CN111048325A - 一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料及其制备方法 - Google Patents
一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料及其制备方法 Download PDFInfo
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Abstract
一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料及其制备方法，属于储能材料技术领域，可解决过渡金属氧化物在超级电容器应用中电导率低、循环稳定性差等问题，将硝酸镍，氯化锰，尿素和氟化铵溶解于去离子水中，充分搅拌均匀后转移至反应釜，将附着还原氧化石墨烯的泡沫镍基底浸没到反应釜中于120℃反应10小时，随后在充氮气的管式炉中350℃下退火2h，得到复合材料镍锰氧化物/石墨烯复合材料，将其进行水热硫化得到镍锰硫化物/石墨烯复合材料。本发明的制备方法简单，易于控制，价格低廉，所制备的电极材料比电容大，倍率性能高，循环稳定性好。在制成器件时，显示出了高的功率密度和能量密度，可作为优良的超级电容器电极材料。
Description
技术领域
本发明属于储能材料技术领域，具体涉及一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料及其制备方法。
背景技术
随着全球经济的飞速发展，石油、煤炭、天然气等传统化石能源被大量消耗，新型绿色能源的发展已成为各国的新课题。21世纪以来，新能源技术已日趋成熟，然而能源的利用仍很大程度上受自然条件的限制，因此电能的存储已成为新能源利用过程中的关键环节，这促使了研究者们对能源高效转换存储设备的广泛研究与探索。超级电容器作为一种新型储能元件，因其具备的可观的储能容量、高输出功率密度、卓越的循环寿命、低成本且环境友好等特点，引起了广泛关注。据储能机理的不同，超级电容器主要分为双电层超级电容器和赝电容超级电容器。双电层电容器(Electrochemical Double-Layer Capacitors，EDLCs)通过极化时电解液中的离子在电极和电解质界面处静电吸附聚集形成双电层来存储电荷。赝电容器(Pseudocapacitance，PCs)，是通过电极表面或者近表面可逆的法拉第反应进行储能，与双电层电容器相比有较大的比容量。
超级电容器的性能主要取决于电极材料。过渡金属氧化物（Ni-Co-O,Co-Mn-O,Ni-Mn-O 等）因其丰富的氧化价态，高的氧化还原活性在超级电容器领域得到了广泛应用。其中，镍锰基氧化物具有理论电容高，电位窗口大等优点，引起了广泛的研究兴趣。然而过渡金属氧化物电导率低，循环稳定性差，限制了其进一步应用。过渡金属硫化物与其相应的氧化物相比具有较高的电导率和电化学活性，将过渡金属氧化物转换成硫化物是提高电化学性能的有效方法。
发明内容
本发明针对过渡金属氧化物电导率低，循环稳定性差，不利于其实际应用的问题，提供作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料及其制备方法。
本发明采用如下技术方案：
一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料，化学通式为Ni-Mn-S/rGO/NF-x，其中x表示硫化反应时间，1 ≤ x ≤ 7。
一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯电极材料的制备方法，包括如下步骤：
第一步，化学还原法在泡沫镍基底上生长还原氧化石墨烯：将氧化石墨烯加入到去离子水中，超声分散得到棕色的分散液，然后向分散液中加入还原剂，搅拌均匀后，得到混合溶液A，将用丙酮、稀盐酸、无水乙醇清洗的泡沫镍基底放入混合溶液A中在90℃的水浴锅中反应6h后，将制备样品取出，洗涤干燥，得到生长有还原氧化石墨烯的泡沫镍基底，记为rGO/NF；
第二步，使用水热法在生长有还原氧化石墨烯的泡沫镍基底上生长镍锰氧化物：将Ni(NO3)2·6H2O，MnCl2·6H2O, CO(NH2)2和NH4F溶解于去离子水和无水乙醇的混合溶剂中，搅拌均匀后得到混合溶液B，将混合溶液B转移至反应釜中，将rGO/NF放入反应釜，在120℃条件下反应10h.待冷却至室温后，将制得的样品取出，洗涤干燥，随后在通入氮气的管式炉中350℃下退火2h得到复合材料Ni-Mn-O/rGO/NF,记为NMO/rGO/NF；
第三步，水热法硫化Ni-Mn-O/rGO/NF：将Na2S·9H2O 溶解于去离子水中，搅拌溶解后，转移至反应釜中，将Ni-Mn-O/rGO/NF放入反应釜中，在120℃条件下保持1-7h，取出洗涤干燥后，得到化学通式为Ni-Mn-S/rGO/NF-x的镍锰硫化物/石墨烯复合材料，记为NMS/rGO/NF-x。
第一步中所述氧化石墨烯和去离子水的比例为1mg:3mL，所述还原剂为抗坏血酸，还原剂与氧化石墨烯的质量比为3:1。
第二步中所述混合溶剂中去离子水和无水乙醇的体积比为6:1，Ni(NO3)2·6H2O和混合溶剂的比例为1mmol:70mL，MnCl2·6H2O和混合溶剂的比例为0.5mmol:70mL，CO(NH2)2和混合溶剂的比例为6mmol:70mL，NH4F和溶剂的比例为2mmol:70mL。
第三步中所述Na2S·9H2O和去离子水的比例为3.5mmol:70mL。
基于上述NMS/rGO/NF-x复合材料设计三电极体系：工作电极为NMS/rGO/NF-x复合材料电极，对电极为铂片电极，参比电极为甘汞电极，
使用型号为CHI660E电化学工作站作为测试仪器。
所述NMS/rGO/NF-x复合材料电极应用于超级电容器或锂离子电池以及其他大电流需求的电池和电器原件领域。
本发明的有益效果如下：
本发明的镍锰硫化物/石墨烯复合材料较相应的镍锰氧化物/石墨烯复合材料电化学性能有极大的提高。石墨烯作为一种新型的碳材料，具有超高的理论表面积，且能提高材料的导电性。结合镍锰硫化物和石墨烯二者的特性，制备的复合材料作为超级电容器的电极材料，具有较高的比电容特性，应用前景十分广泛。
本发明中硫化时间对复合材料的微观形貌和超级电容器比电容有明显的影响。硫化反应3h时，所制备的镍锰硫化物具有良好的纳米片状结构，作为超级电容器的正极材料时具有最大的比电容3374.6 F g-1；此外，以镍锰硫化物/还原氧化石墨烯为器件正极材料、掺氮还原氧化石墨烯作负极材料所组装成的超级电容器器件的能量密度高达58.9Wh kg-1，其优异的性能可作为电极材料应用于超级电容器及锂离子电池等领域。
附图说明
图1为本发明实施例1至实施例5得到的NMO/rGO/NF和不同硫化时间制备NMS/rGO/NF-x复合材料的XRD曲线。
图2为本发明实施例1至实施例5得到的NMO/rGO/NF和不同硫化时间制备的NMS/rGO/NF-x复合材料的场发射扫描电镜图，其中，a为NMO/rGO/NF；b为NMS/rGO/NF-1h；c-d为NMS/rGO/NF-3h；e为NMS/rGO/NF-5h；f为NMS/rGO/NF-7h。
图3为本发明实施例1至实施例5所制备的电极材料在2mol/L的KOH溶液中的伏安循环曲线图。
图4为本发明实施例1至实施例5所制备的电极材料在2mol/L的KOH溶液中的恒流充放电曲线图。
图5为本发明实施例6制备的超级电容器器件所对应的能量密度-功率密度关系图。
具体实施方式
对制备的复合材料的显微组织、电化学性能进行检测、分析和表征：
用MIRA3型扫描电子显微镜进行显微组织分析；
用CHI660E电化学工作站进行电化学性能测试。
实施例1
将10mg氧化石墨烯超声分解于30mL去离子水中，待形成均匀的棕色溶液后，加入30mg抗坏血酸，超声搅拌均匀后，将用丙酮、盐酸、无水乙醇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。
将1mmol的Ni(NO3)2·6H2O，0.5mmol的MnCl2·6H2O, 6mmol的CO(NH2)2和2mmol的NH4F溶解于70mL去离子水和无水乙醇的混合溶剂中（去离子水和乙醇的体积比为6:1），搅拌均匀后转移到反应釜中，并将rGO/NF放入其中，在120℃条件下保持10个小时，用去离子水和乙醇冲洗样品表面，置于60℃干燥12h。随后在通入氮气的管式炉中350℃下退火2h。
将所制备的NMO/rGO/NF复合材料作为超级电容器的正极材料在三电极体系（电解质为2mol/L的KOH）中进行电化学性能测试，其比电容为 1499.0 F g-1。
实施例2
将0.05M的Na2S·9H2O 溶解于70mL去离子水中搅拌溶解后转移到反应釜中，并将实施例1中所制得的NMO/rGO/NF放入其中，在120℃条件下保持1个小时，用去离子水冲洗样品表面，置于60℃干燥一晚。
所制备的复合物将其命名为NMS/rGO/NF-1h，作为超级电容器的正极材料在三电极体系（电解质为2mol/L的KOH）中进行电化学性能测试，其比电容为1971.0 F g-1。
实施例3
将0.05M的Na2S·9H2O 溶解于70mL去离子水中搅拌溶解后转移到反应釜中，并将实施例1中所制得的NMO/rGO/NF放入其中，在120 ℃条件下保持3个小时，用去离子水冲洗样品表面，置于60℃干燥一晚。
所制备的复合物将其命名为NMS/rGO/NF-3h，作为超级电容器的正极材料在三电极体系（电解质为2mol/L的KOH）中进行电化学性能测试，其比电容为3374.6F g-1。
实施例4
将0.05M的Na2S·9H2O 溶解于70mL去离子水中搅拌溶解后转移到反应釜中，并将实施例1中所制得的NMO/rGO/NF放入其中，在120℃条件下保持5个小时，用去离子水冲洗样品表面，置于60℃干燥一晚。
所制备的复合物将其命名为NMS/rGO/NF-5h，作为超级电容器的正极材料在三电极体系（电解质为2mol/L的KOH）中进行电化学性能测试，其比电容为1908.1F g-1。
实施例5
将0.05M的Na2S·9H2O 溶解于70mL去离子水中搅拌溶解后转移到反应釜中，并将实施例1中所制得的NMO/rGO/NF放入其中，在120℃条件下保持7个小时，用去离子水冲洗样品表面，置于60℃干燥一晚。
所制备的复合物将其命名为NMS/rGO/NF-7h，作为超级电容器的正极材料在三电极体系（电解质为2 mol/L的KOH）中进行电化学性能测试，其比电容为1440.2F g-1。
实施例6
将掺氮还原氧化石墨烯、乙炔黑、聚偏氟乙烯按质量比为8:1:1的比例混合，研磨均匀后涂抹到泡沫镍上，80℃干燥12h后作为负极材料，以镍锰硫化物/石墨烯复合材料作为正极材料组装成非对称超级电容器器件，并对其进行电化学性能测试；
所制备的超级电容器非对称器件在功率密度为852.3W kg-1时表现出高达58.9 Wh kg-1的能量密度。
Claims (5)
1.一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料，其特征在于：化学通式为Ni-Mn-S/rGO/NF-x，其中x表示硫化反应时间，1 ≤ x ≤ 7。
2.一种如权利要求1所述的作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料的制备方法，其特征在于：包括如下步骤：
第一步，化学还原法在泡沫镍基底上生长还原氧化石墨烯：将氧化石墨烯加入去离子水中，超声分散得到棕色的分散液，然后向分散液中加入还原剂，搅拌均匀后，得到混合溶液A，将用丙酮、稀盐酸、无水乙醇清洗的泡沫镍基底放入混合溶液A中在90℃的水浴锅中反应6h后，将制备样品取出，洗涤干燥，得到生长有还原氧化石墨烯的泡沫镍基底，记为rGO/NF；
第二步，使用水热法在生长有还原氧化石墨烯的泡沫镍基底上生长镍锰前驱体：将Ni(NO3)2·6H2O，MnCl2·6H2O，CO(NH2)2和NH4F溶解于去离子水和无水乙醇的混合溶剂中，搅拌均匀后得到混合溶液B，将混合溶液B转移至反应釜中，将rGO/NF放入反应釜，在120℃条件下反应10h.待冷却至室温后，将制得的样品取出，洗涤干燥，随后在通入氮气的管式炉中350℃下退火2h，得到化学通式为Ni-Mn-O/rGO/NF的镍锰氧化物/石墨烯复合材料，记为NMO/rGO/NF；
第三步，水热法硫化Ni-Mn-O/rGO/NF：将Na2S·9H2O 溶解于去离子水中，搅拌溶解后，转移至反应釜中，将Ni-Mn-O/rGO/NF放入反应釜中，在120℃条件下保持1-7h，取出洗涤干燥后，得到化学通式为Ni-Mn-S/rGO/NF-x的镍锰硫化物/石墨烯复合材料，记为NMS/rGO/NF-x。
3.根据权利要求2所述的一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料的制备方法，其特征在于：第一步中所述氧化石墨烯和去离子水的比例为1mg:3mL，所述还原剂为抗坏血酸，还原剂与氧化石墨烯的质量比为3:1。
4.根据权利要求2所述的一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料的制备方法，其特征在于：第二步中所述混合溶剂中去离子水和无水乙醇的体积比为6:1，Ni(NO3)2·6H2O和混合溶剂的比例为1mmol:70mL，MnCl2·6H2O和混合溶剂的比例为0.5mmol:70mL，CO(NH2)2和混合溶剂的比例为6mmol:70mL，NH4F和溶剂的比例为2mmol:70mL。
5.根据权利要求2所述的一种作为超级电容器的形貌可控的镍锰硫化物/石墨烯复合材料的制备方法，其特征在于：第三步中所述Na2S·9H2O和去离子水的比例为3.5mmol:70mL。
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