CN108793119A - 一种炭黑和石墨烯微片复合材料制备技术 - Google Patents
一种炭黑和石墨烯微片复合材料制备技术 Download PDFInfo
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Abstract
本发明涉及一种炭黑和石墨烯微片复合材料制备技术。主要涉及一种采用混合煤炭为原料一次性制作完成炭黑和石墨烯微片复合材料的合成技术。其合成方法包括:煤粉破碎:将两种或两种以上煤块或煤粒按照一定比例粉碎细化成煤粉;捏合:将破碎后混合煤粉中加入活化剂中并在常温下搅拌捏合,加热干燥得到混合物;活化:混合物在惰性气体氮气或氩气或氢气气氛下高温活化,得到复合碳化物;复合碳化物先用酸洗涤,再用去离子水洗涤,最后再干燥,得到炭黑与石墨烯微片复合材料。本发明所述方法具有原料储量大、成本低,制备过程简单等优点,易批量生产及应用,将在轮胎、朔料、电池、电容器等领域有直接的应用价值。
Description
技术领域
本发明涉及一种炭黑和石墨烯微片复合材料制备方法,特别涉及一种以煤为碳源的炭黑和石墨烯复合材料的合成方法。
背景技术
碳黑又名炭黑,是一种无定形碳。轻、松而极细的黑色粉末,表面积非常大,范围从10~3000m2/g,是含碳物质(煤、天然气、重油、燃料油等)在空气不足的条件下经不完全燃烧或受热分解而得的产物。比重1.8-2.1。由天然气制成的称“气黑”,由油类制成的称“灯黑”,由乙炔制成的称“乙炔黑”。此外还有“槽黑”、“炉黑”。按炭黑性能区分有“补强炭黑”、“导电炭黑”、“耐磨炭黑”等。可作黑色染料,用于制造中国墨、油墨、油漆等,也用于做橡胶的补强剂。
可用作生产炭黑的原料很多,主要有油类-煤焦油和石油系原料油;天然气和煤层气;焦炉煤气和炼厂气;乙炔气等。目前炭黑生产工艺有炉法,接触法和热裂解法三类,其中炉法因为生产橡胶炭黑,故其产量远远超过后两种,在当今炭黑生产中占主体地位。
石墨烯是碳原子以sp2杂化键合而成的蜂窝状二维材料,其基本结构单元是有机材料中最稳定的六元环。由少于10层的石墨烯为结构单位构成的碳材料,包括但不限于单层石墨烯、双层石墨烯、少层石墨烯、石墨烯微片、石墨烯薄膜、三维石墨烯网络等。由于其优异的导电、导热、机械性能以及化学稳定性,使其在高性能纳电子器件、传感器、纳米复合材料、电化学储能等领域获得广泛应用。
石墨烯的获得主要是通过机械剥离法、化学气相沉积法、氧化石墨烯还原法以及液相剥离法等方法。目前主流生产石墨烯采用的路线基本可分为氧化还原法路线和非氧化还原法路线(化学气相沉积、液相剥离等),氧化还原法生产石墨烯工艺路线基础是Hummers路线,先制成石墨氧化物的中间物。是把鳞片石墨深度氧化,在石墨片层均匀地接上各种含氧基团撑大石墨的层间距,然后超声波设备剥离开石墨片层,最后采用化学还原剂制造出石墨烯。[煤炭加工与综合利用,58,No.5 2014]提供了一种太西无烟煤基石墨制备石墨烯的研究。工艺技术也是基于氧化还原法。这种工艺做出来的石墨烯,由于强烈的氧化过程会造成石墨烯结构的大量缺陷,这些缺陷导致石墨烯导电导热性能的大幅度下降。另外氧化的石墨烯即使经过还原,石墨的片层结构的缺陷也不能被全部修复,石墨烯片层上会含有大量的含氧官能团(5-15%)。氧化还原法的缺点是氧化和还原的操作过程过程复杂繁琐,废酸废水产生量太大,污染严重不容回避。成本仍是石墨烯大规模应用的核心瓶颈。
物理剥离法生产石墨烯,采用天然鳞片石墨为原料通过插层-膨胀-物理剥离制备,或以天然鳞片石墨为原料不经过插层直接物理剥离得到石墨烯。这种方法所制备的石墨烯粉体,优点是石墨烯氧含量很低(≤ 5%)片层结构没有被太多破坏,具有较好的结晶性,导电导热性能优异。制造过程没有使用过多的强酸和化学试剂,生产成本相比氧化还原法低很多。缺点是,如果采用具有性价比平衡的生产方法,加上需要避免深度氧化,所得石墨片层不容易符合小于10层的石墨烯定义。其比表面不易获得超过200m2/g的粉体,剥离开的石墨烯片层之间依然有强烈的范德华力,干燥的时候或是后加工过程中,片层之间很容易二次重叠,从而抵消掉物理剥离过程的功效。
无烟煤的煤化程度较高,目前煤制炭黑以烟煤或无烟煤细粉热解而得。性能接近细粒子热裂炭黑。黑色中性粉末。用作各种天然橡胶和合成橡胶的填充剂、增容剂及补强剂,多用于工业橡胶制品的生产中。炭黑主要用于橡胶制品,炭黑的粒径越细,其补强性能越优越;炭黑结构度越高,其定伸应力及模量越高。细粒径的补强性品种主要用于轮胎胎面,赋予轮胎优良的耐磨性能。
褐煤煤化程度低、较高的碱金属及水分含量,挥发分含量高,有利于在高温热解过程形成更发达孔隙结构。内部芳香结构内包含大量含氧基团,使其具有高反应活性,更容易在制备多孔碳材料中调节碳结构演变及孔隙生成过程。目前褐煤主要用来制备用于水处理及脱除燃煤烟气的低品质(孔隙率低、非碳杂质含量高、结构不稳定)活性焦,少量研究报道通过采用含钾活化剂,通过化学活化过程制备褐煤基活性碳,虽然能够得到较高比表面积活性碳,但由于采用的原料煤结构特性及活化条件的限制,所得多孔碳材料仍为无定型且杂原子含量高。
发明内容
本发明提供了一种炭黑和石墨烯微片复合材料制备方法,利用化学活化法一次性制备炭黑和石墨烯复合材料。解决了一次性生成炭黑和石墨烯微片复合材料的的大规模、低成本制备问题。石墨烯微片复合材料制与传统炭黑相比具有更为优异的导电性、耐磨性,作为永久性功能填料,可以广泛应用电磁波屏蔽材料,高、中压电力电缆屏蔽料,防静电地板、输油管、油箱和胶靴,煤矿用防静电阻燃运输带、导风筒和 PVC管,防静电电子元器件包装材料和炸药包装材料,导电油墨、涂料,以及要求能消除静电的航空轮胎等领域。为实现上述目的,本发明采用以下技术方案:
1)、煤粉粉碎:将一定比例的无烟煤(烟煤、不粘煤、煤焦或其他煤炭)、褐煤的煤块粉碎成100-200目混合煤粉;
2)、捏合:混合煤粉中加入活化剂(H3PO4、ZnCl2、KOH、NaOH或以上任意两种的混合溶液)中并在常温下搅拌捏合1-4小时,在60-80度温度下加热干燥得到混合物;
3)、活化:混合物在惰性气体氮气或氩气或氢气气氛下高温800-1200度,反应0-4h后自然降温,得到复合碳化产物;
4)、洗涤干燥:将复合碳化产物用酸洗涤2-5次,再用去离子水洗涤2-5次,最后再干燥,得到炭黑与石墨烯微片复合材料。
其中,所述活化剂为碱金属氢氧化物,碱土金属的氢氧化物或他们的混合物的溶液;
附图说明
附图1为实施案例1炭黑与石墨烯微片复合材料拉曼光谱数据,附图2为实施案例1炭黑与石墨烯微片复合材料透射电镜图像。附图1拉曼光谱图中的2D峰表明本实施例合成的微孔石墨烯内部包含了大量单层或多层石墨烯结构单元,附图2透射电镜图像能够看出炭黑与石墨烯微片复合材料主要由大量的单层薄纱状石墨烯片层和炭黑颗粒结构组成。附图3为实施案例4炭黑与石墨烯微片复合材料透射电镜图像,附图3透射电镜图像能够看出复合材料只由炭黑颗粒结构组成,没有石墨烯微片结构。
具体发明内容及实施方式
本发明提供的一种炭黑和石墨烯微片复合材料制备方法,利用化学活化法一次性制备炭黑和石墨烯复合材料。解决了一次性生成炭黑和石墨烯微片复合材料的的大规模、低成本制备问题。以无烟煤(烟煤、不粘煤、煤焦或其他煤炭)、褐煤为碳源,分别利用无烟煤(烟煤、不粘煤、煤焦或其他煤炭)、褐煤内部不同的结构组份,采用碳化、活化法,一次性制备获得炭黑和石墨烯微片复合材料。
该制备方法将无烟煤(烟煤、不粘煤、煤焦或其他煤炭)、褐煤按照一定比例进行混合粉碎细化,活化溶液浸渍、捏合、干燥,高温活化,然后采用盐酸或硝酸及去离子水清洗干燥得到本发明所述的炭黑和石墨烯复合材料。以上制程中,高温活化分别将无烟煤(烟煤、不粘煤、煤焦或其他煤炭)碳化,褐煤内部类石墨微晶或片层结构在其自身含有的Mg、Ca等金属杂质的催化下在高温活化过程中会转换成单层或多层石墨烯微片,在活化剂的作用下,对石墨烯片层结构和炭黑进行刻蚀形成更为丰富的微孔结构。活化完成后通过清洗得到本发明所述的炭黑和石墨烯复合材料。以下附图和实施案例对本发明进行具体说明。附图及具体实施方式或实施例都仅是示例性的,而非用于限制本发明。
实施例1:
1)、煤粉碎:将一定比例的无烟煤、褐煤的煤块粉碎成100-200目混合煤粉;
2)、捏合:称取7g的无烟煤细化后煤粉和3g的褐煤细化后煤粉进行混合(无烟煤、褐煤质量比为7∶3),混合煤粉中加入30ml,12mol/L活化剂(KOH溶液)中并在常温下搅拌捏合1-4小时,在60-80度温度下加热干燥得到混合物;
3)、活化:混合物放置于回气氛炉中,升温速率为7度/分钟,在惰性气体氮气气氛下高温1000-1050度,反应2h后自然降温,得到复合碳化产物;
4)、洗涤干燥:将步骤4)产物用酸洗涤2-5次,再用去离子水洗涤2-5次,最后再干燥,得到炭黑与石墨烯微片复合材料。复合材料的氮吸附比表面积为820m2/kg,300%定伸强度/MPa为-9.1。
图1为实施案例1炭黑与石墨烯微片复合材料拉曼光谱数据,附图2为实施案例1炭黑与石墨烯微片复合材料透射电镜图像。拉曼光谱图中的2D峰表明本实施例合成的微孔石墨烯内部包含了大量单层或多层石墨烯结构单元,透射电镜图像能够看出炭黑与石墨烯微片复合材料主要由大量的单层薄纱状石墨烯片层和炭黑颗粒结构组成。
实施例2:
1)、煤粉碎:将一定比例的无烟煤、褐煤的煤块粉碎成100-200目混合煤粉;
2)、捏合:称取3g的无烟煤细化后煤粉和7g的褐煤细化后煤粉进行混合(无烟煤、褐煤质量比为3∶7),混合煤粉中加入30ml,12mol/L活化剂(KOH溶液)中并在常温下搅拌捏合1~4小时,在60-80度温度下加热干燥得到混合物;
3)、活化:混合物放置于回气氛炉中,升温速率为7度/分钟,在惰性气体氮气气氛下高温1000-1050度,反应2h后自然降温,得到复合碳化产物;
4)、洗涤干燥:将步骤4)产物用酸洗涤2~5次,再用去离子水洗涤2~5次,最后再干燥,得到炭黑与石墨烯微片复合材料。复合材料的氮吸附比表面积为1320m2/kg,300%定伸强度/MPa为-11.1。
具体实施方式/实施例3:
1)、煤粉碎:将一定比例的无烟煤、褐煤的煤块粉碎成100-200目混合煤粉;
2)、捏合:称取0g的无烟煤细化后煤粉和10g的褐煤细化后煤粉进行混合(无烟煤、褐煤质量比为0∶10),混合煤粉中加入30ml,12mol/L活化剂(KOH溶液)中并在常温下搅拌捏合1-4小时,在60-80度温度下加热干燥得到混合物;
3)、活化:混合物放置于回气氛炉中,升温速率为7度/分钟,在惰性气体氮气气氛下高温1000-1050度,反应2h后自然降温,得到复合碳化产物;
4)、洗涤干燥:将步骤4)产物用酸洗涤2-5次,再用去离子水洗涤2-5次,最后再干燥,得到炭黑与石墨烯微片复合材料。复合材料的氮吸附比表面积为2120m2/kg,300%定伸强度/MPa为-13.1。
具体实施方式/实施例4:
1)、煤粉碎:将一定比例的无烟煤、褐煤的煤块粉碎成100-200目混合煤粉;
2)、捏合:称取10g的无烟煤细化后煤粉和0g的褐煤细化后煤粉进行混合(无烟煤、褐煤质量比为10∶0),混合煤粉中加入30ml,12mol/L活化剂(KOH溶液)中并在常温下搅拌捏合1-4小时,在60-80度温度下加热干燥得到混合物;
3)、活化:混合物放置于气氛炉中,升温速率为7度/分钟,在惰性气体氮气气氛下高温1000-1050度,反应2h后自然降温,得到复合碳化产物;
4)、洗涤干燥:将步骤4)产物用酸洗涤2-5次,再用去离子水洗涤2-5次,最后再干燥,只得到炭黑材料。得到材料的氮吸附比表面积为120m2/kg,300%定伸强度/MPa为-3.1,透射电镜图片没有石墨烯片层结构,拉曼光谱数据没有双D峰出现。
附图3为实施案例4)炭黑与石墨烯微片复合材料透射电镜图像,透射电镜图像能够看出复合材料只由炭黑颗粒结构组成,没有石墨烯微片结构。
Claims (10)
1.一种炭黑和石墨烯微片复合材料制备技术,包括以下步骤:
步骤一、煤粉粉碎:将一定比例的无烟煤(烟煤、不粘煤、煤焦或其他煤炭)同褐煤的煤块粉碎成100-200目混合煤粉;
步骤二、捏合:混合煤粉中加入活化剂(H3PO4、ZnCl2、KOH、NaOH或以上任意两种的混合溶液)中并在常温下搅拌捏合1-4小时,在60-80度温度下加热干燥得到混合物;
步骤三、活化:混合物在惰性气体氮气或氩气或氢气气氛下高温800-1200度,反应0-4h后自然降温,得到复合碳化产物;
步骤四、洗涤干燥:复合碳化产物用酸洗涤2-5次,再用去离子水洗涤2-5次,最后再干燥,得到炭黑与石墨烯微片复合材料。
2.根据权利要求1所述的制作炭黑和石墨烯微片复合材料方法,其特征在于,活化溶液为H3PO4、ZnCl2、KOH、NaOH或他们的混合物的溶液。
3.根据权利要求1所述的制作炭黑和石墨烯微片复合材料方法,其特征在于,无烟煤(烟煤、不粘煤、煤焦或其他煤炭)与褐煤的质量比为1∶0.1-1∶20。
4.根据权利要求1所述的制作炭黑和石墨烯微片复合材料方法,其特征在于,煤粉与活化溶液质量比为1∶0.1-1∶5。
5.根据权利要求1所述的制作炭黑和石墨烯微片复合材料方法,其特征在于,活化过程气氛为惰性气氛或氢气与惰性气氛混合气氛。
6.根据权利要求1所述的制作炭黑和石墨烯微片复合材料方法,其特征在于活化温度为800℃-1200℃,活化升温速率为1-10℃/min,活化停留时间为0-4h。
7.根据权利要求1所述的制作炭黑和石墨烯微片复合材料方法,其特征在于活化溶液的浓度为0-20mol/L。
8.根据权利要求1所述的制作炭黑和石墨烯微片复合材料方法,其特征在于酸洗采用稀盐酸或硝酸,且酸洗液的浓度为0.5mol/L-3mol/L。
9.根据权利要求1所述的制作炭黑和石墨烯微片复合材料方法,其特征在于所用干燥温度为60-100℃。
10.根据权利要求1所述的制作炭黑和石墨烯微片复合材料方法,其特征在于所用混合煤炭原料中,褐煤为不可缺失的基本原料,可以分别搭配无烟煤、烟煤、不粘煤或其他煤炭、煤焦的一种或多种。
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