CN112563038A - 一种CoMoO4/Ti3C2纳米复合颗粒及其制备方法与应用 - Google Patents
一种CoMoO4/Ti3C2纳米复合颗粒及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种CoMoO4/Ti3C2纳米复合颗粒及其制备方法与应用,该颗粒包括Ti3C2无机层状框架,Ti3C2无机层状框架上附着有CoMoO4纳米颗粒;该纳米复合颗粒的制备方法包括以下步骤:(1)将钼酸钠、硝酸钴、尿素依次溶解于去离子水中,再加入Ti3C2粉末,配制成前驱体溶液;(2)将前驱体溶液进行磁力搅拌、超声分散,进行水热反应;(3)将反应结束的前驱体溶液离心洗涤、真空干燥、研磨后置于保护气体中热处理,热处理完成后进行研磨,即得CoMoO4/Ti3C2纳米复合颗粒;该纳米复合颗粒能够作为电极片应用在超级电容器中。该纳米复合颗粒比表面积高,同时也为离子传输提供了便捷的导电通道,作为电极片应用在超级电容器中时,比电容高、充放电稳定,材料稳定性和分散性好。
Description
技术领域
本发明涉及一种纳米复合颗粒及其制备方法与应用,更具体地,涉及一种CoMoO4/Ti3C2纳米复合颗粒及其制备方法与应用。
背景技术
随着经济的发展,能源需求不断增长,可供开发的能源日益枯竭,人类面临巨大的能源挑战,因此寻求可再生绿色能源是人类亟待解决的难题。超级电容器是一类重要的电化学储能装置,能在极短的时间内储能,又在需要时释放能量,且使用温度范围广、循环寿命长,倍率性能优异。电极材料是超级电容器的重要组成部分,其性能直接决定超级电容器的性能。根据电容储能机理,电极材料分为双电层、赝电容、插层赝电容电极三类。过渡金属氧化物作为赝电容型电极材料通过表面或近表面的快速可逆氧化还原反应来储存电荷,储层的电荷量远高于双电层电极材料。但过渡金属氧化物的电导率低,其循环寿命往往不如双电层电容器。过渡金属氧化物中的双金属氧化物具有较多的氧化态,相比于单金属氧化物,具有更高的比电容。但这类材料纳米结构易于团聚,影响其电化学性能。一般情况下,采用泡沫镍、碳布和石墨烯泡沫等导电性好的材料作为集流体来提高双金属氧化物的导电性,但是这些集流体通常孔径大且比电容低等缺点导致整个电极的空间利用率低和质量比电容低。二维层状纳米碳化物MXene是一类类石墨烯结构的材料,其具有独特的形貌、较小的颗粒尺寸、较大的比表面积和原子级的片层结构、高导电性等特性,在锂离子电池、钠离子电池、超级电容器、气体传感器、光催化等领域具有潜在的应用前景。然而MXene片层容易堆叠、其比表面积减少,影响离子在层间扩散,同时由于MXene材料,例如Ti3C2往往通过化学方法刻蚀获得,其表面存在大量的化学官能团,例如-OH,-F,=O,因此Ti3C2易形成Ti3C2Tx结构,严重限制了电荷的传递。
发明内容
发明目的:本发明的目的是提供一种具有高比表面积、离子扩散迅速的CoMoO4/Ti3C2纳米复合颗粒,本发明的另一目的是提供该纳米复合颗粒的制备方法,本发明的另一目的是提供该纳米复合颗粒的应用。
技术方案:本发明所述的CoMoO4/Ti3C2纳米复合颗粒,包括Ti3C2无机层状框架,Ti3C2无机层状框架上附着有CoMoO4纳米颗粒。
其中,CoMoO4纳米颗粒粒径为30~100nm。
本发明所述的CoMoO4/Ti3C2纳米复合颗粒的制备方法包括以下步骤:
(1)将钼酸钠、硝酸钴、尿素依次溶解于去离子水中,再加入Ti3C2粉末,配制成前驱体溶液;
(2)将前驱体溶液进行磁力搅拌、超声分散,置于反应釜内进行水热反应;
(3)将反应结束的前驱体溶液离心洗涤、真空干燥、研磨后置于保护气体中热处理,热处理完成后进行研磨,即得CoMoO4/Ti3C2纳米复合颗粒。
其中,步骤(1)中的钼酸钠与硝酸钴的摩尔比为1:1~2,Ti3C2粉末与钼酸钠的摩尔比为10:3~13,尿素与钼酸钠的摩尔比为10:3~6,步骤(1)中还加入了表面活性剂,表面活性剂为尿素、聚乙二醇、十六烷基三甲基溴化铵和聚乙烯吡咯烷酮中的至少一种。
其中,步骤(2)中磁力搅拌时间为1~3h,超声时间为0.5~3h,反应釜内衬填充度为50%~80%,水热反应温度为120~180℃,反应时间为8~24h。
其中,步骤(3)中样品真空干燥时间为6~12h,温度为50~70℃;热处理温度为400~600℃,时间为2~6h,升温速率为2~8℃/min。
本发明所述的Ti3C2/CoMoO4纳米复合颗粒能够作为电极片应用在超级电容器中,CoMoO4/Ti3C2纳米复合颗粒沉积在基底上。
其中,电极片通过以下步骤制得:将CoMoO4/Ti3C2纳米复合颗粒与导电炭黑、聚偏氟乙烯混合,再加入N-甲基吡咯烷酮进行磁力搅拌,将搅拌结束的混合材料涂覆于基底上,放在真空烘箱中干燥,即制作成超级电容器的电极片。
其中,CoMoO4/Ti3C2纳米复合颗粒、导电炭黑、聚偏氟乙烯之间的比例为60~90:5~30:5~10,搅拌时间为10~30h,基底为泡沫镍或碳纸,真空烘箱真空度为0.01~0.02Pa,干燥时间为8~24h。
工作原理:CoMoO4作为过渡金属氧化物中的双金属氧化物,Co和Mo具有较多的氧化态,相比于单金属氧化物,其具有更高的比电容。但其纳米结构易于团聚,电化学特性受到抑制。由于Ti3C2是二维层状结构,比表面积大,导电性好,依附于Ti3C2二维层状结构生长CoMoO4纳米颗粒时,CoMoO4不仅包覆于Ti3C2表面,而且内嵌于Ti3C2层间缝隙,在电解液中进行离子交换,电荷传输时,增加了活性物质的活性位点,为电荷传输提供了便捷的导电通道,从而提高了材料的电化学性能。
有益效果:本发明与现有技术相比,其显著优点是:1、通过将CoMoO4与Ti3C2进行有效复合,使得CoMoO4颗粒附着于Ti3C2表面且内嵌于层间缝隙,能够提高材料CoMoO4的比表面积,同时也为电荷传输提供了便捷的导电通道;2、能够作为电极片应用在超级电容器中,比电容高,充放电稳定;3、通过水热法一步生成CoMoO4/Ti3C2纳米复合颗粒,操作简单,周期较短;4、在水热反应中加入表面修饰剂,能够合理地控制材料的生长,减小颗粒之间发生团聚效应,有效提高颗粒的稳定性和分散性。
附图说明
图1是实施例1中CoMoO4/Ti3C2纳米复合颗粒的扫描电镜图。
图2是实施例2中CoMoO4/Ti3C2纳米复合颗粒的扫描电镜图。
图3是实施例1中CoMoO4/Ti3C2纳米复合颗粒的X射线衍射谱。
图4是实施例1中CoMoO4/Ti3C2纳米复合颗粒电极片的充放电性能图。
具体实施方式
实施例1
(1)依次称量0.08g六水合钼酸钠、0.1g六水合硝酸钴、0.07g尿素,完全溶解于50ml去离子水中,得到澄清透明的淡红色溶液,再向溶液中加入0.13g Ti3C2粉末混合后得到前驱体溶液;
(2)将前驱体溶液磁力搅拌1h后,置于超声清洗设备中超声0.5h,得到分散性良好的前驱体溶液,将前驱体溶液倒入已超声清洗干净的聚四氟乙烯内衬中,拧紧反应釜,将其放入鼓风干燥机中在180℃水热反应8h;
(3)待反应结束后将反应釜拧开,倒出内衬中溶液的上清液,将剩下溶液置于离心管,再用乙醇和去离子水反复进行离心冲洗,离心速率为4000r/min,将离心清洗干净的样品放在真空烘箱中50℃干燥12h,取出后研磨至粉末状,再置于管式炉中,通入氩气作为保护气体,400℃下热处理6h,升温速率为2℃/min,热处理后再将样品研磨,即得到CoMoO4/Ti3C2纳米复合颗粒;
(4)将CoMoO4/Ti3C2纳米复合颗粒与导电炭黑、聚偏氟乙烯PVDF按60:30:10的比例混合均匀,再缓慢滴加N-甲基吡咯烷酮NMP进行磁力搅拌12h,将搅拌结束的材料均匀涂覆于泡沫镍基底上,放在真空烘箱中干燥8h,真空度为0.01Pa,即制作成超级电容器的电极片。
如图1所示,CoMoO4/Ti3C2纳米复合颗粒CoMoO4纳米颗粒较为均匀地镶嵌在Ti3C2层状结构表面以及层间缝隙内,颗粒尺寸约为70nm,团聚效应微弱,如图3所示,CoMoO4/Ti3C2纳米复合颗粒没有杂相,且Ti3C2和CoMoO4的特征峰明显,说明其结晶性良好,采用浓度为3mol/L的KOH溶液作电解液,运用三电极体系对电极片进行检测,从图4可以看出,电流密度为1.0A/g,电压范围为0.17-0.52V,计算可得其质量比电容为331.1F/g,图中有明显的电化学平台,充放电性能良好。
实施例2
(1)依次称量0.14g六水合钼酸钠、0.19g六水合硝酸钴、0.14g聚乙二醇PEG,完全溶解于60ml去离子水中,得到澄清透明的淡红色溶液,再向溶液中加入0.17g Ti3C2粉末混合后得到前驱体溶液;
(2)将前驱体溶液磁力搅拌2h后,置于超声清洗设备中超声2h,得到分散性良好的前驱体溶液,将前驱体溶液倒入已超声清洗干净的聚四氟乙烯内衬中,拧紧反应釜,将其放入鼓风干燥机中在160℃水热反应12h;
(3)待反应结束后将反应釜拧开,倒出内衬中溶液的上清液,将剩下溶液置于离心管,再用乙醇和去离子水反复进行离心冲洗,离心速率为8000r/min,将离心清洗干净的样品放在真空烘箱中60℃干燥12h,取出后研磨至粉末状,再置于管式炉中,通入氩气作为保护气体,500℃下热处理4h,升温速率为4℃/min,热处理后再将样品研磨,即得到CoMoO4/Ti3C2纳米复合颗粒;
(4)将CoMoO4/Ti3C2纳米复合颗粒与导电炭黑、聚偏氟乙烯PVDF按70:20:10的比例混合均匀,再缓慢滴加N-甲基吡咯烷酮NMP进行磁力搅拌12h,将搅拌结束的材料均匀涂覆于泡沫镍基底上,放在真空烘箱中干燥12h,真空度为0.01Pa,即制作成超级电容器的电极片。
如图2所示,CoMoO4纳米颗粒紧密附着在Ti3C2表面,分散性较差,且有少许片状结构,这是由于依附的颗粒较多,发生了团聚现象。
实施例3
(1)依次称量0.19g六水合钼酸钠、0.23g六水合硝酸钴、0.21g十六烷基三甲基溴化铵CTAB,完全溶解于70ml去离子水中,得到澄清透明的淡红色溶液,再向溶液中加入0.21g Ti3C2粉末混合后得到前驱体溶液;
(2)将前驱体溶液磁力搅拌2h后,置于超声清洗设备中超声2h,得到分散性良好的前驱体溶液,将前驱体溶液倒入已超声清洗干净的聚四氟乙烯内衬中,拧紧反应釜,将其放入鼓风干燥机中在140℃水热反应16h;
(3)待反应结束后将反应釜拧开,倒出内衬中溶液的上清液,将剩下溶液置于离心管,再用乙醇和去离子水反复进行离心冲洗,离心速率为8000r/min,将离心清洗干净的样品放在真空烘箱中60℃干燥12h,取出后研磨至粉末状,再置于管式炉中,通入氩气作为保护气体,500℃下热处理6h,升温速率为6℃/min,热处理后再将样品研磨,即得到CoMoO4/Ti3C2纳米复合颗粒;
(4)将CoMoO4/Ti3C2纳米复合颗粒与导电炭黑、聚偏氟乙烯PVDF按80:10:10的比例混合均匀,再缓慢滴加N-甲基吡咯烷酮NMP进行磁力搅拌16h,将搅拌结束的材料均匀涂覆于泡沫镍基底上,放在真空烘箱中干燥16h,真空度为0.01Pa,即制作成超级电容器的电极片。
实施例4
(1)依次称量0.25g六水合钼酸钠、0.3g六水合硝酸钴、0.21g聚乙烯吡咯烷酮PVP,完全溶解于80ml去离子水中,得到澄清透明的淡红色溶液,再向溶液中加入0.21g Ti3C2粉末混合后得到前驱体溶液;
(2)将前驱体溶液磁力搅拌2h后,置于超声清洗设备中超声3h,得到分散性良好的前驱体溶液,将前驱体溶液倒入已超声清洗干净的聚四氟乙烯内衬中,拧紧反应釜,将其放入鼓风干燥机中在120℃水热反应24h;
(3)待反应结束后将反应釜拧开,倒出内衬中溶液的上清液,将剩下溶液置于离心管,再用乙醇和去离子水反复进行离心冲洗,离心速率为8000r/min,将离心清洗干净的样品放在真空烘箱中70℃干燥6h,取出后研磨至粉末状,再置于管式炉中,通入氩气作为保护气体,600℃下热处理2h,升温速率为8℃/min,热处理后再将样品研磨,即得到CoMoO4/Ti3C2纳米复合颗粒;
(4)将CoMoO4/Ti3C2纳米复合颗粒与导电炭黑、聚偏氟乙烯PVDF按90:5:5的比例混合均匀,再缓慢滴加N-甲基吡咯烷酮NMP进行磁力搅拌30h,将搅拌结束的材料均匀涂覆于泡沫镍基底上,放在真空烘箱中干燥24h,真空度为0.02Pa,即制作成超级电容器的电极片。
Claims (10)
1.一种CoMoO4/Ti3C2纳米复合颗粒,其特征在于,包括Ti3C2无机层状框架,所述Ti3C2无机层状框架上附着有CoMoO4纳米颗粒。
2.根据权利要求1所述的CoMoO4/Ti3C2纳米复合颗粒,其特征在于,所述CoMoO4纳米颗粒粒径为30~100nm。
3.一种权利要求1所述的CoMoO4/Ti3C2纳米复合颗粒的制备方法,其特征在于,包括以下步骤:
(1)将钼酸钠、硝酸钴、尿素依次溶解于去离子水中,再加入Ti3C2粉末,配制成前驱体溶液;
(2)将前驱体溶液进行磁力搅拌、超声分散,置于反应釜内进行水热反应;
(3)将反应结束的前驱体溶液离心洗涤、真空干燥、研磨后置于保护气体中热处理,热处理完成后进行研磨,即得CoMoO4/Ti3C2纳米复合颗粒。
4.根据权利要求3所述的CoMoO4/Ti3C2纳米复合颗粒的制备方法,其特征在于,所述步骤(1)中的钼酸钠与硝酸钴的摩尔比为1:1~2,Ti3C2粉末与钼酸钠的摩尔比为10:3~13,尿素与钼酸钠的摩尔比为10:3~6。
5.根据权利要求3所述的CoMoO4/Ti3C2纳米复合颗粒的制备方法,其特征在于,所述步骤(1)中还加入了表面活性剂,所述表面活性剂为尿素、聚乙二醇、十六烷基三甲基溴化铵或聚乙烯吡咯烷酮中的至少一种。
6.根据权利要求3所述的CoMoO4/Ti3C2纳米复合颗粒的制备方法,其特征在于,所述步骤(2)中磁力搅拌时间为1~3h,超声时间为0.5~3h,反应釜内衬填充度为50%~80%,水热反应温度为120~180℃,反应时间为8~24h。
7.根据权利要求3所述的一种Ti3C2/CoMoO4纳米复合颗粒的制备方法,其特征在于:所述步骤(3)中样品真空干燥时间为6~12h,温度为50~70℃;热处理温度为400~600℃,时间为2~6h,升温速率为2~8℃/min。
8.一种权利要求1所述的Ti3C2/CoMoO4纳米复合颗粒在超级电容器中作为电极片的应用,其特征在于,所述CoMoO4/Ti3C2纳米复合颗粒沉积在基底上。
9.根据权利要求8所述的应用,其特征在于,所述电极片通过以下步骤制得:将CoMoO4/Ti3C2纳米复合颗粒与导电炭黑、聚偏氟乙烯混合,再加入N-甲基吡咯烷酮进行磁力搅拌,将搅拌结束的混合材料涂覆于基底上,放在真空烘箱中干燥,即制作成超级电容器的电极片。
10.根据权利要求9所述的应用,其特征在于,所述CoMoO4/Ti3C2纳米复合颗粒、导电炭黑、聚偏氟乙烯之间的比例为60~90:5~30:5~10,搅拌时间为10~30h,所述基底为泡沫镍或碳纸,真空烘箱真空度为0.01~0.02Pa,干燥时间为8~24h。
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