CN111403707A - 具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料及制备方法 - Google Patents
具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料及制备方法 Download PDFInfo
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- USBWXQYIYZPMMN-UHFFFAOYSA-N rhenium;heptasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[Re].[Re] USBWXQYIYZPMMN-UHFFFAOYSA-N 0.000 title claims abstract description 62
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Abstract
本发明公开了一种具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料,其特征在于,通过在氮掺杂生物质基碳纤维表面原位生长具有层间缺陷的硫化铼纳米片,而后通过在还原性Ar/H2气氛中退火引入硫空位,得到具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料。本发明制备的复合材料中硫化铼均匀地生长在氮掺杂生物质基碳纤维的表面,具有比表面积大、导电性好、物理化学性质稳定等优点。一维的层间缺陷结构提供了相互连接的通道,以提供额外的离子嵌入/脱出位点。此外,富空位结构有利于钠离子的快速吸附,并且能够改变材料本征态的电荷分布,进而达到增加活性位点和提升材料导电性的目的,因此具有优异的电化学性能。
Description
技术领域
本发明属于金属硫化物-碳材料技术领域,具体涉及一种具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料及其制备方法。
背景技术
锂离子电池因使用寿命长、能量密度高等优点而被广泛应用在便携式储能设备、电动汽车和大规模储能等领域中。但锂离子电池的发展受到锂金属资源匮乏和价格昂贵的挑战。相比较而言,钠在地壳中有更丰富的储量,且分布广泛。因此,钠离子电池已被公认为是替代锂离子电池的首选之一。
硫化铼作为新兴的过渡金属硫化物,具有典型的二维层状结构。此外,其层间极弱的范德华相互作用有利于钠离子扩散和抑制电极材料体积膨胀。然而,作为钠离子电池负极材料时,硫化铼跟传统的二维层状过渡金属硫化物材料面临着相似的问题,其层状结构在电化学循环后易发生不可逆变化。此外,转化反应中产生的多硫化物易与电解液发生副反应,从而引起电化学容量的迅速衰减。因此,对硫化铼材料进行有效的改性,并研究其在钠离子电池工作中的电化学行为,是十分有必要的。近年来,研究者通过开发新的合成方法,成功调控了过渡金属硫化物的化学组成和电子结构,进而获得了更优异的电化学储能性能。事实证明,缺陷工程是调节纳米材料电子结构的一条有效途径。在不同种类的缺陷中,一维的层间缺陷结构可以提供相互连接的通道,以提供额外的离子嵌入/脱出位点。此外,零维的点空位能够有效地调节过渡金属硫化物的电子结构、导电性和表面结构,从而增强其电化学储能性能。
发明内容
本发明所要解决的技术问题是提供一种制备工艺简单、成本低廉、钠离子电池性能优异的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料及其制备方法。
为了达到上述目的,本发明提供了一种具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料,其特征在于,通过在氮掺杂生物质基碳纤维表面原位生长具有层间缺陷的硫化铼纳米片,而后通过在还原性Ar/H2气氛中退火引入硫空位,得到具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料。
本发明还提供了上述具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的制备方法,其特征在于,包括:将高铼酸铵、硫脲、盐酸羟胺溶解于去离子水中,并超声处理,使其分散均匀,得到混合溶液;再将氮掺杂生物质基碳纤维加入该溶液中;转移至水热釜中加热进行水热反应;反应结束后冷却至室温,将产物用乙醇和水的混合溶液洗涤,干燥;最后将得到的产物在Ar/H2气氛下进行退火处理,得到具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料。
优选地,高铼酸铵、硫脲、盐酸羟胺的摩尔比为(1-3):(1-5):(1-3)。
更优选地,所述高铼酸铵、硫脲、盐酸羟胺的摩尔比为1:2.2:2。
优选地,所述水热反应温度为180-220℃,反应时间为20-26h。
更优选地,所述水热反应温度为200℃,反应时间为24h。
优选地,所述干燥为80℃下干燥时间为10-14h。
更优选地,所述干燥为80℃下干燥时间为12h。
优选地,所述退火处理温度为450℃,处理时间为1-3h。
更优选地,所述退火处理温度为450℃,处理时间为2h。
本发明还提供了上述的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料在钠离子电池中的应用。
本发明制备的复合材料中硫化铼均匀地生长在氮掺杂生物质基碳纤维的表面,避免了硫化铼合成过程中易团聚的问题,极大的增加了硫化铼的活性表面积,使复合材料具有比表面积大、导电性好、物理化学性质稳定等优点。一维的层间缺陷结构提供了相互连接的通道,以提供额外的离子嵌入/脱出位点。此外,富空位结构不仅有利于钠离子的快速吸附,而且能够改变材料本征态的电荷分布,进而达到增加活性位点和提升材料导电性的目的。
本发明与现有技术相比,其显著优点:
1、本发明在常规的硫化铼中引入双缺陷结构,是一种简单高效的改性方法。
2、利用氮掺杂生物质基碳纤维作为基板,在其表面均匀生长硫化铼纳米片,避免了硫化铼合成过程中易团聚的问题,极大地增加了硫化铼的活性表面积。
3、本发明制备的复合材料中硫化铼均匀地生长在氮掺杂生物质基碳纤维的表面,具有比表面积大、导电性好、物理化学性质稳定等优点。一维的层间缺陷结构提供了相互连接的通道,以提供额外的离子嵌入/脱出位点。此外,富空位结构有利于钠离子的快速吸附,并且能够改变材料本征态的电荷分布,进而达到增加活性位点和提升材料导电性的目的。
4、本发明基于具有双缺陷结构的硫化铼,并结合氮掺杂生物质基碳纤维作为基板的策略,制备了一种具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料。同时,氮掺杂生物质基碳纤维基板的存在不仅避免了硫化铼严重的团聚现象,且极大地增加了硫化铼的活性表面积,使复合材料具有比表面积大、导电性好、物理化学性质稳定等优点。一维的层间缺陷结构提供了相互连接的通道,以提供额外的离子嵌入/脱出位点。此外,富空位结构的硫化铼纳米片有利于钠离子的快速吸附,因此具有优异的电化学性能。基于该设计策略研发的复合材料在碱金属基电池负极材料领域具有良好的应用前景。
附图说明
图1是本发明具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的制备流程图;
图2是本发明实施例2制备的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的射线衍射(XRD)图谱;
图3是本发明实施例2制备的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的扫描电镜(SEM)图;
图4是将本发明实施例2制备的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料作为钠离子电池所得到的钠离子电池性能图谱;a曲线是所得的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的循环伏安曲线(CV)曲线,b是相应的倍率性能曲线。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
本发明各实施例中所使用试剂如下:
高铼酸铵(国药集团化学试剂有限公司)、硫脲(国药集团化学试剂有限公司)、盐酸羟胺(国药集团化学试剂有限公司);氮掺杂生物质基碳纤维的制备方法参考文献(Small2017,13,1602866)。
实施例1
如图1所示,本实施例提供了一种具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料,具体制备步骤如下:
将高铼酸铵、硫脲、盐酸羟胺以1:2.2:3的摩尔比溶解于去离子水中,并超声处理10min,使其分散均匀,得到混合溶液;再将氮掺杂生物质基碳纤维加入该溶液中,并超声1h;转移至水热釜中加热进行水热反应,反应温度为200℃,时间为24h;反应结束后冷却至室温,将产物用乙醇和水的混合溶液洗涤,并在80℃下干燥12h;最后将得到的产物在Ar/H2气氛下于450℃退火2h,得到具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料。
实施例2
如图1所示,本实施例提供了一种具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料,具体制备步骤如下:
将高铼酸铵、硫脲、盐酸羟胺以1:2.2:2的摩尔比溶解于去离子水中,并超声处理10min,使其分散均匀,得到混合溶液;再将氮掺杂生物质基碳纤维加入该溶液中,并超声1h;转移至水热釜中加热进行水热反应,反应温度为200℃,时间为24h;反应结束后冷却至室温,将产物用乙醇和水的混合溶液洗涤,并在80℃下干燥12h;最后将得到的产物在Ar/H2气氛下于450℃退火2h,得到具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料。
使用X射线衍射、扫描电子显微镜、电化学工作站来表征、测试实施例2所获得的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料,其制备方法为的结构与性能,其结果如下:
(1)XRD测试结果表明:如图2所示,XRD图谱的结果表明实验中得到的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料在2θ=14.5°、33.2°、43.3°、和57.9°处出现明显的4个衍射花样,证明了双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的成功制备,这也直接说明了由本发明所提供的制备方法是切实可行的。
(2)SEM测试结果表明:如图3所示,具有双缺陷结构的硫化铼纳米片均匀的包覆在氮掺杂生物质碳纤维表面,避免了硫化铼的团聚,复合材料的直径大约在100nm左右。
(4)电化学测试结果表明:图4a中第二圈和第五圈的CV曲线接近重合表明具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料具有良好的电化学可逆性;图4b表明具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料具有良好的倍率性能。
Claims (9)
1.一种具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料,其特征在于,通过在氮掺杂生物质基碳纤维表面原位生长具有层间缺陷的硫化铼纳米片,而后通过在还原性Ar/H2气氛中退火引入硫空位,得到具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料。
2.权利要求1所述的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的制备方法,其特征在于,包括:将高铼酸铵、硫脲、盐酸羟胺溶解于去离子水中,并超声处理,使其分散均匀,得到混合溶液;再将氮掺杂生物质基碳纤维加入该溶液中;转移至水热釜中加热进行水热反应;反应结束后冷却至室温,将产物用乙醇和水的混合溶液洗涤,干燥;最后将得到的产物在Ar/H2气氛下进行退火处理,得到具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料。
3.如权利要求2所述的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的制备方法,其特征在于,所述高铼酸铵、硫脲、盐酸羟胺的摩尔比为(1-3):(1-5):(1-3)。
4.如权利要求3所述的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的制备方法,其特征在于,所述高铼酸铵、硫脲、盐酸羟胺的摩尔比为1:2.2:2。
5.如权利要求2所述的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的制备方法,其特征在于,所述水热反应温度为180-220℃,反应时间为20-26h。
6.如权利要求6所述的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的制备方法,其特征在于,所述水热反应温度为200℃,反应时间为24h。
7.如权利要求2所述的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的制备方法,其特征在于,所述干燥为80℃下干燥10-14h。
8.如权利要求2所述的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料的制备方法,其特征在于,所述退火处理温度为450℃,处理时间为1-3h。
9.权利要求1所述的具有双缺陷结构的硫化铼/氮掺杂生物质基碳纤维复合材料在钠离子电池中的应用。
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