性最高。综上所述，W扩散过程同时受扩散距离与扩散时间的影响。

2.4 WC/Fe复合材料复合层的耐磨性与W扩散均匀性间关联机制

亚共晶Fe-Cr-C系合金中含大量低硬度、高韧性的一次奥氏体，硬度、耐磨性较低，而W弥散分布在一次奥氏体枝晶内形成M₆C型碳化物Fe₃W₃C，细化晶粒使复合层冲击韧性未明显降低，且引入硬质相使其硬度明显提高^[20,23]，一定范围内也提高其耐磨性^[24]。W扩散均匀性越高，预制体原孔心处W质量分数越高，形成硬质相越多，硬度也越高，最终提高复合层耐磨性。

3. 结论

采用真空消失模铸渗(V-EPC)工艺制备WC/Fe复合材料，选取预制体孔径孔距比相同孔径不同的蜂窝预制体，并将其原孔壁与原孔心处W质量分数作为W扩散均匀性的判断条件，得如下结论。

(1) WC高温下分解，W由预制体孔壁至孔心处扩散，形成弥散分布的硬质相Fe₃W₃C。

(2)预制体原孔壁与原孔心处W质量分数与硬度相差随孔径增加而先增大后减小，复合层耐磨性的变化亦然。

(3) W扩散均匀性同时受扩散距离与扩散时间的影响。预制体孔径较小时，扩散距离虽短，但扩散时间较短，不利于W扩散；预制体孔径较大时，扩散时间虽长，但扩散距离增长，仍不利于W扩散；预制体孔径适中时，因兼顾扩散距离与扩散时间，利于W扩散。

(4)耐磨性与W扩散均匀性间存在关联，W扩散均匀性越高，预制体原孔心处W质量分数越高，形成硬质相越多，硬度也越高，一定范围内复合层耐磨性也越高。

图 1 铅酸电池负极板的制备流程图

Figure 1. Preparation process of lead-acid battery negative plate

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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

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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

I_ch—Constant current charging current; I_d—Constant current discharge current; SoC—State-of-charge

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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)

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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

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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

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图 7 10 mV/s扫速下−0.8~0.0 V电压范围内E_C、E_{PPy@(C/In₂O₃)}及E_PPy的CV曲线

Figure 7. CV curves of E_C, E_{PPy@(C/In₂O₃)} and E_PPy in the range of −0.8-0.0 V at a scanning rate of 10 mV/s

E_{PPy@(C/In₂O₃)}, E_PPy and E_C—Working electrode prepared by PPy@(C/In₂O₃), PPy and C additive

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图 8 5 mV/s扫速下−1.6~−1.1 V电压范围内E_C、E_{PPy@(C/In₂O₃)}及E_PPy的线性扫描伏安(LSV)曲线

Figure 8. Linear sweep voltammetry (LSV) curves of E_C, E_{PPy@(C/In₂O₃)} and E_PPy from −1.6-−1.1 V at a scanning rate of 5 mV/s

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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

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图 10 ${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ 、L_PPy及L_C的Nyquist图

Figure 10. Nyquist plots of test batteries of ${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ , L_PPy and L_C

${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ , L_PPy and L_C—Lead-acid battery prepared by PPy@(C/In₂O₃), PPy and C additive

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图 11 ${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ 、L_PPy及L_C在0.1 A·s倍率下的放电容量曲线

Figure 11. Discharge capacity curves of ${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ , L_PPy and L_C at 0.1 A·s

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图 12 ${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ 、L_PPy及L_C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 ${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ , L_PPy and L_C at 1 A·s

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图 13 L_C(a)、L_PPy(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 L_C (a), L_PPy (b) and ${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ (c)

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图 14 ${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ 、L_PPy及L_C HRPSoC循环测试结束后负极板的XRD图谱

Figure 14. XRD patterns of negative plates of ${{\text{L}}_{\text{PPy@(C/I}{{\text{n}}_{\text{2}}}{{\text{O}}_{\text{3}}}\text{)}}}$ , L_PPy and L_C after the HRPSoC cycle

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