CN109019563B - 多孔金属复合结构 - Google Patents
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Abstract
本发明涉及一种多孔金属复合结构，包括多孔金属结构和一个碳纳米管结构，该碳纳米管结构固定在所述多孔金属结构的表面，所述碳纳米管结构包括多根碳纳米管，所述多孔金属复合结构包括多个褶皱部。
Description
技术领域
本发明涉及一种多孔金属复合结构。
背景技术
近年来，纳米多孔金属材料在拥有高比表面积、比模量等特性的同时，还兼具金属材料的高导热率、高导电率等优异性能，从而在生物传感、催化、、能量转化与存储、消音吸振、屏蔽、热交换、电化学等领域中有着广阔的应用前景。
然而，如图1所示，现有的皱缩的纳米多孔金属材料中，纳米多孔金属存在韧带连接不完整等现象，因此，该皱缩的纳米多孔金属材料的韧性不好，容易发生脆断，从而影响该皱缩的纳米多孔金属材料的应用。
发明内容
有鉴于此，确有必要提供一种韧性较好的多孔金属复合结构。
一种多孔金属复合结构，包括多孔金属结构和一个碳纳米管结构，该碳纳米管结构固定在所述多孔金属结构的表面，所述碳纳米管结构包括多根碳纳米管，所述多孔金属复合结构包括多个褶皱部。
与现有技术相比较，本发明提供的多孔金属复合结构中碳纳米管固定于所述多孔金属结构的表面，且由于碳纳米管具有良好的韧性，因此所述多孔金属复合结构具有良好的韧性，发生皱缩时不容易脆断。
附图说明
图1是现有技术中褶皱的纳米多孔金膜在高倍镜下的扫描电镜图。
图2是本发明实施例提供的多孔金属复合结构在低倍镜下的扫描电镜图。
图3是本发明实施例提供的多孔金属复合结构在高倍镜下的扫描电镜图。
图4是本发明实施例提供的多孔金属复合结构的扫描电镜图。
图5是本发明实施例图3中褶皱部的结构示意图。
图6是本发明实施例提供的多孔金属复合结构制备方法的流程示意图。
图7是本发明实施例提供的多孔金属复合结构中纳米多孔金膜的扫描电镜表征图。
图8是本发明实施例提供的多孔金属复合结构中第二复合结构的扫描电镜表征图。
图9是本发明实施例提供的多孔金属复合结构中第二复合结构的扫描电镜图。
具体实施方式
以下将结合附图及具体实施例，对本发明提供的多孔金属复合结构及其制备方法作进一步详细说明。
请参阅图2及图3，本发明实施例提供一种多孔金属复合结构，该多孔金属复合结构包括多孔金属结构和一个碳纳米管结构，该碳纳米管结构固定在所述多孔金属结构的表面，所述碳纳米管结构包括多根碳纳米管，所述多孔金属复合结构包括多个褶皱部。
所述多孔金属结构可以为多孔金属膜、多孔金属纳米片等任意结构。所述多孔金属结构呈三维网状，所述多孔金属结构包括多个韧带，该多个韧带之间形成多个孔，所述多个孔可以呈规则分布，如三维双连续网络形式分布，也可以呈不规则分布。所述韧带的材料为金、银、铂中的任意一种。该多个孔的孔径为纳米级，优选的，所述多个孔的孔径小于1000nm。
所述碳纳米管结构可以通过一连接材料固定于所述多孔金属结构表面。具体地，所述碳纳米管结构中的碳纳米管与所述多孔金属结构中的韧带接触形成多个接触面，该接触面周围设置有连接材料，使碳纳米管结构不容易脱离多孔金属结构的表面。优选的，所述连接材料将所述接触面包裹住。所述连接材料可以为有机粘结材料或金属材料。所述有机粘结材料可以为萘酚等具有粘结作用的材料，所述金属材料可以为Au、Ag、Cu等。优选的，所述金属材料与所述多孔金属结构的材料相同，减小金属材料与多孔金属结构中韧带的接触电阻。
请参阅图4及图5，所述多个褶皱部100相互连接形成一连续结构。该褶皱部100由多孔金属结构110和碳纳米管结构120共同弯折构成。这一点也可以从上述图3中看出。在所述褶皱部100处，碳纳米管结构120的褶皱处的碳纳米管可以沿同一方向延伸。具体的，碳纳米管之间通过范德华力首尾相连且沿同一方向排列。可以理解，碳纳米管结构的排列方向也可以不限。
所述褶皱部为不可逆转的变形。由于碳纳米管具有良好的韧性，碳纳米管横穿所述褶皱部，起到加固所述褶皱部的作用，碳纳米管结构与所述多孔金属结构固定形成的多孔金属复合结构具有良好的韧性，褶皱部不容易发生断裂，该多孔金属复合结构具备自支持的性能。
请参阅图6，本发明实施例进一步提供一种多孔金属复合结构的制备方法，其包括以下步骤:
步骤S20，提供一基板；
该基板的材料选择受热能够收缩的材料。优选的，所述基板为塑料板，该塑料板的材料为聚苯乙烯、聚丙烯、聚对苯二甲醇乙二酯等。本实施例中，该塑料板的材料为聚苯乙烯。
步骤S30，在所述基板的表面固定多孔金属结构，形成第一复合结构；
所述固定的方法不限，在某个实施例中，可以通过加热所述基板，使基板稍微熔化从而粘住所述多孔金属结构，优选的，将基板与多孔金属结构在80℃的温度下加热30min～60min；在另外一个实施例中，通过在所述基板与所述多孔金属结构的接触面周围生长金属，具体的，将所述第一复合结构转移到含有Au+、Ag+、Cu+等任意一种金属离子溶液中，在所述含有金属离子的溶液中添加还原剂形成金属颗粒，该金属颗粒通过化学镀的方式沉积在所述多孔金属结构中韧带与碳纳米管结构中碳纳米管的接触处周围，从而使多孔金属结构固定在基板的表面。本实施例中，将基板与多孔金属结构在80℃的温度下加热30min，加热过程中所述基板的表面稍微发生熔融，多孔金属结构粘合在所述基板的表面。
所述多孔金属结构的获取方法不限，可以为目前市场上售卖的各种多孔金属，也可以自行制备。本实施例中，所述多孔金属结构为纳米多孔金膜，该纳米多孔金膜通过化学腐蚀的方法制备得到，具体方法如下：
S31，提供一Au-Ag合金薄膜。
该Au-Ag合金薄膜为表面光滑的薄膜材料，具有银白色的光泽，其厚度范围为50nm-200nm。该Au-Ag合金薄膜的尺寸不限，可以根据需要任意选择。本实施例中，所述Au-Ag合金薄膜的厚度为100nm，该Au-Ag合金薄膜中所述金原子的百分比为35％，银的原子百分比为65％。
S32，将所述Au-Ag合金薄膜放置于浓硝酸溶液中，直到该Au-Ag合金薄膜由银白色变成棕红色，形成纳米多孔金膜。
所述浓硝酸的浓度范围可为50％-80％。通过玻璃片静电吸附将该Au-Ag合金薄膜转移到所述浓硝酸溶液中。本实施例中，所述浓硝酸的浓度为70％。所述Au-Ag合金中的Ag与浓硝酸进行反应，当Ag与浓硝酸反应完全后，所述Au-Ag合金薄膜变成棕红色，此时，所述Au-Ag合金薄膜的表面形成多个不规则的孔，从而形成纳米多孔金膜。
请参阅图7，所述纳米多孔金膜具有多个孔，多个孔之间通过韧带连接，该多个孔的孔径及韧带尺寸与所述Au-Ag合金薄膜腐蚀的时间、浓硝酸浓度等因素有关。
S33，将所述纳米多孔金膜放置于去离子水中进行清洗。
采用玻璃片将所述形成的纳米多孔金膜转移到去离子水中浸泡清洗，在浸泡过程中不断更换去离子水，使残留在所述米多孔金膜韧带上的硝酸彻底清洗掉。
步骤S40，在所述第一复合结构中多孔金属结构的表面固定一个碳纳米管结构，形成第二复合结构；
请参阅图8及图9，所述碳纳米管结构可以机械平铺在所述多孔金属结构的表面，该碳纳米管结构可以为线状结构，如碳纳米管线，或可以为一碳纳米管膜状结构。
所述碳纳米管线可以为一条或多条，当所述碳纳米管线为多条时，该多条碳纳米管线可以并排设置成束状结构，也可以交叉设置成网状结构，或者将该多条碳纳米管线相互扭转形成一相互缠绕的绞线结构。
所述碳纳米管线可以为一非扭转的碳纳米管线或扭转的碳纳米管线。
该非扭转的碳纳米管线包括多个沿该非扭转的碳纳米管线长度方向排列的碳纳米管,该多个碳纳米管基本相互平行，且该碳纳米管的轴向基本平行于该碳纳米管线的长度方向。具体地，该非扭转的碳纳米管线中的沿非扭转碳纳米管线轴向上的相邻的碳纳米管通过范德华力首尾相连。该非扭转的碳纳米管线长度不限，直径为0.5纳米～100微米。进一步地，该非扭转的碳纳米管线可以用有机溶剂处理。
所述扭转的碳纳米管线包括多个绕该扭转的碳纳米管线轴向螺旋排列的碳纳米管。该扭转的碳纳米管线可采用一机械力将所述非扭转的碳纳米管线两端沿相反方向扭转获得。
上述扭转的碳纳米管线和非扭转的碳纳米管线均由于其中的碳纳米管之间通过范德华力紧密结合而使得该扭转的碳纳米管线和非扭转的碳纳米管线均具有自支撑结构。所述自支撑为碳纳米管线不需要大面积的载体支撑，而只要相对两边提供支撑力即能整体上悬空而保持自身线状状态，即将该碳纳米管线置于(或固定于)间隔一定距离设置的两个支撑体上时，位于两个支撑体之间的碳纳米管线能够悬空保持自身线状状态。
所述碳纳米管膜状结构可以为碳纳米管拉膜、碳纳米管絮化膜或碳纳米管碾压膜中任意一种膜状结。两种以上膜状结构的组合。当该碳纳米管膜状结构为两种以上膜状结构，该两种以上膜状结构可以为共面设置或层叠设置，当该两种以上膜状结构层叠设置时，相邻两层碳纳米管膜状结构中碳纳米管之间的夹角可以为0°≤α≤90°。
所述碳纳米管拉膜可以为一层或多层，当碳纳米管拉膜为多层时，该多层碳纳米管拉膜可以为共面设置或层叠设置。本实施例中，所述碳纳米管结构为碳纳米管拉膜，由于该碳纳米管拉膜中的碳纳米管通过范德华力首尾相连且沿同一方向延伸，能够减小所述多孔金属复合结构的内部阻抗，提高其导电性。
所述碳纳米管拉膜为由若干碳纳米管组成的自支撑结构。所述若干碳纳米管基本沿同一方向择优取向排列，所述择优取向排列是指在碳纳米管拉膜中大多数碳纳米管的整体延伸方向基本朝同一方向。而且，所述大多数碳纳米管的整体延伸方向基本平行于碳纳米管拉膜的表面。进一步地，所述碳纳米管拉膜中大多数碳纳米管是通过范德华力首尾相连。具体地，所述碳纳米管拉膜中基本朝同一方向延伸的大多数碳纳米管中每一碳纳米管与在延伸方向上相邻的碳纳米管通过范德华力首尾相连。当然，所述碳纳米管拉膜中存在少数随机排列的碳纳米管，这些碳纳米管不会对碳纳米管拉膜中大多数碳纳米管的整体取向排列构成明显影响。
所述碳纳米管碾压膜可以为一层或多层，当碳纳米管碾压膜为多层时，该多层碳纳米管碾压膜可以为共面设置或层叠设置。
所述碳纳米管碾压膜包括均匀分布的碳纳米管，该碳纳米管无序，沿同一方向或不同方向择优取向排列。优选地，所述碳纳米管碾压膜中的碳纳米管基本沿同一方向延伸且平行于该碳纳米管碾压膜的表面。所述碳纳米管碾压膜中的碳纳米管相互交叠，从而使所述碳纳米管碾压膜的表面较为粗糙。所述碳纳米管碾压膜中碳纳米管之间通过范德华力相互吸引并形成多个间隙。该碳纳米管碾压膜具有很好的柔韧性，可以弯曲折叠成任意形状而不破裂。所述碳纳米管絮化膜可以为一层或多层，当碳纳米管絮化膜为多层时，该多层碳纳米管絮化膜可以为共面设置或层叠设置。
所述碳纳米管絮化膜包括相互缠绕的碳纳米管。该碳纳米管之间通过范德华力相互吸引、缠绕形成网状结构，从而使所述碳纳米管絮化膜的表面较为粗糙。所述碳纳米管絮化膜中的碳纳米管为均匀分布，无规则排列。
所述固定碳纳米管结构的方法有两种：(一)通过有机粘结材料来固定：在所述第一复合结构中碳纳米管结构的表面滴加有机粘结材料，该有机粘结材料通过所述碳纳米管中的间隙进入所述多孔金属结构，该有机粘结材料将所述多孔金属结构和碳纳米管结构的接触面包裹住；(二)通过金属材料固定：将所述第二复合结构转移到含有Au+、Ag+、Cu+等任意一种金属离子溶液中，在所述含有金属离子的溶液中添加还原剂形成金属颗粒，该金属颗粒通过化学镀的方式沉积在所述多孔金属结构中韧带与碳纳米管结构中碳纳米管的接触处周围，从而使多孔金属结构和碳纳米管结构结合在一起。本实施例中，将第一复合结构转移到含有Au+溶液中，采用水合肼对Au+进行还原生成Au，生成的Au包裹所述韧带与碳纳米管的接触面周围。
步骤S50，使所述第二复合结构发生皱缩，形成一多孔金属复合结构。
该第二复合结构发生皱缩的方法不限，只要能够使所述基板、多孔金属结构及碳纳米管结构形成的第二复合结构发生褶皱即可。本实施例中，将所述第二复合结构在160℃的温度下加热2min，该基板发生皱缩，由于所述多孔金属结构固定在所述基板表面，碳纳米管结构固定在所述多孔金属结构表面，因此所述基板发生皱缩的过程中会带动所述多孔金属结构与所述碳纳米管膜一起发生皱缩，此时所述多孔金属结构不容易断裂，形成的多孔复合结构具有良好的韧性。
本发明实施例提供的多孔金属复合结构及其制备方法具有以下优点：其一，碳纳米管具有良好的韧性，提高了多孔金属复合结构的韧性，使多孔金属复合结构不容易发生脆断；其二，由于碳纳米管具有良好的导电性，从而提高了多孔金属复合结构的导电性。
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。
Claims (9)
1.一种多孔金属复合结构，包括多孔金属结构和一个碳纳米管结构，该碳纳米管结构固定在所述多孔金属结构的表面，所述碳纳米管结构包括多根碳纳米管，所述多孔金属复合结构包括多个褶皱部，所述褶皱部由多孔金属结构和碳纳米管结构共同弯折构成。
2.如权利要求1所述的多孔金属复合结构，其特征在于，所述褶皱部处的碳纳米管通过范德华力首尾相连且沿同一方向延伸。
3.如权利要求1所述的多孔金属复合结构，其特征在于，所述多个褶皱部相互连接形成一连续结构。
4.如权利要求1所述的多孔金属复合结构，其特征在于，所述多孔金属结构包括多个韧带，该多个韧带之间形成多个孔。
5.如权利要求4所述的多孔金属复合结构，其特征在于，所述韧带的材料为金、银、铂中的任意一种。
6.如权利要求1所述的多孔金属复合结构，其特征在于，所述多孔金属复合结构进一步包括一连接材料，该连接材料用于将碳纳米管结构固定在所述多孔金属结构的表面。
7.如权利要求6所述的多孔金属复合结构，其特征在于，所述连接材料包裹所述多孔金属结构与碳纳米管结构形成的接触面。
8.如权利要求6所述的多孔金属复合结构，其特征在于，所述连接材料为有机粘结材料或金属材料。
9.如权利要求1所述的多孔金属复合结构，其特征在于，所述碳纳米管结构包括多根沿同一方向延伸的碳纳米管。
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| US10919261B2 (en) | 2021-02-16 |
| TW201902693A (zh) | 2019-01-16 |
| JP6703041B2 (ja) | 2020-06-03 |
| JP2019002072A (ja) | 2019-01-10 |
| CN109019563A (zh) | 2018-12-18 |
| TWI644787B (zh) | 2018-12-21 |
| US20180354228A1 (en) | 2018-12-13 |
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