CN113338038B - 一种氮掺杂中空碳纳米线接枝聚吡咯的制备方法及其用途 - Google Patents
一种氮掺杂中空碳纳米线接枝聚吡咯的制备方法及其用途 Download PDFInfo
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Abstract
一种氮掺杂中空碳纳米线接枝聚吡咯的制备方法及其用途。本发明提供了一种新型碳基电极材料的制备方法,包括如下步骤:一、SiO2纳米线的制备;二、氮掺杂碳中空纳米线的制备;三、偶氮苯改性氮掺杂碳中空纳米线;四、氮掺杂碳中空纳米线接枝聚吡咯电极材料的制备。对该电极材料的电化学性能进行测试,在电流密度为1A/g条件下,比电容为301F/g,循环使用800次后,比电容为初始值的78.1%。该制备方法工艺稳定、易于操作、质量可靠、成本低廉,质量轻,无污染等特点,具有很好的商业化前景。
Description
技术领域
本发明涉及一种氮掺杂中空碳纳米线接枝聚吡咯的制备方法及其用途,属于碳材料和电化学领域。
背景技术
超级电容器作为一种新型的储能装置,具有功率密度高(可达102~104W/kg)、循环寿命长(50万~100万次)、工作温限宽(-40~80℃)、能量密度大、绿色环保等优点,已广泛应用于交通、电力设备、工业与机械等领域。超级电容器的性能很大程度上取决于其电极采用的选用。因此电极材料的研究成为超级电容器研究的重点。超级电容器储能机理可分为双电层电容器和赝电容器两大类。双电层电容器是依靠电解液离子在活性材料表面的可逆吸附实现的。而赝电容器是通过电极表面电活性物质与电解液之间快速的法拉第反应而实现储存。双电层电容器的电极主要为碳材料,包括活性炭、碳纳米管、碳纤维、石墨烯和碳凝胶等。赝电容器电极主要为过渡金属化合物,如二氧化锰、氧化钌、氧化钴、硫化锰等和导电聚合物,如聚苯胺、聚吡咯等。双电层电容器碳材料,它们虽然比表面积大、循环稳定性强,但仍存在低比电容、低能量密度等缺点。因此为了提高碳材料的比电容和能量密度,常常将碳材料与过渡金属化合物或导电聚合物复合。例如,Nguyen等人将氧化石墨烯与氧化镍复合制备复合纳米颗粒,其比容量高达1328F/g,循环使用2000次后,其比电容仍保持87%,表现出良好的循环稳定性(Nguyen B T,et al.,Facile synthesis of three-dimensionalgraphene/nickel oxide nanoparticles composites for high performancesupercapacitor electrodes.Chem,Eng,J,2015,264,603)。Fan等人在静电作用下,将聚苯胺空心球负载在石墨烯上形成复合电极材料,其比电容高达614F/g(Fan W,et al.,Graphene-wrapped polyaniline hollow spheres as novel hybrid electrodematerials for supercapacitor applications,ACS Applied Materials&Interfaces,2013,5,3382)。为了进一步提高碳材料电极的比电容和能量密度,各种各样的复合材料被研究并应于超级电容器的应用中。碳材料与其他材料之间的复合主要是通过物理共混的方式,其之间的作用力主要为静电引力或范德华力。然而两者之间以共价键的形式复合却无相关报道。
发明内容
针对现有技术中的缺陷,本发明的目的是提供一种氮掺杂中空碳纳米线接枝聚吡咯的制备方法及其用途。
一种氮掺杂中空碳纳米线接枝聚吡咯的制备方法,其包括如下步骤:
S1、利用溶胶-凝胶和热致相分离结合的方式制备SiO2纳米线;
S2、将糠醇、乙醇、水和所述SiO2纳米线混合,滴加硫酸,在90℃下进行反应,经过冷却、水稀释、离心和干燥,得到固体产物,将所述固体产物在氩气的保护下,以1~2℃/min的速率加热至180~220℃,保温3~4h后,以2~3℃/min的速率升温至600~650℃,保温6~8h后,将产物浸泡在氢氟酸中,去除模板SiO2,洗涤、干燥得到中空碳纳米线;
S3、将苯胺、盐酸、十二烷基硫酸钠和所述中空碳纳米线混匀后,将滴加过硫酸铵溶液,在3~5℃下反应后,得到聚苯胺/中空碳纳米线复合材料;
S4、将所述聚苯胺/中空碳纳米线复合材料用质量浓度为0.5%的NH4Cl溶液活化后、进行洗涤、干燥,在氮气保护下,加热至250~280℃,保温150~180min,接着加热至900~950℃,保温150~200min,到氮掺杂中空碳纳米线;
S5、将所述氮掺杂中空碳纳米线浸泡在硫酸和硝酸的混合溶液中进行活化后,用二氯亚砜进行酰氯化,得到酰氯改性氮掺杂中空碳纳米线,将偶氮苯和所述酰氯改性氮掺杂中空碳纳米线分散于N,N-二甲基甲酰胺和三乙基胺的混合液中,在氮气的保护下,于120℃进行反应,得到偶氮苯改性氮掺杂中空碳纳米纤维;
S6、将所述偶氮苯改性氮掺杂中空碳纳米纤维和十二烷基硫酸钠加入硫酸溶液中,分散均匀后,加入吡咯,再滴加过硫酸铵的硫酸溶液,常温下进行反应后,得到氮掺杂中空碳纳米线接枝聚吡咯。
作为优选方案,所述SiO2纳米线的制备方法为:
将正硅酸四乙酯加入乙醇和蒸馏水的混合液中,常温下磁力搅拌;加入乙酸继续搅拌反应,得到SiO2溶胶;
将醋酸纤维素加入N,N-二甲基甲酰胺和1,4-二氧六环混合溶剂中,磁力搅拌溶解,加入SiO2溶胶,常温下继续搅拌5h得到淬火液;
将所述淬火液在-50~-10℃下进行热致相分离后,用蒸馏水除去N,N-二甲基甲酰胺、1,4-二氧六环和乙醇,得到醋酸纤维素/SiO2复合纳米线;
将所述醋酸纤维素/SiO2复合纳米线浸泡在浓度为0.1mol/L的NaOH/乙醇溶液中水解24h,蒸馏水洗涤、干燥得到纤维素/SiO2复合纳米线;
将所述纤维素/SiO2复合纳米线在500~650℃下煅烧4~8h,除去纤维素,得到所述SiO2纳米线。
作为优选方案,所述的正硅酸四乙酯和乙酸的质量比为(15~30):(0.05~0.2);乙醇和蒸馏水的质量比为(14~17):(0.5~1.5);所述的淬火液中醋酸纤维素的质量浓度为2~5%,N,N-二甲基甲酰胺和1,4-二氧六环的质量比为(5~10):(2~4)。
作为优选方案,所述硫酸与硝酸的混合溶液中,硫酸和硝酸的质量浓度之比为3:1;酰氯改性氮掺杂中空碳纳米线和偶氮苯的质量比为(1~3):(10~20)。
作为优选方案,所述偶氮苯改性氮掺杂中空碳纳米纤维和吡咯的质量比为(0.9~1.2):(8~12)。
一种由前述方法制备的氮掺杂中空碳纳米线接枝聚吡咯在电极材料中的用途。
一种碳基电极材料的制备方法,其包括如下步骤:将权利要求1所制备的氮掺杂中空碳纳米线接枝聚吡咯和乙炔黑、聚四氟乙烯按照8:1:1的质量比分散在无水乙醇中,超声分散均匀后,涂敷于泡沫镍表面,在60℃下干燥,最后进行压片,得到所述碳基电极材料。
本发明的基本原理为:
1、首先溶胶-凝胶法制备SiO2溶胶,后将该溶胶与醋酸纤维素共混,得到淬火液。将淬火液通过热致相分离、水解、煅烧,出去模板纤维素,得到SiO2纳米线。
2、以SiO2纳米线为模板,糠醇为碳源,通过原位聚合、碳化、洗涤得到中空碳纳米线(HCNF)。以苯胺为氮源,中空碳纳米线为骨架,通过活化、预氧化和碳化得到氮掺杂碳中空纳米线(NHCNF)。
3、将氮掺杂碳中空纳米线活化,后与二氯亚砜反应引入酰氯,最后将产物与偶氮苯反应得到偶氮苯改性氮掺杂碳中空纳米线(ANHCNF-Azo)。
4、以ANHCNF-Azo为骨架、十二烷基苯磺酸钠为表面活性剂、过硫酸铵为引发剂,采用乳液聚合方法将吡咯接枝聚合到骨架上得到氮掺杂碳中空纳米线接枝聚吡咯(ANHCFN-g-PPy)。
与现有技术相比,本发明具有如下的有益效果:
1、氮掺杂碳中空纳米线接枝聚吡咯电极材料,利用中空纳米纤维的高孔隙率和大比表面积,提高了电解质与电极之间的浸润性。
2、将聚吡咯负载到碳基材料上,克服了单一碳基材料比电容低的缺点,大大提高了电极材料的比电容。
3、与普通的导电聚合物和碳基材料复合相比,将导电聚合物接枝到碳基材料上,由于在聚吡咯和碳中空纳米线之间形成了共价键连接,提高了电子在聚吡咯和碳中空纳米线之间的传输,大大提高了材料的比电容。
4、将氮掺杂到碳中空纳米线上,由于氮掺杂引入的含氮官能团能够带来准法拉第效应,有效提高电极的比容量。
5、该制备方法工艺稳定、易于操作、质量可靠、成本低廉,质量轻,无污染等特点,具有很好的商业化前景。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:
图1为本发明氮掺杂中空碳纳米线接枝聚吡咯的制备路线图;
图2为本发明实施例1制备的氮掺杂中空碳纳米线接枝聚吡咯扫描电镜图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
1)SiO2纳米线
将6g正硅酸四乙酯加入5g乙醇和0.7g蒸馏水的混合溶剂中,常温下磁力搅拌3h。上述溶液中加入0.04g乙酸继续搅拌反应5h,使正硅酸四乙酯水解,得到SiO2溶胶。取0.4g醋酸纤维素加入8g N,N-二甲基甲酰胺(DMF)和3g 1,4-二氧六环(DO)混合溶剂中,50℃磁力搅拌溶解,加入2g SiO2溶胶,常温下继续搅拌5h得到淬火液。
将淬火液放入-25℃冰箱中,淬冷200min。淬冷结束后将溶液快速拿出,加入500mL蒸馏水萃取,除去溶剂N,N-二甲基甲酰胺、1,4-二氧六环和乙醇,每隔6h换水一次,连续换水5次。样品冷冻干燥24h,得到醋酸纤维素/SiO2复合纳米线。将醋酸纤维素/SiO2复合纳米线浸泡在浓度为0.1mol/L的NaOH/乙醇溶液中水解24h,蒸馏水洗涤、干燥得到纤维素/SiO2复合纳米线。将纤维素/SiO2复合纳米线置于马弗炉中500℃下煅烧7h,除去纤维素,得到SiO2纳米线。
2)氮掺杂碳中空纳米线
将1.2g糠醇、0.09g SiO2纳米线、10mL乙醇、3g水混合,磁力搅拌,滴加浓度为4mol/L硫酸4mL,90℃加热磁力搅拌反应3h,冷却,水稀释,离心,干燥得到固体产物,将固体产物在氩气保护下,从常温升温到180℃,升温速率1.8℃/min,保温4h,接着从180℃升温至650℃,升温速率3℃/min,保温6h。将产物浸泡在氢氟酸中,去除模板SiO2,洗涤、干燥得到中空碳纳米线(NHCNF)。
将0.2g中空碳纳米线、2g苯胺、10g盐酸、0.2g十二烷基硫酸钠加入三口烧瓶中,磁力搅拌形成混合液,将10g浓度为0.3mol/L过硫酸铵溶液滴加到混合液中,在3℃下反应5h后,得到聚苯胺/中空碳纳米线复合材料。将聚苯胺/中空碳纳米线复合材料用质量浓度为0.5%的NH4Cl溶液活化、洗涤、干燥。氮气保护下,从25℃升温到280℃,保温180min,接着从280℃升温到900℃,保温180min,到氮掺杂碳中空纳米线。
3)偶氮苯改性氮掺杂碳中空纳米线
将0.2g氮掺杂碳中空纳米线浸泡在硫酸和硝酸的混合溶液中5h,混合溶液中硫酸与硝酸的质量浓度比为3:1。洗涤、干燥得到活化氮掺杂碳中空纳米线。将活化氮掺杂碳中空纳米线浸泡在15mL的二氯亚砜中3h,将羧基转变为酰氯,浸泡结束后取出干燥,得到酰氯改性氮掺杂碳中空纳米线,简写为ANHCNF-COCl。
在三口烧瓶中加入30mL N,N-二甲基甲酰胺和5mL三乙基胺中,将0.2gANHCNF-COCl和3g偶氮苯加入三口烧瓶中,氮气保护条件下,120℃反应30h,产物过滤、乙醇洗涤、干燥得到偶氮苯改性氮掺杂碳中空纳米纤维,简写为ANHCNF-Azo。
4)氮掺杂碳中空纳米线接枝聚吡咯
将0.09g ANHCNF-Azo和0.3g的十二烷基硫酸钠加入50mL 1mol/L的硫酸溶液中,磁力搅拌30min,形成混合液。然后加入1.2g吡咯。将0.8g的过硫酸铵溶解在50mL 1mol/L硫酸溶液中。将过硫酸铵溶液逐滴加入混合液中,常温下磁力搅拌反应4h,反应结束后,将混合物倒入250mL丙酮中,过滤,沉淀物用大量蒸馏水洗涤、干燥,得到氮掺杂碳中空纳米线接枝聚吡咯,简写为ANHCNF-g-PPy。反应路线如图1所示。ANHCNF-g-Ppy材料的扫描电镜如图2所示,从图中可知,纳米线已被聚吡咯包裹,说明聚吡咯已成功接枝到纳米线上。
本实施例制备得到的ANHCNF-g-PPy材料的孔隙率为89.4%、比表面积为66.4m2/g。将ANHCNF-g-PPy与乙炔黑和PTFE按8:1:1的质量比混合在无水乙醇中,超声分散40min后,涂覆在泡沫镍上,于60℃真空干燥6h,然后在10MPa压力下压片,制得ANHCNF-g-PPy电极。对该电极材料的电化学性能进行测试,在电流密度为1A/g条件下,比电容为289F/g,循环使用800次后,电容为初始值的80.1%。
实施例2
1)SiO2纳米线
将5g正硅酸四乙酯加入6g乙醇和0.6g蒸馏水的混合溶剂中,常温下磁力搅拌3h。上述溶液中加入0.04g乙酸继续搅拌反应5h,使正硅酸四乙酯水解,得到SiO2溶胶。取0.5g醋酸纤维素加入7g N,N-二甲基甲酰胺(DMF)和4g 1,4-二氧六环(DO)混合溶剂中,50℃磁力搅拌溶解,加入2.3g SiO2溶胶,常温下继续搅拌5h得到淬火液。
将淬火液放入-30℃冰箱中,淬冷250min。淬冷结束后将溶液快速拿出,加入500mL蒸馏水萃取,除去溶剂N,N-二甲基甲酰胺、1,4-二氧六环和乙醇,每隔6h换水一次,连续换水5次。样品冷冻干燥24h,得到醋酸纤维素/SiO2复合纳米线。将醋酸纤维素/SiO2复合纳米线浸泡在浓度为0.1mol/L的NaOH/乙醇溶液中水解24h,蒸馏水洗涤、干燥得到纤维素/SiO2复合纳米线。将纤维素/SiO2复合纳米线置于马弗炉中550℃下煅烧6h,除去纤维素,得到SiO2纳米线。
2)氮掺杂碳中空纳米线
将1g糠醇、0.07g SiO2纳米线、10mL乙醇、4g水混合,磁力搅拌,滴加浓度为4mol/L硫酸4mL,90℃加热磁力搅拌反应3h,冷却,水稀释,离心,干燥得到固体产物,将固体产物在氩气保护下,从常温升温到200℃,升温速率2℃/min,保温3.5h,接着从200℃升温至600℃,升温速率2.5℃/min,保温7h。将产物浸泡在氢氟酸中,去除模板SiO2,洗涤、干燥得到中空碳纳米线(NHCNF)。
将0.15g中空碳纳米线、1.5g苯胺、10g盐酸、0.2g十二烷基硫酸钠加入三口烧瓶中,磁力搅拌形成混合液,将10g浓度为0.3mol/L过硫酸铵溶液滴加到混合液中,在3℃下反应5h后,得到聚苯胺/中空碳纳米线复合材料。将聚苯胺/中空碳纳米线复合材料用质量浓度为0.5%的NH4Cl溶液活化、洗涤、干燥。氮气保护下,从25℃升温到300℃,保温200min,接着从300℃升温到950℃,保温160min,到氮掺杂碳中空纳米线。
3)偶氮苯改性氮掺杂碳中空纳米线
将0.15g氮掺杂碳中空纳米线浸泡在硫酸和硝酸的混合溶液中5h,混合溶液中硫酸与硝酸的质量浓度比为3:1。洗涤、干燥得到活化氮掺杂碳中空纳米线。将活化氮掺杂碳中空纳米线浸泡在15mL的二氯亚砜中3h,将羧基转变为酰氯,浸泡结束后取出干燥,得到酰氯改性氮掺杂碳中空纳米线,简写为ANHCNF-COCl。
在三口烧瓶中加入30mL N,N-二甲基甲酰胺和5mL三乙基胺中,将0.15gANHCNF-COCl和2.5g偶氮苯加入三口烧瓶中,氮气保护条件下,120℃反应30h,产物过滤、乙醇洗涤、干燥得到偶氮苯改性氮掺杂碳中空纳米纤维,简写为ANHCNF-Azo。
4)氮掺杂碳中空纳米线接枝聚吡咯
将0.09g ANHCNF-Azo和0.3g的十二烷基硫酸钠加入50mL 1mol/L的硫酸溶液中,磁力搅拌30min,形成混合液。然后加入0.9g吡咯。将0.8g的过硫酸铵溶解在50mL 1mol/L硫酸溶液中。将过硫酸铵溶液逐滴加入混合液中,常温下磁力搅拌反应4h,反应结束后,将混合物倒入250mL丙酮中,过滤,沉淀物用大量蒸馏水洗涤、干燥,得到氮掺杂碳中空纳米线接枝聚吡咯,简写为ANHCNF-g-PPy。
本实施例制备得到的ANHCNF-g-PPy材料的孔隙率为90.1%、比表面积为67.2m2/g。将ANHCNF-g-PPy与乙炔黑和PTFE按8:1:1的质量比混合在无水乙醇中,超声分散40min后,涂覆在泡沫镍上,于60℃真空干燥6h,然后在10MPa压力下压片,制得ANHCNF-g-PPy电极。对该电极材料的电化学性能进行测试,在电流密度为1A/g条件下,比电容为287F/g,循环使用800次后,电容为初始值的76.1%。
实施例3
1)SiO2纳米线
将7g正硅酸四乙酯加入8g乙醇和0.7g蒸馏水的混合溶剂中,常温下磁力搅拌3h。上述溶液中加入0.05g乙酸继续搅拌反应5h,使正硅酸四乙酯水解,得到SiO2溶胶。取0.34g醋酸纤维素加入10g N,N-二甲基甲酰胺(DMF)和3g 1,4-二氧六环(DO)混合溶剂中,50℃磁力搅拌溶解,加入2.2g SiO2溶胶,常温下继续搅拌5h得到淬火液。
将淬火液放入-20℃冰箱中,淬冷220min。淬冷结束后将溶液快速拿出,加入500mL蒸馏水萃取,除去溶剂N,N-二甲基甲酰胺、1,4-二氧六环和乙醇,每隔6h换水一次,连续换水5次。样品冷冻干燥24h,得到醋酸纤维素/SiO2复合纳米线。将醋酸纤维素/SiO2复合纳米线浸泡在浓度为0.1mol/L的NaOH/乙醇溶液中水解24h,蒸馏水洗涤、干燥得到纤维素/SiO2复合纳米线。将纤维素/SiO2复合纳米线置于马弗炉中500℃下煅烧7h,除去纤维素,得到SiO2纳米线。
2)氮掺杂碳中空纳米线
将1.1g糠醇、0.08g SiO2纳米线、10mL乙醇、3.5g水混合,磁力搅拌,滴加浓度为4mol/L硫酸4mL,90℃加热磁力搅拌反应3h,冷却,水稀释,离心,干燥得到固体产物,将固体产物在氩气保护下,从常温升温到220℃,升温速率2℃/min,保温4h,接着从220℃升温至620℃,升温速率2℃/min,保温6h。将产物浸泡在氢氟酸中,去除模板SiO2,洗涤、干燥得到中空碳纳米线(NHCNF)。
将0.2g中空碳纳米线、1.6g苯胺、10g盐酸、0.2g十二烷基硫酸钠加入三口烧瓶中,磁力搅拌形成混合液,将10g浓度为0.3mol/L过硫酸铵溶液滴加到混合液中,在3℃下反应5h后,得到聚苯胺/中空碳纳米线复合材料。将聚苯胺/中空碳纳米线复合材料用质量浓度为0.5%的NH4Cl溶液活化、洗涤、干燥。氮气保护下,从25℃升温到260℃,保温180min,接着从260℃升温到900℃,保温180min,到氮掺杂碳中空纳米线。
3)偶氮苯改性氮掺杂碳中空纳米线
将0.15g氮掺杂碳中空纳米线浸泡在硫酸和硝酸的混合溶液中5h,混合溶液中硫酸与硝酸的质量浓度比为3:1。洗涤、干燥得到活化氮掺杂碳中空纳米线。将活化氮掺杂碳中空纳米线浸泡在15mL的二氯亚砜中3h,将羧基转变为酰氯,浸泡结束后取出干燥,得到酰氯改性氮掺杂碳中空纳米线,简写为ANHCNF-COCl。
在三口烧瓶中加入30mL N,N-二甲基甲酰胺和5mL三乙基胺中,将0.15gANHCNF-COCl和2.8g偶氮苯加入三口烧瓶中,氮气保护条件下,120℃反应30h,产物过滤、乙醇洗涤、干燥得到偶氮苯改性氮掺杂碳中空纳米纤维,简写为ANHCNF-Azo。
4)氮掺杂碳中空纳米线接枝聚吡咯
将0.12g ANHCNF-Azo和0.3g的十二烷基硫酸钠加入50mL 1mol/L的硫酸溶液中,磁力搅拌30min,形成混合液。然后加入1.1g吡咯。将0.8g的过硫酸铵溶解在50mL 1mol/L硫酸溶液中。将过硫酸铵溶液逐滴加入混合液中,常温下磁力搅拌反应4h,反应结束后,将混合物倒入250mL丙酮中,过滤,沉淀物用大量蒸馏水洗涤、干燥,得到氮掺杂碳中空纳米线接枝聚吡咯,简写为ANHCNF-g-PPy。
本实施例制备得到的ANHCNF-g-PPy材料的孔隙率为88.5%、比表面积为65.1m2/g。将ANHCNF-g-PPy与乙炔黑和PTFE按8:1:1的质量比混合在无水乙醇中,超声分散40min后,涂覆在泡沫镍上,于60℃真空干燥6h,然后在10MPa压力下压片,制得ANHCNF-g-PPy电极。对该电极材料的电化学性能进行测试,在电流密度为1A/g条件下,比电容为301F/g,循环使用800次后,电容为初始值的78.1%。
对比例1
与实施例1不同之处在于:步骤4)中ANHCNF-Azo的添加量为0,最终得到聚吡咯,简写为PPy。PPy材料的孔隙率为48.1%、比表面积为1.01m2/g。制得的电极材料,在电流密度为1A/g条件下,比电容为91F/g,循环使用800次后,电容为初始值的70.1%。
对比例2
与实施例1不同之处在于:步骤4)中将ANHCNF-Azo替换为ANHCNF,最终得到ANHCNF/聚吡咯复合材料,简写为AHCNF/PPy材料。该材料的孔隙率为85.1%、比表面积为45.1m2/g,制得的电极材料,在电流密度为1A/g条件下,比电容为189F/g,循环使用800次后,电容为初始值的68.1%。
对比例3
与实施例1不同之处在于:步骤2)中SiO2纳米线的添加量为0,经过步骤2)后得到氮掺杂活性碳(NAC),最终得到氮掺杂活性碳接枝聚吡咯,简写为NAC-g-PPy。该材料的孔隙率为70.1%、比表面积为31.1m2/g,制得的电极材料,在电流密度为1A/g条件下,比电容为201F/g,循环使用800次后,电容为初始值的66.1%。
对比例4
与实施例1不同之处在于:步骤3)中将氮掺杂碳中空纳米线该为碳中空纳米线,最终得到碳中空纳米线接枝聚吡咯,简写为AHCNF-g-PPy。该材料的孔隙率为88.7%、比表面积为69.1m2/g,制得的电极材料,在电流密度为1A/g条件下,比电容为222F/g,循环使用800次后,电容为初始值的61.1%。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (7)
1.一种氮掺杂中空碳纳米线接枝聚吡咯的制备方法,其特征在于,包括如下步骤:
S1、利用溶胶-凝胶和热致相分离结合的方式制备SiO2纳米线;
S2、将糠醇、乙醇、水和所述SiO2纳米线混合,滴加硫酸,在90℃下进行反应,经过冷却、水稀释、离心和干燥,得到固体产物,将所述固体产物在氩气的保护下,以1~2℃/min的速率加热至180~220℃,保温3~4h后,以2~3℃/min的速率升温至600~650℃,保温6~8h后,将产物浸泡在氢氟酸中,去除模板SiO2,洗涤、干燥得到中空碳纳米线;
S3、将苯胺、盐酸、十二烷基硫酸钠和所述中空碳纳米线混匀后,将滴加过硫酸铵溶液,在3~5℃下反应后,得到聚苯胺/中空碳纳米线复合材料;
S4、将所述聚苯胺/中空碳纳米线复合材料用质量浓度为0.5%的NH4Cl溶液活化后、进行洗涤、干燥,在氮气保护下,加热至250~280℃,保温150~180 min,接着加热至900~950 ℃,保温150~200 min,到氮掺杂中空碳纳米线;
S5、将所述氮掺杂中空碳纳米线浸泡在硫酸和硝酸的混合溶液中进行活化后,用二氯亚砜进行酰氯化,得到酰氯改性氮掺杂中空碳纳米线,将偶氮苯和所述酰氯改性氮掺杂中空碳纳米线分散于N,N-二甲基甲酰胺和三乙基胺的混合液中,在氮气的保护下,于120℃进行反应,得到偶氮苯改性氮掺杂中空碳纳米纤维;
S6、将所述偶氮苯改性氮掺杂中空碳纳米纤维和十二烷基硫酸钠加入硫酸溶液中,分散均匀后,加入吡咯,再滴加过硫酸铵的硫酸溶液,常温下进行反应后,得到氮掺杂中空碳纳米线接枝聚吡咯。
2.如权利要求1所述的氮掺杂中空碳纳米线接枝聚吡咯的制备方法,其特征在于,所述SiO2纳米线的制备方法为:
将正硅酸四乙酯加入乙醇和蒸馏水的混合液中,常温下磁力搅拌;加入乙酸继续搅拌反应,得到SiO2溶胶;
将醋酸纤维素加入N,N-二甲基甲酰胺和1,4-二氧六环混合溶剂中,磁力搅拌溶解,加入SiO2溶胶,常温下继续搅拌5 h得到淬火液;
将所述淬火液在-50~-10℃下进行热致相分离后,用蒸馏水除去N,N-二甲基甲酰胺、1,4-二氧六环和乙醇,得到醋酸纤维素/SiO2复合纳米线;
将所述醋酸纤维素/SiO2复合纳米线浸泡在浓度为0.1 mol/L的NaOH/乙醇溶液中水解24h,蒸馏水洗涤、干燥得到纤维素/SiO2复合纳米线;
将所述纤维素/SiO2复合纳米线在500~650℃下煅烧4~8 h,除去纤维素,得到所述SiO2纳米线。
3.如权利要求2所述的氮掺杂中空碳纳米线接枝聚吡咯的制备方法,其特征在于,所述的正硅酸四乙酯和乙酸的质量比为(15~30):(0.05~0.2);乙醇和蒸馏水的质量比为(14~17):(0.5~1.5);所述的淬火液中醋酸纤维素的质量浓度为2~5%,N,N-二甲基甲酰胺和1,4-二氧六环的质量比为(5~10):(2~4)。
4.如权利要求1所述的氮掺杂中空碳纳米线接枝聚吡咯的制备方法,其特征在于,
所述硫酸与硝酸的混合溶液中,硫酸和硝酸的质量浓度之比为3:1;酰氯改性氮掺杂中空碳纳米线和偶氮苯的质量比为(1~3):(10~20)。
5.如权利要求1所述的氮掺杂中空碳纳米线接枝聚吡咯的制备方法,其特征在于,所述偶氮苯改性氮掺杂中空碳纳米纤维和吡咯的质量比为(0.9~1.2):(8~12)。
6.一种由权利要求1所述方法制备的氮掺杂中空碳纳米线接枝聚吡咯在电极材料中的用途。
7.一种碳基电极材料的制备方法,其特征在于,包括如下步骤:将权利要求1所述制备方法得到的氮掺杂中空碳纳米线接枝聚吡咯和乙炔黑、聚四氟乙烯按照8:1:1的质量比分散在无水乙醇中,超声分散均匀后,涂敷于泡沫镍表面,在60℃下干燥,最后进行压片,得到所述碳基电极材料。
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