CN109036877B - 多孔型石墨烯/过渡金属硫属化合物薄膜的制备方法 - Google Patents
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Abstract
本发明公开了一种多孔型石墨烯/过渡金属硫属化合物薄膜的制备方法。所述方法将赝电容材料过渡金属硫属化物分散液和石墨烯分散液混合,真空抽滤,得到含水量为10%~20%的薄膜,冷冻干燥后,置于300~800℃下煅烧,得到多孔型石墨烯/过渡金属硫属化合物薄膜。本发明利用单层或少层金属硫化物作为赝电容材料负载在石墨烯表层来修改石墨烯表面的电子结构和化学环境,采用真空抽滤和冷冻干燥相结合制备多孔型薄膜。本发明的薄膜具有稳定的孔隙结构及活性物质的高效利用率,展示出了较好的电化学稳定性,其倍率性能显著提高,扫速从10增加到200mV s‑1,容量保持率为89%。
Description
技术领域
本发明属于柔性超级电容器技术领域,涉及一种多孔型石墨烯/过渡金属硫属化合物薄膜的制备方法。
背景技术
超级电容器作为一种新型储能元器,可提供大功率并且具有超长寿命,在混合动力电动车和应急电源等领域具有广泛的应用前景。尤其是柔性器件,在日常生活中的应用愈来愈广。但其能量密度低,应用受到严重制约。比容量作为提高柔性超级电容器能量密度的一个关键因素。为提高电极材料的性能,需要具有高稳定性和高活性的赝电容材料。
目前,制备石墨烯多孔膜、石墨烯/金属硫化物复合材料的方法包括水热法、硬模板法、电化学沉积法和真空抽滤法等(AcsAppl Mater.Interfaces,2015,7,17388;Adv.Mater.2014,26,8163;Angew.Chem.Int.Ed,2015,54,4651)等。A.Bissett等(Characterization of MoS2-graphene composites for high performance coin cellsupercapacitors,AcsAppl Mater.Interfaces,2015,7,17388)针对金属硫化物导电性比较差的问题,利用真空抽滤法将金属硫化物分散液和石墨烯分散液制备成膜来进一步提高材料的导电性,并证明了其在水系电解液中具有较好的电化学性能。此制备方法简单,但是石墨烯片层的堆叠大大降低了活性材料的利用率。Sun等利用水热法制备的石墨烯/金属硫化物气凝胶(J.Power Sources,2016,331,180),基于其特殊的孔性分布,大大提高了活性物质的利用率,使材料的电化学稳定性得到改善。以及利用造孔物质制备孔型分布均匀的薄膜(CN104609410A),此法虽可实现,但对移除造孔物质所需的反应条件的控制要求相对较高,不适合大规模生产。同时,此类材料仍有不足之处,比如结构易碎,物理性能差,会大大降低材料在柔性器件中的电化学稳定性。
因此,经过人们的不断研究,发现过渡金属硫属化物复合材料在化学电源领域有很大的潜在价值,特别是以二硫化钼、二硫化钨等为基础的超级电容器电极材料。
发明内容
本发明的目的在于提供一种多孔型石墨烯/过渡金属硫属化合物薄膜的制备方法。该方法采用真空抽滤和冷冻干燥相结合,制备了孔径分布均匀的多孔型复合材料薄膜,其电化学稳定性显著提高。
实现本发明目的的技术方案如下:
多孔型石墨烯/过渡金属硫属化合物薄膜的制备方法,具体步骤如下:
将过渡金属硫属化合物分散液与石墨烯分散液混合均匀,真空抽滤,得到含水量为10%~20%的薄膜,冷冻干燥后,置于300~800℃下煅烧,得到多孔型石墨烯/过渡金属硫属化合物薄膜。
优选地,所述的过渡金属硫属化合物可以是二硫化钨、二硫化钼、二硒化钨、二硒化钼、二碲化钨、二碲化钼等可剥离的二维层状材料。
优选地,所述的过渡金属硫属化合物分散液的浓度为0.2~0.4mg/mL,石墨烯分散液的浓度为5~20mg/mL,过渡金属硫属化合物与石墨烯的摩尔比为1:2~2:1。
优选地,所述的煅烧时间为1~3h。
与现有技术相比,本发明具有以下优点:
本发明通过石墨烯自组装并结合冷冻干燥法,制备了金属硫化物分布均匀的多孔型柔性膜。本发明利用单层或少层金属硫化物作为赝电容材料负载在石墨烯表层来修改石墨烯表面的电子结构和化学环境,制备的多孔型薄膜具有稳定的孔隙结构及活性物质的高效利用率,展示出了较好的电化学稳定性,其倍率性能显著提高,扫速从10增加到200mV s-1,容量保持率为89%。
附图说明
图1为样品1的SEM截面图。
图2为样品1的HRTEM图。
图3为样品1在柔性器中的循环伏安图。
图4为样品1-5在柔性器中的倍率性能图。
图5为样品2在柔性器中的循环伏安图。
图6为样品5的SEM截面图。
具体实施方式
下面结合实施例和附图对本发明作进一步详述。
实施例1离子嵌入法制备MoS2分散液,MoS2/石墨烯(1:1)多孔薄膜电极的制备
利用锂离子嵌入法制备MoS2分散液。称取500mgMoS2分散于100mL环己烷中,在氮气氛围下将混合溶液升至80℃。此时,加入10mL丁基锂,在90℃反应三天。将冷却后抽滤获得的粉末置于超纯水中超声90分钟,利用离心处理3次,最后得到MoS2分散液。
将MoS2分散液与5mg mL-1石墨烯分散液按质量比1:1混合均匀,水浴超声30分钟,通过真空抽滤控制残留水分的量为10%,并结合冷冻干燥法获得初步样品。将样品放置于管式炉中央,在高纯氩气和氢气的混合氛围下升温至400℃恒温1小时,制得多孔型石墨烯/MoS2薄膜(样品1)。
电极材料的制备过程和电解质制备方法如下:将5gPVA和5g硫酸溶液溶于50mL水溶液,将上述溶液在80℃下搅拌2小时并且超声10分钟用于除去气泡,至此,固态电解液制备完成。剪裁多孔型石墨烯/MoS2薄膜成2厘米×1厘米的矩形,并将该材料置于镀金聚对苯二甲酸乙二醇酯上,然后在70℃的热作用下,使两片材料结合。图1是该电极材料的扫描电镜图,从图中可以看出该电极材料具有均匀的多孔结构的薄膜型材料。图2是该电极材料的透射电镜扫描图。图3是该电极材料在酸性固态电解质中的循环伏安图。图4为样品1-5在柔性器中的倍率性能图。从图4中可以看出样品1是一种高容量的电极材料。当扫速为10mV s-1时,比容量高达199F g-1;随着扫速增加至200mV s-1,电极材料展示出较好的倍率性能,为89%。
实施例2超声降解法制备MoS2分散液,MoS2/石墨烯(1:1)多孔薄膜电极的制备
超声波降解法制备MoS2分散液。称取500mgMoS2分散于50mlN,N-二甲基甲酰胺溶液,利用尖端超声的方法将该混合液分散。超声完毕后,将该混合液静置24小时,之后取上层液体,利用离心机离心三次,最后得到MoS2分散液。
将MoS2分散液与5mg mL-1石墨烯分散液按质量比1:1混合均匀,水浴超声30分钟,通过真空抽滤并结合冷冻干燥法获得初步样品。将样品放置于管式炉中央,在高纯氩气和氢气的混合氛围下升温至400℃恒温1小时,制得多孔型石墨烯/MoS2薄膜(样品2)。
电极材料的制备过程和电解质制备方法如下:将5gPVA和5g硫酸溶液溶于50ml水溶液,将上述溶液在80℃下搅拌2小时并且超声10分钟用于除去气泡,至此,固态电解液制备完成。剪裁多孔型石墨烯/MoS2薄膜成2厘米×1厘米的矩形,并该材料置于镀金聚对苯二甲酸乙二醇酯上,然后在70℃的热作用下,使两片材料结合。图5是样品2在固态酸性电解质中的循环伏安图。图4为样品1-5在柔性器中的倍率性能图。从图4中可以看出样品2是一种高容量的电极材料。当扫速为10mV s-1时,比容量高达175F g-1;随着扫速增加至200mV s-1,电极材料展示出较好的倍率性能,为80%。
对比例1
本实施例与实施例1中材料的制备及柔性器件的组装基本相同,不同的是分别控制含水量为5%(样品3)和25%(样品4)。从图4中可以看出,含水量过高或者过低,多孔膜均展现出较差的电化学稳定能。和样品1同等的测试条件下,在扫速为10mVs-1时,样品3的比电容为153F g-1,倍率性能为74%,样品4的比容量为161F g-1,倍率性能为71%。
对比例2
本对比例与实施例1中材料的制备和柔性器件的组装基本相同,不同之处是电极材料在制备过程中未涉及到冷冻干燥处理,而是直接在真空状态下抽滤成膜,再经过高温活化,最终制得石墨烯/MoS2薄膜(样品5)。图6是该膜的SEM截面图,石墨烯片层有序叠加,无多孔结构,并且电化学稳定性较差,其比容量为108F g-1,倍率性能仅为64%。
Claims (6)
1.多孔型石墨烯/过渡金属硫属化合物薄膜的制备方法,其特征在于,具体步骤如下:
将过渡金属硫属化合物分散液与石墨烯分散液混合均匀,真空抽滤,得到含水量为10%~20%的薄膜,冷冻干燥后,置于300~800℃下煅烧,得到多孔型石墨烯/过渡金属硫属化合物薄膜。
2.根据权利要求1所述的制备方法,其特征在于,所述的过渡金属硫属化合物选自二硫化钨、二硫化钼、二硒化钨、二硒化钼、二碲化钨或二碲化钼可剥离的二维层状材料。
3.根据权利要求1所述的制备方法,其特征在于,所述的过渡金属硫属化合物分散液的浓度为0.2~0.4mg/mL。
4.根据权利要求1所述的制备方法,其特征在于,所述的石墨烯分散液的浓度为5~20mg/mL。
5.根据权利要求1所述的制备方法,其特征在于,所述的过渡金属硫属化合物与石墨烯的摩尔比为1:2~2:1。
6.根据权利要求1所述的制备方法,其特征在于,所述的煅烧时间为1~3h。
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