CN114883117A - 一种复合碳纳米管的制备方法 - Google Patents
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Abstract
本发明涉及一种复合碳纳米管的制备方法。它先制备Ni/MgO催化剂,将Ni/MgO催化剂置于管式炉的气流上游区域,通入乙烯,进行第一次加热处理,再将Ni/MgO催化剂移至管式炉气流下游区域,持续通入乙烯,并进行第二次加热处理,然后在氩气保护下冷却至室温,收集产物进行提纯;所述第一次加热处理温度为750℃,保温20min,第二次加热处理温度为950℃,保温20min。该制备方法可制备得到有两种不同管径碳纳米管组成的复合碳纳米管,显著提高了材料的电化学性能及性能稳定性。
Description
本发明是专利申请号202110534272.X、发明名称为“一种具有分级结构的碳纳米管复合材料及其制备方法”的分案申请。
技术领域
本发明涉及碳纳米材料的制备技术领域,尤其涉及一种复合碳纳米管的制备方法。
背景技术
近年来,高导电性和高比表面积的碳纳米材料被广泛应用于电极材料来制备超级电容器。其中,具有分级结构的碳纳米材料用作超级电容器电极材料时,能量密度和功率密度都能得到大幅提升,但具体应用时仍然面临不小挑战。例如,以石墨烯为基体材料制备得到的海绵状三维多孔材料,具有良好的孔结构,优良的导电性和重量较轻等优点,是构建具有分级结构的超级电容器电极材料的优秀候选材料,但是石墨烯层与层之间存在着强烈的π–π相互作用,导致石墨烯会重新堆叠得到石墨,而且石墨烯基分级结构的电极材料合成工艺成本高,难以扩大规模。碳纳米管具有优异的导电性和电子传输性能,被认为是一种很有前途的超级电容器电极材料。然而,基于碳纳米管的超级电容器能量密度水平仍然需要提升才能满足应用需求。
发明内容
本发明目的在于提供一种复合碳纳米管的制备方法,该制备方法可制备得到有两种不同管径碳纳米管组成的复合碳纳米管,显著提高了材料的电化学性能及性能稳定性。
本发明目的通过如下技术方案实现:
一种复合碳纳米管的制备方法,其特征在于:先制备Ni/MgO催化剂,将Ni/MgO催化剂置于管式炉的气流上游区域,通入乙烯,进行第一次加热处理,再将Ni/MgO催化剂移至管式炉气流下游区域,持续通入乙烯,并进行第二次加热处理,然后在氩气保护下冷却至室温,收集产物进行提纯;所述第一次加热处理温度为750℃,保温20min,第二次加热处理温度为950℃,保温20min;所述复合碳纳米管是由管径为5~10nm的细碳纳米管和管径约为200nm的粗碳纳米管构成,所述粗碳纳米管具有分枝结构,细纳米管螺旋缠绕在粗碳纳米管表面。
本发明中管径较细碳纳米管螺旋缠绕在较粗管径分枝状碳纳米管表面,形成了复合碳纳米管。螺旋缠绕的细碳纳米管具有较高比表面积,提高了吸附的电荷量,管径较粗碳纳米管具有分枝状结构,增加了电荷传输的通道,二者协同作用,能够明显加速离子转移速度,缩短离子转移距离,从而改善电化学性能。
作为进一步优化,上述乙烯的气流量优选为100~120mL/min。
本发明通过分两步处理,第一步先将催化剂置于碳源气流上游,在较低温度下,乙烯气流与制备的大颗粒Ni/MgO催化剂接触反应,改变了生成的碳纳米管的生长方向,从而形成分枝结构,生成粗管径分枝状碳纳米管,在此过程中,Ni/MgO催化剂经高温及与碳源反应后,粒径减小,分散成较小尺寸结构附着在粗管径碳纳米管表面,第二步将生成的粗管径分枝状碳纳米管和催化剂成分下移至气流下游,在较高温度下再次催化乙烯反应,生成极小管径的碳纳米管,最终螺旋缠绕在粗管径碳纳米管表面,即形成了复合碳纳米管。
作为进一步优化,上述Ni/MgO催化剂是以Ni(NO3)2和Mg(NO3)2溶于去离子水中得溶液A,再加入氢氧化钠溶液得溶液B,然后将溶液B进行回流、过滤、洗涤、干燥后,将产物置于管式炉中,在空气中煅烧,然后在H2和Ar的混合气氛下,继续保温30~40min;上述溶液A中Ni2+和Mg2+的浓度总和为0.2mol/L,氢氧化钠溶液的浓度为2.5mol/L,氢氧化钠溶液与去离子水的体积比为1:4;上述回流温度为95℃,回流时间为12h。
作为进一步优化,上述空气中煅烧的温度为600~620℃,煅烧时间为2h,所述H2和Ar的气流量分别为100~120mL/min和 300~360mL/min,H2和Ar的气流量比为1:3;所述提纯是将收集的产物依次用盐酸溶液、氢氧化钠溶液和去离子水清洗,然后在80℃下真空干燥;所述盐酸溶液的浓度为4~5mol/L,氢氧化钠溶液的浓度为12~13mol/L。
本发明通过先进行回流处理,然后在空气环境下煅烧,再在一定气流量比例的H2和Ar的混合气氛下制备的Ni/MgO催化剂,在乙烯作为碳源制备粗管径碳纳米管的体系中,碳源与催化剂的反应过程中,有效改变了纳米管的生长方向,从而形成分枝结构。
最具体的,上述复合碳纳米管的制备方法,其特征在于,按如下步骤进行:
(1)将Ni(NO3)2和Mg(NO3)2溶于去离子水中,使得Ni2+和Mg2+的浓度总和为0.2mol/L,再加入2.5mol/L的氢氧化钠溶液得混合液,氢氧化钠溶液与去离子水的体积比为1:4,然后将混合液在95℃下回流12h,然后过滤,将过滤产物用去离子水洗涤、冷冻干燥后,将产物在空气氛围中,于600~620℃下煅烧2h,再在H2和Ar的混合气氛下以相同温度继续煅烧30~40min,得到由MgO作为基底支撑Ni纳米颗粒产物,即为Ni/MgO催化剂,所述H2和Ar的气流量分别为100~120mL/min和 300~360mL/min,H2和Ar的气流量比为1:3;
(2)将Ni/MgO催化剂置于管式炉气流上游区域,按照100~120mL/min的气流量通入乙烯,将管式炉加热至740~760℃,保持15~25min,然后将Ni/MgO催化剂移至管式炉气流下游区域,将管式炉加热至940~960℃,保持15~25min,然后在Ar保护下冷却至室温,收集产物;
(3)将产物依次用4~5mol/L的盐酸溶液、12~13mol/L的氢氧化钠溶液和去离子水洗涤,然后在80℃下真空干燥。
本发明具有如下技术效果:
本发明提供了一种复合碳纳米管的制备方法,该方法制备得到了有两种不同管径碳纳米管组成的复合碳纳米管,其中超细管径碳纳米管管径为5~10nm,粗管径分枝结构碳纳米管管径为200nm左右,超细管径的碳纳米管螺旋缠绕具有较粗管径分枝结构碳纳米管比表面积增加,增加吸附的电荷量,粗管径分枝结构增加了电荷转移的流通路径,二者协同作用,从而增加了电荷转移速率,缩短了电荷转移距离,提高了材料的电化学性能,其功率密度达到73.2Wh·kg-1,当电流密度为1A/g时,其比电容为252.6F/g,是单一粗管径分枝状碳纳米管的1.4倍,具有优异的循环稳定性,循环10000次以后,依然保持极高的电容保有率,管径分布均匀性好,保证了材料优异的电化学性能及性能稳定性。
附图说明
图1:本发明制备的复合碳纳米管的结构示意图。
图2:本发明制备的复合碳纳米管的扫描电镜图。
图3:本发明制备的复合碳纳米管的透射电镜图。
图4:本发明制备的复合碳纳米管的X射线衍射图。
图5:本发明制备的复合碳纳米管的能量密度-功率密度曲线图。
图6:本发明制备的复合碳纳米管循环10000次以上的电容保有率。
图7:本发明制备的复合碳纳米管与对比例1制备的单一粗管径分枝状的碳纳米管的性能对比图。
具体实施方式
下面通过实施例对本发明进行具体的描述,有必要在此指出的是,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,该领域的技术人员可以根据上述本发明内容对本发明作出一些非本质的改进和调整。
实施例1
一种复合碳纳米管的制备方法,按如下步骤进行:
(1)将Ni(NO3)2和Mg(NO3)2溶于去离子水中,使得Ni2+和Mg2+的浓度总和为0.2mol/L,再加入2.5mol/L的氢氧化钠溶液得混合液,氢氧化钠溶液与去离子水的体积比为1:4,然后将混合液在95℃下回流12h,然后过滤,将过滤产物用去离子水洗涤、冷冻干燥后,将产物在空气氛围中,于600℃下煅烧2h,再在H2和Ar的混合气氛下以相同温度继续煅烧35min,得到由MgO作为基底支撑Ni纳米颗粒产物,即为Ni/MgO催化剂,所述H2和Ar的气流量分别为100mL/min和 300mL/min,H2和Ar的气流量为1:3;
(2)将Ni/MgO催化剂置于管式炉气流上游区域,按照100mL/min的气流量通入乙烯,将管式炉加热至750℃,保持20min,然后将Ni/MgO催化剂移至管式炉气流下游区域,将管式炉加热至950℃,保持20min,然后在Ar保护下冷却至室温,收集产物;
(3)将产物依次用5mol/L的盐酸溶液、13mol/L的氢氧化钠溶液和去离子水洗涤,然后在80℃下真空干燥。
从图1可知本发明制备的复合碳纳米管较粗管径的碳纳米管具有分枝结构,从图中放大位置可看出较细管径碳纳米管螺旋缠绕在较粗管径分枝状碳纳米管表面。
图2和图3分别是本发明制备的复合碳纳米管的扫描电镜图和透射电镜图,从图中可以看出,较粗管径的碳纳米管具有明显的分枝结构,其管径为200nm左右,较细管径的碳纳米管的管径为5~10nm,并管螺旋缠绕于较粗管径具有分枝状的碳纳米管表面。
如图5所示,本发明制备的复合碳纳米管的功率密度达到73.2Wh·kg-1,需要说明的是,由于横坐标功能密度的值跨度比较大,为了方便绘制曲线图,本领域均通常会将横坐标进行简化如图5表述。
将本发明制备的复合碳纳米管进行循环伏安测试,结果如图6所示,循环10000次以后,依然保持很高的电容保有率,具有优异的电化学循环稳定性。
对比例1
一种碳纳米管的制备方法,包括如下步骤:
步骤一:采用与实施例1步骤一工艺制备出Ni/MgO催化剂;
步骤二:将Ni/MgO催化剂置于管式炉中,按照100mL/min的气流量通入乙烯,将管式炉加热至750℃,保持20min,然后在Ar保护下冷却至室温,收集产物;
步骤三:与实施例1中步骤三相同。
对比例1制备的产物中只存在较促管径的碳纳米管,并没有像本发明一样出现的管径在5~10nm的碳纳米管在较粗管径表面进行螺旋缠绕。
通过实施例1和对比例1的性能对比,本发明制备的细管径碳纳米管缠绕较粗管径分枝状碳纳米管的复合碳纳米管的最大能量密度是对比例1的1.4倍以上。
将本发明制备的复合碳纳米管采用1mol/L的硫酸溶液作为电解液,检测其性能,当电流密度为1A/g时,其比电容为252.6F/g,当电流密度增大到10A/g时,比电容为176F/g,远远高于对比例1制备的单一粗管径分枝状碳纳米管,具体如图7所示。
实施例2
一种复合碳纳米管的制备方法,按如下步骤进行:
(1)将Ni(NO3)2和Mg(NO3)2溶于去离子水中,使得Ni2+和Mg2+的浓度总和为0.2mol/L,再加入2.5mol/L的氢氧化钠溶液得混合液,氢氧化钠溶液与去离子水的体积比为1:4,然后将混合液在95℃下回流12h,然后过滤,将过滤产物用去离子水洗涤、冷冻干燥后,将产物在空气氛围中,于620℃下煅烧2h,再在H2和Ar的混合气氛下以相同温度继续煅烧40min,得到由MgO作为基底支撑Ni纳米颗粒产物,即为Ni/MgO催化剂,所述H2和Ar的气流量分别为110mL/min和 330mL/min;
(2)将Ni/MgO催化剂置于管式炉气流上游区域,按照110mL/min的气流量通入乙烯,将管式炉加热至740℃,保持25min,然后将Ni/MgO催化剂移至管式炉气流下游区域,将管式炉加热至940℃,保持25min,然后在Ar保护下冷却至室温,收集产物;
(3)将产物依次用4mol/L的盐酸溶液、12mol/L的氢氧化钠溶液和去离子水洗涤,然后在80℃下真空干燥。
实施例3
一种复合碳纳米管的制备方法,按如下步骤进行:
(1)将Ni(NO3)2和Mg(NO3)2溶于去离子水中,使得Ni2+和Mg2+的浓度总和为0.2mol/L,再加入2.5mol/L的氢氧化钠溶液得混合液,氢氧化钠溶液与去离子水的体积比为1:4,然后将混合液在95℃下回流12h,然后过滤,将过滤产物用去离子水洗涤、冷冻干燥后,将产物在空气氛围中,于600℃下煅烧2h,再在H2和Ar的混合气氛下以相同温度继续煅烧30min,得到由MgO作为基底支撑Ni纳米颗粒产物,即为Ni/MgO催化剂,所述H2和Ar的气流量分别为120mL/min和 360mL/min;
(2)将Ni/MgO催化剂置于管式炉气流上游区域,按照120mL/min的气流量通入乙烯,将管式炉加热至760℃,保持15min,然后将Ni/MgO催化剂移至管式炉气流下游区域,将管式炉加热至960℃,保持15min,然后在Ar保护下冷却至室温,收集产物;
(3)将产物依次用4.5mol/L的盐酸溶液、12.5mol/L的氢氧化钠溶液和去离子水洗涤,然后在80℃下真空干燥。
Claims (5)
1.一种复合碳纳米管的制备方法,其特征在于:先制备Ni/MgO催化剂,将Ni/MgO催化剂置于管式炉的气流上游区域,通入乙烯,进行第一次加热处理,再将Ni/MgO催化剂移至管式炉气流下游区域,持续通入乙烯,并进行第二次加热处理,然后在氩气保护下冷却至室温,收集产物进行提纯;所述第一次加热处理温度为750℃,保温20min,第二次加热处理温度为950℃,保温20min;所述复合碳纳米管是由管径为5~10nm的细碳纳米管和管径约为200nm的粗碳纳米管构成,所述粗碳纳米管具有分枝结构,细纳米管螺旋缠绕在粗碳纳米管表面。
2.如权利要求1所述复合碳纳米管的制备方法,其特征在于:所述乙烯的气流量优选为100~120mL/min。
3.如权利要求1或2所述复合碳纳米管的制备方法,其特征在于:所述Ni/MgO催化剂是以Ni(NO3)2和Mg(NO3)2溶于去离子水中得溶液A,再加入氢氧化钠溶液得溶液B,然后将溶液B进行回流、过滤、洗涤、干燥后,将产物置于管式炉中,在空气中煅烧,然后在H2和Ar的混合气氛下,继续保温30~40min;所述溶液A中Ni2+和Mg2+的浓度总和为0.2mol/L,氢氧化钠溶液的浓度为2.5mol/L,氢氧化钠溶液与去离子水的体积比为1:4;所述回流温度为95℃,回流时间为12h。
4.如权利要求1至3任一所述复合碳纳米管的制备方法,其特征在于:所述空气中煅烧的温度为600~620℃,煅烧时间为2h,所述H2和Ar的气流量分别为100~120mL/min和 300~360mL/min,H2和Ar的气流量比为1:3;所述提纯是将收集的产物依次用盐酸溶液、氢氧化钠溶液和去离子水清洗,然后在80℃下真空干燥;所述盐酸溶液的浓度为4~5mol/L,氢氧化钠溶液的浓度为12~13mol/L。
5.一种复合碳纳米管的制备方法,其特征在于,按如下步骤进行:
(1)将Ni(NO3)2和Mg(NO3)2溶于去离子水中,使得Ni2+和Mg2+的浓度总和为0.2mol/L,再加入2.5mol/L的氢氧化钠溶液得混合液,氢氧化钠溶液与去离子水的体积比为1:4,然后将混合液在95℃下回流12h,然后过滤,将过滤产物用去离子水洗涤、冷冻干燥后,将产物在空气氛围中,于600~620℃下煅烧2h,再在H2和Ar的混合气氛下以相同温度继续煅烧30~40min,得到由MgO作为基底支撑Ni纳米颗粒产物,即为Ni/MgO催化剂,所述H2和Ar的气流量分别为100~120mL/min和 300~360mL/min,H2和Ar的气流量比为1:3;
(2)将Ni/MgO催化剂置于管式炉气流上游区域,按照100~120mL/min的气流量通入乙烯,将管式炉加热至740~760℃,保持15~25min,然后将Ni/MgO催化剂移至管式炉气流下游区域,将管式炉加热至940~960℃,保持15~25min,然后在Ar保护下冷却至室温,收集产物;
(3)将产物依次用4~5mol/L的盐酸溶液、12~13mol/L的氢氧化钠溶液和去离子水洗涤,然后在80℃下真空干燥。
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