| 引用本文: | 王彪,陈鼎智,马安宁,郑渝,邓姝皓.聚苯胺纳米线复合材料的制备与储能性分析[J].中国表面工程,2023,36(3):121~131 |
| WANG Biao,CHEN Dingzhi,MA Anning,ZHENG Yu,DENG Shuhao.Synthesis and Electrochemical Properties of Intercalated Polyaniline Nanowire Composites[J].China Surface Engineering,2023,36(3):121~131 |
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| 聚苯胺纳米线复合材料的制备与储能性分析 |
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王彪1,2, 陈鼎智1, 马安宁1,2, 郑渝1, 邓姝皓1,2
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1.中南大学材料科学与工程学院 长沙 410083;2.中南大学有色金属材料科学与工程教育部重点实验室 长沙 410083
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| 摘要: |
| 针对软、硬模板法制备纳米线的缺陷，提出一种步骤简单、快速且低成本的方法来获得直径均匀的 PANI 纳米线复合材料，并对所制备出的 PANI 纳米线复合材料进行表征和电化学性能研究。首先，采用阳极氧化剥离法，分别在硝酸体系、 磷酸还原体系及硫酸体系中对表面光滑的石墨板进行电化学剥离处理。随后，在经过电化学剥离后的粗糙石墨表面上进行电聚合，从而得到 PANI 纳米线复合材料。表征分析发现，经电化学剥离处理的石墨纸表面分别生成具有大量活性点的石墨烯和氧化石墨烯，与 PANI 结合显著提高了 PANI 的导电性。其中硝酸体系制备的聚苯胺复合材料(PANI / GO)微观为纳米线组成的三维网状结构；磷酸还原体系制备的聚苯胺复合材料(PANI / GR1)微观是纳米线和纳米片层混合结构；硫酸体系制备的聚苯胺复合材料(PANI / GR2)的微观结构介于二者之间。以镁合金和上述三种 PANI 复合材料为电极，制备出简易的海水电池。使其在电流密度为 3.75 mA·cm?2 下放电至 0.9 V 时止。三种电池的比能量分别为 540、228 和 363 mWh·g?1 ，结果表明 PANI / GO 的储能性最优。随后进行的 Tafel 曲线分析和交流阻抗分析表明，PANI / GO 复合电极的导电性和稳定性优异、比表面积大，有利于与电解液充分接触，促进离子在其上的传输和扩散，因而电池反应的极化小，电化学性能最优，有望应用于电池正极材料。 |
| 关键词: 电化学剥离 聚苯胺 纳米线 正极 海水电池 |
| DOI：10.11933/j.issn.1007?9289.20211208003 |
| 分类号:TQ152 |
| 基金项目: |
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| Synthesis and Electrochemical Properties of Intercalated Polyaniline Nanowire Composites |
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WANG Biao1,2, CHEN Dingzhi1, MA Anning1,2, ZHENG Yu1, DENG Shuhao1,2
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1.School of Materials Science and Engineering, Central South University, Changsha 410083 , China;2.Key Laboratory of Nonferrous Metal Materials Science and Engineering of Ministry of Education,Central South University, Changsha 410083 , China
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| Abstract: |
| Conductive polyaniline(PANI) is characterized by a high conductivity, easy doping, reversible electrochemical activity, good uniformity, good thermal stability, and high stability in air. Additionally, it has a high potential for application in batteries and other fields. However, PANI exhibits different morphologies, structures, and performances when synthesized under different conditions. Nanoscale PANI composites have promising applications in the development of small, lightweight, and convenient devices. Among them, PANI composites with a nanowire structure are conducive for electron transfer because of the reduced ion diffusion distance and migration, which provides the optimal energy storage effect for use as an electrode material in batteries. Presently, conductive PANI with a nanowire structure is typically prepared using a hard or soft template method. Based on the defects of the template method, a simple, fast, and low-cost method was proposed to synthesize uniform-sized PANI nanowire composites and study their electrochemical performance. The synthesis of PANI nanowire composites was a two-step process. The first step involved the electrochemical stripping of the graphite plates. An anodic oxidation stripping method was used to prepare a rough surface graphite plate in a nitric acid, phosphoric acid reduction, and sulfuric acid system. The second step included the polymerization of the PANI to obtain a PANI nanowire composite, which was performed on a graphite plate after electrochemical stripping treatment. The results showed that the surface roughness, layer spacing, and specific surface area of the graphite plates were increased after electrochemical stripping. Additionally, the XRD and FI-IR analyses revealed that graphene oxide and graphene were generated on the surface of the electrochemically-peeled graphite plates, thereby providing many active points for the electropolymerization process in the second step. Using an SEM analysis, the micromorphology of the PANI composite(PANI / GO) synthesized using a nitric acid system was found to be a three-dimensional network structure composed of nanowires with a diameter of approximately 100 nm. The micromorphology of the PANI composite synthesized using a phosphoric acid reduction system (PANI / GR1) was a mixture of nanosheets and nanowires with a diameter of approximately 50 nm, whereas that of the PANI composite synthesized using a sulfuric acid system(PANI / GR2) was nanowires with a diameter of approximately 80 nm. Subsequently, the electrochemical properties of the PANI composites were investigated. First, their energy storage properties were studied using a simple seawater battery that was prepared using a magnesium alloy and a PANI composite material as the electrodes. The battery started discharging at a current density of 3.75 mA·cm?2 and stopped at 0.9 V, and the specific energies were 540, 228 and 363 mWh·g?1 . The results showed that PANI / GO exhibited the optimal energy-storage performance. Subsequently, Tafel curves and AC impedance diagrams were used to analyze the electrochemical properties of the three PANI composites, where a larger reaction current density and smaller Tafel curve slope angle was found to produce a semi-circle with a smaller diameter. The steep slope of the AC impedance diagram indicates that the polarization of the battery reaction of the PANI / GO composite electrode is the lowest, its reaction speed is the fastest, and its electrochemical performance is optimal owing to its excellent conductivity, stability, and large specific surface area, which are conducive for providing a sufficiently close approach with the electrolyte and promoting the transmission and diffusion of ions. Therefore, the proposed PANI / GO nanowire composite can be used as battery cathode material. Moreover, its preparation method provides a theoretical and practical basis for the controllable synthesis of other conductive polymer composites. |
| Key words: electrochemical stripping polyaniline nanowire cathode sea-water battery |
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