现代化工

现代化工 ›› 2026, Vol. 46 ›› Issue (4) : 116-121. DOI: 10.16606/j.cnki.issn0253-4320.2026.04.020

科研与开发

石墨烯基聚苯胺复合结构及其增强的电容性能

作者信息 +

Graphene-based polyaniline composite structure and its enhanced capacitive performance

Author information +

文章历史 +

Received		Published
2025-06-27		2026-04-20
Issue Date	Revised Date
2026-04-16	2025-06-27

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摘要

以还原氧化石墨烯(rGO)为载体制备了卷曲状、二维平面膜层和花瓣状3种不同空间结构的聚苯胺(PANI)复合材料,分析其形貌、结构及电容性能。结果表明,水热处理后具有花瓣状空间结构的石墨烯基聚苯胺复合材料(PANI/FS-rGO)在电容性能上表现优异,在25℃时,5 mV/s下比电容为480 F/g,2 A/g下能量密度为160.9 Wh/kg,分别是纯PANI的2.11倍和1.98倍;在2 A/g下循环测试1 000次后,能量密度保持率为92%;测试温度变化至0℃或50℃时仍表现出良好的稳定性。该性能优势可归为花瓣状rGO载体与PANI之间的强π-π共轭作用及其构建的空间通道对电容性能增强的协同效应。

Abstract

Polyaniline (PANI) composites with three distinct spatial structures—curly shape,two-dimensional planar film layer,and flower-like shape—were synthesized using reduced graphene oxide (rGO) as the support.The morphology,structure,and capacitive performance of the composites were analyzed.The results show that the graphene-based PANI composite with a flower-like structure (PANI/FS-rGO),obtained through hydrothermal treatment,exhibits excellent capacitive performance.At 25℃ and a scan rate of 5 mV/s,the specific capacitance reaches 480 F/g,and at 2 A/g,the energy density is 160.9 Wh/kg,which are 2.11 times and 1.98 times higher than that of pure PANI,respectively.After 1000 cycles at 2 A/g,the energy density retention rate is 92%.The composite also maintains good stability when the temperature changes to 0℃ or 50℃.This performance enhancement is attributed to the strong π-π conjugation between the flower-like rGO support and PANI,as well as the synergistic effect of the spatial channels they create,which further enhances the capacitive performance.

Graphical abstract

关键词

电容 / 复合材料 / 空间结构 / 石墨烯 / 聚苯胺

Key words

capacitor / composite materials / spatial structure / graphene / polyaniline

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ext=[AuthorCompanyExt(id=1251590010291319123, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1251527922537689795, companyId=1251590010282930513, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=College of New Energy and Materials, Ningde Normal University, Ningde 352100, China), AuthorCompanyExt(id=1251590010299707732, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1251527922537689795, companyId=1251590010282930513, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=宁德师范学院新能源与材料学院, 福建宁德 352100)])])] 林玲玲,王佳伟,李萍,叶陈清. 石墨烯基聚苯胺复合结构及其增强的电容性能[J]. , 2026, 46(4): 116-121 DOI:10.16606/j.cnki.issn0253-4320.2026.04.020

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随着全球能源结构向清洁低碳转型,储能技术成为研究重点。超级电容器因其高功率密度、快速充放电和长循环寿命,在智能电网、电动汽车等领域具有重要应用^[1-2]。然而,现有电极材料的能量密度等性能仍无法满足日益增长的需求,亟需开发更高性能的电极材料^[3-4]。

石墨烯因其优异的导电性、化学稳定性和大比表面积,成为理想的超级电容器电极材料^[5-6]。然而,石墨烯片层容易堆叠,导致比表面积显著下降,从而限制了电解液离子的传输^[7]。将石墨烯与导电聚合物(如聚苯胺,PANI)复合,是提升电极比电容的有效途径^[8-9]。PANI能够通过可逆的氧化还原反应提供赝电容效应,从而提升电容器的能量密度。然而,PANI本身较差的导电性以及在充放电过程中产生的体积膨胀问题,依然限制了其在实际应用中的性能^[10]。

为了克服现有电极材料的局限,研究者们提出了多种空间结构优化策略,以提升复合材料的电化学性能^[11-12]。例如,将PANI限制在石墨烯的三维骨架中^[13-14],不仅能够有效缓解PANI的体积膨胀,还能通过石墨烯的高导电性增强电荷转移。同时,合理设计的孔道结构,如中孔结构^[15]和分级多孔结构^[16],有助于提高活性位点密度并优化离子和电子的传输路径,从而显著提升电极的比电容和能量密度。此外,设计具有高表面积的复合纤维^[17]或异质结^[18],能够进一步增强电极的电化学活性。这些结构提高了材料的稳定性,缓解了充放电过程中产生的机械应力,进而提升了循环寿命。因此,通过独特的空间设计,复合材料有希望从多方面优化电极性能,有效提高超级电容器的综合效能。

本文以卷曲状(Curly Shape,CS)、二维平面膜(Two-Dimensional Planar Film Layer,2D)和水热处理后具有花瓣状结构(Flower-Like Shape,FS)的还原氧化石墨烯(rGO)为载体,制备3种不同空间结构的石墨烯基PANI复合材料(PANI/rGO):PANI/CS-rGO、PANI/2D-rGO、PANI/FS-rGO,分析其形貌和结构,并在1 mol/L H₂SO₄溶液中,采用循环伏安法(CV)和恒流充放电法(GCD)测试其比电容、能量密度及循环稳定性等电容性能。

1 试剂与仪器

1.1 实验试剂

苯胺,上海阿拉丁试剂有限公司;浓磷酸(H₃PO₄)、过硫酸铵[(NH₄)₂S₂O₈]、六水合三氯化铁(FeCl₃·6H₂O)、抗坏血酸(AA)、氢氧化钠(NaOH)、无水乙醇,均为分析纯,国药集团化学试剂有限公司;Nafion溶液(5% D520全氟磺酸型),美国DuPont公司;氧化石墨烯分散液(GO,2 mg/mL)、高纯GO粉体,苏州碳丰石墨烯科技有限公司;实验用水为18.2 MΩ Milli-Q超纯水。

1.2 实验仪器

采用场发射扫描电子显微镜(SEM,SU8010型,日本日立公司)观察样品表面形貌。样品的化学组成和分子结构通过傅里叶变换红外光谱仪(FT-IR,Nicolet iS10型,美国Thermo Scientific)和激光拉曼光谱仪(Raman,HR Evolution型,日本HORIBA)进行表征,其中拉曼测试采用532 nm激光激发。表面元素组成及其化学态分析使用X射线光电子能谱仪(XPS,ESCALAB 250XI型,美国Thermo Electron),以Al Kα射线(hν=1486.6 eV)作为激发源。

2 实验方法

2.1 PANI和PANI/rGO粉体的制备

在50 mL纯水中加入2 mL H₃PO₄和100 μL 0.1 mol/L FeCl₃溶液,搅拌均匀后,加入100 μL苯胺单体,继续搅拌30 min以促进苯胺的均匀分散。随后,将0.3 g (NH₄)₂S₂O₈溶解于5 mL 10%(质量分数)H₃PO₄溶液中,溶解完全后,缓慢滴加至反应体系中并搅拌1 h。反应结束后,产物通过过滤分离,使用纯水、含100 mmol/L AA的2%(质量分数)H₃PO₄溶液和无水乙醇清洗,自然晾干得到PANI粉末。

花瓣状空间结构GO载体(FS-GO)的水热处理:将0.8 g高纯GO粉体、50 mg FeCl₃·6H₂O分散于50 mL纯水中,搅拌2 h后,用0.1 mol/L NaOH调节至pH=7.0,在120℃水热反应釜中反应2 h。此时GO在中性条件下,在Fe³⁺作用下折叠成花瓣状空间结构。产物经过滤、纯水和乙醇洗涤后室温干燥。

PANI/rGO粉体的合成是在PANI合成基础上进行的,即在PANI反应过程中,在加入2 mL H₃PO₄之前将含50 mg固体质量的不同形态的GO(高纯度GO粉体、GO分散液或水热处理后的FS-GO)加入反应体系中,最终制得对应的PANI/CS-rGO、PANI/2D-rGO和PANI/FS-rGO 3种不同空间结构的复合粉体。

2.2 电化学性能测试

将5 mm玻碳电极用氧化铝浆料抛光,超声清洗后晾干备用。将2 mg粉体与10 μL 5% Nafion乙醇溶液混合,超声分散30 min,取13 μL悬浮液滴加至电极表面,晾干后重复1次,形成涂层。电化学测试在三电极体系中进行,玻碳电极为工作电极,石墨为对电极,饱和甘汞为参比电极。所有测试在CHI660D电化学工作站上进行,使用1 mol/L H₂SO₄溶液,利用CV和GCD测试电容性能;在无特殊说明情况下,测试温度为25℃。

3 结果与分析

3.1 形貌分析

图1展示了所制备材料的SEM形貌。PANI为直径约50 nm的不规则短棒状纤维[图1(a)]。PANI/CS-rGO复合材料呈卷曲状空间结构,PANI均匀负载在rGO表面并形成一定厚度的复合物膜层,膜层表面可以观察到均匀的PANI凸起[图1(b)]。PANI/2D-rGO复合材料呈现为二维平面薄膜层结构,该结构由分散较好的GO分散液制备得到,PANI均匀地生长在rGO薄层上并层层堆积[图1(c)]。水热处理后的PANI/FS-rGO复合材料可以明显观察到花瓣状骨架及其形成的开放式空间结构,PANI不仅生长在rGO表面,还填充在花瓣间隙中[图1(d)]。

3.2 样品结构分析

图2为所制备材料的FT-IR谱图。纯PANI的特征吸收峰^[19-20]如下:1 564 cm^-1处的峰归属于苯环的C=C伸缩振动,1 485 cm^-1处的峰对应芳香胺的C=N伸缩振动,1 299 cm^-1处的峰源于苯环的C—N伸缩振动,1 136 cm^-1处的峰为苯环C—H面内弯曲振动所致,而820 cm^-1处的峰则来自1,4-二取代芳环的C—H弯曲振动。在PANI/rGO复合材料中,可观察到1 185 cm^-1处的特征峰向高波数方向移动,表明PANI与rGO之间存在相互作用。此外,在1 635 cm^-1附近出现的吸收峰对应于石墨烯sp²杂化碳的C=C伸缩振动^[19-20]。所有样品在 1 085 cm^-1和1 720 cm^-1附近均未明显观察到归属于rGO的C—O—C和C=O伸缩振动峰^[19-20],说明大部分的rGO已被还原。

图3为样品的Raman光谱。纯PANI在1 483 cm^-1(νC=N)、1 405 cm^-1(νC—N⁺)、1 222 cm^-1(νC—N)和1 161 cm^-1(νC—H)处显示出特征振动峰^[21-22]。与rGO复合后,这些峰的强度均有所降低。在石墨烯特征峰区域,1 346 cm^-1处的D峰源于sp³杂化碳的缺陷诱导散射,而1 586 cm^-1处的G峰则对应sp²杂化碳的面内振动。D峰与G峰的强度比(I_D/I_G)可用于评估石墨烯的结构无序度^[21-22]。当PANI与不同结构rGO复合后,I_D/I_G值变化表明PANI与rGO之间存在显著相互作用。其中,PANI/FS-rGO的I_D/I_G值最高,PANI/CS-rGO次之,PANI/2D-rGO最低。I_D/I_G值的增大不仅证实了GO的有效还原,还表明还原过程中形成了更多无序石墨微区。这种结构无序度的提升有助于增强材料的电导率,促进电荷转移过程。

图4呈现了样品的XPS C 1s和N 1s精细谱。以C 1s标准峰(284.8 eV)为基准进行结合能校准。C 1s谱[图4(a)]可解卷积为5个组分:284.8 eV(C—C)、285.4 eV(C=C)、286.6 eV(C—N)、288.5 eV(C—O/C=O)和292.1 eV(π-π^*)^[23-24]。PANI与rGO复合后,C—O/C=O键含量显著增加(PANI/FS-rGO和PANI/CS-rGO尤为突出),而 C=C和C—N峰强度相对降低,其中C=C峰的减弱更为显著。这种变化证实了rGO与PANI间存在强π-π堆叠作用,且FS-rGO和CS-rGO结构更利于这种相互作用的形成。

N 1s谱[图4(b)]解析显示3个特征峰:398.5 eV(亚胺氮,—N=)、399.7 eV(胺氮,—NH—)和401.9 eV(季氮,—N⁺)^[23-24]。纯PANI以—NH—为主导,同时存在少量氧化态氮(—N=和—N⁺)。复合后,—N=和—N⁺的相对含量明显增加,表明π-π共轭促进了共轭氮结构的形成,这一效应在PANI/FS-rGO和PANI/CS-rGO中最为显著,与C 1s谱分析结果高度吻合。

3.3 电容性能分析

3.3.1 CV及比电容分析

图5展示了不同材料电极在5 mV/s扫描速率下的CV曲线。图中,PANI/rGO复合电极的电流密度均高于纯PANI电极,表明与rGO复合提升了材料的电容性能。其中,PANI/FS-rGO(花瓣状结构)和PANI/2D-rGO(二维平面结构)的电流密度,尤其是PANI/FS-rGO,明显高于PANI/CS-rGO(卷曲状结构),说明电极的微观形貌对电容性能具有重要影响。PANI/FS-rGO的优异性能可归因于其花瓣状rGO载体与PANI之间的强π-π共轭作用,以及独特的开放结构形成了有效的空间通道,显著提升了离子传输效率,使材料在高电流密度下仍能保持优异的电容性能。值得注意的是,尽管Raman和XPS表征结果表明,PANI/2D-rGO中的π-π堆叠相互作用弱于PANI/CS-rGO,但其独特的薄层堆积结构可能弥补了这一不足,即在制备过程中高度分散的GO促使PANI与rGO形成交替堆叠的插层结构(如PANI/rGO/PANI/rGO),从而赋予复合材料独特的电容性能。

图6为所制得材料电极CV测试时比电容随扫描速率变化的关系曲线。在5 mV/s扫描速率下,各电极的比电容分别为:纯PANI 228 F/g,PANI/CS-rGO 238 F/g,二者差异不显著;而PANI/2D-rGO和PANI/FS-rGO分别达到346 F/g和480 F/g,分别是纯PANI的1.52倍和2.11倍,其中具有花瓣状结构的PANI/FS-rGO比电容增强显著。此外,随着扫描速率增加至50 mV/s,虽然所有材料的比电容均有所降低,但PANI/2D-rGO和PANI/FS-rGO仍保持明显的性能优势,体现了该微观结构在电容性能方面的优势。

3.3.2 GCD及能量密度分析

图7展示了各材料电极在2 A/g下单次充放电的GCD曲线。图中,纯PANI电极的充放电时间最短为217.6 s,而与rGO复合后电极的充放电时间均有不同程度延长,PANI/CS-rGO、PANI/2D-rGO和PANI/FS-rGO电极的充放电时间分别为235.2、313.6 s和416.0 s,分别是PANI电极的1.08倍、1.44倍和1.91倍,再次证实了空间结构调控在电极材料电容性能提升中的重要作用。

图8为不同材料电极进行GCD测试时能量密度与电流密度的关系曲线。在2 A/g电流密度下,PANI、PANI/CS-rGO、PANI/2D-rGO和PANI/FS-rGO电极材料的能量密度分别为81.1、92.6、132.9 Wh/kg和160.9 Wh/kg。其中,PANI/FS-rGO电极的能量密度是PANI的1.98倍,表明其在提升能量密度方面的优势。此外,随着电流密度的增加,所有电极材料的能量密度均呈下降趋势,表现为典型的聚合物赝电容材料的电容特征。

3.3.3 不同测试温度下GCD及能量密度分析

图9展示了不同测试温度下各电极材料单次充放电GCD曲线。结果显示,测试温度从25℃升高至50℃时,纯PANI电极的充放电时间略微减少至94.8%,而在0℃时,充放电时间显著下降至71.1%。

这种变化归因于高温提高了离子迁移速率,但同时增加了电极的电阻,从而限制了PANI电容性能的提升;低温则导致离子迁移速率减缓并成为影响PANI性能的关键因素,从而显著降低充放电性能。

相比之下,PANI/rGO复合材料在测试温度变化时表现出良好的稳定性。在温度升高至50℃时,PANI/rGO复合电极的充放电时间虽变化幅度较小但略有增加;当温度降至0℃时,PANI/CS-rGO、PANI/2D-rGO和PANI/FS-rGO的充放电时间分别缩短至85.7%、87.8%和88.9%,相比较PANI表现出良好的抗衰减性能。该结果表明PANI/rGO复合材料在温度变化下具有较强的适应性和稳定性。

图10展示了不同测试温度下PANI/FS-rGO电极进行GCD测试时能量密度与电流密度的关系。在2 A/g的电流密度下,PANI/FS-rGO电极在0℃和50℃时的能量密度分别为145.7 Wh/kg和164.5 Wh/kg,分别为25℃时能量密度160.9 Wh/kg的90.5%和102.2%。此外,虽然变温情况下,随着电流密度的增加,PANI/FS-rGO电极的能量密度有所下降,但其下降幅度受温度影响较小,表现出良好的稳定性。

3.3.4 循环稳定性

表1展示了不同材料电极及其测试温度变化时的能量密度和循环稳定性。在25℃、2 A/g电流密度下循环测试1 000次后,PANI、PANI/CS-rGO、PANI/2D-rGO和PANI/FS-rGO的能量密度保持率分别为71%、84%、86%和92%。其中,PANI/FS-rGO的能量密度保持率比PANI提高了21%。这一结果验证了PANI/FS-rGO中rGO与PANI的强π-π共轭作用及其花瓣状开放结构对电容性能的协同提升作用,从而显著提高了电极的循环稳定性。

在0℃和50℃下,PANI/FS-rGO电极循环测试1 000次后的能量密度保持率分别降至85%和80%,其中高温下的衰减更为显著。该原因可能为,低温下离子迁移受限,长时间循环充放电导致电极结构发生不可逆膨胀和收缩,而高温则加速副反应,破坏电极结构或形成阻抗层,导致电容性能显著下降。尽管如此,PANI/FS-rGO在1 000次循环后的能量密度仍高于其他材料,表明其在电容性能上具有明显优势。

4 结论

本文制备了3种不同空间结构的PANI/rGO复合电极材料:卷曲状、二维平面膜层和花瓣状,并对其形貌、结构及电容性能进行表征。测试结果表明,水热法制备的花瓣状PANI/FS-rGO电极材料在电容性能上优于PANI及其他两种结构的PANI/rGO复合材料。在25℃测试条件下,PANI/FS-rGO电极材料在1 mol/L H₂SO₄溶液中,5 mV/s时比电容达到480 F/g,2 A/g时能量密度为160.9 Wh/kg,在 2 A/g下经过1 000次循环充放电后能量密度保持率为92%;当测试温度变化至0℃或50℃时仍表现出良好的稳定性。表明花瓣状rGO载体与PANI之间的强π-π共轭作用及其空间结构对电容性能的提升具有显著的协同效应。该研究证实了空间结构调控在电极材料性能提升中的关键作用,为高性能超级电容器的材料设计提供了新思路。

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