CN112875657A - 硒化锰/还原氧化石墨烯纳米复合材料制备方法及其应用 - Google Patents
硒化锰/还原氧化石墨烯纳米复合材料制备方法及其应用 Download PDFInfo
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- UMUKXUYHMLVFLM-UHFFFAOYSA-N manganese(ii) selenide Chemical compound [Mn+2].[Se-2] UMUKXUYHMLVFLM-UHFFFAOYSA-N 0.000 title claims abstract description 57
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Abstract
本发明提供硒化锰/还原氧化石墨烯纳米复合材料制备方法及其应用。先以锰粉、硒粉为原料,采用直流电弧法制备出硒化锰纳米颗粒,再将均匀混合的硒化锰纳米颗粒与氧化石墨烯悬浊液冷冻干燥,然后将其在5%NH3/Ar混合气体氛围中煅烧,即可得硒化锰/还原氧化石墨烯纳米复合材料。本发明还公开了其在超级电容器方面的应用,将硒化锰/还原氧化石墨烯纳米复合材料涂覆在泡沫镍上,在1A/g的电流密度下,其质量比电容为176.6F/g。
Description
技术领域
本发明属于无机纳米材料制备的技术领域,特别涉及了一种制备硒化锰/还原氧化石墨烯纳米复合材料的方法。
背景技术
复合材料是指采用材料制备技术将不同性质的两种或多种材料优化组合而成的新材料。它不仅能保持各组分材料性能的优点,还能通过各组分性能的互补和关联克服单一组成材料的缺陷,并获得优于单一组分材料的综合性能。
石墨烯是一种由单层碳原子紧密堆积成的二维蜂窝状晶格结构的多功能材料。它具有较大的比表面积、卓越的导电性,在电化学领域具有重要的应用前景。但由于石墨烯片层间存在极强的范德华力,使石墨烯在应用时易发生堆叠团聚,导致其有效面积降低,影响其电化学性能。将纳米材料与石墨烯进行复合,能有效阻止石墨烯堆叠团聚,增加比表面积,且二者复合可以同时保留纳米材料和石墨烯材料的特性并提升材料电化学性能。例如,Li等人采用溶剂热法所制备的ZnMn2O4/rGO复合电极材料在2A/g的电流密度下比电容为763.4F/g(Journal of Light Industry,2020,35(03),44-51);Li等人采用共沉淀法制备的CoMn2O4/rGO复合电极材料具有较好的电化学性能(J.Chin.Ceram.Soc.,2021,49(01),167-173)。
硒化锰是一种典型的过渡金属硒化物,共有三种晶体结构:α-MnSe(岩盐矿结构),β-MnSe(纤锌矿结构)和γ-MnSe(闪锌矿结构),其中α相是热力学最稳定的相。硒化锰具有良好的导电性,主要应用在电容器电极材料、钠离子电池电极材料、稀磁半导体材料、温差电材料和太阳能电池等方面。目前MnSe的制备方法有溶剂热法、水热法、化学气相沉积法等。例如,Javed等人采用溶剂热合成法制备出α-MnSe纳米微花(Chem.Eng.J.,2020,382,122814);Sahoo等人采用水热法合成出α-MnSe纳米颗粒(Electrochim.Acta,2018,268,403-410)。但以上方法相较于直流电弧法具有原材料复杂、合成时间长、环境不友好等缺点。将硒化锰纳米材料与石墨烯进行复合,能够有效阻止石墨烯堆叠,同时也能使硒化锰纳米材料分散开,增加比表面积,且二者复合可以提升材料导电性,增大电极电容,从而提升其电化学性能。
发明内容
本发明主要提供一种硒化锰/还原氧化石墨烯纳米复合材料的制备方法,此方法生产成本低、操作简单,且合成产物产量高、纯度高,可用作超级电容器电极材料。
本发明具体技术方案如下:
1.首先将锰粉、硒粉按1:1的摩尔比混合,然后将混合粉末充分研磨使其混合均匀且颗粒大小相近。研磨后将混合粉末放入定制的压片模具中,并将模具放入压片装置中,粉末被压制成圆柱形块体。
2.将块体放入阳极铜锅中,并将阴极钨棒垂直固定于铜锅上,且使其尖端在块体中心位置,密封反应室。
3.将反应室气压抽至小于10Pa,然后通入氩气反复洗气两次以上,洗气结束后通入氩气,使反应室内气体压强保持在60kPa。启动设备的冷却循环系统,打开直流弧焊机开关,设置电流参数为60-160A,反应10-15min后,关闭直流弧焊机开关,终止反应,经冷却钝化后在顶盖和水冷壁处得到纯净的硒化锰纳米颗粒。
4.将硒化锰纳米颗粒配制成浓度为2g/L的悬浊液,并将其与0.5g/L的氧化石墨烯悬浊液按体积比1:(0.5-2)混合,超声分散后放在磁力搅拌器上搅拌。
5.将混合溶液进行冷冻干燥,得到蓬松的棕色硒化锰/氧化石墨烯,并将其在5%NH3/Ar混合气体氛围中300-500℃煅烧30-60min,升温速度为2℃/min即可得棕色硒化锰/还原氧化石墨烯纳米复合材料。
本发明制备硒化锰/还原氧化石墨烯纳米复合材料的优点在于:硒化锰纳米颗粒均匀地分布在石墨烯表面;原材料简单、制备方法操作简单、合成时间短、可重复性高。
附图说明
图1硒化锰纳米颗粒和硒化锰/还原氧化石墨烯纳米复合材料的X射线衍射(XRD)谱图。
图2硒化锰纳米颗粒和硒化锰/还原氧化石墨烯纳米复合材料的扫描电子显微镜(SEM)图。
图3硒化锰/还原氧化石墨烯纳米复合材料的(a)透射电子显微镜(TEM)图,(b)高分辨透射电子显微镜(HRTEM)图。
图4(a)不同扫描速率下硒化锰/还原氧化石墨烯电极的CV曲线图,(b)不同电流密度下硒化锰/还原氧化石墨烯电极的恒电流充放电(GCD)曲线图。
具体实施方式
为使本领域技术人员更好地理解本发明,现结合附图及较佳实施例更加具体地描述本发明。
实施例1制备最佳硒化锰/还原氧化石墨烯纳米复合材料的全过程及电化学性能测试。
首先按1:1的摩尔比称量锰粉、硒粉,其中锰粉质量为0.6148g,硒粉质量为0.8844g。然后在玛瑙研钵中将混合粉末充分研磨使其混合均匀且颗粒大小相近。研磨后将混合粉末放入定制的压片模具中,并将模具放入压片装置中,粉末被压制成圆柱形块体。再将圆柱形块体放入阳极铜锅中。并将作为阴极的钨棒垂直固定于铜锅上,调整阴极钨棒,使其在块体中心位置。
用真空泵将反应室气压抽至小于10Pa,然后通入氩气反复洗气两次以上。洗气结束后通入氩气,使反应室内气体压强保持在60kPa。启动设备的冷却循环系统,打开直流弧焊机开关,设置电流参数为140A,进行引弧,起弧反应10min后,关闭直流弧焊机开关,终止反应。在氩气氛围下冷却、钝化2h后在顶盖和水冷壁附近收集到的黄绿色粉末为硒化锰纳米颗粒。
将硒化锰纳米颗粒配制成浓度为2g/L的悬浊液,并将其与0.5g/L的氧化石墨烯悬浊液按体积比1:1混合,超声分散15min后放到磁力搅拌器上搅拌15min。
将悬浊液进行冷冻干燥,温度为-60℃,时间为48h,得到蓬松的棕色硒化锰/氧化石墨烯,并将其在5%NH3/Ar混合气体氛围中400℃煅烧30min,升温速度为2℃/min即可得棕色硒化锰/还原氧化石墨烯纳米复合材料。
将制备的硒化锰/还原氧化石墨烯纳米复合材料作为活性物质,以乙炔黑为导电剂,PTFE(聚四氟乙烯)为粘结剂,酒精为溶剂,按活性物质:导电剂:粘结剂=8:1:1的质量比混合,涂覆在泡沫镍上作为工作电极。以铂片为对电极,汞/氧化汞为参比电极,6M的氢氧化钾溶液为电解液,在电化学工作站上进行电化学测试。
图1给出了上述方法制备的硒化锰纳米颗粒与硒化锰/还原氧化石墨烯纳米复合材料的X射线衍射(XRD)谱图。通过和标准卡片JCPDS No.11-0683谱图比对,我们制备出的MnSe纳米晶是立方相的α-MnSe,谱图峰型尖锐,衍射谱的背底基线较为平直,表明样品的结晶性较好,且与石墨烯复合后材料衍射峰峰位仍与标准卡片谱图峰位吻合,无其他杂峰出现。
图2a给出了上述方法制备的硒化锰纳米颗粒的扫描电子显微镜(SEM)图,从图中可以看出样品为高度聚集的粒度分布均匀的纳米颗粒,颗粒直径为10-100nm。图2b给出了上述方法制备的硒化锰/还原氧化石墨烯纳米复合材料的扫描电子显微镜(SEM)图,从图可以看出硒化锰纳米颗粒在石墨烯表面具有较高的分散性,每平方微米的石墨烯上有7-8个硒化锰纳米颗粒。
图3a给出了硒化锰/还原氧化石墨烯纳米复合材料的透射电子显微镜(TEM)图。从图中我们可以看出其形貌与扫描电子显微镜(SEM)图中所观察到的一致,硒化锰纳米颗粒均匀地分布在石墨烯表面。图3b给出了硒化锰/还原氧化石墨烯纳米复合材料的高分辨透射电子显微镜(HRTEM)图。从图中我们可以看出晶体晶格间距d值为0.1980nm,为α-MnSe的(220)面。
图4a给出了不同扫描速率下硒化锰/还原氧化石墨烯纳米复合材料电极的CV曲线图。在氢氧化钾溶液中,电极在不同扫描速率(10–50mV/s)下的循环伏安曲线显示出可逆的氧化还原峰,这属于法拉第(电池型)电极的特征,可归因于法拉第氧化还原反应。图4b给出了不同电流密度下硒化锰/还原氧化石墨烯纳米复合材料电极的恒电流充放电(GCD)曲线图。在放电过程中观察到了明显的电压平台,这与其CV结果一致,再次表明了法拉第行为。根据质量比电容计算公式可算出,在电流密度为1A/g下其质量比电容为176.6F/g。
以上所述仅为本发明的是实施例,并非因此限制本发明的范围,凡是对本发明的技术方案进行等效结构或等效流程变换,或直接或间接运用在其他相关技术领域,均应落入本发明的专利保护范围内。
Claims (6)
1.硒化锰/还原氧化石墨烯纳米复合材料制备方法,其特征在于:将锰粉、硒粉按照摩尔比为1:1的比例混合均匀并压块;将压块置于直流电弧放电装置反应室内的阳极铜锅中,阴极钨棒垂直固定于铜锅上;将反应室抽成真空后通入氩气,铜锅及水冷壁中通循环冷却水,启动直流弧焊机,设置电流参数,反应10-15min;在氩气环境中降温、钝化,于顶盖及水冷壁处收集到的黄绿色粉末为硒化锰纳米颗粒;将浓度为2g/L的硒化锰纳米颗粒悬浊液和0.5g/L的氧化石墨烯悬浊液按体积比1:(0.5-2)混合超声分散后移入磁力搅拌器中搅拌均匀;将混合溶液进行冷冻干燥,得到蓬松的棕色硒化锰/氧化石墨烯,将其在5%NH3/Ar混合气体氛围中300-500℃煅烧30-60min,升温速率为2℃/min,即可得硒化锰/还原氧化石墨烯纳米复合材料。
2.根据权利要求1所述的硒化锰/还原氧化石墨烯纳米复合材料制备方法,其特征在于:锰粉、硒粉的纯度为99.99%及以上。
3.根据权利要求1所述的硒化锰/还原氧化石墨烯纳米复合材料制备方法,其特征在于:反应室内气体压强为10-60kPa。
4.根据权利要求1所述的硒化锰/还原氧化石墨烯纳米复合材料制备方法,其特征在于:电流保持在60-160A。
5.根据权利要求1所述的硒化锰/还原氧化石墨烯纳米复合材料制备方法,其特征在于:超声分散和磁力搅拌时间为10-15min。
6.根据权利要求1所述的硒化锰/还原氧化石墨烯纳米复合材料制备方法,其特征在于:冷冻干燥条件为-60℃,24-72h。
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