CN115547705A - 氮磷共掺杂碳气凝胶材料及其制备方法 - Google Patents
氮磷共掺杂碳气凝胶材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及超级电容器电极材料制备技术领域,具体公开了一种氮磷共掺杂碳气凝胶材料及其制备方法。以漂白针叶木浆为基制备纳米纤维素,含N、P双元素的无机或有机物为掺杂剂,用一步掺杂法通过超声混合,冷冻干燥、高温炭化制得N、P双掺杂多孔的三维网状、性能优异、结构稳定的碳气凝胶。与现有技术相比,本发明所选原料来源广泛,价格低廉,制备的碳气凝胶中孔结构良好、氮和磷分布均匀、电化学性能优异,为开发价格低廉、可持续利用、柔韧性好、电化学性能优异、循环稳定性好的超级电容器提供了有效的途经。
Description
技术领域
本发明涉及超级电容器电极材料制备技术领域,具体涉及一种氮磷共掺杂碳气凝胶材料及其制备方法。
背景技术
多孔的碳材料,特别是碳气凝胶(CAs),作为电极材料已得到广泛研究。CAs的特殊结构可以提供用于电解质离子/电子迁移的有效扩散/传质通道和用于静电吸引的多个活性位点,从而使电极具有优异的电化学性能。在最近的研究中,研究发现,CAs在电极材料的制备过程中仍然存在一些缺点,包括昂贵有害的前体和复杂的制备过程。纳米纤维素气凝胶是CAs最有希望的候选材料之一,因为其环保和可持续的来源、卓越的机械强度、较大的比表面积和令人印象深刻的柔性。纳米纤维素气凝胶具有高活性-OH基团,可轻松修饰表面,并通过共价键或氢键与导电填料结合,制备高性能电极。Y.Ma等报道了以细菌纤维素前驱体制备了超轻的碳气凝胶并应用于超级电容器中,比电容达158F.g-1(J.Mater.Chem.A,2021,9,900)。
总的来说,这些优点使得通过冷冻干燥和碳化从纳米纤维素中衍生出的CAs具有优异的性能,包括大的比表面积、高比电容、良好的循环稳定性以及良好的能量密度和功率密度。但由于纳米纤维素碳气凝胶其双电层的储能机制,且制备的碳气凝胶孔大多数为微孔结构,致使很难被电解液渗透,拥有比较低的比电容和能量密度,而杂原子掺杂是改善碳材料物理化学性能的有效策略。如申请号CN107265438A专利中公开了一种以细菌纤维素为碳气凝胶的前驱体,通过浸渍磷酸二氢铵溶液,炭化后得到碳气凝胶,但是选择的细菌纤维素为前驱体需要经过长时间的浸泡、酸洗,耗时且不环保;通过浸渍掺杂的方法同样存在处理周期耗时较长的缺陷。再如申请号CN108238596A中以吡咯和甲醛、乙二醛、戊二醛为单体合成聚合物凝胶材料制成碳气凝胶,其中所选单体有害且价格昂贵;炭化活化的温度较高易造成能源损耗。又如在申请号CN105692587A中,在NH3氛围下掺杂N,但是NH3对人体有较大的毒性,且在高温下分解产物有氢气,过程复杂且危险。
发明内容
针对以上现有技术存在的缺点和不足,为了进一步改善纳米纤维素碳气凝胶的现有的缺点,本发明提供一种氮磷共掺杂碳气凝胶材料及其制备方法,通过选取价格低廉的无机或有机物为掺杂剂,用一步掺杂法掺杂N、P双元素方式,制备具有微孔和介孔多级孔道结构的具有优异电化学性能的碳气凝胶。为开发价格低廉、可持续利用、柔韧性好、电化学性能优异、循环稳定性好的超级电容器提供了有效的途经。
本发明可以通过以下技术方案来实现:
一种氮磷共掺杂碳气凝胶材料的制备方法,氮磷共掺杂碳气凝胶材料用于超级电容器的电极材料,该方法包括以下步骤:
(1)氧化纳米纤维素的制备:将漂白针叶木浆分散在pH为10~10.5去离子水中,搅拌均匀,以NaCIO和NaBr为催化剂,TEMPO(2,2,6,6-四甲基哌啶基-1-氧基)为氧化剂进行氧化,反应结束后用去离子水清洗至中性,最后进行抽滤冷冻干燥制得氧化纳米纤维素(TOCNFs),得到的TOCNFs电荷密度为200~1800μmol/g。
(2)碳气凝胶的制备:将含N、P双元素的无机或有机物和步骤(1)制备的氧化纳米纤维素于去离子水中超声混合,超声的功率为800~1800W(时间一般20~60min),然后经过溶剂交换后用液氮进行速冻,最后冷冻干燥24~48h,制得气凝胶,将气凝胶进行在氮气氛围下碳化,得到N、P双掺杂多孔的三维网状、性能优异、结构稳定的碳气凝胶材料;其中含N、P双元素的无机或有机物和冻干后的氧化纳米纤维素的质量比为1~4:5。
进一步的,含N、P双元素的无机物为聚磷酸铵,聚磷酸铵与氧化纳米纤维素的质量比为2:5。
进一步地,步骤(2)中碳化的程序为以5~10℃/min的升温速率,升温至600~800℃,持续2~5h。
一种如上所述方法制备的氮磷共掺杂碳气凝胶材料。
一种如上所述氮磷共掺杂碳气凝胶材料的应用,用于制备超级电容器的电极材料,具体方法为:将氮磷共掺杂碳气凝胶研磨后与碳黑和PVDF混合,再置于超声清洗器中超声混合,干燥,即得到用于超级电容器的氮磷共掺杂的电极材料。
进一步地,所述的氮磷共掺杂碳气凝胶、碳黑与PVDF的质量比为8:0.8~1.2:0.8~1.2。
与现有技术相比,本发明取得了如下有益效果:采用一步掺杂法掺杂N、P双元素方式,制备具有微孔和介孔多级孔道结构的碳气凝胶,操作简单,用时短,且制备的多孔碳材料具有高比表面,N、P元素分散均匀,提高了碳材料的表面润湿性、导电性,并提供了更多的化学活性位点,增强了电极材料储电能力,改善了电化学稳定性并且具有极高的比电容(比目前公开的或已经发表的文献(CN201710997775.4、CN201910279884.1、CN201810841339.2)数据高几倍);本发明通过一步法掺杂N、P双元素的方法改变了纳米纤维素的热解路线,使纳米纤维素热解后的残碳量提高,提高了纳米纤维碳气凝胶的产量;利用漂白针叶木浆为基制备纳米纤维素为碳前驱体,节约成本,廉价环保;而选择的无机或有机物无毒无味,不产生腐蚀气体,吸湿性小,热稳定性高,是一种性能优良的非卤阻燃剂,有效的提高了材料安全性。
附图说明
为了更清楚地说明本发明具体实施方式中的技术方案,下面将对具体实施方式描述中所需要使用的附图作简单地介绍。
图1为纤维素在不同氧化程度下的红外光谱图。
图2对比例与实施例1~4中不同电流密度下碳气凝胶材料的CV图。
图3对比例与实施例1~4中不同电流密度下碳气凝胶材料的GCD图。
图4实施例1中碳气凝胶的元素分布图。
图5对比例(A)与实施例1的接触角示意图(B)。
具体实施方式
下面结合实施例对本发明做进一步说明。实施例给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
下面结合附图和具体实施例对本发明进行详细说明(以下实施例和对比例中炭黑、PVDF为制备电极所需的辅助试剂药品,测试中实际工作电极已计算排除掉这两种试剂)。
实施例1
(1)称取3g漂白针叶木浆,分散在500ml去离子水中,搅拌均匀,加20mL2mg/mL的TEMPO溶液、400mg的NaBr为催化剂,1.5mmol的NaCIO为氧化剂进行氧化,在氧化过程中滴加0.5M NaOH调节pH为10-10.5,反应结束后用去离子水清洗至中性,最后进行抽滤干燥。
(2)APP-CA的制备:称取0.2g聚磷酸铵(APP)和0.5g氧化纳米纤维溶于100ml去离子水中在1200W大功率下超声混合,将混合液进行叔丁醇溶剂交换后用液氮进行速冻,最后放在冷冻干燥机中进行48h干燥过夜,制备得出气凝胶,将气凝胶进行在氮气氛围下800℃下碳化2h,得到碳气凝胶材料1(APP-CA-1)。
碳气凝胶电化学性能测试:
采用电化学工作站,在三电极体系中对制备的氮磷共掺杂碳电极进行电化学性能测试。工作电极为氮磷共掺杂碳气凝胶,对电极为碳棒电极,参比电极为Ag/AgCl电极。以6MKOH溶液作为电解液,测试CV曲线和GCD曲线。
实施例2
实施例2与实施例1相比,区别在于:聚磷酸铵与冻干后的样品的质量比为1:5,其它操作相同,得到碳气凝胶2(APP-CA-2)。
实施例3
实施例3与实施例1相比,区别在于:聚磷酸铵与冻干后的样品的质量比为3:5,其它操作相同,得到碳气凝胶3(APP-CA-3)。
实施例4
实施例4与实施例1相比,区别在于:聚磷酸铵与冻干后的样品的质量比为4:5,其它操作相同,得到碳气凝胶4(APP-CA-4)。
实施例5
实施例5与实施例1相比,区别在于:N、P双元素的无机或有机物等质量替换为磷酸氢二胺(DAP),其它操作相同,得到碳气凝胶5。
对比例
对比例与实施例1相比,区别在于:不加N、P双元素的无机或有机物,其他操作相同,得到碳气凝胶。
表1掺杂聚磷酸铵前后碳气凝胶的性能变化
表2提供了对比例与实施例1~5碳气凝胶的表征结果(电流密度为1Ag-1)
项目 | 比电容(F g<sup>-1</sup>) |
对比例 | 161.2 |
实施例1 | 1518.8 |
实施例2 | 924.1 |
实施例3 | 1088.8 |
实施例4 | 713.2 |
实施例5 | 313.8 |
由上述实施例可看出,本发明氮磷共掺杂碳气凝胶,方法简单成本低廉,制得的碳复合气凝胶具有较高的比表面积、分布合理的三维多孔结构,用作超级电容器电极材料时具有比电容大、循环稳定性好的特性,适用于高能量密度﹑高功率密度、长寿命的超级电容器,具有较高的实用价值。
在这里示出和描述的所有示例中,除非另有规定,任何具体值应被解释为仅仅是示例性的,而不是作为限制,因此,实施例的其他示例可以具有不同的值以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (6)
1.一种氮磷共掺杂碳气凝胶材料的制备方法,氮磷共掺杂碳气凝胶材料用于超级电容器的电极材料,其特征在于:包括以下步骤:
(1)氧化纳米纤维素的制备:将漂白针叶木浆分散在pH为10~10.5去离子水中,搅拌均匀,以NaCIO和NaBr为催化剂,TEMPO(2,2,6,6-四甲基哌啶基-1-氧基)为氧化剂进行氧化,反应结束后用去离子水清洗至中性,最后进行抽滤冷冻干燥制得电荷密度为200~1800μmol/g的氧化纳米纤维素;
(2)碳气凝胶的制备:将含N、P双元素的无机或有机物和步骤(1)制备的氧化纳米纤维素于去离子水中超声混合,超声的功率为800~1800W,然后经过溶剂交换后用液氮进行速冻,最后冷冻干燥24~48h,制得气凝胶,将气凝胶在氮气氛围下碳化,得到N、P双掺杂的碳气凝胶材料;其中含N、P双元素的无机或有机物和冻干后的氧化纳米纤维素的质量比为1~4:5。
2.根据权利要求1所述的氮磷共掺杂碳气凝胶材料的制备方法,其特征在于:步骤(2)中超声时间为20~60min。
3.根据权利要求1所述的氮磷共掺杂碳气凝胶材料的制备方法,其特征在于:步骤(2)中含N、P双元素的无机物为聚磷酸铵,聚磷酸铵与氧化纳米纤维素的质量比为2:5。
4.根据权利要求1所述的氮磷共掺杂碳气凝胶材料的制备方法,其特征在于:步骤(2)中含N、P双元素的无机或有机物为磷酸氢二胺、磷酸铵、聚磷酸铵、聚磷腈中的任意一种或两种。
5.根据权利要求1所述的氮磷共掺杂碳气凝胶材料的制备方法,其特征在于:步骤(2)中碳化的程序为以5~10℃/min的升温速率,升温至600~800℃,持续2~5h。
6.如权利要求1至5中任一项所述方法制备的氮磷共掺杂碳气凝胶材料。
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