石墨烯及其复合材料的制备与储能应用
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摘要
电化学超级电容器(ESC)是一种新型储能器件,它介于蓄电池和传统静电电容器之间,具有容量高、功率大、可逆性好、循环寿命长、环境稳定性好等优点,有着广阔的应用前景,因而它受到了广大研究者的青睐。对于电容器来说,最关键的是其电极材料。石墨烯是一种新发展起来的碳材料,它具有比表面积大、导电性能好等优点,是一种良好的电极材料。但是单一的石墨烯比容量有限,难以充分发挥其优异性能。导电聚苯胺具有原料成本低、合成工艺简单、化学和环境稳定性好等优点,是一种良好的电极材料。但是纯聚苯胺作为电极材料时,在长期充放电过程中,循环稳定性差、比容量低等缺点限制了其应用,因而它是一种需要修饰的电极材料。活性碳纤维由于其导电性能好、强度高、比表面积大等优点成为了电容器电极材料研究热点,但是纯碳纤维表观密度低、耐酸性能差等缺点,因而需要对其表面进行修饰。采用石墨烯修饰聚苯胺和活性碳纤维,可提高其电化学性能。
本文主要研究了石墨烯及其复合材料的制备及电化学性能,并比较石墨烯、碳纳米管在其复合材料中电化学性能优劣。采用透射电镜、扫描电镜、XRD等测试手段,对材料形貌和结构进行了表征；并且表征了材料的电化学性能,主要是采用循环伏安、恒电流充放电等电化学测试手段来测试表征的。具体研究内容如下：
1.采用Hummers方法制备氧化石墨烯,之后分别采用化学还原法和高温氢气还原法还原得到石墨烯。比较两种方法得到的石墨烯可以看出,CGR电化学性能更为优异,比电容、循环稳定性更高,其比电容达到104.4F/g。
2.采用原位聚合法制备了石墨烯/聚苯胺复合材料(CGR/PANI)和碳纳米管/聚苯胺复合材料(CNTs/PANI),探讨了石墨烯与碳纳米管与聚苯胺聚合得到的复合材料性能优劣。通过电化学测试可以看出,石墨烯/聚苯胺复合材料的电化学性能比碳纳米管/聚苯胺复合材料的电化学性能更好,其比电容达到148.4F/g。
3.采用浸渍法及高温还原法制得石墨烯/活性碳纤维复合材料(GR/ACF),采用化学气相沉积法(CVD)在活性碳纤维上生长碳纳米管制备碳纳米管/活性碳纤维复合材料(CNTs/ACF)。通过电化学测试可以看出石墨烯/活性碳纤维复合材料比电容、循环稳定性高于纯碳纤维和碳纳米管/活性碳纤维复合材料。
Electrochemical Supercapacitor (ESC) is a new kind of energy storage device with many outstanding properties, such as high specific capacity, good reversibility, long cycle life, good environmental stability and wide application perspectives. Supercapacitors are increasingly gaining attention because they fill a gap between batteries and ordinary capacitors. The choosing of the electrode material is the critical factor to the preparation of electrochemical capacitor. Graphene has been the most promising candidate of electrode materials since its discovery.owing to the many advantages graphene has like large specific surface area, great electrical conductivity and so on. However, supercapacitors, which are consisted of pure graphene, do not demonstrate desired capacitance as expected. Polyaniline (PANI) is a common conducting polymer, which has been considered as an important electrode material due to its cost efficiency, operation simplicity, high chemical and environmental stability. Unfor tunately, supercapacitors comprising electrodes which are made up of pure PANI, do not fulfill people's need of high capacitance, long cycle life. Active carbon fiber (ACF) has long been used as electrode material and other field with high significance because of its good conductivity, high strength and large specific surface area. Whereas pure ACF need to be futher modified forhigh apparent density, good acid resistance and so forth. In order to improve the electrochemical performance of the supercapacitors, graphene are employed to modify the PANI and ACF.
In this paper, we primarily studied the preparation and their electrochemical properties of graphene and its composites, and comparing the properties of graphene and CNTs in their composites. Morphology and structure of the obtained materials were characterized by transmission electron microscope (TEM), field effect scanning electron microscopy (FE-SEM). X-Ray Diffraction was also adopted to analyze the component of the obtained material. In addition, the electrochemical performances of the obtained materials were characterized by cyclic voltammograms (CV), galvanostatic charging/discharging. The detailed information is listed as follows:
1-Graphene oxide was prepared by Hummers method. And then the obtained graphene oxide was reduced by chemical method and high temperature hydrogen reduction process respectively. Comparing the two reduction methods mentioned above, graphene obtained by chemical method has better electrochemical performance withthe specific capacitance of104.4F/g(organic electrolyte).
2. The CGR/PANI and CNTs/PANI composites were papered by in-situ polymeri-zation. In contrast to CNTs/PANI composites, CGR/PANI composites have better electrochemical performance and the specific capacitance of148.4F/g (organic electrolyte).
3. By first immersing ACF into GO water solution, followed by hydrogen reduction at high temperature, the GR/ACF composites was achieved. While CNTs/ACF were prepared by chemical vapor deposition (CVD). The results showed that the graphene/ACF composites have higher specific capacity and cycling stability compared to CNTs/ACFand ACF.
本文主要研究了石墨烯及其复合材料的制备及电化学性能,并比较石墨烯、碳纳米管在其复合材料中电化学性能优劣。采用透射电镜、扫描电镜、XRD等测试手段,对材料形貌和结构进行了表征；并且表征了材料的电化学性能,主要是采用循环伏安、恒电流充放电等电化学测试手段来测试表征的。具体研究内容如下：
1.采用Hummers方法制备氧化石墨烯,之后分别采用化学还原法和高温氢气还原法还原得到石墨烯。比较两种方法得到的石墨烯可以看出,CGR电化学性能更为优异,比电容、循环稳定性更高,其比电容达到104.4F/g。
2.采用原位聚合法制备了石墨烯/聚苯胺复合材料(CGR/PANI)和碳纳米管/聚苯胺复合材料(CNTs/PANI),探讨了石墨烯与碳纳米管与聚苯胺聚合得到的复合材料性能优劣。通过电化学测试可以看出,石墨烯/聚苯胺复合材料的电化学性能比碳纳米管/聚苯胺复合材料的电化学性能更好,其比电容达到148.4F/g。
3.采用浸渍法及高温还原法制得石墨烯/活性碳纤维复合材料(GR/ACF),采用化学气相沉积法(CVD)在活性碳纤维上生长碳纳米管制备碳纳米管/活性碳纤维复合材料(CNTs/ACF)。通过电化学测试可以看出石墨烯/活性碳纤维复合材料比电容、循环稳定性高于纯碳纤维和碳纳米管/活性碳纤维复合材料。
Electrochemical Supercapacitor (ESC) is a new kind of energy storage device with many outstanding properties, such as high specific capacity, good reversibility, long cycle life, good environmental stability and wide application perspectives. Supercapacitors are increasingly gaining attention because they fill a gap between batteries and ordinary capacitors. The choosing of the electrode material is the critical factor to the preparation of electrochemical capacitor. Graphene has been the most promising candidate of electrode materials since its discovery.owing to the many advantages graphene has like large specific surface area, great electrical conductivity and so on. However, supercapacitors, which are consisted of pure graphene, do not demonstrate desired capacitance as expected. Polyaniline (PANI) is a common conducting polymer, which has been considered as an important electrode material due to its cost efficiency, operation simplicity, high chemical and environmental stability. Unfor tunately, supercapacitors comprising electrodes which are made up of pure PANI, do not fulfill people's need of high capacitance, long cycle life. Active carbon fiber (ACF) has long been used as electrode material and other field with high significance because of its good conductivity, high strength and large specific surface area. Whereas pure ACF need to be futher modified forhigh apparent density, good acid resistance and so forth. In order to improve the electrochemical performance of the supercapacitors, graphene are employed to modify the PANI and ACF.
In this paper, we primarily studied the preparation and their electrochemical properties of graphene and its composites, and comparing the properties of graphene and CNTs in their composites. Morphology and structure of the obtained materials were characterized by transmission electron microscope (TEM), field effect scanning electron microscopy (FE-SEM). X-Ray Diffraction was also adopted to analyze the component of the obtained material. In addition, the electrochemical performances of the obtained materials were characterized by cyclic voltammograms (CV), galvanostatic charging/discharging. The detailed information is listed as follows:
1-Graphene oxide was prepared by Hummers method. And then the obtained graphene oxide was reduced by chemical method and high temperature hydrogen reduction process respectively. Comparing the two reduction methods mentioned above, graphene obtained by chemical method has better electrochemical performance withthe specific capacitance of104.4F/g(organic electrolyte).
2. The CGR/PANI and CNTs/PANI composites were papered by in-situ polymeri-zation. In contrast to CNTs/PANI composites, CGR/PANI composites have better electrochemical performance and the specific capacitance of148.4F/g (organic electrolyte).
3. By first immersing ACF into GO water solution, followed by hydrogen reduction at high temperature, the GR/ACF composites was achieved. While CNTs/ACF were prepared by chemical vapor deposition (CVD). The results showed that the graphene/ACF composites have higher specific capacity and cycling stability compared to CNTs/ACFand ACF.
引文
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