CN111039332B - 一种多功能双层纳米线层状复合材料的制备方法及其应用 - Google Patents
一种多功能双层纳米线层状复合材料的制备方法及其应用 Download PDFInfo
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Abstract
一种多功能双层纳米线层状复合材料的制备方法及其应用，属于化工材料技术领域，本发明的目的在于提供一种具有低过电位，高面电容和良好倍率性能且具有良好稳定性的多功能双层纳米线层状复合材料的制备方法及其应用。将负载有氧化还原石墨烯的泡沫镍置于硝酸钴和尿素的混合溶液，经过120℃保温10h反应形成CoO纳米线前驱体；将前驱体放入含有硝酸钴、硝酸镍、尿素和氟化铵的混合溶液，置于120‑160℃箱式炉，保温6h，取出样品，得到双层纳米线前驱体，经300‑500℃退火得到多功能双层纳米线层状复合材料。本发明的原料储量丰富易得，价格低廉，而且性能优异，过电位小，面电容大，倍率性能高，循环稳定性较好。
Description
技术领域
本发明属于化工材料技术领域，具体涉及一种多功能双层纳米线层状复合材料的制备方法及其应用。
背景技术
在现有世界能源格局中，煤炭、石油、天然气等传统能源仍占有相当大比例，化石燃料的过度消耗造成了严重的能源短缺和环境污染，这促使研究人员探索能量转换和储存装置。环境友好的电化学能量***，包括电化学全水解和超级电容器，被认为是未来能量转换和储存技术的核心。
氢作为一种环境友好的可再生能源，可以通过水的分解得到。水的分解被广泛认为是大规模氢能生产的一条有希望和有吸引力的途径，在氢能量供应中起着重要的作用。水的电解过程包括两个重要的反应：阴极上的析氢反应（HER）和阳极上的析氧反应（OER）。电催化析氢反应被认为是高效制氢的重要途径之一。
然而，在实际应用中，由于动力学能垒和材料本身稳定性差造成的高过电位（η），电解效率受到严重阻碍，较大程度地限制了大规模水电解的发展。HER和OER的过电位不可避免，但尽可能的降低过电位对于电催化剂来说非常重要。Pt基材料是目前公认最有效的HER电催化剂，而Ru/Ir氧化物是一种高活性的OER电催化剂，但高成本和稀缺性几乎限制了它们的大规模实际应用。
在储能材料方面，超级电容器具有功率密度高、充放电快、循环寿命长等优点，被称为最有前途的实用电容器器件。随着新能源的研发日趋成熟，高容量电源***的得以发展，将新能源成功应用在汽车上，成为新能源利用的研究焦点。超级电容器的出现解决了这一领域的瓶颈，它是一种介于传统静电电容器和二次电池之间的一种新型储能装置，综合保留了蓄电池与传统电容器的优势，并弥补了不足之处。超级电容器的充放电过程可以在极短的时间内完成，其电化学稳定性强，具有超长的寿命，放置时间长且性能基本不变，工作的温度范围广，可达70至-40℃。它在国民经济、科学技术和日常生活中得到了广泛的应用，对缓解能源与环境危机、提高人类生活水平有着重要影响，已成为全球经济发展的一个新热点。超级电容器根据储能机理的不同分为双电层电容器和法拉第准电容器（赝电容器）。在相同的电极面积的情况下，后者的容量是前者的10-100倍。过渡金属Mn、Ni、Co、V等的氧化物是研发赝电容器的有效选择，而因其稳定的电压窗口小，能量密度较低等因素，制备高面电容性能的复合双金属氧化物，使其具有两者及其以上元素的共有性质是目前的研究热点。
将能量转换和能量储存整合为一种材料将是未来研究的重点。因此，实现这些绿色能源***的一个重要挑战是开发能有效转换和储存能量的电极材料。
发明内容
本发明的目的在于提供一种具有低过电位，高面电容和良好倍率性能且具有良好稳定性的多功能双层纳米线层状复合材料的制备方法及其应用。
本发明采用如下技术方案：
一种多功能双层纳米线层状复合材料的制备方法，包括如下步骤：
第一步，将氧化石墨烯置于蒸馏水中超声1h形成均匀的棕色溶液，加入抗坏血酸，超声搅拌均匀后，得到分散液，将清洗干净的泡沫镍置于分散液中，并在水浴锅90℃条件下，沉积6h，取出后，用去离子水冲洗，置于60℃条件下干燥12h，得到负载还原氧化石墨烯的泡沫镍rGO/NF；
第二步，将Co(NO3)2·6H2O和尿素溶于水形成混合溶液A，将rGO/NF置于混合溶液A中，经过箱式炉120℃保温10h，得到CoO纳米线前驱体；
第三步，将Co(NO3)2·6H2O、Ni(NO3)2·6H2O、尿素和氟化铵溶于水形成均匀的混合溶液B，将CoO纳米线前驱体置于混合溶液B中，转移至120-160℃箱式炉中反应，保温6h后，取出样品，得到双层纳米线前驱体，经300-500℃退火，得到层状CoNiO2/CoO材料，记为CoNiO2/CoO-X-Y，其中，X是水热温度，Y是退火温度。
第一步中所述氧化石墨烯和蒸馏水的比例为1mg：3mL，氧化石墨烯和抗坏血酸的质量比为1:3。
第二步中所述Co(NO3)2·6H2O和尿素的摩尔比为1:5，混合溶液A的体积为35mL。
第三步中所述Co(NO3)2·6H2O、Ni(NO3)2·6H2O、尿素和氟化铵的摩尔比为1.5:1.5:15:8，混合溶液B的体积为30mL。
一种多功能双层纳米线层状复合材料应用于全水解或超级电容器。
本发明的有益效果如下：
本发明的多功能双层纳米线层状复合材料具有较低的析氢过电位，较高的面电容特性，其生产原料价格低廉、制备过程简单、生产效率高、对设备要求低的特点，应用广泛。
本发明制备的多功能双层纳米线层状复合材料CoNiO2/Co-140-400在1M KOH环境中进行析氢反应达到阴极电流密度10 mA cm-2时需要70mV，全水解中达到10 mA cm-2的电流密度时需要1.57V，在2M KOH环境下在1 mA cm-2电流密度下可达 5.37 F cm-2，可应用于全水解和超级电容器等领域，用途广泛。
附图说明
图1是由实施例1-2得到的CoNiO2/Co-140-400纳米线层状复合材料的 XRD曲线。
图2是由实施例1-2获得的CoNiO2/CoO-140-400纳米线层状复合材料的典型扫描电镜照片。
图3是由实施例1-4获得的CoNiO2/CoO-X-400纳米线层状复合材料的析氢极化曲线。
图4是由实施例1，2，5，6获得的CoNiO2/CoO-140-Y纳米线层状复合材料的析氢极化曲线。
图5是由实施例1，2，7获得的CoNiO2/CoO-140-400纳米线层状复合材料的全水解曲线。
图6是由实施例1-2获得的CoNiO2/CoO-140-400纳米线层状复合材料的恒流充放电关系曲线。
具体实施方式
实施例1
将10 mg氧化石墨烯超声置于30 mL蒸馏水中，超声1h形成均匀的棕色溶液后，加入30 mg抗坏血酸，超声搅拌均匀后，将清洗干净的泡沫镍放置于分散液中，并在水浴锅90℃条件下沉积6小时，取出后用去离子水冲洗样品表面，置于60℃条件下干燥12 h得到rGO/NF。
实施例2
将rGO/NF置于1.019g Co(NO3)2·6H2O和1.051g 尿素混合形成的35mL均匀溶液，经过箱式炉120℃保温10h充分反应形成CoO纳米线前驱体；将前驱体放入含有1.5mmol Co(NO3)2·6H2O、1.5mmol Ni(NO3)2·6H2O、15mmol 尿素和8mmol 氟化铵的30mL均匀混合溶液，转移至聚四氟乙烯内衬并置于140℃箱式炉中反应，保温6h，取出样品，得到双层纳米线前驱体，经400℃退火得到层状CoNiO2/CoO-140-400材料。
实施例3
将rGO/NF置于1.019g Co(NO3)2·6H2O和1.051g 尿素混合形成的35mL均匀溶液，经过箱式炉120℃保温10h充分反应形成CoO纳米线前驱体；将前驱体放入含有1.5mmol Co(NO3)2·6H2O、1.5mmol Ni(NO3)2·6H2O、15mmol 尿素和8mmol 氟化铵的30mL均匀混合溶液，转移至聚四氟乙烯内衬并置于120℃箱式炉中反应，保温6h，取出样品，得到双层纳米线前驱体，经400℃退火得到层状CoNiO2/CoO-120-400材料。
实施例4
将rGO/NF置于1.019g Co(NO3)2·6H2O和1.051g 尿素混合形成的35mL均匀溶液，经过箱式炉120℃保温10h充分反应形成CoO纳米线前驱体；将前驱体放入含有1.5mmol Co(NO3)2·6H2O、1.5mmol Ni(NO3)2·6H2O、15mmol 尿素和8mmol 氟化铵的30mL均匀混合溶液，转移至聚四氟乙烯内衬并置于160℃箱式炉中反应，保温6h，取出样品，得到双层纳米线前驱体，经400℃退火得到层状CoNiO2/CoO-160-400材料。
实施例5
将rGO/NF置于1.019g Co(NO3)2·6H2O和1.051g 尿素混合形成的35mL均匀溶液，经过箱式炉120℃保温10h充分反应形成CoO纳米线前驱体；将前驱体放入含有1.5mmol Co(NO3)2·6H2O、1.5mmol Ni(NO3)2·6H2O、15mmol 尿素和8mmol 氟化铵的30mL均匀混合溶液，转移至聚四氟乙烯内衬并置于140℃箱式炉中反应，保温6h，取出样品，得到双层纳米线前驱体，经300℃退火得到层状CoNiO2/CoO-140-300材料。
实施例6
将rGO/NF置于1.019g Co(NO3)2·6H2O和1.051g 尿素混合形成的35mL均匀溶液，经过箱式炉120℃保温10h充分反应形成CoO纳米线前驱体；将前驱体放入含有1.5mmol Co(NO3)2·6H2O、1.5mmol Ni(NO3)2·6H2O、15mmol 尿素和8mmol 氟化铵的30mL均匀混合溶液，转移至聚四氟乙烯内衬并置于140℃箱式炉中反应，保温6h，取出样品，得到双层纳米线前驱体，经500℃退火得到层状CoNiO2/CoO-140-500材料。
实施例7
将CoNiO2/CoO-140-400材料分别作为阴极和阳极组装成两电极全水解装置，进行全水解测试。
从图1可知，CoNiO2/CoO-140-400材料是由CoNiO2和CoO两相共存的复合材料。
从图2可知，CoNiO2/CoO-140-400是由直径不同的两种针状共存的复合材料，其中粗针的直径大约为130-160nm，细针的直径大约为70-75nm。
从图3可知，CoNiO2/CoO-140-400材料在10mA cm-2的电流密度下需要更少的过电位 (70mV)，相对于CoNiO2/CoO-120-400 (100mV)，CoNiO2/CoO-160-400 (82mV),表现出更优的催化性能。说明140℃是该实验最佳水热温度。
从图4可知，CoNiO2/CoO-140-400材料在10mA cm-2的电流密度下需要更少的过电位 (70mV)，相对于CoNiO2/CoO-140-300 (195 mV)，CoNiO2/CoO-140-500 (159 mV)，表现出更优的催化性能。说明400℃是该实验最佳退火温度。
从图5可知，CoNiO2/CoO-140-400‖CoNiO2/CoO-140-400应用于全水解， 10mA cm-2的电流密度下需要电压1.57 V。
从图6可知，CoNiO2/CoO-140-400在1mAcm-2的电流密度下，其面电容达到5.37Fcm-2。
Claims (4)
1.一种多功能双层纳米线层状复合材料的制备方法，其特征在于：包括如下步骤：
第一步，将氧化石墨烯置于蒸馏水中超声1h形成均匀的棕色溶液，加入抗坏血酸，超声搅拌均匀后，得到分散液，将清洗干净的泡沫镍置于分散液中，并在水浴锅90℃条件下，沉积6h，取出后，用去离子水冲洗，置于60℃条件下干燥12h，得到负载还原氧化石墨烯的泡沫镍rGO/NF；
所述氧化石墨烯和蒸馏水的比例为1mg：3mL，氧化石墨烯和抗坏血酸的质量比为1:3；
第二步，将Co(NO3)2·6H2O和尿素溶于水形成混合溶液A，将rGO/NF置于混合溶液A中，经过箱式炉120℃保温10h，得到CoO纳米线前驱体；
第三步，将Co(NO3)2·6H2O、Ni(NO3)2·6H2O、尿素和氟化铵溶于水形成均匀的混合溶液B，将CoO纳米线前驱体置于混合溶液B中，转移至120-160℃箱式炉中反应，保温6h后，取出样品，得到双层纳米线前驱体，经300-500℃退火，得到层状CoNiO2/CoO材料，记为CoNiO2/CoO-X-Y，其中，X是水热温度，Y是退火温度。
2.根据权利要求1所述的一种多功能双层纳米线层状复合材料的制备方法，其特征在于：第二步中所述Co(NO3)2·6H2O和尿素的摩尔比为1:5，混合溶液A的体积为35mL。
3.根据权利要求1所述的一种多功能双层纳米线层状复合材料的制备方法，其特征在于：第三步中所述Co(NO3)2·6H2O、Ni(NO3)2·6H2O、尿素和氟化铵的摩尔比为1.5:1.5:15:8，混合溶液B的体积为30mL。
4.一种利用权利要求1-3任意一项所述的多功能双层纳米线层状复合材料的制备方法制备的多功能双层纳米线层状复合材料应用于全水解或超级电容器。
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