CN106450268A - 多孔四氧化三锰/石墨烯复合材料及其制备方法 - Google Patents
多孔四氧化三锰/石墨烯复合材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种多孔四氧化三锰/石墨烯复合材料及其制备方法。其制备方法如下：将氧化石墨溶液与甘露醇溶液混合均匀，加入高锰酸钾溶液反应一段时间后，加入还原剂，95℃搅拌反应，过滤、洗涤、干燥，即得本发明的多孔四氧化三锰/石墨烯复合材料。该材料由复合均一的四氧化三锰与石墨烯自组装形成三维网络结构的多孔块体，因此具有比表面积大、颗粒大小均一等特点，可应用于锂电池、超级电容器、催化、污水治理等领域。如作为锂电池负极材料，可逆比容量可达1523 mAh/g，首次库伦效率为68%，且在大电流下具有稳定的循环性能，显现出优越的电性能。此外，与传统的制备方法比，该材料的制备方法具有设备简单，操作简便易控，生产成本低等特点，适于产业化。
Description
技术领域
本发明涉及一种多孔四氧化三锰/石墨烯复合材料及其制备方法。
背景技术
能源是人类社会发展及生存的一个重要的物质基础。近年来，石油资源的日益耗竭及环境的恶化，对人类的生存和发展造成了威胁。因此，为了人类的生存、发展以及日益增长的能源需求，绿色新能源的开发和使用迫在眉睫。锂离子电池，以其体积小、质量轻、比能量高、无记忆效应、无污染、寿命长等优点，成为备受关注的新一代绿色高能充电电池。但是，随着全球工业化进程的加深，目前商业化所用的锂离子负极材料——碳的较低的储锂能力（理论比容量仅为372 mAh/g）已难以适应便携式仪器设备、电动汽车电源等领域的发展和需求，因此，研发出新的具有更高比容量的锂离子负极材料成为当务之急。
四氧化三锰（Mn3O4）资源丰富，且与其它过渡金属氧化物或衍生物相比，具有价格低廉、无毒、安全等优势，因此是一类极具发展潜力的动力锂离子电池电极材料。虽然其具有较高的理论比容量(~936mA h g-1)，但是因其自身电导率（~10-7 -10-8S cm-1）低以及在脱嵌锂过程中体积缩胀而粉碎使其有效物质减少，导致使用Mn3O4作为锂电池负极活性材料的首次库伦效率低，循环稳定性和倍率性能差，从而限制了它在锂离子电池中的应用。为了解决上述问题，人们采用了许多方法，如添加表面活性剂、制备Mn3O4/C复合材料等。
石墨烯是一种由碳原子Sp2杂化成六边形晶格的二维单层片状材料，具有柔展性好、导热导电率高、机械强度大、化学稳定性高等特点，被誉为“万能材料”，在电池、电容器、触摸屏、传感器等领域有着广泛的应用前景，受到各国政府的广泛关注。因此，人们对四氧化三锰/石墨烯复合材料的制备进行了一系列研究。Shuang-Yu Liu等（Electrochimica Acta.，2012,66, 271-278）通过在氧化石墨烯与四水合醋酸锰中加入乙二醇和氢氧化钠，在180℃水热条件下反应12h得到具有三明治结构的石墨烯/四氧化三锰复合材料；中国专利（专利公开号:CN105514363A）公开了一步水热法制备石墨烯/四氧化三锰纳米复合材料的方法：即以氧化石墨烯与四水合醋酸锰为原料，160℃下水热法反应72h得到，其中四氧化三锰颗粒生长在石墨稀表面；YuRong Ren 等(RSC Adv., 2015, 5, 59208–59217）则以氧化石墨烯、四水氯化锰为原料，加入聚乙烯吡咯烷酮、氨水、还原剂硼氢化钠在140℃下通过水热反应制得石墨烯/四氧化三锰复合材料。虽然水热法具有反应温和、颗粒尺寸均一等优势，但是由于温度、压力（温度为100~200℃、压力为1MPa~4MPa）的需求，使其必须采用密闭容器作为反应容器。这不仅增加了设备的成本，加大制备工艺的复杂性，且使得材料的制备过程难于“实时”调控，产品的可重复性差。这些导致上述制备方法所得四氧化三锰/石墨烯复合物存在四氧化三锰颗粒尺寸过大，石墨烯堆叠团聚，复合不均匀等现象。以此作为锂电负极材料，导致电极材料容量低、循环稳定性差等问题。
现有研究表明：构建具有多孔结构的复合物，不仅能有效抑制石墨烯片层间的团聚，为锂离子提供更多的传输通道，缩短传输路径，提高其倍率性能；而且有利于石墨烯与氧化物的复合，抑制颗粒的长大，从而有效减缓脱嵌锂过程体积缩胀导致的影响，提高其比容量、首次库伦效率和循环寿命。但目前具有类似结构的多孔四氧化三锰/石墨烯复合材料还未见报道。本发明在此提供一种多孔三维网络结构四氧化三锰/石墨烯复合材料及其制备方法。与传统的制备方法比，其反应条件温和、可控、操作步骤简单，因此具有较高的实际应用价值。
发明内容
本发明的目的之一在于提供一种多孔四氧化三锰/石墨烯复合材料，以填补四氧化三锰/石墨烯复合材料的合成方法，并降低四氧化三锰/石墨烯复合材料合成工艺的难度和合成成本，推动其产业化。
本发明的目的之二在于提供该多孔四氧化三锰/石墨烯复合材料的制备方法。
为解决上述问题，本发明采用的技术方案如下：
1.一种多孔四氧化三锰/石墨烯复合材料，其特征在于该复合材料是由四氧化三锰与石墨烯自组装形成三维网络结构的多孔无规则块体，所述的四氧化三锰的粒径为：10～16nm；所述的四氧化三锰与石墨烯的质量比为8～32：1；所述的四氧化三锰与石墨烯的质量比为8～32：1。
一种制备上述的多孔四氧化三锰/石墨烯复合材料的方法，其特征在于该方法的具体步骤为：
a)将浓度为0.075～0.75g/L的氧化石墨溶液与浓度为0.9～2.7g/L的甘露醇溶液均匀混合，所述的氧化石墨与甘露醇的质量比计算为0.086～1.73：1。
b)在室温下，加入浓度为0.1～0.4 mol/L的高锰酸钾溶液于上述混合溶液中，搅拌1-2h；所述的氧化石墨与高锰酸钾的质量比计算为0.015～0.3：1。
c)加入还原剂，该还原剂与高锰酸钾的质量比为0.2～5：1，并在85～100℃温度下，搅拌0.5～1.5h，经过滤，去离子水和酒精洗涤，烘干，即得到多孔四氧化三锰/石墨烯复合材料。上述的还原剂为水合肼或硼氢化钠。
本发明具有如下有益效果：
1）该方法相比现有的技术，不仅原料易得，工艺简单，操作简单，并且成本低易于产业化。
2）由本发明制备的多孔四氧化三锰/石墨烯复合材料可广泛作为锂离子电池、超级电容器电极材料、催化剂等相关领域的理论研究和应用。
附图说明
图1为不同实施例所制得多孔四氧化三锰/石墨烯复合材料的X射线衍射（XRD）谱。
其中：1代表实施例1，2代表实施例2，3代表实施例3，4代表实施例4
图2为实施例1所制得样品的拉曼谱图。
图3为实施例1所制得的多孔四氧化三锰/石墨烯复合材料的扫描电镜图。
图4为不同实施例所制得多孔四氧化三锰/石墨烯复合材料的氮气吸附、脱附等温曲线图（1）和孔径分布图（2）。其中：1代表实施例1，2代表实施例2，3代表实施例3，4代表实施例。
图5为实施例1所制得样品在50mA/g下前两次的充放电曲线图（1）和在1A/g下充放电的循环性能图（2）。
具体实施方式
下面结合实施例对本发明做进一步详细，完整地说明，但并不限制本发明的内容。
实施例1：将10 mL 浓度为0.0036 g/mL氧化石墨溶液与200 mL浓度为0.001 g/mL的甘露醇溶液混合均匀，加入40 mL浓度为0.187 mol/L的高锰酸钾水溶液混合，超声1-2h，加入0.35 mL水合肼（50 %）并置于95℃油浴中，搅拌反应一段时间；过滤，洗涤（去离子水、酒精）3~5次，80 ℃烘干，即得多孔四氧化三锰/石墨烯复合材料。
电性能测试：以本实施例所制得的多孔四氧化三锰/石墨烯样品为活性物质制作锂电池负极材料。具体过程如下：将所得复合电极材料、导电炭黑或乙炔黑（在此采用乙炔黑）和粘结剂（如聚四氟乙烯、羧酸甲基纤维素、聚乙烯醇等，在此采用聚四氟乙烯）按照质量比8：1：1混合，滴加一定量1-甲基-2吡咯烷酮或乙醇并充分研磨均匀后，将其涂敷于铜箔上，经真空干燥箱干燥24小时后备用。在充有氩气的手套箱中，以1 M LiPF6/EC+DMC+EMC（1:1:1）为电解液，金属锂片为对电极和参比电极，并与所得复合电极材料组装成扣式电池。
图1中的1曲线为本实施例所制得样品的XRD图，所得样品的XRD图谱与Mn3O4(JCPDS #24-0734)标准谱吻合，说明生成了四氧化三锰；
图2 为本实施例所制得样品的拉曼谱图，1330cm-1处的吸收峰为 D峰,代表了碳原子的晶格缺陷和石墨层的完整度，1605cm-1 处为G峰，反应了碳sp2的杂化结构和石墨烯的结晶度，这两个峰的存在说明材料中有石墨烯的存在。而图中的吸收峰317、374、475和652cm-1来自于晶体Mn3O4，除此外并未发现其它物质的特征吸收峰，结合图1的曲线1，可以确定所得材料为纯相四氧化三锰/石墨烯纳米复合材料。
图3为本实施例所制得样品的扫描电镜图。根据不同分辨率照片可知：所得样品是由尺寸均一的四氧化三锰纳米颗粒与石墨烯均匀复合，并自组装形成三维网络类海绵状的无规则多孔块体；且四氧化三锰的粒径为~12nm。
图 4中的1曲线为本实施例所制得样品的氮气吸附、脱附等温曲线图和孔径分布图。经计算，本实施例所得样品的比表面积为183 m2/g，孔径分布为3~15 nm（平均孔径为7.6nm）；
图5为本实施例所制得样品在50mA/g下前两次的充放电曲线图和在1A/g下充放电的循环性能图。由图5（1）可知在50mA/g充放电速率下首次库伦效率为68%，可逆比容量为1523mAh/g，远高于四氧化三锰与石墨烯的理论比容量937 和744mAh/g。由图5（2）可知在1A/g充放电速率下其可逆比容量仍可达740mAh/g，是目前商业化用碳电极的理论值的2倍，且循环100次后能稳定保持72%的容量。
上述结果表明：该结构的四氧化三锰/石墨烯复合材料，不仅具有大的比表面积、丰富的孔，而且作为锂离子负极材料，具有良好的综合电化学性能。
实施例2
将5 mL 浓度为0.0036 g/mL氧化石墨溶液与200 mL浓度为0.001 g/mL的甘露醇溶液混合均匀；
其余步骤与实施例1相同。
图1的2曲线 为本实施例所制得样品的XRD图；
图4中的2曲线为本实施例所制得样品的氮气吸附、脱附等温曲线图和孔径分布图；
经分析和计算得，本实施例所制得样品的形貌和相结构与实施例1基本一致，差异之处在于本实施例所制得复合材料中的四氧化三锰纳米颗粒的尺寸比实施例1中的大，为~15nm，这可由其XRD和BET数据充分证实：（1）XRD与实施例1相比，衍射峰明显增强且变锐，说明复合材料的结晶质量有所增加，即颗粒尺寸增大；（2）BET结果显示，本实施例所得样品的比表面积为154 m2/g，孔径分布为3~22 nm（平均孔径为11.9nm）。作为锂电负极材料，该复合材料可逆比容量为959mAh/g，首次库伦效率为50%，在1A/g充放电速率下循环100次后能稳定保持50%的容量，显示出较好的电化学性能。
实施例3
将15 mL 浓度为0.0036 g/mL氧化石墨溶液与200 mL浓度为0.001 g/mL的甘露醇溶液混合均匀；
其余步骤与实施例1相同。
图1的3曲线为本实施例所制得样品的XRD图；
图 4中的3曲线为本实施例所制得样品的氮气吸附、脱附等温曲线图和孔径分布图；
经分析和计算，得知本实施例所制得样品的形貌和相结构与实施例1基本一致，差异之处在于本实施例所制得复合材料中的四氧化三锰纳米颗粒的尺寸比实施例1中的小，为~10nm，这可由其XRD和BET数据充分证实：（1）XRD与实施例1相比，衍射峰明显减弱，说明复合材料的颗粒尺寸减小；（2）BET结果显示，本实施例所得样品的比表面积为309m2/g，孔径分布为3~6 nm（平均孔径为4.3nm）。作为锂电负极材料，该复合材料具有良好的电化学综合性能：首次库伦效率为64.7%，可逆比容量为1060mAh/g，在1A/g充放电速率下其可逆比容量为490mAh/g，且循环100次后能保持57%的容量。
实施例4
选用NaBH4作为还原剂：加入 2.5 mL浓度为2.8 M的NaBH4溶液并置于95 ℃油浴中搅拌反应一段时间；
其余步骤与实施例1相同。
图1的4曲线为本实施例所制得样品的XRD图；
图 4中的4曲线为本实施例所制得样品的氮气吸附、脱附等温曲线图和孔径分布图；
经分析和计算，本实施例所制得样品的形貌和相结构与实施例1基本一致，差异之处在于本实施例所制得复合材料中的四氧化三锰纳米颗粒的尺寸比实施例1中的大，为~20nm，这可由其XRD和BET数据充分证实：（1）XRD与实施例1相比，衍射峰明显增强，说明复合材料的颗粒尺寸增大；（2）BET结果显示，本实施例所得样品的比表面积为134m2/g，孔径分布为3~10 nm（平均孔径为5.3nm）。作为锂电负极材料，该复合材料也显示出较为良好的电化学综合性能：首次库伦效率为65%，可逆比容量为970 mAh/g，在1A/g充放电速率下其可逆比容量为390mAh/g，且循环100次后能保持69%的容量。
Claims (3)
1.一种多孔四氧化三锰/石墨烯复合材料，其特征在于该复合材料是由四氧化三锰与石墨烯自组装形成三维网络结构的多孔无规则块体，所述的四氧化三锰的粒径为：10～20nm；所述的四氧化三锰与石墨烯的质量比为8～32：1。
2.一种制备根据权利要求1所述的多孔四氧化三锰/石墨烯复合材料的方法，其特征在于该方法的具体步骤为：
a)将浓度为0.075～0.75g/L的氧化石墨溶液与浓度为0.9～2.7g/L的甘露醇溶液均匀混合，所述的氧化石墨与甘露醇的质量比计算为0.086～1.73：1；
b)在室温下，加入浓度为0.1～0.4 mol/L的高锰酸钾溶液于上述混合溶液中，搅拌1-2h；所述的氧化石墨与高锰酸钾的质量比计算为0.015～0.3：1；
c)加入还原剂，该还原剂与高锰酸钾的质量比为0.2～5：1，并在85～100℃温度下，搅拌0.5～1.5h，经过滤，去离子水和酒精洗涤，烘干，即得到多孔四氧化三锰/石墨烯复合材料。
3.根据权利要求2所述的方法，其特征在于所述的还原剂为水合肼或硼氢化钠。
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