CN108103616B - 一种氮掺杂的木质素基碳纤维复合材料的制备方法 - Google Patents
一种氮掺杂的木质素基碳纤维复合材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种氮掺杂的木质素基碳纤维复合材料的制备方法,所述制备方法包括:1)将聚合物溶于有机溶剂中,再加入尿素制备纺丝液;2)静电纺丝制备纳米纤维前驱体;3)对步骤2)中所得的纤维前驱体在空气中干燥后,浸入苯胺/盐酸溶液中,随后逐滴滴加过硫酸铵的盐酸溶液,保温反应;4)预氧化;5)管式炉中煅烧,得到氮掺杂的木质素基碳纤维。本发明所用碱木质素为原料,来源广泛,绿色环保,生产成本低。采用尿素和聚苯胺作为氮源,提高了碳纤维氮含量,同时氮分布均一,可有效地提高碳纤维电化学性能。
Description
技术领域
本发明属于材料领域,具体而言,涉及一种氮掺杂的木质素基碳纤维复合材料的制备方法和应用。
背景技术
超级电容器,也称为电化学电容器,由于其具有较高的功率密度,快速充/放电速率,和极好的循环寿命,超级电容器成为极具前景的器件。根据其电荷存储机制,超级电容器通常分为两种类型:双电层电容器,电容是通过在电极/电解液表面,可逆的离子吸附/解吸的电荷量产生的;另一种是赝电容器,其电容来源于可逆的氧化还原反应。多数碳材料,如活性炭、纳米碳纤维、碳纳米管和石墨烯,通常具有双电层电容。而导电聚合物如聚苯胺和聚吡咯通常被用作赝电容器。因为这两种电容器具有不同的电荷存储机理,双电层电容器具有较高的能量密度和较长的循环寿命,但其比电容较低;而赝电容器具有较高的比电容和能量密度,但其稳定性较低、循环寿命差。因此,为提高其导电性能,我们将具有双电层电容的纳米碳纤维与具有赝电容的聚苯胺复合来发挥它们各自的优点以达到协同作用。此外,现有技术中往往通过掺杂硼、硫和氮等杂原子,提高碳材料的电化学性能。
近年来,新型的碳纳米材料(如石墨烯、碳纳米管,介孔碳,等等)都表现出优良的性能作为超级电容器。然而,这些碳材料,不可再生、制备条件苛刻和成本高限制了它们的广泛应用。木质素作为最重要的可再生资源之一,是仅次于纤维素的第二大自然聚合物。它是由苯丙烷结构单元组成,并且存在大量的化学基团,如甲氧基、酚基和羟基。
静电纺丝是一种通过电压来压迫聚合物或聚合物混合液流体喷射来制备纳米纤维的方法。该方法制备的氮掺杂的木质素基碳纤维复合材料具有均匀的纤维直径、高氮含量和高石墨结构,这种独特的结构对提高电容性能非常重要,同时也为低成本、可再生的生物质原料提供了高价值的应用前景。
现有技术中已有多种通过静电纺丝技术制备基于木质素的纳米纤维的方法,例如中国专利201180026569.X,201010104518.1以及201710043185.4等,但这些已有的木质素的纳米纤维并不能很好地应用于超级电容器,因此还需要进一步开发具有例如更高比电容的电化学性能的纳米纤维。
发明内容
针对以上现有技术存在的问题,根据本发明的一个方面,本发明的一个目的在于提供一种氮掺杂的木质素基碳纤维复合材料的制备方法,该方法以环境友好可再生的木质素为碳源,所用木质素原料来源广泛、价格低廉,可以降低碳纤维的成本。同时制备的碳纤维复合材料具有均匀的纤维直径、高氮含量和石墨结构,可有效地提高其电化学性能。
根据本发明的氮掺杂的木质素基碳纤维复合材料的制备方法,包括以下步骤:
1)将聚合物溶于N,N-二甲基甲酰胺(DMF)有机溶剂中,充分搅拌,配成质量分数为13%~15%的均一溶液,将尿素加入制备的聚合物溶液中,继续搅拌完全溶解,即得纺丝液;
2)设置静电纺丝电压为10-18kv,接收距离10-18cm,推进速率0.3ml/h-1.0ml/h,用锡箔纸收集高压静电纺丝制得的纳米纤维前驱体;
3)对步骤2)中所得的纤维前驱体在空气中干燥后,浸入苯胺/盐酸溶液中10-24h,其中苯胺的质量分数为0.1%,随后逐滴滴加含有质量分数为2.5g/L的过硫酸铵的盐酸溶液40ml,并保持温度在0~4℃,3-5h;
4)对步骤3)所得的纳米纤维经去离子水洗数次后,置于60℃干燥箱中干燥12h后,将其置于管式炉中空气气氛下260℃预氧化1h;
5)将步骤4)所得氧化后的纤维置于管式炉的惰性氮气气氛下煅烧,煅烧温度为800~900℃,煅烧时间1-3h,得到氮掺杂的木质素基碳纤维。
优选地,步骤1)中所述的聚合物选自为碱木质素(LN)和聚丙烯腈(PAN)的混合物。
优选地,步骤1)中所述聚丙烯腈(PAN)具有约150,000的重均分子量(Mw),由MACKLIN生产,产品批号为823208。
优选地,步骤1)中所述碱木素、聚丙烯腈和尿素的用量重量比例为1:5-7:0.5-1,优选为1:6.5:0.8。
优选地,步骤3)中所述盐酸浓度为1mol/L。
优选地,根据本发明所述氮掺杂的木质素基碳纤维复合材料的制备方法无需添加胶黏剂、增稠剂、增白剂等辅料。
根据本发明的另一个方面,本发明的另一个目的在于提供一种氮掺杂的木质素基碳纤维复合材料,所述复合材料由根据本发明的上述制备方法制备得到。
根据本发明的另一个方面,本发明的另一个目的在于提供所述氮掺杂的木质素基碳纤维复合材料在储能电池方面的应用。
有益效果
1、本发明所用碱木质素为原料,来源广泛,绿色环保,生产成本低。
2、本发明采用尿素和聚苯胺作为氮源,提高了碳纤维氮含量,同时氮分布均一,可有效地提高碳纤维电化学性能。
3、本发明采用静电纺丝法制备氮掺杂的木质素基碳纤维复合材料,设备简单,操作性强。
4、本发明选择性制备的氮掺杂的木质素基碳纤维复合材料,具有一定的柔韧性,可直接用于电化学测试,无需添加胶黏剂,电化学性能可有效的提高。
附图说明
图1为实施例3碳纤维的扫描电镜图。
图2a为根据本实施例制备的碳纤维的透射电镜图,图2b为根据本实施例制备的碳纤维的直径的分布图。
图3为实施例2和实施例3的X射线衍射图。
图4为实施例2和实施例3在电流密度为1A/g下的充放电循环曲线。
图5为实施例2和实施例3在扫描速率5mV/s下的循环伏安曲线。
具体实施方式
以下,将详细地描述本发明。在进行描述之前,应当理解的是,在本说明书和所附的权利要求书中使用的术语不应解释为限制于一般含义和字典含义,而应当在允许发明人适当定义术语以进行最佳解释的原则的基础上,根据与本发明的技术方面相应的含义和概念进行解释。因此,这里提出的描述仅仅是出于举例说明目的的优选实例,并非意图限制本发明的范围,从而应当理解的是,在不偏离本发明的精神和范围的情况下,可以由其获得其他等价方式或改进方式。
优选地,在根据本发明的制备方法的步骤1)中所述LN、PAN和尿素的的用量比例为1:5-7:0.5-1,优选范围为1:6.5:0.8。若聚丙烯腈比重太大,则溶液粘度过大,纺丝过程易堵塞;过小,则纺丝过程中纳米纤维不易成丝,纺丝易断裂。因此,适宜的比重有益于纤维纺丝,同时纤维直径分布均匀。
优选地,步骤2)中静电纺丝电压为10-18kv,接收距离10-18cm,推进速率0.3ml/h-1.0ml/h,纺丝随电压升高,接收距离加大,推进速率减缓,所得纺丝直径越细。优选地,静电纺丝电压优选为15kv,接收距离优选15cm,推进速率优选为0.5ml/h。
优选地,步骤3中滴加含有质量分数为2.5g/L的过硫酸铵的盐酸溶液40mL,从而与苯胺发生氧化还原聚合反应,生成具有导电性能的聚苯胺。
当木质素在惰性气体环境中碳化时,木质素石墨结构碳可以通过局部的sp2π键来表现优异的电子传导率。因此,本发明的发明人选用木质素作为可持续性碳前体,和聚丙烯腈、尿素来制备碳纳米纤维,并复合苯胺来进一步提高碳纤维的氮含量。
在下文中,将参照附图详细地描述本公开的优选的实施方式。在描述之前,应当了解在说明书和所附权利要求中使用的术语,并不应解释为局限于一般及辞典意义,而是应当基于允许发明人为最好的解释而适当定义术语的原则,基于对应于本发明技术层面的意义及概念进行解释。因此,在此的描述仅为说明目的的优选实例,而并非是意指限制本发明的范围,因而应当了解的是,在不偏离本发明的精神和范围下可以做出其他等同实施和修改。除非特别说明,以下实施例中使用的试剂和仪器均为市售可得产品。
实施例2
室温下,将0.65g PAN,0.1g LN溶于5ml DMF中,在磁力搅拌器上充分搅拌至完全溶解,将0.08g尿素加入制备的聚合物溶液中,继续搅拌至完全溶解,制得纺丝液。用10ml的注射器抽取纺丝液,设置纺丝电压为15kv,接收距离15cm,推进速率0.5ml/h,并用锡箔纸收集高压静电纺丝制得的纳米纤维前驱体,置于空气中干燥12h。将干燥后的纳米纤维前驱体,浸入重量百分比浓度为0.1%苯胺/盐酸(盐酸浓度为1mol/L,40ml)溶液中12h,随后逐滴滴加含有10g过硫酸铵的40ml盐酸(1mol/L)溶液,并保持温度在0~4℃,4h。所得的纳米纤维经去离子水洗数次后,置于60℃干燥箱中干燥12h后,随后将其置于管式炉中空气气氛下260℃预氧化1h。将氧化后的纤维置于管式炉的惰性氮气气氛下煅烧,升温速率为5℃/h,煅烧温度为800℃,煅烧时间2h,得到LCNFs/PANI/N-8碳纤维。
电化学性能测试:在1mol/l的硫酸电解液中,电流密度为1A/g,LCNFs/PANI/N-8碳纤维的比电容为101.4F/g。
图3为实施例2和实施例3的X射线衍射图,从中可以进一步的确定碳纤维中含有PANI组分,并且从图中可以看出随着煅烧温度的增加,碳纤维的石墨化程度也有所增加。
图4为实施例2和实施例3在电流密度为1A/g下的充放电循环曲线。
图5为实施例2和实施例3在扫描速率5mV/s下的循环伏安曲线。从图4和图5中可以看出随着木质素、氮掺杂及煅烧温度的提高,所得的碳纤维的比电容也有所增加。
实施例3
除了将预氧化后的纤维置于管式炉的惰性氮气气氛下煅烧,升温速率为5℃/h,煅烧温度为900℃,煅烧时间2h,得到LCNFs/PANI/N-9碳纤维之外,其余与实施例2相同。
电化学性能测试:在1mol/l的硫酸电解液中,电流密度为1A/g,LCNFs/PANI/N-9碳纤维的比电容为199.5F/g。
图1为根据本实施例制备的碳纤维的扫描电镜图,从图中可以看出纳米碳纤维的尺寸较均一,并在表面复合PANI。图2a为根据本实施例制备的碳纤维的透射电镜图,图2b为根据本实施例制备的碳纤维的直径的分布图。
对比实施例1
室温下,将0.65g PAN溶于5ml DMF中,在磁力搅拌器上充分搅拌至完全溶解,制得纺丝液。用10ml的注射器抽取纺丝液,设置纺丝电压为15kv,接收距离15cm,推进速率0.5ml/h,并用锡箔纸收集高压静电纺丝制得的纳米纤维前驱体,置于空气中干燥12h。将干燥得到的PAN纳米纤维,将其置于管式炉中空气气氛下260℃预氧化1h。将氧化后的纤维置于管式炉的惰性氮气气氛下煅烧,升温速率为5℃/h,煅烧温度为800℃,煅烧时间2h,得到CNFs-8碳纤维。
电化学性能测试:在1mol/l的硫酸电解液中,电流密度为1A/g,CNFs-8碳纤维的比电容为46.3F/g。
对比实施例2
室温下,将0.65g PAN,0.1g LN溶于5ml DMF中,在磁力搅拌器上充分搅拌至完全溶解,制得纺丝液。用10ml的注射器抽取纺丝液,设置纺丝电压为15kv,接收距离15cm,推进速率0.5ml/h,并用锡箔纸收集高压静电纺丝制得的纳米纤维前驱体,置于空气中干燥12h。将干燥得到的PAN/LN纳米纤维,将其置于管式炉中空气气氛下260℃预氧化1h。将氧化后的纤维置于管式炉的惰性氮气气氛下煅烧,升温速率为5℃/h,煅烧温度为800℃,煅烧时间2h,得到LCNFs-8碳纤维。
电化学性能测试:在1mol/l的硫酸电解液中,电流密度为1A/g,LCNFs-8碳纤维的比电容为77.8F/g。
对比实施例3
室温下,将0.65g PAN(Mw~150,000),0.1g LN溶于5ml DMF中,在磁力搅拌器上充分搅拌至完全溶解,将0.08g尿素加入制备的聚合物溶液中,继续搅拌至完全溶解,制得纺丝液。用10ml的注射器抽取纺丝液,设置纺丝电压为15kv,接收距离15cm,推进速率0.5ml/h,并用锡箔纸收集高压静电纺丝制得的纳米纤维前驱体,置于空气中干燥12h。将干燥得到的PAN/LN/尿素纳米纤维,将其置于管式炉中空气气氛下260℃预氧化1h。将氧化后的纤维置于管式炉的惰性氮气气氛下煅烧,升温速率为5℃/h,煅烧温度为800℃,煅烧时间2h,得到LCNFs/N-8碳纤维。
在1mol/l的硫酸电解液中,电流密度为1A/g,LCNFs/N-8碳纤维的比电容为85.5F/g。
电化学性能实验
利用电化学工作站CHI660D,采用三电极体系对氮掺杂的木质素基碳纤维复合材料进行电化学测试。所制得的氮掺杂的木质素基碳纤维作为工作电极,甘汞电极作为参比电极,铂丝电极作为对电极,电解液为1mol/l的硫酸溶液。通过不同扫描速率的循环伏安曲线和不用电流密度下的恒电流充放电曲线,来计算碳纤维电极材料的比电容。
对实施例3的碳纤维复合材料在4A/g的电流密度下进行1000次循环充放电后,电容仍保持初始值的82%。
Claims (7)
1.一种氮掺杂的木质素基碳纤维复合材料的制备方法,包括以下步骤:
1)将聚合物溶于N,N-二甲基甲酰胺有机溶剂中,充分搅拌,配成质量分数为13%~15%的均一溶液,将尿素加入制备的聚合物溶液中,继续搅拌完全溶解,即得纺丝液,所述聚合物选自为碱木质素和聚丙烯腈的混合物,所述碱木素、聚丙烯腈和尿素的重量比例为1:5-7:0.5-1;
2)设置静电纺丝电压为10-18kv,接收距离10-18cm,推进速率0.3ml/h-1.0ml/h,用锡箔纸收集高压静电纺丝制得的纳米纤维前驱体;
3)对步骤2)中所得的纤维前驱体在空气中干燥后,浸入苯胺/盐酸溶液中10-24h,其中苯胺的质量分数为0.1%,随后逐滴滴加含有质量分数为2.5g/L的过硫酸铵的盐酸溶液40ml,并保持温度在0~4℃,3-5h;
4)对步骤3)所得的纳米纤维经去离子水洗数次后,置于60℃干燥箱中干燥12h后,将其置于管式炉中空气气氛下260℃预氧化1h;
5)将步骤4)所得氧化后的纤维置于管式炉的惰性氮气气氛下煅烧,煅烧温度为800~900℃,煅烧时间1-3h,得到氮掺杂的木质素基碳纤维。
2.根据权利要求1所述的氮掺杂的木质素基碳纤维复合材料的制备方法,其特征在于,步骤1)中所述聚丙烯腈具有150,000的重均分子量(Mw)。
3.根据权利要求1所述的氮掺杂的木质素基碳纤维复合材料的制备方法,其特征在于,步骤1)中所述碱木素、聚丙烯腈和尿素的用量重量比例为1:6.5:0.8。
4.根据权利要求1所述的氮掺杂的木质素基碳纤维复合材料的制备方法,其特征在于,步骤3)中所述盐酸浓度为1mol/L。
5.根据权利要求1所述的氮掺杂的木质素基碳纤维复合材料的制备方法,其特征在于,所述制备方法无需添加胶黏剂、增稠剂、增白剂辅料。
6.一种氮掺杂的木质素基碳纤维复合材料,所述复合材料由根据权利要求1至5中任意一项所述的制备方法制备得到。
7.根据权利要求6所述的氮掺杂的木质素基碳纤维复合材料在储能电池方面的应用。
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