CN108470629A - 一种镍离子掺杂聚噻吩/石墨烯复合电极材料及其制备方法 - Google Patents
一种镍离子掺杂聚噻吩/石墨烯复合电极材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种镍离子掺杂聚噻吩/石墨烯复合电极材料及其制备方法,属于功能高分子材料的制备技术领域。该制备方法包括以下步骤:(1)利用酰氯化石墨烯(GO‑COCl)和3‑乙醇噻吩反应,制备以酯键连接的噻吩基石墨烯(GO‑Th);(2)将步骤(1)制备的GO‑Th、氯化镍(NiCl2)和3,4‑乙烯二氧噻吩(EDOT)依次加入到氯仿中,利用化学氧化聚合反应制备Ni2+掺杂聚(3,4‑乙烯二氧噻吩)/石墨烯复合材料,即为所述镍离子掺杂聚噻吩/石墨烯复合电极材料。本发明制备的复合电极材料不仅具有较高的比电容,而且具有优异的电化学循环稳定性,在超级电容器领域具有广阔的应用前景。
Description
技术领域
本发明属于功能高分子材料的制备技术领域,具体涉及一种镍离子掺杂聚噻吩/石墨烯复合电极材料及其制备方法。
背景技术
聚噻吩是一种重要的结构型导电高分子材料,由于具有高的电导率、良好的环境稳定性和易于调控的分子链结构等特点,其也是一种重要的超级电容器的电极材料。但是,聚噻吩用做超级电容器的电极材料时,本身存在比电容较低的缺点,理论研究表明,其比容量最高只能达到210 F/g。针对这个缺点,研究人员发现利用质子酸掺杂聚噻吩,可以有效提高其比电容。江杰青(江杰清, 李巍, 刘东志, 田建华, 郭亚芳, 周雪琴; 聚(3,4-乙撑二氧噻吩)/樟脑磺酸复合材料的合成及电化学性能, 精细化工, 2012, 29(6): 541~541.)以樟脑磺酸为掺杂剂、三氯化铁为氧化剂,通过化学氧化法合成了聚(3,4-乙撑二氧噻吩)/樟脑磺酸复合材料。研究表明,当两者物质的量的比为2:1时,复合材料具有良好的导电性能和电化学性能,电导率为10.4 S/cm,经150次循环充放电后容量仍保持在140 F/g以上。石墨烯具有大的比表面积和优异的机械性能。研究发现,将共轭聚合物和石墨烯进行复合,石墨烯在复合材料中形成空间网络支撑结构,可以显著增加共轭聚合物和电解质的接触面积,从而增大共轭聚合物的比电容。但是未处理的石墨烯之间由于存在层与层之间的范德华力,容易发生团聚,难以在共轭聚合物中均匀分散。因此,要发挥石墨烯改进复合材料的先进性,必须在界面和性质设计的基础上,对其进行有效的功能化改性处理。
发明内容
本发明的目的在于针对现有技术中聚噻吩的比电容较低这一缺点,提供一种镍离子掺杂聚噻吩/石墨烯复合电极材料及其制备方法。本发明制备的复合电极材料不仅具有较高的比电容,而且具有优异的电化学循环稳定性,在超级电容器领域具有广阔的应用前景。
为实现上述目的,本发明采用如下技术方案:
一种镍离子掺杂聚噻吩/石墨烯复合电极材料的制备方法,包括以下步骤:
(1)利用酰氯化石墨烯(GO-COCl)(何亚萍, 杨晓慧, 韩权, 霍燕燕; 4-[(5-氯-吡啶)偶氮]-1,3-二氨基苯功能化氧化石墨烯的制备, 西安文理学院学报(自然科学版), 2017,20(3): 90~93.)和3-乙醇噻吩反应,制备以酯键连接的噻吩基石墨烯(GO-Th);
(2)将步骤(1)制备的GO-Th、氯化镍(NiCl2)和3,4-乙烯二氧噻吩(EDOT)依次加入到氯仿中,利用化学氧化聚合反应制备Ni2+掺杂聚(3,4-乙烯二氧噻吩)/石墨烯复合材料,即为所述镍离子掺杂聚噻吩/石墨烯复合电极材料。
更具体的步骤如下:
(1)将0.4~1 g GO-COCl加入到100~500 mL三氯甲烷(CHCl3)中,在室温下超声30~60min,制备GO-COCl的分散液;向上述分散液中加入2~10 g 3-乙醇噻吩和3~15 g吡啶,在氮气(N2)保护下,70~90 ℃磁搅拌反应20~30 h。反应结束后,利用离心机分离出黑色粉末,并用200~500 mL无水乙醇充分洗涤,在-50 ℃下冷冻干燥24 h,制备GO-Th;
(2)将0.1~0.2 g GO-Th加入到200~500 mL CHCl3中,在室温下超声30~90 min,制备GO-Th的分散液;向上述分散液中加入1~6 g NiCl2,在室温下超声5~30 min,再加入1~8 gEDOT,在室温下继续超声5~20 min;在N2保护下,将1.5~12 g 三氯化铁(FeCl3)加入到上述混合液中,升温至30~50 ℃,磁搅拌反应4~8 h;反应结束后,将混合液倒入甲醇中沉降,沉降后得到的黑色粉末反复用去离子水和甲醇洗涤、过滤至滤液无色;在60 ℃下真空干燥24h制备Ni2+掺杂聚(3,4-乙烯二氧噻吩)/石墨烯复合材料,即为所述镍离子掺杂聚噻吩/石墨烯复合电极材料。
一种如上所述的制备方法制得的镍离子掺杂聚噻吩/石墨烯复合电极材料。
现有技术中,利用酰氯化石墨烯和3-噻吩甲酸进行酸酐化反应,制备以酸酐键连接的噻吩基石墨烯(孙成龙, 董延茂, 李佳轩, 朱广爱, 戴旭; 聚3-己基噻吩/氧化石墨烯复合材料的制备与光学性能研究, 2016, 44(2): 95-97, 101.)。本发明中的噻吩基团和石墨烯是通过酯键连接。
本发明与现有技术相比具有以下优点:
(1)本发明将噻吩基团和石墨烯通过酯键连接,酯键比酸酐键具有更强的化学稳定性,所以本发明制备的噻吩基石墨烯在化学氧化聚合过程中具有更加优异的稳定性;同时在本发明制备的复合材料中,石墨烯和聚噻吩分子链之间具有更大的连接强度,这有利于提高复合材料的比电容与电化学循环稳定性;
(2)GO-Th和Ni2+超声分散后,Ni2+通过配位键与石墨烯的噻吩基团的硫(S)原子络合;当加入EDOT单体后,上述Ni2+再与EDOT单体的S原子络合,将EDOT单体吸附在石墨烯周围。当加入FeCl3后,引发EDOT单体与石墨烯上的噻吩基团共同进行化学氧化反应,发生以石墨烯上的噻吩基团为起点的EDOT单体的聚合反应;这种投料顺序有利于生成的聚噻吩覆盖在石墨烯的表面,借助石墨烯的大比表面积和优异的机械性能,提高聚噻吩和电解质的接触面积以及有助于在复合材料中形成以石墨烯为骨架的支撑结构,从而可以提高复合材料的比电容和电化学循环稳定性;
(3)在复合材料中,石墨烯和聚噻吩分子链之间通过酯键连接;这不仅可以显著改善石墨烯在聚噻吩基体中的分散效果,而且可以提高聚噻吩和石墨烯之间的结合强度;此外,Ni2+和聚噻吩分子链中S原子的配位作用,可以诱导聚噻吩分子链定向排列,形成结构规整的聚噻吩分子链,有助于提高复合材料的比电容与电化学循环稳定性;
(4)本发明所制备的镍离子掺杂聚噻吩/石墨烯复合材料在充放电电流密度分别为0.2g/A、0.5 g/A、1 g/A和2 g/A时,比电容分别为207 F/g、196 F/g、182 F/g和161 F/g,比聚噻吩的分别提高234 %、270 %、344 %和632 %,循环1000次后,比电容的保持率为93%,比聚噻吩的提高24 %;因该种材料具有较高的比电容和较优异的电化学循环稳定性,主要用于制备超级电容器用电极。
具体实施方式
以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例1
一种镍离子掺杂聚噻吩/石墨烯复合电极材料的制备方法,具体步骤为:
(1)将0.4 g GO-COCl加入到100 mL CHCl3中,在室温下超声30 min,制备GO-COCl的分散液;向上述分散液中加入2 g 3-乙醇噻吩和3 g吡啶,在N2保护下,70 ℃磁搅拌反应30h;反应结束后,利用离心机分离出黑色粉末,并用200 mL无水乙醇充分洗涤,在-50 ℃下冷冻干燥24 h,制备GO-Th;
(2)将0.1 g GO-Th加入到200 mL CHCl3中,在室温下超声30 min,制备GO-Th的分散液;向上述分散液中加入1 g NiCl2,在室温下超声5 min,再加入1 g EDOT,在室温下继续超声5 min;在N2保护下,将1.5 g FeCl3加入到上述混合液中,升温至30 ℃,磁搅拌反应8h;反应结束后,将混合液倒入甲醇中沉降,沉降后得到的黑色粉末反复用去离子水和甲醇洗涤、过滤至滤液无色;在60 ℃下真空干燥24 h制备Ni2+掺杂聚(3,4-乙烯二氧噻吩)/石墨烯复合材料。
实施例2
一种镍离子掺杂聚噻吩/石墨烯复合电极材料的制备方法,包括以下步骤:
(1)将0.7 g GO-COCl加入到300 mL CHCl3中,在室温下超声45 min,制备GO-COCl的分散液;向上述分散液中加入6 g 3-乙醇噻吩和9 g吡啶,在N2保护下,80 ℃磁搅拌反应25h;反应结束后,利用离心机分离出黑色粉末,并用400 mL无水乙醇充分洗涤,在-50 ℃下冷冻干燥24 h,制备GO-Th;
(2)将0.15 g GO-Th加入到400 mL CHCl3中,在室温下超声60 min,制备GO-Th的分散液;向上述分散液中加入4 g NiCl2,在室温下超声20 min,再加入5 g EDOT,在室温下继续超声10 min;在N2保护下,将8 g FeCl3加入到上述混合液中,升温至40 ℃,磁搅拌反应6 h;反应结束后,将混合液倒入甲醇中沉降,沉降后得到的黑色粉末反复用去离子水和甲醇洗涤、过滤至滤液无色;在60 ℃下真空干燥24 h制备Ni2+掺杂聚(3,4-乙烯二氧噻吩)/石墨烯复合材料。
实施例3
一种镍离子掺杂聚噻吩/石墨烯复合电极材料的制备方法,包括以下步骤:
(1)将1 g GO-COCl加入到500 mL CHCl3中,在室温下超声60 min,制备GO-COCl的分散液;向上述分散液中加入10 g 3-乙醇噻吩和15 g吡啶,在N2保护下,90 ℃磁搅拌反应20h;反应结束后,利用离心机分离出黑色粉末,并用500 mL无水乙醇充分洗涤,在-50 ℃下冷冻干燥24 h,制备GO-Th;
(2)将0.2 g GO-Th加入到500 mL CHCl3中,在室温下超声90 min,制备GO-Th的分散液;向上述分散液中加入6 g NiCl2,在室温下超声30 min,再加入8 g EDOT,在室温下继续超声20 min。在N2保护下,将12 g FeCl3加入到上述混合液中,升温至50 ℃,磁搅拌反应4h;反应结束后,将混合液倒入甲醇中沉降,沉降后得到的黑色粉末反复用去离子水和甲醇洗涤、过滤至滤液无色;在60 ℃下真空干燥24 h制备Ni2+掺杂聚(3,4-乙烯二氧噻吩)/石墨烯复合材料。
对比例1
将1 g EDOT加入到200 mL CHCl3中,在室温下超声5 min。在N2保护下,将1.5 g FeCl3加入到上述溶液中,升温至30 ℃,磁搅拌反应8 h。反应结束后,将混合液倒入甲醇中沉降,沉降后得到的黑色粉末反复用去离子水和甲醇洗涤、过滤至滤液无色。在60 ℃下真空干燥24 h制备聚(3,4-乙烯二氧噻吩)。
对比例2
将4 g NiCl2加入到400 mL CHCl3中,在室温下超声20 min,再加入5 g EDOT,在室温下继续超声10 min。在N2保护下,将8 g FeCl3加入到上述混合液中,升温至40 ℃,磁搅拌反应6 h。反应结束后,将混合液倒入甲醇中沉降,沉降后得到的黑色粉末反复用去离子水和甲醇洗涤、过滤至滤液无色。在60 ℃下真空干燥24 h制备Ni2+掺杂聚(3,4-乙烯二氧噻吩)。
对比例3
将0.2 g 氧化石墨烯(GO)加入到500 mL CHCl3中,在室温下超声90 min,制备GO的分散液。向上述分散液中加入6 g NiCl2,在室温下超声30 min,再加入8 g EDOT,在室温下继续超声20 min。在N2保护下,将12 g FeCl3加入到上述混合液中,升温至50 ℃,磁搅拌反应4h。反应结束后,将混合液倒入甲醇中沉降,沉降后得到的黑色粉末反复用去离子水和甲醇洗涤、过滤至滤液无色。在60 ℃下真空干燥24 h制备Ni2+掺杂聚(3,4-乙烯二氧噻吩)/石墨烯复合材料。
将80 %产物、15 %乙炔炭黑和5 %聚偏氟乙烯混合均匀涂在不锈钢网上作为工作电极,以铂丝作为对电极,以饱和甘汞电极作为参比电极,以1 mol/L硫酸水溶液作为电解液,利用恒流充放电方法测试实施例和对比例所制备产物的比电容,利用循环伏安法测试实施例和对比例所制备产物的电化学循环稳定性,其中,电压范围为-0.2~0.8 V,充放电电流密度分别为0.2 g/A、0.5 g/A、1 g/A和2 g/A,扫描速率为100 mV/s。测试结果如下表1所示。
表1 性能测试结果
从三组实施例和三组对比例的测试结果可以看出,三组实施例所制备的复合材料的比电容和电化学循环稳定性均得到明显提高。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (4)
1.一种镍离子掺杂聚噻吩/石墨烯复合电极材料的制备方法,其特征在于:包括以下步骤:
(1)利用酰氯化石墨烯—GO-COCl和3-乙醇噻吩反应,制备以酯键连接的噻吩基石墨烯—GO-Th;
(2)将步骤(1)制备的GO-Th、氯化镍和3,4-乙烯二氧噻吩依次加入到氯仿中,利用化学氧化聚合反应制备镍离子掺杂聚噻吩/石墨烯复合电极材料。
2.根据权利要求1所述的镍离子掺杂聚噻吩/石墨烯复合电极材料的制备方法,其特征在于:步骤(1)具体为:将0.4~1 g GO-COCl加入到100~500 mL三氯甲烷中,在室温下超声30~60 min,制备GO-COCl的分散液;然后向GO-COCl的分散液中加入2~10 g 3-乙醇噻吩和3~15 g吡啶,在氮气保护下,在70~90 ℃磁搅拌反应20~30 h;反应结束后,利用离心机分离出黑色粉末,并用200~500 mL无水乙醇充分洗涤,在-50 ℃下冷冻干燥24 h,制备GO-Th。
3.根据权利要求1所述的镍离子掺杂聚噻吩/石墨烯复合电极材料的制备方法,其特征在于:步骤(2)具体为:将0.1~0.2 g GO-Th加入到200~500 mL CHCl3中,在室温下超声30~90 min,制备GO-Th的分散液;向GO-Th的分散液中加入1~6 g NiCl2,在室温下超声5~30min,再加入1~8 g 3,4-乙烯二氧噻吩,在室温下继续超声5~20 min,得混合液;在N2保护下,将1.5~12 g 三氯化铁加入到上述混合液中,升温至30~50 ℃,磁搅拌反应4~8 h;反应结束后,将反应液倒入甲醇中沉降,沉降后得到的黑色粉末反复用去离子水和甲醇洗涤、过滤至滤液无色;在60 ℃下真空干燥24 h制备镍离子掺杂聚噻吩/石墨烯复合电极材料。
4.一种如权利要求1-3任一项所述的制备方法制得的镍离子掺杂聚噻吩/石墨烯复合电极材料。
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