CN114864893A - 一种双碳封装的CoS2/CoO多孔异质结复合材料及其制备方法和应用 - Google Patents
一种双碳封装的CoS2/CoO多孔异质结复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明将性能良好的金属硫化物异质结和双层碳骨架结构结合,提供了一种双碳封装的CoS2/CoO多孔异质结复合材料及其制备方法和应用,该复合材料包括:3D开放骨架结构的海海绵状碳和还原氧化石墨烯组成的双层碳骨架以及CoS2/CoO多孔异质结纳米颗粒,且CoS2/CoO多孔异质结纳米颗粒封装于双层碳骨架中。该复合材料具有良好的导电性、稳定的电极结构和良好的储能性能,可作为高性能钠离子电池负极材料。该复合材料的制备方法工艺简单、条件温和,产物形貌稳定、纯度高,且产物处理方便简洁,适合于中等规模工业生产,且对其他碳基纳米复合材料的制备具有一定的普适性。
Description
技术领域
本发明属于复合材料技术领域,具体涉及一种双碳封装的CoS2/CoO多孔异质结复合材料、该复合材料的制备方法及其在钠离子电池负极材料中的应用。
背景技术
随着生态环境的恶化和化石能源的减少,社会对生态友好型和可持续的能源的需求日益迫切。锂离子电池由于其循环寿命长、能量密度高,被认为是近年来最重要的可持续存储设备。锂离子电池虽然应用广泛,但存在成本高、资源有限等问题,这些问题制约了锂离子电池的发展。钠离子电池是最有前景的储能设备之一,也是最有希望替代锂离子电池的储能设备之一。钠离子电池由于钠资源丰富、成本低廉而受到研究者的广泛关注。然而,钠离子电池的大规模应用仍然存在一些问题。Na和Li属于同一主族,Na的嵌入/脱出机理与Li的相似,但由于Na+半径较大(比Li+大43%),很难嵌入电极。与正极材料相比,负极材料的发展稍显滞后,负极材料的研究成为钠离子电池发展的迫切任务。
常见的钠离子电池负极材料主要有碳材料、金属氧、硫化物和合金等。与其它材料相比,金属硫化物具有较高的理论容量和较低的氧化还原电位,从而具有成为钠离子电池负极的应用前景。但是金属硫化物作为钠离子电池负极材料存在一些缺陷,例如:金属硫化物较低的导电性以及其在钠化、脱钠化过程中存在较为严重的体积膨胀现象,有待于进一步改进。
发明内容
特别构筑的双层碳骨架结构(双碳结构)包含内部起支撑作用的3D开放骨架结构的海海绵状硬碳和外部起保护作用的还原氧化石墨烯。其中,海海绵状硬碳具有良好的导电性,能够有效促进电荷在电极材料内部的快速分布,避免电荷聚集导致电压升高,还能够帮助电解液在电极内扩散,改善电极材料的阻抗。还原氧化石墨烯具有独特的二维(2D)薄层蜂窝结构和优异的电学性能,还原氧化石墨烯应用于钠离子电池负极材料能够抑制体积膨胀,稳定电极结构。通过构筑异质结能够增强金属硫化物的本征导电性。
为解决现有技术的问题,本发明将性能良好的金属硫化物异质结和双层碳骨架结构结合起来,充分利用它们的优点,提供了一种双碳封装的CoS2/CoO多孔异质结复合材料及其制备方法。
本发明的具体技术方案如下:
本发明提供的双碳封装的CoS2/CoO多孔异质结复合材料,其特征在于,包括:3D开放骨架结构的海海绵状碳和还原氧化石墨烯组成的双层碳骨架以及CoS2/CoO多孔异质结纳米颗粒。
本发明提供的双碳封装的CoS2/CoO多孔异质结复合材料,还可以具有这样的技术特征,CoS2/CoO多孔异质结纳米颗粒封装于双层碳骨架中。
本发明还提供了一种上述双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,其特征在于,包括如下步骤:步骤S1,通过超声喷雾热解法制备得到3D开放骨架结构的海海绵状碳;步骤S2,通过调控表面亲疏水性法在3D开放骨架结构的海海绵状碳的碳骨架上生长小尺寸的Co-ZIFs纳米颗粒,得到中间体一;步骤S3,通过气相原位硫化法原位硫化中间体一的Co-ZIFs纳米颗粒,在碳骨架的还原作用下,得到中间体二;步骤S4,通过吸附组装法使表面带有负电荷的中间体二吸附组装带正电荷的氨基化氧化石墨烯,得到中间体三;步骤S5,将中间体三在惰性气体中退火得到双碳封装的CoS2/CoO多孔异质结复合材料。
本发明提供的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,还可以具有这样的技术特征,其中,步骤S2中调控表面亲疏水性法制备中间体一的具体过程为:将3D开放骨架结构的海海绵状碳分散于第一溶剂中,加入表面活性剂搅拌均匀,加入钴源和有机物配体进行搅拌反应,用第一溶剂洗涤反应产物,干燥得到中间体一。
本发明提供的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,还可以具有这样的技术特征,其中,步骤S3中气相原位硫化法制备中间体二的具体过程为:将中间体一和过量硫源放置在管式炉中,在惰性气体保护下程序升温至预置温度进行反应,用能较好溶解硫的洗液洗涤管内的反应产物,干燥得到中间体二。
本发明提供的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,还可以具有这样的技术特征,其中,步骤S4中吸附组装法制备中间体三的具体过程为:将中间体二分散于第二溶剂中,逐滴加入分散良好的所述氨基化氧化石墨烯的溶液,搅拌反应后用洗液洗涤反应产物,干燥得到中间体三。
本发明提供的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,还可以具有这样的技术特征,其中,调控表面亲疏水性法制备中间体一的具体过程中:第一溶剂为甲醇,3D开放骨架结构的海海绵状碳分散于甲醇的浓度为0.25~2mg/mL;表面活性剂为聚乙烯吡咯烷酮,浓度为1~20mg/mL;钴源为六水合硝酸钴,浓度为5~10mg/mL;有机物配体为2-甲基咪唑,浓度为10~20mg/mL;搅拌反应的反应时间为1~4h。
本发明提供的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,还可以具有这样的技术特征,其中,气相原位硫化法制备中间体二的具体过程中:硫源为升华硫粉,惰性气体为氮气或氩气,反应时间为1~4h,洗液为二硫化碳。
本发明提供的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,还可以具有这样的技术特征,其中,吸附组装法制备中间体三的具体过程中:第二溶剂为去离子水,中间体二和氨基化氧化石墨烯的质量比为2:1~8:1,搅拌反应的反应时间为2~4h,洗液为去离子水。
本发明还提供了上述双碳封装的CoS2/CoO多孔异质结复合材料在钠离子电池负极材料中的应用。
发明的作用与效果
由于本发明是将高储钠活性的CoS2/CoO多孔异质结和双层碳骨架结构结合,制备出具有夹层结构的双碳封装的CoS2/CoO多孔异质结复合材料。夹层结构中,CoS2/CoO多孔异质结能够在缓解体积膨胀的同时贡献高的储钠容量,双层碳骨架结构具有加速化学反应动力学和增强结构稳定性的作用,这种夹层结构大大提高了SIB负极材料的比容量和循环稳定性。
因此本发明提供的双碳封装的CoS2/CoO多孔异质结复合材料及其制备方法,具有如下优势:
1.双碳封装的CoS2/CoO多孔异质结复合材料具有良好的导电性和储能性能,作为高性能钠离子电池负极材料能够稳定电极结构;
2.该制备方法中原料均为廉价的市售化学试剂,原料储量丰富,工业成本低;
3.该制备方法工艺简单、条件温,产物形貌稳定、纯度高,且产物处理方便简洁,适合于中等规模工业生产;
4.该制备方法对制备其他碳基纳米复合材料具有一定的普适性。
附图说明
图1是本发明实施例一中产物的微观结构张照片;
图2是本发明实施例一中产物的XRD谱图和高分辨XPS谱图;
图3是本发明实施例二中中间体一(OFC@Co-ZIFs)的SEM照片;
图4是本发明实施例三中双碳封装的CoS2/CoO多孔异质结复合材料的SEM照片。
具体实施方式
以下通过实施例说明本发明的具体步骤,但不受实施例限制。
在本发明中使用的术语,除非另有说明,一般具有本领域普通技术人员通常理解的含义。
在以下实施例中,未详细描述的各种过程和方法是本领域中公知的常规方法。
下述实施例中所采用的试剂为普通商业途径购得,未注明的实验操作及实验条件参考本领域的常规操作及常规条件。
下述实施例中所采用的试剂纯度均不低于化学纯。
以下结合附图来说明本发明的具体实施方式。
<实施例一>
本实施例提供了一种双碳封装的CoS2/CoO多孔异质结复合材料,其制备步骤如下:
步骤S1,配制1.5mol/L的氯乙酸钠水溶液150mL,超声20min使溶液分散均匀,加入自制的超声喷雾器中,溶液在超声波的驱动下被雾化成细小的水雾,由1.5L/min的氮气吹入700℃的管式炉中,反应2h后用乙醇收集管壁的黑色粉体产物,用75vol%乙醇水溶液洗涤5次,干燥得到3D开放骨架结构的海海绵状碳(OFC);
步骤S2,将10mg OFC溶于20mL甲醇中,超声分散20min,在高速搅拌下,加入100mg聚乙烯吡咯烷酮(PVP,(C6H9NO)n),搅拌1h,然后加入0.1456g六水合硝酸钴(Co(NO3)2·6H2O),搅拌1h,最后加入0.328g 2-甲基咪唑,反应4h,用甲醇洗涤3次后,于真空干燥箱中烘干得到中间体一(OFC@Co-ZIFs);
步骤S3,将OFC@Co-ZIFs与过量升华硫粉放入管式炉中,在N2的保护下,首先以5℃/min的升温速率升温至200℃,保温2h稳定结构,继续以2℃/min的速率升温至400℃,反应2h,反应产物冷却至室温,用二硫化碳(CS2)洗涤3次,于真空干燥箱中烘干制得中间体二(OFC@CoS2/CoO);
步骤S4,将OFC@CoS2/CoO超声分散于去离子水中,制得水分散液,浓度为1mg/mL,将氨基化氧化石墨烯粉末配置成0.5mg/L GO溶液,在温和搅拌下,等量的GO溶液逐滴加入到水分散液中,温和搅拌4h,用去离子水洗涤多次后,真空干燥制得中间体三(OFC@CoS2/CoO@GO);
步骤S5,取适量的OFC@CoS2/CoO@GO放置在管式炉中,在500℃,氩气保护下,退火1h,即得双碳封装的CoS2/CoO多孔异质结复合材料。
图1是本发明实施例一中各步骤产物的微观结构张照片。其中,图1(a)是本实施例中步骤S1的产物OFC的SEM照片;图1(b)是本实施例中步骤S2的产物OFC@Co-ZIFs的SEM照片;图1(c)是本实施例中步骤S3的产物OFC@CoS2/CoO的SEM照片;图1(d)是本实施例中步骤S5的产物双碳封装的CoS2/CoO多孔异质结复合材料的SEM和TEM照片。
图2是本发明实施例一产物的XRD谱图和高分辨XPS谱图。
对本实施例制得的双碳封装的CoS2/CoO多孔异质结复合材料进行结构分析,结果如图2所示,图(2a)是OFC@CoS2/CoO和双碳封装的CoS2/CoO多孔异质结复合材料的XRD图谱,图(2b)、图(2c)和图(2d)分别是CoS2/CoO多孔异质结复合材料的主要元素C1s、Co2p和S2p元素的高分辨XPS谱图。通过对Co2p图谱分峰,表明本实施例制得的双碳封装的CoS2/CoO多孔异质结复合材料的结构和其理论结构一致。
<实施例二>
本实施例提供了不同OFC添加量制备的双碳封装的CoS2/CoO多孔异质结复合材料,其制备步骤如下:
步骤S1,配制1.5mol/L的氯乙酸钠水溶液150mL,超声20min使溶液分散均匀,加入自制的超声喷雾器中,溶液在超声波的驱动下被雾化成细小的水雾,由1.5L/min的氮气吹入700℃的管式炉中,反应2h后用乙醇收集管壁的黑色粉体产物,用75vol%乙醇水溶液洗涤5次,干燥得到OFC;
步骤S2,将10mg、15mg和20mg的OFC分别溶于3份20mL甲醇中,超声分散20min,在高速搅拌下,各自加入100mg PVP,搅拌1h,然后各自加入0.1456g六水合硝酸钴,搅拌1h,最后各自加入0.328g 2-甲基咪唑,反应4h,分别用甲醇洗涤3次后,于真空干燥箱中烘干得到3种不同OFC量的OFC@Co-ZIFs;
步骤S3,将3种OFC@Co-ZIFs分别与过量升华硫粉放入管式炉中,在N2的保护下,首先以5℃/min的升温速率升温至200℃,保温2h稳定结构,继续以2℃/min的速率升温至400℃,反应2h,反应产物冷却至室温,用二硫化碳(CS2)洗涤3次,于真空干燥箱中烘干制得3种不同OFC量的OFC@CoS2/CoO;
步骤S4,将3种OFC@CoS2/CoO分别超声分散于去离子水中,制得3份水分散液,浓度均为1mg/mL,将氨基化氧化石墨烯粉末配置成0.5mg/L GO溶液,在温和搅拌下,与每份水分散液等量的GO溶液逐滴加入到3份水分散液中,温和搅拌4h,用去离子水洗涤多次后,真空干燥制得3种不同OFC量的OFC@CoS2/CoO@GO;
步骤S5,将3种OFC@CoS2/CoO@GO分别取适量放置在管式炉中,在500℃,在氩气保护下,退火1h,即得3种不同OFC量的双碳封装的CoS2/CoO多孔异质结复合材料。
图3是本发明实施例二中中间体一(OFC@Co-ZIFs)的SEM照片。其中图3(a)、3(b)和3(c)分别是10mg、15mg和20mg OFC制备的OFC@Co-ZIFs的SEM照片,由图3(a)、3(b)和3(c)所示,不同添加量的OFC制备的OFC@Co-ZIFs的形貌相似,但OFC和ZIFs比例存在明显差异。
<实施例三>
本实施例提供了不同中间体二(OFC@CoS2/CoO)与氨基化氧化石墨烯质量比制备的双碳封装的CoS2/CoO多孔异质结复合材料,其制备步骤如下:
步骤S1,配制1.5mol/L的氯乙酸钠水溶液150mL,超声20min使溶液分散均匀,加入自制的超声喷雾器中,溶液在超声波的驱动下被雾化成细小的水雾,由1.5L/min的氮气吹入700℃的管式炉中,反应2h后用乙醇收集管壁的黑色粉体产物,用75vol%乙醇水溶液洗涤5次,干燥得到OFC;
步骤S2,将10mg OFC溶于20mL甲醇中,超声分散20min,在高速搅拌下,加入100mg聚乙烯吡咯烷酮(PVP,(C6H9NO)n),搅拌1h,然后加入0.1456g六水合硝酸钴(Co(NO3)2·6H2O),搅拌1h,最后加入0.328g 2-甲基咪唑,反应4h,用甲醇洗涤3次后,于真空干燥箱中烘干得到中间体一(OFC@Co-ZIFs);
步骤S3,将OFC@Co-ZIFs与过量升华硫粉放入管式炉中,在N2的保护下,首先以5℃/min的升温速率升温至200℃,保温2h稳定结构,继续以2℃/min的速率升温至400℃,反应2h,反应产物冷却至室温,用二硫化碳(CS2)洗涤3次,于真空干燥箱中烘干制得中间体二(OFC@CoS2/CoO);
步骤S4,取3份中间体二(OFC@CoS2/CoO)分别超声分散于去离子水中,制得3份水分散液,浓度均为1mg/mL,将氨基化氧化石墨烯粉末配置成0.5mg/L GO溶液,在温和搅拌下,按照中间体二的水分散液与GO溶液体积比为4:1、2:1和1:1,取适量的GO溶液(此时中间体二和氨基化氧化石墨烯的质量比分别为8:1、4:1和2:1),在温和搅拌下,逐滴加入到3份水分散液中,温和搅拌4h,用去离子水洗涤多次后,真空干燥制得3份中间体三(OFC@CoS2/CoO@GO);
步骤S5,将3份OFC@CoS2/CoO@GO分别取适量放置在管式炉中,在500℃,在氩气保护下,退火1h,即得3份双碳封装的CoS2/CoO多孔异质结复合材料。
图4是本发明实施例三中双碳封装的CoS2/CoO多孔异质结复合材料的SEM照片。其中图4(a)、4(b)和4(c)分别是中间体二和氨基化氧化石墨烯的质量比分别为8:1、4:1和2:1时制备的双碳封装的CoS2/CoO多孔异质结复合材料的SEM照片,由图4(a)、4(b)和4(c)所示,不同中间体二(OFC@CoS2/CoO)与氨基化氧化石墨烯质量比制备的双碳封装的CoS2/CoO多孔异质结复合材料,外层氨基化氧化石墨烯(rGO)的包裹状态和复合材料的结构存在明显差异。
以上是对实施例的详细描述,方便本领域的技术人员能正确理解和使用本发明。凡本领域的技术人员依据本发明在现有技术基础上,不经过创新性的劳动,仅通过分析、类推或有限列举等方法得到的改进或修改技术方案,都应该在由权利要求书所确定的保护范围内。
Claims (10)
1.一种双碳封装的CoS2/CoO多孔异质结复合材料,其特征在于,包括:
3D开放骨架结构的海海绵状碳和还原氧化石墨烯组成的双层碳骨架以及CoS2/CoO多孔异质结纳米颗粒。
2.根据权利要求1所述的双碳封装的CoS2/CoO多孔异质结复合材料,其特征在于,
所述CoS2/CoO多孔异质结纳米颗粒封装于所述双层碳骨架中。
3.一种如权利要求1或2所述的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,其特征在于,包括如下步骤:
步骤S1,通过超声喷雾热解法制备得到所述3D开放骨架结构的海海绵状碳;
步骤S2,通过调控表面亲疏水性法在所述3D开放骨架结构的海海绵状碳的碳骨架上生长小尺寸的Co-ZIFs纳米颗粒,得到中间体一;
步骤S3,通过气相原位硫化法原位硫化所述中间体一的所述Co-ZIFs纳米颗粒,在所述碳骨架的还原作用下,得到中间体二;
步骤S4,通过吸附组装法使表面带有负电荷的所述中间体二吸附组装带正电荷的氨基化氧化石墨烯,得到中间体三;
步骤S5,将所述中间体三在惰性气体中退火得到所述双碳封装的CoS2/CoO多孔异质结复合材料。
4.根据权利要求3所述的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,其特征在于,
其中,步骤S2中所述调控表面亲疏水性法制备所述中间体一的具体过程为:
将所述3D开放骨架结构的海海绵状碳分散于第一溶剂中,加入表面活性剂搅拌均匀,加入钴源和有机物配体进行搅拌反应,用所述第一溶剂洗涤反应产物,干燥得到所述中间体一。
5.根据权利要求3所述的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,其特征在于,
其中,步骤S3中所述气相原位硫化法制备所述中间体二的具体过程为:
将所述中间体一和过量硫源放置在管式炉中,在惰性气体保护下程序升温至预置温度进行反应,用能较好溶解硫的洗液洗涤管内的反应产物,干燥得到所述中间体二。
6.根据权利要求3所述的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,其特征在于,
其中,步骤S4中所述吸附组装法制备所述中间体三的具体过程为:
将所述中间体二分散于第二溶剂中,逐滴加入分散良好的所述氨基化氧化石墨烯的溶液,搅拌反应后用洗液洗涤反应产物,干燥得到所述中间体三。
7.根据权利要求4所述的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,其特征在于:
其中,所述第一溶剂为甲醇,所述3D开放骨架结构的海海绵状碳分散于甲醇的浓度为0.25~2mg/mL,
所述表面活性剂为聚乙烯吡咯烷酮,浓度为1~20mg/mL,
所述钴源为六水合硝酸钴,浓度为5~10mg/mL,
所述有机物配体为2-甲基咪唑,浓度为10~20mg/mL,
所述搅拌反应的反应时间为1~4h。
8.根据权利要求5所述的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,其特征在于:
其中,所述硫源为升华硫粉,
所述惰性气体为氮气或氩气,
所述反应的反应时间为1~4h,
所述洗液为二硫化碳。
9.根据权利要求6所述的双碳封装的CoS2/CoO多孔异质结复合材料的制备方法,其特征在于:
其中,所述第二溶剂为去离子水,
所述中间体二和所述氨基化氧化石墨烯的质量比为2:1~8:1,
所述搅拌反应的反应时间为2~4h,
所述洗液为去离子水。
10.如权利要求1或2所述的双碳封装的CoS2/CoO多孔异质结复合材料在钠离子电池负极材料中的应用。
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