CN107161982A - 石油焦基石墨烯及其制备方法和应用 - Google Patents
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
本发明属于纳米碳材料技术领域,具体涉及石油焦基石墨烯及其制备方法和应用。包括以下步骤:(1)将蒙脱土超声分散于去离子水中,加入十六烷基三甲基溴化铵,在搅拌条件下水热反应后,过滤洗涤干燥,得到十六烷基三甲基溴化铵改性的蒙脱土;(2)将步骤(1)所得十六烷基三甲基溴化铵改性的蒙脱土溶于氢氧化钠溶液中,然后加入石油焦基双亲性碳质材料,在反应釜中水热反应后,过滤洗涤干燥;(3)将步骤(2)所得固体放入到管式炉中在氩气气氛下高温碳化,最后先后用氢氧化钠溶液和盐酸溶液洗涤,得到石油焦基石墨烯。可用作超级电容器的电极材料,在碱性电解液中,表现出大的比电容、高的倍率性、高的电化学稳定性的优点。
Description
技术领域
本发明属于纳米碳材料技术领域,具体涉及石油焦基石墨烯及其制备方法和应用。
背景技术
进入21世纪以来,可再生能源受到广泛关注。由于可再生能源受地区和气候条件影响较大,具有间歇性的特点,导致产能不稳定,并网发电困难,因而急需高能量密度和功率密度的储能器件。超级电容器是一种新型储能元件,也被称为电化学电容器。与其他储能器件相比,超级电容器功率密度高,充放电速度快,循环寿命长,安全环保,得到了科学家的广泛研究,可以应用在便携式电子产品、可再生制动系统、能源管理、即时开关等方面。
超级电容器的电极材料以碳材料为主。与零维、一维的碳材料相比,相同质量条件下,二维的碳材料可以提供更大的比表面积,提供更多的活性位点,而且二维的碳材料相互连接形成网络,具有开放的孔隙结构,有利于物质的快速吸附和传递。石墨烯是一种典型的二维碳材料,其双侧表面都可以形成双电层。优异的力学性能、高的导电性、大的比表面积和高的化学稳定性,使得石墨烯作为超级电容器电极材料具有巨大的潜力。
石油焦是一种炼化企业副产品,随着我国加工原油重质化趋势,我国石油焦产量逐年增加,石油焦的开发利用成为炼油行业的难题。石油焦具有含碳量高、灰分少、价格低廉的优点,且石油焦由大量的稠环芳烃组成,结构致密,含有大量的石墨微晶结构,非常适合作为先进碳材料的前驱体,但是其不溶于任何有机溶剂,限制了其高附加值利用。石油焦经过浓硫酸和浓硝酸氧化后,可以得到双亲性碳质材料。其制备的双亲性碳质材料含有许多含氧官能团,可以溶于碱性溶液和部分的有机溶剂,为制备先进碳材料奠定了基础。本申请以石油焦为原料制备石墨烯作为超级电容器的电极材料,不仅实现了石油焦的增值利用,而且提供了一类有潜力的超级电容器电极材料。
发明内容
鉴于此,本发明的目的在于提供石油焦基石墨烯及其制备方法和应用,该方法利用石油焦为碳源,十六烷基三甲基溴化铵改性的蒙脱土为模板,在静电力作用下,碳源插入蒙脱土的层间形成复合物,高温碳化后,先后用氢氧化钠溶液和盐酸溶液去除模板蒙脱土得到二维的石墨烯。石油焦含有大量的石墨微晶,在蒙脱土的层间限域作用下,通过调控碳源与模板剂质量比和碳化温度来控制二维石墨烯的微观结构,将其用作超级电容器的电极材料,从而影响其电化学性能。
本发明采用的技术方案如下:
一种石油焦基石墨烯的制备方法,包括以下步骤:
(1)将蒙脱土超声分散于去离子水中,加入十六烷基三甲基溴化铵,在搅拌条件下水热反应后,过滤洗涤干燥,得到十六烷基三甲基溴化铵改性的蒙脱土;
(2)将步骤(1)所得十六烷基三甲基溴化铵改性的蒙脱土溶于氢氧化钠溶液中,然后加入石油焦基双亲性碳质材料,在反应釜中水热反应后,过滤洗涤干燥;
(3)将步骤(2)所得固体放入到管式炉中在氩气气氛下高温碳化,最后先后用氢氧化钠溶液和盐酸溶液洗涤,得到石油焦基石墨烯。
所述步骤(1)中,蒙脱土分散于去离子水中所得的蒙脱土水溶液的浓度为0.01~0.04g/mL。
所述步骤(1)中,蒙脱土与十六烷基三甲基溴化铵的质量比为4:1~2:1。
所述步骤(1)中,水热温度为50~90℃,水热时间为3~12h。
所述步骤(2)中,氢氧化钠溶液的浓度为0.001~0.1mol/L,十六烷基三甲基溴化铵改性的蒙脱土溶于氢氧化钠溶液后,所得溶液中十六烷基三甲基溴化铵改性的蒙脱土的浓度为0.01~0.04g/mL。
所述步骤(2)中,十六烷基三甲基溴化铵改性的蒙脱土与石油焦基双亲性碳质材料的质量比为10:1~2:1。
所述步骤(2)中,水热温度为80~160℃,水热时间为12~48h。
所述步骤(3)中,高温碳化的升温速率为1~5℃/min,碳化温度为600~1500℃,碳化时间为1~5h。
所述方法制备得到的石油焦基石墨烯。
所述的石油焦基石墨烯作为超级电容器的电极材料的应用。
与现有技术相比,本发明具有如下优异技术效果:
本发明采用廉价的炼化企业副产品石油焦为碳源,十六烷基三甲基溴化铵改性的蒙脱土为模板剂,合成了具有较大比表面积的石油焦基石墨烯。石油焦含有大量的石墨微晶,蒙脱土的层间限域作用使得石油焦基石墨烯具有优良的微观结构特点,高的比表面积可以提供更多的活性位点,石墨化结构的出现有利于电子传递,表面官能图的调控增强了表面润湿性,用作超级电容器的电极材料,在碱性电解液中,表现出大的比电容、高的倍率性、高的电化学稳定性的优点。
附图说明
图1为石油焦基石墨烯(实施例2)的氮气吸脱附等温线及孔径分布图;
图2为石油焦基石墨烯(实施例3)的透射电子显微图;
图3为石油焦基石墨烯(实施例3)的扫描电子显微图;
图4为石油焦基石墨烯(实施例4)的拉曼光谱;
图5为石油焦基石墨烯(实施例1)的XRD谱图;
图6为石油焦基石墨烯(实施例2)在扫描速率为10mV/s时的循环伏安曲线;
图7为石油焦基石墨烯(实施例2)在不同电流密度下的比电容变化曲线;
具体实施方式
以下结合附图和实施例对本发明做进一步解释:
实施例1
(1)将4g蒙脱土超声分散于200mL去离子水中,分量加入1g十六烷基三甲基溴化铵,在60℃水浴中搅拌4h,过滤洗涤干燥后,得到十六烷基三甲基溴化铵改性的蒙脱土;
(2)将1g步骤(1)所得的十六烷基三甲基溴化铵改性的蒙脱土溶于50mL、0.01mol/L的氢氧化钠溶液中,然后加入0.1g石油焦基双亲性碳质材料,在反应釜中120℃水热24h后,过滤洗涤干燥;
(3)将步骤(2)所得固体放入到管式炉中在氩气气氛下以速率5℃/min升温到700℃碳化3h,最后用氢氧化钠溶液和盐酸溶液洗涤,得到石油焦基石墨烯。
图5为实施例1制备的石油焦基石墨烯的XRD谱图;从图中可以看出,样品在25°附近具有一个宽的峰,代表着石墨的(002)晶面的衍射峰;在43°的宽的衍射峰,对应石墨的(100)晶面。相比其他碳材料,如以酚醛树脂、蔗糖等为碳前驱体,使用石油焦为碳前驱体,由于石墨微晶的存在,在蒙脱土的层间限域作用,使得石墨微晶紧密堆叠,因此局部石墨化程度较高。另外XRD谱图中只有碳材料的峰,说明经过碱洗和酸洗后,模板剂蒙脱土已经完全除去。
实施例2
(1)将10g蒙脱土超声分散于500mL去离子水中,分量加入5g十六烷基三甲基溴化铵,在80℃水浴中搅拌6h,过滤洗涤干燥后,得到十六烷基三甲基溴化铵改性的蒙脱土;
(2)将1g步骤(1)所得的十六烷基三甲基溴化铵改性的蒙脱土溶于50mL、0.01mol/L的氢氧化钠溶液中,然后加入0.2g石油焦基双亲性碳质材料,在反应釜中100℃水热48h后,过滤洗涤干燥;
(3)将步骤(2)所得固体放入到管式炉中在氩气气氛下以速率2℃/min升温到1000℃碳化2h,最后用氢氧化钠溶液和盐酸溶液洗涤,得到石油焦基石墨烯。
图1为实施例2制备的石油焦基石墨烯的氮气吸脱附等温线及孔径分布图;从图中可以看出吸脱附等温线的类型为IV等温线,具有明显的滞后回环,表明具有大量介孔存在,滞后回环为H3型孔,表明孔为层状孔。同时由表1中实施例2数据可知,其比表面积可达618m2/g。将所制备的石油焦基石墨烯作为超级电容器的电极材料,其大的比表面积和介孔的存在,有利于电解质离子的传递,有利于超级电容器的倍率性的提高。
图6为实施例2制备的石油焦基石墨烯在扫描速率为10mV/s时的循环伏安曲线;从图中可以看出,图形为类矩形,表明石油焦基石墨烯具有较好的双电容储能特性,同时在电压为-0.4~-1V时产生了较大的赝电容储能,这与其含有较多含氧官能团有关。
图7为实施例2制备的石油焦基石墨烯在不同电流密度下的比电容变化曲线;从图中可以看出,在电流密度为0.2A/g时,C5-900的比电容值达到了161.8F/g;在电流密度为20A/g时,其电容值达到了115.9F/g,其比电容保持率为72%。这表明石油焦基石墨烯用作超级电容器的电极材料,在碱性电解液中,表现出大的比电容、高的倍率性等优点。
实施例3
(1)将5g蒙脱土超声分散于250mL去离子水中,分量加入3g十六烷基三甲基溴化铵,在70℃水浴中搅拌8h,过滤洗涤干燥后,得到十六烷基三甲基溴化铵改性的蒙脱土;
(2)将1g步骤(1)所得的十六烷基三甲基溴化铵改性的蒙脱土溶于50mL、0.01mol/L的氢氧化钠溶液中,然后加入0.4g石油焦基双亲性碳质材料,在反应釜中150℃水热12h后,过滤洗涤干燥;
(3)将步骤(2)所得固体放入到管式炉中在氩气气氛下以速率5℃/min升温到800℃碳化3h,最后用氢氧化钠溶液和盐酸溶液洗涤,得到石油焦基石墨烯。
图2为实施例3制备的石油焦基石墨烯的透射电子显微图,图3为实施例3制备的石油焦基石墨烯的扫描电子显微图;从图2和图3中可以看出石油焦基石墨烯的片层结构,片层之间存在大的孔道,有利于电极材料中电解液离子的扩散,大的片层提供了更多的界面,有利于离子的吸附。
实施例4
(1)将4g蒙脱土超声分散于200mL去离子水中,分量加入2g十六烷基三甲基溴化铵,在70℃水浴中搅拌6h,过滤洗涤干燥后,得到十六烷基三甲基溴化铵改性的蒙脱土;
(2)将1g步骤(1)所得的十六烷基三甲基溴化铵改性的蒙脱土溶于50mL、0.01mol/L的氢氧化钠溶液中,然后加入0.2g石油焦基双亲性碳质材料,在反应釜中110℃水热27h后,过滤洗涤干燥;
(3)将步骤(2)所得固体放入到管式炉中在氩气气氛下以速率3℃/min升温到900℃碳化2h,最后用氢氧化钠溶液和盐酸溶液洗涤,得到石油焦基石墨烯。
图4为实施例4制备的石油焦基石墨烯的拉曼光谱;从图中可以看出,峰位置在1360cm-1处为D峰,与碳材料的杂乱程度或者石墨的缺陷有关;峰位置在1592cm-1处为G峰,这是由sp2碳原子的面内振动,代表着石墨层的存在;峰位置在2670cm-1处为2D峰,表征碳材料的石墨化程度;ID/IG的值为0.96,表明其具有一定的石墨化程度。碳材料石墨化程度的提高,有利于电子的传递。
表1为实施例所得石油焦基石墨烯的比表面积和孔结构数据,从表1中可以看出,所制备的石油焦基石墨烯的比表面积在390m2/g以上,实施例2所制备的样品比表面积高达618m2/g,同时石油焦基石墨烯具有较大的介孔面积和总孔容,其平均孔径在3nm以上,通过控制不同的制备参数,实现对石油焦基石墨烯孔结构的调控。
表1石油焦基石墨烯的比表面积和孔结构数据
最后说明的是,以上优选实施例仅用以说明本发明的技术方案而非限制,尽管通过上述优选实施例已经对本发明进行了详细的描述,但本领域技术人员应当理解,可以在形式上和细节上对其作出各种各样的改变,而不偏离本发明权利要求书所限定的范围。
Claims (10)
1.一种石油焦基石墨烯的制备方法,其特征在于,包括以下步骤:
(1)将蒙脱土超声分散于去离子水中,加入十六烷基三甲基溴化铵,在搅拌条件下水热反应后,过滤洗涤干燥,得到十六烷基三甲基溴化铵改性的蒙脱土;
(2)将步骤(1)所得十六烷基三甲基溴化铵改性的蒙脱土溶于氢氧化钠溶液中,然后加入石油焦基双亲性碳质材料,在反应釜中水热反应后,过滤洗涤干燥;
(3)将步骤(2)所得固体放入到管式炉中在氩气气氛下高温碳化,最后先后用氢氧化钠溶液和盐酸溶液洗涤,得到石油焦基石墨烯。
2.根据权利要求1所述的石油焦基石墨烯的制备方法,其特征在于:所述步骤(1)中,蒙脱土分散于去离子水中所得的蒙脱土水溶液的浓度为0.01~0.04g/mL。
3.根据权利要求1或2所述的石油焦基石墨烯的制备方法,其特征在于:所述步骤(1)中,蒙脱土与十六烷基三甲基溴化铵的质量比为4:1~2:1。
4.根据权利要求3所述的石油焦基石墨烯的制备方法,其特征在于:所述步骤(1)中,水热温度为50~90℃,水热时间为3~12h。
5.根据权利要求1所述的石油焦基石墨烯的制备方法,其特征在于:所述步骤(2)中,氢氧化钠溶液的浓度为0.001~0.1mol/L,十六烷基三甲基溴化铵改性的蒙脱土溶于氢氧化钠溶液后,所得溶液中十六烷基三甲基溴化铵改性的蒙脱土的浓度为0.01~0.04g/mL。
6.根据权利要求1或5所述的石油焦基石墨烯的制备方法,其特征在于:所述步骤(2)中,十六烷基三甲基溴化铵改性的蒙脱土与石油焦基双亲性碳质材料的质量比为10:1~2:1。
7.根据权利要求6所述的石油焦基石墨烯的制备方法,其特征在于:所述步骤(2)中,水热温度为80~160℃,水热时间为12~48h。
8.根据权利要求1所述的石油焦基石墨烯的制备方法,其特征在于:所述步骤(3)中,高温碳化的升温速率为1~5℃/min,碳化温度为600~1500℃,碳化时间为1~5h。
9.一种如权利要求1-8任意一项所述方法制备得到的石油焦基石墨烯。
10.一种如权利要求9所述的石油焦基石墨烯作为超级电容器的电极材料的应用。
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