CN103764553A - 纳米片-纳米管复合材料、其生产方法以及由其获得的产品 - Google Patents

纳米片-纳米管复合材料、其生产方法以及由其获得的产品 Download PDF

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CN103764553A
CN103764553A CN201280029880.4A CN201280029880A CN103764553A CN 103764553 A CN103764553 A CN 103764553A CN 201280029880 A CN201280029880 A CN 201280029880A CN 103764553 A CN103764553 A CN 103764553A
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carbon nano
discrete
graphene
nanotube
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CN103764553B (zh
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克莱夫·P·博什尼亚克
库尔特·W·斯沃格
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Designed Nanotubes LLC
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Abstract

本发明公开了离散的纳米管和纳米片的生产方法和组合物以及其生产方法。离散的纳米管/纳米片组合物可用于制造制品以提供优越的机械和电性能。它们也可用作用于化学反应的催化剂和催化剂载体。

Description

纳米片-纳米管复合材料、其生产方法以及由其获得的产品
本申请要求2011年6月23日提交的题名为“GRAPHENE-CARBONNANOTUBE COMPOSITES,METHODS FOR PRODUCTIONTHEREOF AND PRODUCTS OBTAINED THEREFROM”的美国临时专利申请序列号61/500,562的优先权，其全部内容通过引用并入本文。
技术领域
本发明涉及纳米片和纳米管的生产方法和组合物。
背景技术
本发明涉及纳米片和纳米管的组合物，其中纳米片的至少一部分具有散布在两个纳米片之间的至少一个纳米管。特别地，描述了碳纳米管和石墨烯结构的剥离和分散，得到了容易分散在多种介质中的高长径比的经表面改性的碳纳米管/石墨烯组合物。本文中的石墨烯结构意指包括石墨烯和含氧石墨烯结构。本文中的碳纳米管意指包括碳纳米管和氧化碳纳米管。碳纳米管或石墨烯的含氧结构包括但不限于附接于碳表面的羧酸、酰胺、缩水甘油基和羟基基团。
这些纳米片-纳米管混合物可通过表面活性剂或改性剂进一步改性。本发明还涉及具有材料例如弹性体材料、热固性材料、热塑性材料、陶瓷材料和电活性材料或光活性材料的纳米片-纳米管复合材料。石墨烯-碳纳米管组合物也可用作用于化学反应的催化剂。另外，本发明涉及以高产率生产这样的复合材料的方法。
目前，固态碳纳米管作为手性或非手性形式的混合物的团聚纳米管束生产。已开发了多种方法来在溶液中解开或松开碳纳米管的束。例如，可通过侵蚀性氧化手段使碳纳米管大幅度缩短然后作为单个纳米管分散在稀溶液中。这些管具有不适合于高强度复合材料的低长径比。碳纳米管也可在表面活性剂存在下通过超声处理作为个体分散在非常稀的溶液中。用于将碳纳米管分散在溶液中的示例性表面活性剂包括例如十二烷基硫酸钠和PLURONICS。在一些情况下，可由聚合物包覆的碳纳米管制备单个化的碳纳米管的溶液。还已使用多糖、多肽、水溶性聚合物、核酸、DNA、多核苷酸、聚酰亚胺和聚乙烯吡咯烷酮在非常稀的溶液中制备单个化的单壁碳纳米管溶液。稀释范围通常在mg/升的范围中并且不适合于商业使用。
如果在介质（例如水）中剥离石墨烯（即，分离的单个片而不是堆叠的），由不相容性引起的热力学能和石墨烯非常高的表面积导致了片的再组合，并且片变得非常难以分离成单个片。同样地，如果要将石墨烯氧化，如果片是成束的，则仅有石墨烯的边缘易于进行反应。
在本发明中，可在无机片之间插入直径范围为1纳米至100纳米的离散的管。特别地，可在石墨烯片之间插入碳纳米管，从而限制其团聚并有助于在宽范围材料（包括液体和固体）中的剥离。此外，由于现在片是分离的，所以反应可保留在石墨烯片的表面，以得到例如含氧石墨烯结构。管的直径可用于控制片间距离。选择不同直径的管可导致分子或离子在片之间的受控传输。
鉴于以上内容，纳米片-离散的纳米管组合物及用于获得它们的方法在本领域中是相当令人感兴趣的。提出了离散的纳米管/单一无机片（特别是碳纳米管/石墨烯组合物）的多个用途，包括例如，储能装置（例如，超电容器、超级电容器和电池）、场发射器、导电膜、导线、光敏材料、药物递送和膜过滤器。离散的碳纳米管/石墨烯组合物在材料复合物中作为增强剂的用途是所述组合物预期具有重要实用性的另一个领域。材料包括例如聚合物、陶瓷、橡胶、水泥。应用包括轮胎、粘合剂和工程结构（如风力叶片、飞行器等）。
发明内容
本发明的一个实施方案包括包含散布有至少一部分离散的纳米管的无机片（称为纳米片）的组合物，其中单个片的厚度小于10纳米，所述离散的纳米管的直径范围为约1纳米至150纳米并且长径比为约10至500。优选地，无机片是石墨烯并且离散的纳米管是碳纳米管。无机片与纳米管的重量比的范围为约1:100至100:1。纳米片和纳米管的混合物可还包含选自热塑性材料、热固性材料和弹性体的聚合物和/或选自陶瓷、粘土、硅酸盐、金属络合物和盐的无机材料。
本发明的另一个实施方案包括纳米片和纳米管的混合物，其可还包含至少一种电活性材料，所述混合物可用在例如储能装置或光生伏打电池中。
本发明的又一个实施方案是纳米片和纳米管的组合物，其还包含至少一种过渡金属络合物或活性催化剂物质。活性催化剂可与离散的纳米管或无机片或其组合经离子键连接或共价连接。化学反应可包括使组合物与例如但不限于烯烃和炔烃、含氧化学部分、含氮化学部分、含卤素化学部分和含磷化学部分相接触。组合物可以是用于气相反应的粉末形式或用于溶液和淤浆相反应的液体混合物形式。
本发明的另一个实施方案是用于制备石墨烯碳纳米管复合材料的方法，所述方法包括：a）将非离散的石墨烯和非离散的碳纳米管纤维悬浮在酸性溶液中一段时间；b）任选地搅拌所述悬浮液；c）超声处理所述石墨烯-碳纳米管的悬浮液以形成石墨烯-离散的碳纳米管纤维；以及d）从酸中分离所得的石墨烯-离散的碳纳米管组合物后使用固/液分离进行进一步处理，其中所述分离包括过滤。
本发明的另一个实施方案是用于制备无机片-碳纳米管复合材料的方法，所述方法包括：a）将非离散的碳纳米管纤维悬浮于酸性溶液中一段时间；b）超声处理碳纳米管的所述悬浮液以形成离散的碳纳米管纤维；c）从酸中分离所得的经氧化的离散的碳纳米管组合物；d）用水或其它液体洗涤经氧化的离散的碳纳米管以移除酸；e）任选地用表面活性剂和超声处理使离散的经氧化的碳纳米管和无机片再分散；f）任选地添加聚合物；g）任选地添加过渡金属络合物；h）任选地添加电活性材料；i）任选地添加陶瓷；j）分离混合物并任选地干燥。
本发明的另一个实施方案是所制造制品（例如轮胎、工业用橡胶件或风力叶片）部件形式的组合物纳米片和纳米管。组合物也可用于电池、电容器、光生伏打电池的催化剂和催化剂载体。展望了另外的用途，但不限于膜、导电油墨、传感器以及静态管理和电磁屏蔽。
附图说明
为了更全面地理解本公开及其优点，现参照以下描述并结合附图来描述本公开的具体实施方案，在附图中：
图1示出了具有本发明离散的碳纳米管的石墨烯片的二次电子显微照片。放大率为200,000X。
图2示出了具有本发明离散的碳纳米管的磷酸铁锂和氢氧化镁片的二次电子显微照片。放大率为5,060X。
图3示出了具有本发明离散的碳纳米管的磷酸锆片的二次电子显微照片。放大率为155,000X。
具体实施方式
在以下描述中阐述了某些细节例如具体的量、尺寸等，以便提供对本文中所公开的实施方案的透彻理解。但是，对于本领域普通技术人员明显的是，本公开可在没有这些具体细节的情况下实施。在许多情况下，由于关于这些考虑等的细节对于获得本公开的全面理解而言不是必须的并且在相关领域普通技术人员的技能范围内，所以省略了这样的细节。
虽然本文中使用的大多数术语是本领域普通技术人员知道的，但是应理解，当没有明确定义时，术语应理解为采用本领域普通技术人员目前承认的意思。在术语的构成使得其无意义或基本无意义的情况下，定义应取自韦氏词典2009年第3版。定义和/或解释不应从相关或不相关的其他专利申请、专利或公开并入，除非本说明书中有特别指出或者当这样的并入对于保持有效性是必要的时。
纳米管是直径为至少1纳米并且至多100纳米的管状结构。纳米管的实例是单壁碳纳米管、双壁碳纳米管和多壁碳纳米管或二氧化钛纳米管。长径比定义为管长度与管直径之比。纳米片定义为厚度小于10纳米的可辨别的片。
离散的经氧化的碳纳米管，或者称为剥离的碳纳米管，可使用浓硫酸和硝酸的组合通过例如氧化的方法从即制（as-made）的成束的碳纳米管获得。成束的碳纳米管可由任意已知的方法例如化学气相沉积、激光烧蚀和高压一氧化碳合成制备。成束的碳纳米管可以多种形式存在，包括例如烟灰、粉末、纤维和绒毛纸（bucky paper）。此外，成束的碳纳米管可具有任意长度、直径或手性。基于其手性和壁的数目，碳纳米管可以是金属性的、半金属性的、半导体性的或非金属性的。离散的经氧化的碳纳米管可包括例如单壁碳纳米管、双壁碳纳米管或多壁碳纳米管及其组合。
石墨烯是碳的同素异形体，其结构是sp2键合的碳原子以蜂巢晶格密集的一个原子厚的碳原子的平面片。石墨的结晶或“薄片”形式由堆叠在一起的多个石墨烯片组成。石墨烯片堆叠以形成平面间距为0.335nm的石墨。石墨烯是一些碳同素异形体包括石墨、木炭、碳纳米管和富勒烯的基本结构元件。其也可被认为是无限大的芳香族分子（平面多环芳烃族的极限情况）。用于得到石墨烯的一种方法由将低浓度的石墨混合在溶剂例如N-甲基吡咯烷酮中然后超声处理组成。最后通过离心从石墨烯中分离未剥离的石墨。
本领域普通技术人员将认识到，利用特殊类型的纳米管或纳米片所阐明的本发明的多个具体方面可同样地利用其他类型纳米管和纳米片在本公开的精神和范围内实施。
实施例1
在经表面活性剂稳定的水性悬浮液中评价离散的碳纳米管和石墨烯的分散特征
将石墨烯（莱斯大学）和直径约13nm的多壁碳纳米管（C-9000,C-Nano）分别以1:3的重量比组合。在3:1硫酸（96%,KMG）/硝酸（70%,Honeywell）溶液中制备混合物的1%w/v分散体，使用超声发生器浴进行超声处理，同时将浴的温度维持在30℃至35℃的范围内3小时。超声处理之后，在5μm PVDF膜（Whatman）上用200mL量的水对每种制剂进行布氏过滤。在真空炉中在80℃下将样品干燥2小时。电子显微照片将示出隔开石墨烯片的碳纳米管，例如图1所示。
将0.05g干燥的石墨烯碳纳米管混合物和0.15g十二烷基硫酸钠（Sigma-Aldridge）添加到20mL量瓶中并用水填充至20mL的刻度。将烧瓶在浴中超声处理1小时，以上述的相同方式监测温度。超声处理之后，用水将1mL样品稀释至最终总碳浓度为2.5×10-5g/mL并且通过UV-vis分光光度计（BioSpec-1601,Shimadzu）进行评价。在测量第一吸光度光谱之后，在500nm波长下在5、15、30、45和60分钟时间段处对相同试样进行分析以评价混合物在水中的稳定性。60分钟后在500nm下初始吸光度值的衰减确定为0.4%。
比较例1
比较例1重复如实施例1的实验步骤，不同之处在于仅使用石墨烯。60分钟后在500nm下初始吸光度值的衰减确定为12.1%。
比较例2
比较例2重复如实施例1的实验步骤，不同之处在于仅使用多壁碳纳米管。60分钟后在500nm下初始吸光度值的衰减确定为0%。
通过UV光谱法示出实施例1的离散的碳纳米管通过散布在石墨烯片之间为石墨烯分散体提供了稳定性。
实施例2
在玻璃瓶中将氧化水平为8重量百分比的0.039克多壁碳纳米管添加到0.0401克磷酸铁锂和40克去离子水中。使用超声处理器浴在25℃下将样品超声处理13分钟，其后通过目测没有观察到碳纳米管颗粒。然后将1ml经超声处理的混合物与0.14ml去离子水中氢氧化镁的0.1%重量/体积混合物混合，然后用更多的去离子水稀释使得体积为4ml。在25℃下将该最终的混合物超声处理另外的15分钟。为了通过电子显微镜进行检查，然后将一滴该溶液放置在碳带上并干燥。结果见图2，示出了表面上和片之间的碳纳米管。
实施例3
具有磷酸锆纳米片（Zr(HPO4)2·2H2O）的离散的多壁碳纳米管
将10mg多壁碳纳米管放置在Zr(HPO4)2·H2O和四丁基氢氧化铵的2mL混合物（5重量%的Zr(HPO4)2·H2O；Zr(HPO4)2·H2O:四丁基氢氧化铵之比为1:0.8）中，制备了碳纳米管的分散溶液。然后将溶液稀释至30mL，然后超声处理2小时。将溶液静置至少24小时。将一滴该溶液放置在碳带上并干燥。二次电子显微镜图片图3揭示了散布有离散的碳纳米管的大约片直径为200纳米的磷酸锆纳米片。

Claims (16)

1.一种组合物，其包含：
单个片厚度小于10纳米的无机片；
其中所述无机片散布有离散的纳米管，所述纳米管具有从约1纳米至150纳米的范围内的直径，并且所述纳米管具有从约10至500的范围内的长径比。
2.根据权利要求1所述的组合物，其中所述无机片是石墨烯纳米片。
3.根据权利要求1所述的组合物，其中所述无机片和离散的管以约1:100至100:1的重量比存在。
4.根据权利要求1所述的组合物，其还包含选自热塑性材料、热固性材料和弹性体的聚合物。
5.根据权利要求1所述的组合物，其还包含选自陶瓷、粘土、硅酸盐、金属络合物和盐的无机材料。
6.根据权利要求1所述的组合物，其还包含至少一种电活性材料。
7.根据权利要求1所述的组合物，其还包含至少一种过渡金属络合物或活性催化剂物质。
8.一种制备石墨烯碳纳米管复合材料的方法，其包括以下步骤：
a）将非离散的石墨烯和非离散的碳纳米管纤维悬浮在酸性溶液中一段时间以形成悬浮液；
b）搅拌所述悬浮液；
c）超声处理所述石墨烯-碳纳米管的悬浮液以形成石墨烯-离散的碳纳米管纤维；以及
d）在使用固/液分离进一步处理之前从所述酸性溶液中分离所述石墨烯-离散的碳纳米管纤维；
其中所述固/液分离包括过滤。
9.一种制备无机片-碳纳米管复合材料的方法，其包括步骤：
a）将非离散的碳纳米管纤维悬浮在酸性溶液中一段时间以形成悬浮液；
b）超声处理碳纳米管的所述悬浮液以形成离散的碳纳米管纤维；
c）从所述酸性溶液中分离所述离散的碳纳米管纤维；
d）用水或另一种液体洗涤所述离散的碳纳米管纤维；
e）任选采用表面活性剂和超声处理，使所述离散的碳纳米管纤维和无机片再分散；
f）任选地添加聚合物；
g）任选地添加过渡金属络合物；
h）任选地添加电活性材料；
i）任选地添加陶瓷；以及
j）分离出混合物并任选地干燥。
10.根据权利要求1所述的组合物在制品例如轮胎、工业橡胶件或风力叶片中的用途。
11.根据权利要求1所述的组合物在电池中的用途。
12.根据权利要求1所述的组合物在电容器中的用途。
13.根据权利要求1所述的组合物在太阳能电池中的用途。
14.根据权利要求1所述的组合物在用于气相反应的催化剂或催化剂载体的粉末或液体混合物中的用途。
15.根据权利要求1所述的组合物在用于溶液和淤浆相反应的催化剂或催化剂载体的液体或固体混合物中的用途。
16.根据权利要求1所述的组合物在用于地基、道路或桥梁的混凝土混合物中的用途，或者在用于生坯（green-ware）以生产陶瓷件的陶瓷混合物中的用途。
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