CN104603885B - 整体碳纳米管和金属复合材料及制备方法 - Google Patents

整体碳纳米管和金属复合材料及制备方法 Download PDF

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CN104603885B
CN104603885B CN201380038990.1A CN201380038990A CN104603885B CN 104603885 B CN104603885 B CN 104603885B CN 201380038990 A CN201380038990 A CN 201380038990A CN 104603885 B CN104603885 B CN 104603885B
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J·A·瓦森克祖克
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Abstract

在一个实施方式中，提供整体碳纳米管和金属复合材料。该整体碳纳米管和金属复合材料包括含有多个碳纳米管的整体碳纳米管材料层和施加在整体碳纳米管材料层上的金属膜。金属膜渗透进入单个碳纳米管之间的空隙以减少多个碳纳米管之间的电阻。

Description

整体碳纳米管和金属复合材料及制备方法
背景技术
本公开的领域一般地涉及复合材料，以及更具体地涉及整体碳纳米管和金属复合材料。
至少一些已知的碳纳米管(CNT)由通常被称为“石墨烯”的一个原子厚的石墨片形成。该片被卷成具有纳米级直径以及微米级长度的圆筒。已知的CNT展现出非凡的强度和电性质，并且是热的有效导体。CNT的两种最常见类型是由单层石墨烯形成的单壁碳纳米管(SWCNT)和由多个同心圆筒或围绕自身卷曲的石墨烯片形成的多壁碳纳米管(MWCNT)。
CNT是轻质的并且有非常高的弹性模量。CNT的传导性能依赖于直径和沿着管延伸的六方碳晶格的手性。六方晶格沿管缠绕的微小变化能够导致CNT具有金属或者半导体的功能。例如，平行于管轴的六方排列产生被称作“扶手椅式”构造的金属结构。相反，碳键围绕管圆周的交替排列产生被称作“Z字形”构造的半导体结构。虽然单个的CNT可以是高导电的，多个CNT之间的高接触电阻导致整体CNT材料的低电导率。
发明简述
根据本发明的一个方面，提供整体碳纳米管和金属复合材料。整体碳纳米管和金属复合材料包括含有多个碳纳米管的整体碳纳米管材料层以及施加在整体碳纳米管材料层上的金属膜。金属膜渗透进入单个碳纳米管之间的空隙以减小多个碳纳米管之间的电阻。
有利地，多个碳纳米管的至少一部分是金属碳纳米管。有利地，多个碳纳米管包含单壁碳纳米管和多壁碳纳米管的至少一种。有利地，整体碳纳米管材料层是无纺片和纱的至少一种。有利地，利用化学气相沉积方法、化学镀膜方法、溅射方法和物理气相沉积方法中的至少一种将金属膜施加在整体碳纳米管材料层上。有利地，金属膜包含铝、镍、铜、钛、银、金和铬中的至少一种。
根据本发明另一个方面，提供整体碳纳米管和金属复合材料带。整体碳纳米管和金属复合材料带包括连接至第二整体碳纳米管和金属复合材料的第一整体碳纳米管和金属复合材料。第一和第二整体碳纳米管和金属复合材料各自包括含有多个碳纳米管的整体碳纳米管材料层和施加在整体碳纳米管材料层上的金属膜。金属膜渗透进入单个碳纳米管之间的空隙以减少多个碳纳米管之间的电阻。
有利地，利用超声波焊接方法和超声波增材制造方法的至少一种将第一整体碳纳米管和金属复合材料连接至第二整体碳纳米管和金属复合材料。有利地，所述多个碳纳米管的至少一部分是金属碳纳米管。有利地，多个碳纳米管包含单壁碳纳米管和多壁碳纳米管的至少一种。有利地，整体碳纳米管材料层是无纺片和纱的至少一种。有利地，利用化学气相沉积方法、化学镀膜方法、溅射方法和物理气相沉积方法的至少一种将金属膜施加在所述整体碳纳米管材料层上。
根据本发明的又一方面，提供制备整体碳纳米管和金属复合材料的方法。该方法包括形成包含多个碳纳米管的第一整体碳纳米管材料层，以及在整体碳纳米管材料层上沉积金属膜。金属膜渗透进入单个碳纳米管之间的空隙以减小多个碳纳米管之间的电阻。
有利地，该方法包括制备第二整体碳纳米管和金属复合材料，以及连接第二整体碳纳米管和金属复合材料至第一整体碳纳米管和金属复合材料以形成整体碳纳米管和金属复合材料带。优选地，该方法进一步包括利用超声波焊接方法和超声波增材制造方法的至少一种连接第二整体碳纳米管和金属复合材料至第一整体碳纳米管和金属复合材料。有利地，形成第一整体碳纳米管材料层包含利用金属碳纳米管形成所述层的至少一部分。有利地，形成第一整体碳纳米管材料层包含利用单壁碳纳米管和多壁碳纳米管的至少一种形成所述层的至少一部分。有利地，形成第一整体碳纳米管材料层包含利用无纺片和纱的至少一种形成所述层的至少一部分。有利地，沉积金属膜包含利用化学气相沉积方法、化学镀膜方法、溅射方法和物理气相沉积方法的至少一种将金属膜施加在整体碳纳米管材料层上。有利地，沉积金属膜包含将铝、镍、铜、钛、银、金和铬的至少一种施加在整体碳纳米管材料层上。
附图说明
图1是示例性整体CNT和金属复合材料的示意图；
图2是示例性整体CNT和金属复合材料带的示意图；以及
图3是制备整体CNT和金属复合材料带的示例性方法的方框图。
发明详述
图1图解了包括整体CNT材料层12以及一个或多个薄的金属膜或层14的示例性整体碳纳米管(CNT)复合材料10。在该示例性实施方式中，分别地，整体CNT层12包括相对的第一和第二面16和18，并且在每面16和18上沉积金属膜层14。图2图解了通过将整体CNT层12焊接在一起制备的示例性整体CNT和金属复合材料带20，其将被更详细地描述。本文所述的方法生产具有高的重量归一化电导率(weight-normalized electrical conductivity)、高导热性和高机械强度的整体CNT和金属复合材料带20。
在该示例性实施方式中，整体CNT层12是由多个金属CNT(未显示)制备的，例如“扶手椅型”CNT，其每个以基本平行于每个CNT管轴的手性角度定向。当形成每个CNT的石墨烯片(未显示)以扶手椅型手性卷绕时，每个形成的CNT具有增强的金属性质并且对于非常高的电流密度具有增强的容量。可选地，除了金属CNT之外，整体CNT层12还可包括许多半导体CNT(未显示)。在该示例性实施方式中，整体CNT层12是无纺片或纱。可选地，可使用任何能够使复合材料10如本文所述起作用的其他形式整体CNT层12。
在该示例性实施方式中，金属膜14施加在CNT层的面16和18上并且渗透进入单个CNT之间的空隙。在该示例性实施方式中，用于形成金属膜14的金属量足以在大量的CNT之间促进低电阻互连。在该示例性实施方式中，金属膜14是渗透进入整体CNT层12并且覆盖大部分CNT的铝薄膜。可选地，金属膜14可以是任何导电金属或金属的结合，其使整体CNT和金属复合材料10能够如本文所述起作用。在该示例性实施方式中，金属膜14通过化学气相沉积和/或化学镀膜法直接施加在CNT层12上。因此，在该示例性实施方式中，所述方法促进在整体CNT层的空隙内沉积金属。可选地，金属膜14可通过溅射和/或物理气相沉积方法施加。然而，可以使用任何其他使整体CNT和金属复合材料10能够如本文所述起作用的金属沉积方法。
在该示例性实施方式中，多个整体CNT和金属复合材料10通过焊接方法连接到一起，该方法形成整体CNT和金属复合材料带20。在该示例性实施方式中，以及如图2所示，三个CNT和金属复合材料10沿着它们的面16和/或18连接在一起。此外，CNT和金属复合材料10可以以端对端的方位结合(未显示)。而且，任何数量的CNT和金属复合材料10可连接在一起以形成具有任何期望长度、宽度和/或厚度的整体CNT和金属复合材料带20。在该示例性实施方式中，CNT和金属复合材料10是通过超声波焊接方法结合在一起的。可选地，CNT和金属复合材料10通过超声波增材制造(UAM)方法结合在一起，该方法顺序地将图案化金属层连接在一起以生产具有复杂内部空腔的网形产品。
图3图解了制备整体CNT和金属复合材料带20的示例性方法100。方法100包括102从多个单壁碳纳米管(SWCNT)和/或多壁碳纳米管(MWCNT)形成多个CNT材料层12。在该示例性实施方式中，CNT材料层12是无纺片或纱。该方法进一步包括104在CNT材料层12的一个或多个面16和18上沉积金属膜14以形成整体CNT和金属复合材料10。在该示例性实施方式中，金属膜14通过化学气相沉积、化学镀膜法、溅射和物理气相沉积方法中的至少一种沉积。该方法也包括106将多个整体CNT和金属复合材料10连接在一起以形成整体CNT和金属复合材料带20。在该示例性实施方式中，整体CNT和金属复合材料10通过超声波焊接和超声波增材制造方法的至少一种连接在一起。
实施例
在一个实施例中，整体CNT材料层12的无纺片由具有直径在大约2nm至大约5nm之间的单个SWCNT、具有直径在大约20nm至大约50nm之间的单个MWCNT、或二者的结合制备。每个整体CNT层12形成具有在大约20μm至大约100μm之间的横截面厚度。整体CNT和金属复合材料10通过用大约(0.3μm)的金属材料涂布整体CNT层12的每面16和18形成。例如，在该示例性实施方式中，金属材料例如铝、铜、镍、钛、银、金或铬或者其任意结合可以用于形成金属复合材料10。可选地，可使用使金属复合材料10能够如本文所述起作用的任何金属材料。将产生的整体CNT和金属复合材料10通过超声波焊接方法连接在一起以形成整体CNT和金属复合材料带20。超声波焊接方法促进减少在复合材料10内的空间(openspace)并且减少每个整体CNT和金属复合材料的厚度大约20％。因此，整体CNT和金属复合材料10具有降低的在单个CNT之间的电阻以及降低的电阻。在该实施例中，整体CNT和金属复合材料带20制备为具有粗略测量1cm宽、10cm长的尺寸并且是一个至几个复合材料10厚。
如本文所述，整体CNT和金属复合材料制备为具有优于其他材料如铜和铝的增加的比电导率。另外，复合材料展现出高电导率、高导热性和高机械强度。用以上技术形成的整体CNT复合材料减少了单个CNT之间的接触电阻并且减少了每个整体CNT和金属复合材料内的空间。进一步地，将多个整体CNT和金属复合材料连接，形成高强度、高度导电的整体CNT和金属复合材料带。具有优越性质的整体CNT复合材料使其对于应用例如EMI屏蔽、输电线路的导线、航天器线束和电动机是理想的。
在条款A1-B15中描述了根据本公开的发明主题的说明性的、非排他性的实施例：
A1.整体碳纳米管和金属复合材料10，其包括：
含有多个碳纳米管的整体碳纳米管材料层12；和
施加在所述整体碳纳米管材料层12上的金属膜14，所述金属膜14渗透进入单个碳纳米管之间的空隙以减少所述多个碳纳米管之间的电阻。
A2.根据条款A1所述的复合材料10，其中所述多个碳纳米管的至少一部分是金属碳纳米管。
A3.根据条款A1-A2任一项所述的复合材料10，其中所述多个碳纳米管包括单壁碳纳米管和多壁碳纳米管的至少一种。
A4.根据条款A1-A3任一项所述的复合材料10，其中所述整体碳纳米管材料层12是无纺片和纱的至少一种。
A5.根据条款A1-A4任一项所述的复合材料10，其中所述金属膜14采用化学气相沉积方法、化学镀膜方法、溅射方法和物理气相沉积方法的至少一种施加在所述整体碳纳米管材料层12上。
A6.根据条款A1-A5任一项所述的复合材料10，其中所述金属膜14包括铝、镍、铜、钛、银、金和铬的至少一种。
A7.根据条款A1-A6任一项所述的复合材料10，包括：
连接至第二整体碳纳米管和金属复合材料10的第一整体碳纳米管和金属复合材料10以形成整体碳纳米管和金属复合材料带20。
B8.制备整体碳纳米管和金属复合材料10的方法100，所述方法100包括：
102形成包含多个碳纳米管的第一整体碳纳米管材料层12；以及
104在整体碳纳米管材料层12上沉积金属膜14，所述金属膜14渗透进入单个碳纳米管之间的空隙以减少多个碳纳米管之间的电阻。
B9.根据条款B8所述的方法100，进一步包括制备第二整体碳纳米管和金属复合材料10，以及106连接第二整体碳纳米管和金属复合材料10至第一整体碳纳米管和金属复合材料10以形成整体碳纳米管和金属复合材料带20。
B10.根据条款B9所述的方法100，进一步包括利用超声波焊接方法和超声波增材制造方法的至少一种连接第二整体碳纳米管和金属复合材料10至第一整体碳纳米管和金属复合材料10。
B11.根据条款B8-B10任一项所述的方法100，其中形成第一整体碳纳米管材料层12包括使用金属碳纳米管形成所述层12的至少一部分。
B12.根据条款B8-B11任一项所述的方法100，其中形成所述第一整体碳纳米管材料层12包括使用单壁碳纳米管和多壁碳纳米管的至少一种形成所述层12的至少一部分。
B13.根据条款B8-B12任一项所述的方法100，其中形成第一整体碳纳米管材料层12包括使用无纺片和纱的至少一种形成所述层12的至少一部分。
B14.根据条款B8-B13任一项所述的方法100，其中沉积金属膜14包括利用化学气相沉积方法、化学镀膜方法、溅射方法和物理气相沉积方法的至少一种将金属膜14施加在所述整体碳纳米管材料层12上。
B15.根据条款B8-B14任一项所述的方法100，其中沉积金属膜14包括将铝、镍、铜、钛、银、金和铬的至少一种施加在整体碳纳米管材料层12上。
该书面描述利用实施例以公开各种实施方式，包括最佳方式，并且还使本领域任何技术人员能够实行这些实施方式，包括制造和使用任何设备或系统以及实施任何结合的方法。专利性范围由权利要求书限定，并且可包括本领域技术人员想到的其他实施例。如果这些其他实施例具有不与权利要求书字面语言不同的结构部件，或者如果它们包括与权利要求书的字面语言无实质差异的等效结构部件，则它们将在权利要求书的范围内。

Claims (6)

1.整体碳纳米管和金属复合材料带(20)，其至少包括连接至第二整体碳纳米管和金属复合材料(10)的第一整体碳纳米管和金属复合材料(10)，所述第一整体碳纳米管和金属复合材料以及所述第二整体碳纳米管和金属复合材料包括：
含有多个碳纳米管的整体碳纳米管材料层(12)；和
施加在所述整体碳纳米管材料层(12)上的金属膜(14)，所述金属膜(14)渗透进入单个碳纳米管之间的空隙以减少所述多个碳纳米管之间的电阻，其中所述整体碳纳米管材料层(12)是无纺片和纱的至少一种，并且其中至少一部分所述多个碳纳米管未被所述金属膜覆盖，并且
其中利用超声波焊接方法和超声波增材制造方法的至少一种连接所述第二整体碳纳米管和金属复合材料(10)至所述第一整体碳纳米管和金属复合材料(10)。
2.根据权利要求1所述的整体碳纳米管和金属复合材料带(20)，其中所述多个碳纳米管的至少一部分是金属碳纳米管。
3.根据权利要求1所述的整体碳纳米管和金属复合材料带(20)，其中所述多个碳纳米管包括单壁碳纳米管和多壁碳纳米管的至少一种。
4.制备整体碳纳米管和金属复合材料带(20)的方法(100)，所述整体碳纳米管和金属复合材料带(20)至少包括连接至第二整体碳纳米管和金属复合材料(10)的第一整体碳纳米管和金属复合材料(10)，所述第一整体碳纳米管和金属复合材料以及所述第二整体碳纳米管和金属复合材料通过如下步骤形成：
(102)形成包含多个碳纳米管的第一整体碳纳米管材料层(12)；以及
(104)在所述整体碳纳米管材料层(12)上沉积金属膜(14)，所述金属膜(14)渗透进入单个碳纳米管之间的空隙以减少所述多个碳纳米管之间的电阻，其中所述整体碳纳米管材料层(12)是无纺片和纱的至少一种，并且其中至少一部分所述多个碳纳米管未被所述金属膜覆盖，
所述方法包括利用超声波焊接方法和超声波增材制造方法的至少一种连接所述第二整体碳纳米管和金属复合材料(10)至所述第一整体碳纳米管和金属复合材料(10)以形成所述整体碳纳米管和金属复合材料带(20)。
5.根据权利要求4所述的制备整体碳纳米管和金属复合材料带(20)的方法(100)，其中沉积所述金属膜(14)包括利用化学气相沉积方法、化学镀膜方法、溅射方法和物理气相沉积方法的至少一种将所述金属膜(14)施加在所述整体碳纳米管材料层(12)上。
6.根据权利要求4所述的制备整体碳纳米管和金属复合材料带(20)的方法(100)，其中沉积所述金属膜(14)包括将铝、镍、铜、钛、银、金和铬的至少一种施加在所述整体碳纳米管材料层(12)上。
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