WO2021102931A1 - 一种增加氧化石墨烯宏观组装材料塑性的方法 - Google Patents

一种增加氧化石墨烯宏观组装材料塑性的方法 Download PDF

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WO2021102931A1
WO2021102931A1 PCT/CN2019/122041 CN2019122041W WO2021102931A1 WO 2021102931 A1 WO2021102931 A1 WO 2021102931A1 CN 2019122041 W CN2019122041 W CN 2019122041W WO 2021102931 A1 WO2021102931 A1 WO 2021102931A1
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graphene oxide
macroscopic assembly
macroscopic
plasticity
plasticizer
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PCT/CN2019/122041
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French (fr)
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高超
李鹏
许震
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浙江大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide

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  • the invention relates to the field of nanomaterials, in particular to a method for increasing the plasticity of graphene oxide macroscopic assembly materials, and belongs to a method for subsequent plasticization on the basis of existing graphene oxide macroscopic assembly materials.
  • the purpose of the present invention is to provide a method for increasing the plasticity of graphene oxide macroscopic assembly materials, so as to overcome the problem of insufficient plasticity of graphene macroscopic materials in the prior art.
  • the present invention adopts the following technical scheme: a method for increasing the plasticity of the graphene oxide macroscopic assembly material, the method is: the graphene oxide macroscopic assembly material is immersed in a plasticizer, and the plasticizer fully penetrates the graphene oxide macroscopic material layer In the meantime, the interval between the graphene oxide sheets reaches 1.1-1.8 nm.
  • the plasticizer is a single solvent or a mixture of multiple solvents with a polarity parameter between 0.3 and 0.75. After plasticizer intercalation, the interlayer spacing of graphene oxide will gradually increase. As the layer spacing increases, the interaction between layers decreases, and the macroscopic material begins to show plastic deformation.
  • the layer spacing is in the range of 1.1-1.8nm, the plastic deformation reaches the highest value, and the elongation at break can reach 34%; The layer spacing continues to increase, and the interaction between the layers is too weak, resulting in slippage between the graphene oxide layers, showing a lower elongation at break.
  • the plasticization is uniform, and the layer spacing after plasticization is uniform.
  • the layer spacing can be obtained by dividing the total thickness by the number of layers and the X-ray diffraction method.
  • the layer spacing can be adjusted by adjusting the type of plasticizer.
  • the plasticizing effect is optimal.
  • the plasticizer is ethanol, acetone, isopropanol, acetic acid, ethyl acetate, methanol, water, glycerol, propylene glycol, ethylene glycol, triethylene glycol, tetraethylene glycol, and five ethylene glycol.
  • the graphene oxide macroscopic assembly material can be graphene oxide fiber, graphene oxide film, graphene oxide ribbon fiber, graphene oxide non-woven fabric, graphene oxide aerogel, etc.
  • the form of graphene oxide macroscopic assembly material can be graphene oxide fiber, graphene oxide film, graphene oxide ribbon fiber, graphene oxide non-woven fabric, graphene oxide aerogel, etc. The form of graphene oxide macroscopic assembly material.
  • the graphene oxide macroscopic assembly material is obtained by selecting large pieces of graphene oxide to assemble, so as to further improve the plasticity. Macroscopic materials constructed using large-size graphene oxide can exhibit greater plastic deformation capabilities.
  • the beneficial effect of the present invention is that: the present invention uses a plasticizer, inserts the plasticizer between the layers of graphene oxide, weakens the interaction between the layers of graphene oxide, and makes the macroscopic graphene oxide products exhibit plastic deformation.
  • the content of the plasticizer inserted between the layers can change the layer spacing of the graphene oxide macro material, and then adjust the plastic deformation ability of the graphene oxide macro material.
  • the larger the graphene oxide sheet is to construct the macroscopic material the greater the ability of plastic deformation can be shown.
  • Figure 1 shows the mechanical curves of the fibers obtained in Example 1 before and after plasticization.
  • Figure 2 shows the plastic deformation ability of the macroscopic material obtained by plasticizing graphene oxide films composed of graphene oxide sheets of different sizes.
  • Graphene oxide macro-fiber material is prepared by liquid crystal wet spinning
  • the plasticized graphene oxide fiber has a breaking elongation of 34% and a plastic deformation interval close to 31%. This obvious plastic deformation makes the graphene oxide macroscopic material more likely to be processed into different forms of products. Highly oriented and high-strength graphene fibers can be obtained by subsequent stretching, which is a simple and reliable plasticizing method.
  • others include ethanol, acetone, isopropanol, acetic acid, ethyl acetate, methanol, water, glycerol, propylene glycol, ethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, Hydrochloric acid, organic amines, etc. or their mixed plasticizers, as long as the polarity parameter is between 0.3 and 0.75, by simply controlling the plasticizing time, the graphene macroscopic material can be plasticized, and the elongation at break can reach 34%.
  • the graphene oxide macroscopic membrane material is prepared by coating and drying
  • the obtained plasticized graphene oxide macroscopic film material has an elongation at break of 18%.
  • the graphene oxide macroscopic ribbon fiber material also known as graphene oxide ribbon, is prepared by liquid crystal wet spinning;
  • the obtained plasticized graphene oxide macroscopic tape has an elongation at break of 13%.
  • a graphene oxide sheet with a size of 100.7um is used to prepare a graphene oxide macroscopic membrane material by spreading and drying;
  • a graphene oxide sheet with a size of 15.8um is used to prepare the graphene oxide macroscopic membrane material by spreading and drying;

Abstract

本发明公开了一种增加氧化石墨烯宏观组装材料塑性的方法，是一种对氧化石墨烯制品，如氧化石墨烯膜，氧化石墨烯纤维，氧化石墨烯带子以及氧化石墨烯气凝胶增塑的一种有效手段，该方法如下：将氧化石墨烯气凝胶等宏观组装材料，放置于塑化剂中浸泡，使得宏观材料中插层适量塑化剂，塑化剂的插层使得氧化石墨烯片间距增加，当层间距增加至1.1-1.8nm之间时，氧化石墨烯的宏观组装材料便展现出极大的塑性变形的能力。本发明是一种增加氧化石墨烯宏观组装材料塑性的方法，简单可控，实用性极强。

Description

一种增加氧化石墨烯宏观组装材料塑性的方法 技术领域
本发明涉及纳米材料领域，特别是一种增加氧化石墨烯宏观组装材料塑性的方法，属于在现有氧化石墨烯宏观组装材料的基础上，进行后续塑化的方法。
背景技术
2004年，英国曼彻斯特大学A.K.Geim教授课题组运用机械剥离法成功制备石墨烯，并将其悬挂于微型金架上，推翻了完美二维晶体结构无法在非绝对零度下稳定存在的这一论断。换言之，自由态的石墨烯在室温下可以稳定存在；而在相同条件下，其他任何己知材料都会被氧化或分解，甚至在相当于其单层厚度10倍时就变得不稳定。从结构上说，石墨烯(Graphene)是紧密堆积成二维蜂窝状晶格结构的sp2杂化单层碳原子晶体，层内碳原子以共价键的形式连接，具有超高的强度(120GPa)，因此以石墨烯作为源头材料构建特定结构的碳基材料，从而实现碳质功能材料纳米结构的设计和可控以及宏量地制备已经逐渐引起全球科学家的关注。但是这种二维片状分子具有的无机特性，使得其宏观组装材料表现出极强的脆性，如石墨纤维断裂伸长率仅有不足1％，K1100的模量甚至超过1000GPa。
目前来看，类似于传统无机材料，如陶瓷，石墨烯宏观材料作为一种二维无机材料，仍然保留着很大程度的脆性，这种本质的脆性使得材料加工成为困难。高分子和金属作为当今社会使用最为广泛的材料，很大程度上是因为其塑性变形，正是塑性变形的存在使得材料具有很大潜力被加工成各种制品。因此，今后石墨烯宏观材料若要应用在社会中，对其增塑有着十分重大的意义。
发明内容
本发明的目的在于提供一种增加氧化石墨烯宏观组装材料塑性的方法，以克服现有技术中石墨烯宏观材料塑性不足的问题。
本发明采用以下技术方案：一种增加氧化石墨烯宏观组装材料塑性的方法，该方法为：将氧化石墨烯宏观组装材料浸泡于塑化剂中，塑化剂充分渗透入氧化石墨烯宏观材料层间，使氧化石墨烯片层间的间距达到1.1-1.8nm。所述塑化剂为极性参数为0.3-0.75之间的单一溶剂或多种溶剂混合液。经过塑化剂插层，氧化石墨烯的层间距会逐渐增加。随着层间距的增加，层间相互作用减少，宏观材料开始表现出塑性变形，当层间距在1.1-1.8nm的范围内时，塑性变形达到最高值，断裂伸长率可达34％；当层间距继续增加，由于层间相互作用太弱， 导致氧化石墨烯层之间发生滑移，表现出较低的断裂伸长率。
上述方法中，由于浸泡过程的均匀性，塑化作用均匀，塑化后层间距均匀，层间距可以通过总厚度除以层数以及X射线衍射方法来获得。
上述方法中，可以通过调控塑化剂的种类来调控上述层间距。塑化剂极性参数越大，塑化剂与GO相亲性越好，层间距越大。在层间距为1.1-1.8nm之间时，塑化作用达到最佳。
进一步地，所述塑化剂为乙醇、丙酮、异丙醇、乙酸、乙酸乙酯、甲醇、水、丙三醇、丙二醇、乙二醇、三乙二醇、四乙二醇、五乙二醇、盐酸、有机胺、聚乙二醇、聚乙烯醇中的一种或多种组成的混合物。
进一步地，所述步骤1中，氧化石墨烯宏观组装材料可以是氧化石墨烯纤维，氧化石墨烯薄膜、氧化石墨烯带状纤维，氧化石墨烯无纺布以及氧化石墨烯气凝胶等各种形式的氧化石墨烯宏观组装材料。
进一步地，通过选择大片的氧化石墨烯组装得到所述氧化石墨烯宏观组装材料，来进一步提高塑性。使用大尺寸氧化石墨烯构筑的宏观材料可以表现出更大的塑性变形能力。
本发明的有益效果在于：本发明使用塑化剂，将塑化剂插入到氧化石墨烯的层间，减弱氧化石墨烯层间的相互作用，使得氧化石墨烯宏观制品表现出塑性变形，通过控制塑化剂插入层间的含量，可以改变氧化石墨烯宏观材料的层间距，进而调节氧化石墨烯宏观材料的塑性变形能力。同时越大的氧化石墨烯片构筑的宏观材料，能表现出更大的塑性变形的能力。
附图说明
图1为实施例1得到的增塑前后纤维的力学曲线。
图2为不同尺寸的氧化石墨烯片构成的氧化石墨烯膜经塑化处理后得到的宏观材料表现出的塑性变形的能力。
具体实施方式
实施例1
(1)通过液晶湿法纺丝制备得到氧化石墨烯宏观纤维材料；
(2)将氧化石墨烯宏观纤维浸泡于乙酸中，使乙酸充分渗透入氧化石墨烯宏观材料层间，此时氧化石墨烯纤维的层间距为1.4nm；
(3)得到的增塑的氧化石墨烯宏观纤维。
增塑后的氧化石墨烯纤维具有34％的断裂伸长率，接近31％的塑性变形区 间，这种明显的塑性变形使得氧化石墨烯宏观材料具有更多可能被加工成不同形式的制品，也可以通过后续拉伸的方式得到高度取向高强度的石墨烯纤维，是一种简单可靠的增塑方法。
另外，经测试，其他包括乙醇、丙酮、异丙醇、乙酸、乙酸乙酯、甲醇、水、丙三醇、丙二醇、乙二醇、三乙二醇、四乙二醇、五乙二醇、盐酸、有机胺等或其混合塑化剂，只要极性参数为0.3-0.75之间，通过简单的控制塑化时间，均可使得石墨烯宏观材料塑化，断裂伸长率可达34％。
同时其他插入层间的高分子，小分子，只要满足层间距在1.1-1.8nm之间，均可以表现出增塑的效果。
实施例2
(1)通过铺膜干燥的方式制备得到氧化石墨烯宏观膜材料；
(2)将氧化石墨烯宏观膜浸泡于乙二醇中，使乙二醇充分渗透入氧化石墨烯膜层间，此时氧化石墨烯膜的层间距为1.8nm；
(3)得到的增塑的氧化石墨烯宏观膜材料，具有18％的断裂伸长率。
实施例3
(1)通过液晶湿法纺丝制备得到氧化石墨烯宏观带状纤维材料，亦称氧化石墨烯带子；
(2)将氧化石墨烯带子浸泡于丙酮中，使丙酮充分渗透入氧化石墨烯宏观材料层间，此时氧化石墨烯纤维的层间距为1.1nm；
(3)得到的增塑的氧化石墨烯宏观带子，具有13％的断裂伸长率。
实施例4
(1)采用尺寸为100.7um的氧化石墨烯片，通过铺膜干燥的方式制备得到氧化石墨烯宏观膜材料；
(2)将氧化石墨烯宏观膜浸泡于不同塑化剂中，使塑化剂充分渗透入氧化石墨烯膜层间，得到不同层间距的氧化石墨烯膜，响应的，不同层间距的氧化石墨烯膜的断裂伸长率见图2。
实施例5
(1)采用尺寸为15.8um的氧化石墨烯片，通过铺膜干燥的方式制备得到氧化石墨烯宏观膜材料；
(2)将氧化石墨烯宏观膜浸泡于不同塑化剂中，使塑化剂充分渗透入氧化石墨烯膜层间，得到不同层间距的氧化石墨烯膜，响应的，不同层间距的氧化石墨烯膜的断裂伸长率见图2。

Claims (4)

  1. 一种增加氧化石墨烯宏观组装材料塑性的方法，其特征在于，该方法为：将氧化石墨烯宏观组装材料浸泡于塑化剂中，塑化剂充分渗透入氧化石墨烯宏观材料层间，使氧化石墨烯片层间的间距达到1.1-1.8nm。所述塑化剂为极性参数为0.3-0.75之间的单一溶剂或多种溶剂混合液。
  2. 根据权利要求1所述的增加氧化石墨烯宏观组装材料塑性的方法，其特征在于，所述塑化剂为乙醇、丙酮、异丙醇、乙酸、乙酸乙酯、甲醇、水、丙三醇、丙二醇、乙二醇、三乙二醇、四乙二醇、五乙二醇、盐酸、有机胺、聚乙二醇、聚乙烯醇中的一种或多种组成的混合物。
  3. 根据权利要求1所述的增加氧化石墨烯宏观组装材料塑性的方法，其特征在于，所述步骤1中，氧化石墨烯宏观组装材料可以是氧化石墨烯纤维，氧化石墨烯薄膜、氧化石墨烯带状纤维，氧化石墨烯无纺布以及氧化石墨烯气凝胶等各种形式的氧化石墨烯宏观组装材料。
  4. 根据权利要求1所述的增加氧化石墨烯宏观组装材料塑性的方法，其特征在于，通过选择大片的氧化石墨烯组装得到所述氧化石墨烯宏观组装材料，来进一步提高塑性。
PCT/CN2019/122041 2019-11-29 2019-11-29 一种增加氧化石墨烯宏观组装材料塑性的方法 WO2021102931A1 (zh)

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CN110316725A (zh) * 2019-07-23 2019-10-11 浙江大学 一种高密度高强度石墨烯框架材料及其制备方法

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US20180144843A1 (en) * 2012-11-02 2018-05-24 Nanotek Instruments, Inc. Graphene oxide-coated graphitic foil and processes for producing same
CN109311053A (zh) * 2016-06-07 2019-02-05 纳米技术仪器公司 用于碱金属电池的基于石墨烯-金属混杂泡沫的电极
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