CN102026916B - 具有高的碳氧比的官能化的石墨烯片 - Google Patents
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Abstract
本发明提供具有至少约为23∶1的碳氧摩尔比的官能化的石墨烯片及其制备方法。
Description
该发明是使用国家科学基金会(National Science Foundation)授予的批准号为CMS-0609049和美国国家航空航天局(NASA)授予的批准号为NCC1-02037的政府资助完成的。政府在本发明中享有确定的权益。
技术领域
本发明涉及具有低氧含量的官能化的石墨烯片和它们的制备方法。
背景技术
热剥离氧化石墨(thermal exfoliated graphite oxide)(TEGO)(还被称为官能化的石墨烯片(functionalized graphene sheet))已经公开于美国专利申请出版US2007/0092432;Schniepp,H.C.等人.物理化学杂志(J.Phys.Chem.B.)2006,110,8535-8539;McAllister,M.j.等人.化学材料(Chem.Materials)2007 19,4396-4404;和Kudin,N.k等人纳米快报(Nano Letters)2008,8,36-41,这里将它们引入本文作为参考。采用氧化剂和插层剂(intercalant)或其它氧化方法对石墨处理形成的氧化石墨,具有高的氧含量。在氧化石墨的热剥离过程中,所述氧化石墨上的氧官能化位点分解发出含氧气体,其从系统中释放出来,得到热剥离氧化石墨,其通常在摩尔基础上具有比起始的氧化石墨低的氧含量。前面的文献公开了具有在约1.5∶1至20∶1之间碳氧摩尔比的氧化石墨的形成。
但是,在很多应用中,希望获得具有更高碳氧比的官能化的石墨烯片(FGS)。例如,氧官能团的量可能影响FGS与聚合物基质的反应性(当其被用作加强填料时)和/或影响FGS界面处吸收层的性质;氧的存在对于某些应用可是有害的;FGS上存在含氧官能团可能干扰π共轭系统,这可以降低材料的导电性。
发明内容
这里公开的和权利要求所要求的是具有至少约23∶1的碳氧摩尔比的官能化的石墨烯片。本文进一步公开的和权利要求所要求的是含有具有至少约23∶1的碳氧摩尔比的官能化的石墨烯片的聚合物复合材料或树脂,以及用于制备所述官能化的石墨烯片的方法。
附图说明
图1表示适合用于制备本发明官能化的石墨烯片的装置的截面示意图。
具体实施方式
本文使用的术语“碳氧比”指在FGS中碳与氧的摩尔比。通过元素分析来确定碳氧比,并将得到的重量比换算成摩尔比。
本发明的FGS(本文这里称作“高碳氧比的官能化的石墨烯片”或者“FGS-HCO”)具有至少约23∶1的碳氧摩尔比,或优选为至少约25∶1。在本发明的一些实施方式中,所述的碳氧比为至少约28∶1或至少约35∶1,或至少约50∶1,或至少约75∶1,或至少约100∶1,或至少约200∶1,或至少约300∶1,或至少约400∶1,或至少约500∶1,或至少约750∶1,或至少约1000∶1,或至少约1500∶1,或至少约2000∶1。
将氧化石墨和/或具有低的碳氧比(例如至多20∶1碳氧比)的FGS在至少约750℃的温度、还原性的气氛条件下(例如,在系统中用惰性气体或氢气吹扫)加热一段时间,该时间足以使这些起始原料反应得到FGS-HCO,形成本发明的FGS-HCO。本文将热加工称作“还原”。使用的温度优选为至少约850℃,或更优选为至少约950℃,或进一步优选为至少约1000℃。使用的温度优选在约750至3000℃之间,或更优选在约850至2500℃之间,或进一步优选在约950至约2500℃之间。加热时间优选为至少约2分钟,或更优选为至少约5分钟。在一些实施方式中,加热时间至少约为15分钟,或约30分钟,或约45分钟,或约60分钟,或约90分钟,或约120分钟,或约150分钟。在加热过程中,温度可以在这些范围内变化。
所述的加热可以在多种条件下进行,包括在惰性气氛(例如氩或氮)或还原性气氛中,例如氢(包括在惰性气体例如氩或氮中稀释的氢),或在真空下。所述的加热可以在任何适宜的容器中进行,例如熔凝硅石(fused silica)或无机或陶瓷容器或金属容器。所述被加热的原料(包括任何起始原料(即氧化石墨和/或FGS-HCO)和任何产品或中间体)可以装在单批次反应容器中的基本不变的位置,或者在连续或批量反应中,在反应过程中通过一个以上容器进行转运。可以采用任何合适的装置进行加热,包括使用熔炉或红外加热器。图1给出了可以用于本发明的装置的实例,将在实施例部分对其进行更详细地描述。该装置或类似的装置可以应用在本发明的很多实施方式中,并且不必具有与所述实施例中描述的装置相同的尺寸。也不必具有完全相同的结构或形式。
氧化石墨可以本领域所知的任何方法进行制造,例如通过包括使用一种以上的化学氧化剂和可选择地插层剂(intercalating agent)(例如硫酸)对石墨进行氧化的方法。氧化剂的实例包括硝酸、硝酸钠和钾、高氯酸盐、过氧化氢、高锰酸钠和钾、五氧化二磷、重亚硫酸盐(bisulfite)等。优选的氧化剂包括KClO4;HNO3和KClO3;KMnO4和/或NaMnO4;KMnO4和NaNO3;K2S2O8和P2O5和KMnO4;KMnO4和HNO3;和HNO3。优选的插层剂(intercalation)包括硫酸。还可采用插层剂对石墨进行处理和进行电化学氧化。
在优选的方法中,石墨被氧化为氧化石墨,随后对其进行热剥离以形成如US2007/0092432所描述的热剥离氧化石墨的形式的高表面积FGS。这样形成的FGS在其X射线或电子衍射图像中可能显示很少或没有与石墨或氧化石墨一致的特征(signature)。剥离(包括氧化石墨的剥离)优选在至少500℃以上的温度下进行,优选在500至3000℃的温度下。
本发明的FGS-HCO优选具有约250至约2630m2/g的表面积。在本发明的一些实施方式中,所述的FGS-HCO基本、几乎完全或完全包括充分剥离的石墨单片(通常称为“石墨烯”),而在其它的实施方式中,其可以包括部分剥离的石墨片,其中,两个以上的石墨层没有被彼此剥离。所述的FGS-HCO可以包括充分剥离和部分剥离的石墨片的混合物。
所述的表面积更优选为约300至约2630m2/g,或更优选为约350至约2400m2/g,或进一步优选为约400至约2400m2/g,更进一步优选为约500至约2400m2/g,或再进一步优选为约800至约2400m2/g。在另一个优选的实施方式中,表面积为约300至约1100m2/g。单石墨片具有2630m2/g的最大计算表面积。所述表面积包括所有值或它们之间(subvalue)次值的表面积,特别包括400、500、600、700、800、900、100、110、1200、1300、1400、1500、1600、1700、1800、1900、2000、2100、2200、2300、2400、2500和2630m2/g。
可以采用氮吸附/BET法或优选地亚甲基蓝(MB)染色法测定表面积。
所述染色法进行如下:将已知量的FGS加入到烧瓶中。然后将每克FGS至少1.5g的MB加入到烧瓶中。向烧瓶中加入乙醇,并且所述的混合物超声破碎约15分钟。然后蒸发乙醇,并且向烧瓶中加入已知量的水以再次溶解游离的MB。优选通过对样品进行离心,使未溶解的物质沉降。采用紫外-可见分光光度计通过测定相对于标准浓度在λmax=298nm处的吸收测定溶液中MB的浓度。
开始加入的MB的量与由紫外-可见分光光度计测定的溶液中存在的量之间的差异被认定为是被吸收到FGS表面上的MB的量。使用每一mg被吸附的MB覆盖2.54m2的表面的值计算FGS的表面积。
所述的FGS-HCO优选具有约40至约0.1kg/m3的堆积密度(bulk density)。所述的堆积密度包括所有值或它们之间的次值的堆积密度,特别包括0.5、1、5、10、15、20、25、30和35kg/m3。
本发明的FGS-HCO可用于多种应用。所述的FGS-HCO可以单独使用(以片、膜、模制品(molded article)等的形式),或与其它成分联合(例如混合)使用,或在固体或悬浮液等中使用。例如,它们可以与粘合剂共同形成涂料(包括墨水和颜料)或膜,或与一种以上的聚合物材料共同形成复合材料或树脂来使用。所述的联合可以是以涂料、印刷材料、膜、片、模和挤出制品(包括由例如注塑、吹塑、压塑、柱塞压出等方法形成的制品)的形式。可以使用任何合适的方法将所述的FGS-HCO加入到复合材料或树脂中,所述的方法包括但不限于与聚合物混合(blending)(例如热熔混合),在固化前与热固性单体混和(mixing),或者与单体混和然后聚合。所述的复合材料或树脂可以可选择地含有附加的成分。
聚合材料可以是热固性的、热塑性的、可不熔融加工的聚合物等。聚合物的实例包括丙烯腈/丁二烯/苯乙烯(ABS)、聚碳酸酯(PC)、聚酰胺(包括聚对苯二甲酰胺)、聚酯(包括聚对苯二甲酸丁二酯(PBT)、聚对苯二甲酸乙二酯(PET)等)、聚苯醚(PPO)、聚砜(PSU)、聚醚酮(PEK)、聚醚醚酮(PEEK)、聚酰亚胺、聚甲醛(POM)、聚乳酸、聚丙烯腈、苯乙烯/丙烯腈聚合物(SAN)、聚醚酰亚胺、聚苯乙烯(包括高抗冲聚苯乙烯)、液晶聚合物(LCP)、芳香族聚酰胺(例如凯夫拉尔()和诺梅克斯())、聚四氟乙烯(PTFE)、氟化乙烯丙烯聚合物(FEP)、聚氟乙烯、聚偏氟乙烯、聚偏氯乙烯、聚氯乙烯、聚烯烃(例如聚乙烯和聚丙烯和烯烃共聚物)、聚醋酸乙烯酯、聚甲基丙烯酸甲酯和其它丙烯酸酯聚合物、聚硅氧烷(包括聚二亚甲基硅氧烷)、弹性体(包括但不限于聚氨酯(polyurethane)、共聚醚酯(copolyetherester))、橡胶(包括丁基橡胶)、苯乙烯/丁二烯共聚物、聚异丙烯、天然橡胶、和聚硅氧烷、环氧聚合物、聚脲、醇酸树脂、纤维素聚合物、聚醚(例如聚环氧乙烷(poly(ethylene oxide))和聚环氧丙烷(poly(propylene oxide)))等。
在本发明的一个实施方式中,当所述的FGS-HCO用于与其它原料混合时,所述的复合材料是导电性的,且优选具有至少约10-6S/m的导电率。在本发明的实施方式中,当希望所述的复合材料是半导体时,它们优选具有约10-6S/m至约105S/m的导电率,或更优选为10-5S/m至约105S/m。在本发明其它的实施方式中,所述的涂料具有至少约100S/m的导电率,或至少约1000S/m,或至少约104S/m,或至少约105S/m,或至少约106S/m。在所述的材料为所述的FGS-HCO与粘合剂或聚合物混合的情况下(包括所述的混合物是液体形式时),可以在所述混合物干燥、固化、交联或其它处理后测定所述的导电率。
在一些实施方式中,相比于具有较低的碳氧比(包括20∶1以下的比)的相似的材料,以纯的形式和/或混合物或与其它材料的复合材料的本发明的官能化的石墨烯片均具有改善的导电率。
实施例
氧化石墨的制备
根据Staudenmaier,L.Ber.Stsch.Chem.Ges.1898,31,1481和Schniepp,H.C.等人.J.Phys.Chem.B.2006,110,8535-8539(及其资助信息)以及McAllister,M.j.等人.Chem.Materials 2007 19,4396-4404所公开的方法,采用硫酸、硝酸和氯酸钾对石墨进行处理制备氧化石墨。
复合材料导电率的测定
将足量的分子量为4,000,000的聚环氧乙烷(PEO)与1∶1(体积/体积)的乙醇和去离子水的混合物混合以制备每毫升总的溶剂中含有40mg PEO的混合物,来制备PEO溶液。搅拌过夜,得到了均相的PEO原料溶液。在表1和表2中的实施例和比较例的情况下,所述的PEO从联合碳化物公司(UnionCarbide Corp)获得,而在表3中的实施例和比较例的情况下,其得自奥德里奇化学公司(Aldrich Chemicals)。
对表1-3的还原样品称重,在所述的FGS中加入足量的浓缩的普朗尼克()(由巴斯夫(BASF)提供的环氧乙烷/环氧丙烷共聚物表面活性剂)水溶液(通常为2mg/ml),得到具有1∶1重量比的还原材料与Pluronic F127的混合物。加入充足的去离子水,得到每1ml水含有1mg FGS的悬浮液。得到的悬浮液在冰浴中以20%的占空系数(duty cycle)声处理(sonicate)5分钟。然后将1ml还原材料悬浮液加入到3ml PEO原料溶液中,所得混合物搅拌3-5分钟直到均相。
将两块铜板(22mm×22mm)用特氟龙(Teflon)胶带包裹,在下端留下1mm未覆盖的铜。然后用螺钉将所述的板紧紧连结至电解槽(cell)(23mm×46mm的内部底面积,32mm的高度)侧壁的较短一侧。将所述的混合物倒入所述的电解槽中,在加热板上保持50℃,直至所有的溶剂被蒸发以形成附着在所述铜板上的膜。基于FGS、和PEO的总重量,所得到的膜含有6.52重量%的FGS,6.52重量%的和86.96重量%的PEO。将所述的板提起以使所述的膜从电解槽中剥离,并将所述膜切成长方形的形状以排除不均匀的(多孔的或较薄的)区域。最终的膜长度、宽度和厚度分别在约10-32mm、约7-22mm和约6-39μm的范围内。
将铜带彼此平行地连结在所述膜的两个末端,以使得它们覆盖所述膜的整个宽度。通过所述的铜带将电源(泰克(Tektronix)PS 252G程控电源,泰克公司(Tektronix Inc.),俄勒冈,比佛顿)和万用表(福禄克(Fluke)27万用表,福禄克公司(Fluke Corp.),华盛顿,埃弗里特)与所述的膜串联。应用电势差(5-20V),并用万用表监控电流。使用带有两个电极的静电计(吉时利(Keithley)6514,吉时利仪器公司(Keithley Instruments Inc.),俄亥俄,克里夫兰)测定沿着电流方向的两个点之间的电势差。使用在所述膜上测定的电势与电流来求得根据欧姆定律的电阻,即R=V/I,其中R、V和I分别是电阻、电压和电流。电阻率(σ)通过σ=RA/L求得,其中A和L是电流通过其流动的膜的截面和在其上测定电势差的长度。导电率(κ)由κ=1/σ求得。在所述膜的不同点进行两次测定,线性平均被报告为导电率。
在除了实施例5和实施例11的每种情况下,均测定两次,结果进行平均并示于表1-3。在实施例3和实施例9的情况下,进行单次测定,结果报告于所述的表中。
其它分析方法
C∶O比是由元素分析结果确定的摩尔比。使用采用氮吸附技术的BET法进行表面积的测定。
还原方法A:实施例1-15和比较例1-3:
本方法中使用至多达两个步骤。在步骤I中,FGS被放置在刚玉舟(aluminaboat)中,并插入内径(ID)25mm、长1.3m的一端密封的石英管中。所述石英管的另一端用橡胶塞封住。通过橡胶塞插入进气口和热电偶,并以具有95∶5的摩尔比的氮/氢气体混合物用10分钟将样品冲入,然后将所述的管插进被预热至如表1-3所示的温度的管式炉中,并保持所述表中所示的时间。
在步骤II中,将所述的材料(FGS或步骤I的产品)放置在石墨炉(Astro-1000,由热能技术公司(Thermal Technologies)提供)中100毫托(mTorr)的氩气的气氛下,时间和温度示于表2和表3(在表1中的实验情况下没有进行步骤II)。以20℃/分钟的速度将所述的材料加热至需要的温度,并在该温度下保持所述表中所示的时间。
表1
表2
表3
还原方法B:实施例13-25和比较例2-8:
采用图1的以截面示意形式所示的装置剥离(在实验中指表4中的“Exfol”法)氧化石墨(GO)。将石英管10装入垂直的红外炉12中,并保持在约1040℃。所述的管具有约35mm的外径,并从所述炉的上方延伸约50cm至点16,由该点进入该炉。管10另外的约50cm被封装在炉中。管10从点18延伸约45cm以上,在该点其从该炉探出(exit)。管10包含位于点18上方约15cm的玻璃熔块(glass frit)14和外径(o.d)大约(ca.)为10mm的开口石英内管20,其通过管10的中间延伸至所述熔块上方约8.5cm。管20的上部穿过管10的壁,在管10中其形成了进口26。管10的底部开口28连接至进气口、出气口或真空口(未示出),并且顶部出口30连接至过滤器22,过滤器22又被顺序连接至泵24。开口26、28和30连接至可用于将其与装置外部的环境隔离的阀(未示出)。
由氩气流将氧化石墨通过进口26连续输送到管10中,其在管10中发生反应,所得到的剥离产品经出口30离开并由过滤器22收集。开口28还可用于将氩气导入系统或使系统成为真空。
使用两种方式操作所述的还原实验(在表4中称为“Red.”法)。可以以与用于剥离的相似的连续的方式将以前制备的FGS再次通过所述的管,但以含有4摩尔%氢的氩作为载气。可选择地,通过进口26将氧化石墨或FGS导入管10中并保持一段时间(表4中“保持时间”标题下给出),而不使其经出口30离开,同时以含有4摩尔%氢的氩气混合物连续冲洗管10。通过进口26(有时通过开口28)引导所述的氢/氩混合物。表4中给出了对于每个实施例或比较例通过每个开口的气流的速度。在实施例19的情况下,通过开口28将真空应用到所述的系统中,并以表4所示的流速通过开口26和30引导所述的氢氩混合物。通过元素分析确定得到的产品的碳氧比。
使用的GO起始原料来自于数个批号,示于表4。在实施例20-22的情况下,起始原料是比较例5制备的FGS;在实施例24的情况下,起始原料是比较例7制备的FGS;在实施例25的情况下,起始原料是比较例8制备的FGS。
表4
Claims (20)
1.高碳氧比的官能化的石墨烯片,其具有至少为25:1的碳氧摩尔比,其中,所述高碳氧比的官能化的石墨烯片是通过包含如下步骤的方法来形成:(a)形成具有低于23:1的碳氧摩尔比的官能化的石墨烯片;以及(b)在至少750℃的温度下对所述具有低于23:1的碳氧摩尔比的官能化的石墨烯片加热一段时间,该时间足以产生所述高碳氧比的官能化的石墨烯片。
2.根据权利要求1所述的官能化的石墨烯片,其中,所述的碳氧比至少为28:1。
3.根据权利要求1所述的官能化的石墨烯片,其中,所述的碳氧比至少为50:1。
4.根据权利要求1所述的官能化的石墨烯片,其中,所述的碳氧比至少为75:1。
5.根据权利要求1所述的官能化的石墨烯片,其进一步具有300至2630m2/g的表面积。
6.根据权利要求1所述的官能化的石墨烯片,其进一步具有350至2400m2/g的表面积。
7.根据权利要求1所述的官能化的石墨烯片,其进一步具有400至2400m2/g的表面积。
8.根据权利要求1所述的官能化的石墨烯片,其进一步具有500至2400m2/g的表面积。
9.根据权利要求1所述的官能化的石墨烯片,其进一步具有800至2400m2/g的表面积。
10.一种聚合物复合材料或树脂,其含有权利要求1的官能化的石墨烯片和至少一种聚合物。
11.根据权利要求10所述的复合材料或树脂,其中,所述的聚合物是丙烯腈/丁二烯/苯乙烯、聚碳酸酯、聚酰胺、聚对苯二甲酰胺、聚酯、聚对苯二甲酸丁二酯、聚对苯二甲酸乙二酯、聚苯醚、聚砜、聚醚酮、聚醚醚酮、聚酰亚胺、聚甲醛、聚乳酸、聚丙烯腈、苯乙烯/丙烯腈聚合物、聚醚酰亚胺、聚苯乙烯、高抗冲聚苯乙烯、液晶聚合物、芳香族聚酰胺、聚四氟乙烯、氟化乙烯丙烯聚合物、聚氟乙烯、聚偏氟乙烯、聚偏氯乙烯、聚氯乙烯、聚烯烃、聚乙烯、聚丙烯、聚醋酸乙烯酯、丙烯酸酯聚合物、聚甲基丙烯酸甲酯、聚硅氧烷、聚二亚甲基硅氧烷、弹性体、共聚醚酯、橡胶、丁基橡胶、苯乙烯/丁二烯共聚物、聚异丙烯、天然橡胶、和聚硅氧烷、环氧聚合物、聚脲、醇酸树脂、纤维素聚合物和聚醚中的一种或多种。
12.根据权利要求10所述的复合材料,其具有至少10-6S/m的导电率。
13.根据权利要求10所述的复合材料,其具有至少100S/m的导电率。
14.根据权利要求10所述的复合材料,其具有至少104S/m的导电率。
15.一种用于制备官能化的石墨烯片的方法,所述官能化的石墨烯片具有至少为25:1的碳氧摩尔比,所述的方法包括:(a)形成具有低于23:1的碳氧摩尔比的官能化的石墨烯片;以及(b)在至少750℃的温度下对具有低于23:1的碳氧摩尔比的官能化的石墨烯片加热一段时间,该时间足以产生碳氧摩尔比为至少25:1的高碳氧摩尔比的官能化的石墨烯片。
16.根据权利要求15所述的方法,其中,所述的温度为至少850℃,所述的加热时间至少为2分钟。
17.根据权利要求15所述的方法,其中,所述的温度为至少950℃,所述的加热时间至少为2分钟。
18.根据权利要求15所述的方法,其中,所述的加热时间至少为15分钟。
19.根据权利要求15所述的方法,其中,所述的加热在惰性气氛下进行。
20.根据权利要求15所述的方法,其中,所述的加热在还原性气氛下进行。
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US10017632B2 (en) | 2018-07-10 |
US20180291182A1 (en) | 2018-10-11 |
WO2009134492A3 (en) | 2009-12-23 |
CN102026916A (zh) | 2011-04-20 |
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