WO2023108378A1 - 具有特定截面形态特征的气凝胶纤维及其制备方法与装置 - Google Patents

具有特定截面形态特征的气凝胶纤维及其制备方法与装置 Download PDF

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WO2023108378A1
WO2023108378A1 PCT/CN2021/137642 CN2021137642W WO2023108378A1 WO 2023108378 A1 WO2023108378 A1 WO 2023108378A1 CN 2021137642 W CN2021137642 W CN 2021137642W WO 2023108378 A1 WO2023108378 A1 WO 2023108378A1
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fiber
graphene
graphene oxide
dimensional
nanosheets
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高超
李鹏
刘英军
许震
王子秋
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浙江大学
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Priority to US18/434,741 priority patent/US20240175169A1/en

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D13/00—Complete machines for producing artificial threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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    • D10B2101/00—Inorganic fibres
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    • D10B2401/00—Physical properties
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    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/16—Physical properties antistatic; conductive

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  • the invention relates to the field of nanomaterials, in particular to an airgel fiber with specific cross-sectional shape characteristics and a preparation method and device thereof.
  • Airgel fiber is an emerging material that combines the excellent properties of airgel and fiber. It refers to the gel fiber prepared by wet spinning through freeze-drying or normal pressure drying. Fiber varieties with high specific surface area and high porosity.
  • a two-dimensional sheet molecule is a molecule with a huge aspect ratio with a monoatomic layer thickness. Taking graphene as an example, it has extremely high tensile strength, Young's modulus, high electrical conductivity, and room temperature the highest thermal conductivity. In addition to typical high porosity and other characteristics, airgel fibers prepared with two-dimensional sheet-like molecules have more excellent mechanical-electrical-thermal properties.
  • the arrangement shape will also affect the effective transmission of electrons and phonons between the two-dimensional nanosheets with high electrical and thermal conductivity, and affect the conductivity of airgel fibers. Therefore, finding a strategy to effectively and precisely control the order of the two-dimensional sheet arrangement inside the airgel fiber has become a major research direction.
  • airgel fibers with specific cross-sectional morphological characteristics can be prepared, thereby promoting the practical application of airgel fibers.
  • the Gaochao Research Group of Zhejiang University invented a macroscopic graphene fiber with single-layer graphene as the assembly unit, creating a new way to prepare carbon fiber from natural graphite.
  • pure graphene fiber shows excellent characteristics in terms of thermal conductivity, which is much higher than that of traditional carbon fiber.
  • the mechanical properties of graphene fiber are mediocre.
  • its single-filament mechanical strength can reach 3.4GPa
  • its modulus has not yet reached Breaking through 400GPa is inconsistent with the law that the modulus and thermal conductivity of traditional carbon fibers are improved at the same time, that is, the thermal conductivity of graphene fibers far exceeds that of traditional carbon fibers, but its modulus is lower than that of traditional carbon fibers.
  • High thermal conductivity and high modulus are two key indicators for simultaneous improvement in traditional carbon fibers, and are usually closely related to the degree of orientation and density of fibers.
  • the orientation degree of graphene fibers can reach more than 90%.
  • graphene fibers are directly assembled from single-layer graphene. Ultimately determines the density of graphene fibers, so improving the order of the two-dimensional graphene sheet arrangement in graphene fibers will improve the density of graphene fibers, thereby preparing graphene fibers with high modulus and high thermal conductivity.
  • the present invention provides an airgel fiber with specific cross-sectional morphology and its preparation method and device, and obtains a graphene fiber with high modulus and high thermal conductivity.
  • This application is aimed at two-dimensional planar nanosheets. Based on the unique huge aspect ratio of two-dimensional planar nanosheets, it has a good lyotropic liquid crystal phenomenon; based on the unique macromolecules of two-dimensional planar nanosheets, it has the dynamic stability of liquid crystals.
  • a hydrogel fiber with a specific structure is formed. After the gel fiber is freeze-dried, an airgel fiber with a specific cross-sectional shape is obtained.
  • the primary graphene oxide fibers can be obtained after the hydrogel fibers are dried and densified, and the graphene oxide fibers with high modulus and high thermal conductivity can be obtained by plasticizing and stretching, chemical reduction and heat treatment. .
  • the airgel fiber with specific cross-sectional shape characteristics of the present invention is composed of two-dimensional nanosheets, and the fiber cross-section is arranged in concentric circular sheets or radial helical sheets.
  • the preparation method of the above-mentioned airgel fiber is: extruding the dispersion liquid of the two-dimensional nanosheet into the coagulation bath, and then fixing the structure after solidification to obtain the airgel fiber with specific cross-sectional shape characteristics; the extrusion speed includes The axial speed in the out direction and the circumferential rotational speed perpendicular to the axial speed.
  • circumferential velocity is brought about by introducing circumferential rotational shear force into the dispersion of two-dimensional nanosheets.
  • the two-dimensional nanosheets are graphene oxide, graphene, Mxene, molybdenum disulfide, montmorillonite nanosheets with two-dimensional anisotropy and various mixed two-dimensional nanosheets.
  • the concentration of the dispersion of the two-dimensional nanosheets is greater than 1 mg/g.
  • the present invention also relates to a device for preparing airgel fibers with specific cross-sectional morphological characteristics, at least including an extruding device, a coagulation bath and a freeze-drying system; the extruding device includes a spinning tube, and the spinning There is a circumferential rotational shear force inside the tube.
  • the rotor is located at the axial center of the spinning tube.
  • the rotor in the spinning tube rotates along its axis.
  • the present invention also provides a graphene fiber with high modulus and high thermal conductivity, which is composed of graphene two-dimensional nanosheets, and the cross section of the fiber is arranged in concentric circular sheets, and the two-dimensional graphene nanosheets are arranged along the axial direction.
  • the graphene sheets constitute a plurality of graphite crystals with an axial length of more than 200nm and a radial length of more than 100nm; the graphene fiber density is greater than or equal to 1.9g/cm 3 .
  • the present invention also relates to the preparation method of the above-mentioned graphene fiber, the method is: extruding the dispersion liquid of the graphene oxide two-dimensional nanosheet into the coagulation bath, and obtaining the nascent graphene oxide fiber after drying; Stretching, chemical reduction and heat treatment to obtain graphene fibers with high modulus and high thermal conductivity; wherein, the extrusion speed includes the axial speed along the extrusion direction and the circumferential rotational speed perpendicular to the axial speed.
  • circumferential velocity is brought about by introducing circumferential rotational shear force into the dispersion of two-dimensional nanosheets.
  • the dispersion of the graphene oxide two-dimensional nanosheets is an aqueous phase dispersion of graphene oxide, a DMF phase dispersion, a DMAc phase dispersion, a DMSO phase dispersion, and the coagulation bath is ethyl acetate, dichloromethane , acetic acid, ethanol, isopropanol, chloroform, acetone, etc. and their mixed coagulation baths, or aqueous coagulation baths of high-valence salts, and the high-valence salts are calcium chloride, ferrous chloride or ferric sulfate.
  • plasticizing and stretching refers to: stretching the fiber by immersing it in a plasticizer
  • the plasticizer is selected from: glycerol, propylene glycol, ethylene glycol, triethylene glycol, acetone, isopropanol , acetic acid, methanol, tetraethylene glycol, pentaethylene glycol, hydrochloric acid, dilute sulfuric acid, organic amines, etc. or their mixed plasticizers.
  • the reagents used in the chemical reduction are hydroiodic acid, hydrazine hydrate, sodium ascorbate, stannous chloride, etc., and the heat treatment temperature is 1300-3000 degrees Celsius.
  • the present invention also provides the application of the above fiber in sensing, phase change energy storage, and catalytic energy.
  • airgel fibers with specific cross-sectional morphological characteristics can be prepared, which solves the problem that the two-dimensional nanosheets inside the airgel fiber cannot be precisely adjusted for sheet arrangement, thereby Improve the mechanical properties and conductivity of airgel fibers, and promote the practical application of airgel fibers.
  • the present invention improves the orderliness of the graphene sheet arrangement inside the fiber by constructing a graphene fiber structure with a specific structure, thereby improving the density of the final heat-treated graphene fiber, so that the crystallinity of graphene during heat treatment is significantly improved, and the crystal The size is significantly increased, which greatly improves the thermal conductivity and modulus of graphene fibers.
  • Figure 1 is a schematic diagram of a self-made rotary extrusion spinning device.
  • Figure 2 shows the rotor structure in the rotary extrusion device.
  • Figure 3 shows the cross-sectional morphology of graphene oxide airgel fibers prepared at different graphene liquid crystal spinning liquid concentrations and different rotor speeds.
  • Figure 4 shows the cross-sectional shapes of three typical graphene oxide airgel fibers, including a is a random distribution cross-sectional structure; b is a concentric cross-sectional structure; c is a helical cross-sectional structure.
  • Figure 5 is the mechanical curve of graphene fibers.
  • Concentric GF is the graphene fiber after coagulation, drying and heat treatment of gel fibers distributed in concentric circles; Random GF is graphene after coagulation, drying and heat treatment of gel fibers distributed randomly fiber.
  • the cross-sectional morphology of the prepared graphene oxide airgel fibers is shown in Fig. 4a.
  • the cross-sectional morphology of the prepared graphene oxide airgel fibers is shown in Figure 4b. This is because graphene oxide is a kind of macromolecule, and liquid crystal has good dynamic stability, so that its specific structure can be maintained after passing through the rotating flow field, and finally the arrangement structure of graphene macromolecules after passing through the rotating flow field It is continued to graphene oxide airgel fibers and corresponding graphene airgel fibers.
  • the cross-sectional shape of the airgel fiber is mainly determined by the concentration of the graphene oxide liquid crystal spinning solution and the rotor speed.
  • the concentration of the graphene oxide solution determines whether it can form liquid crystals.
  • the concentration of the graphene oxide solution is above 0.1 wt% to form liquid crystals.
  • the rotor speed increases, and the cross-section of the graphene oxide airgel fiber first assumes a concentric circle structure, and when the speed is further increased, the fiber cross-section presents a helical structure.
  • Regulating the graphene oxide concentration to form liquid crystals is common knowledge in the art, and those skilled in the art can regulate the cross-sectional morphology of the gel fiber according to the above-mentioned law of rotational speed.
  • the prepared heat-treated graphene airgel fiber After testing, the prepared heat-treated graphene airgel fiber has a higher thermal conductivity, reaching 15W/(m K), in contrast, the thermal conductivity of the disorderly arranged graphene airgel fiber is only insufficient. 10W/(m K), high thermal conductivity graphene airgel fiber framework can be used for thermal, electrical, and photoresponsive functional materials.
  • the dried graphene oxide fibers are subjected to chemical reduction of hydroiodic acid and heat treatment at 2700 degrees to obtain graphene fibers with high modulus and high thermal conductivity.
  • the graphene fiber prepared from the concentric gel fiber has a strength of 3GPa, a modulus of 833GPa, and a thermal conductivity of 1590W/(m K).
  • the mechanical curve is shown in Figure 5 Concentric GF.
  • the dried graphene oxide fibers are subjected to chemical reduction of hydroiodic acid and heat treatment at 2700 degrees to obtain graphene fibers prepared from randomly distributed gel fibers.
  • the graphene fiber without microfibrillation has a strength of 3.1GPa, a modulus of 343GPa, and a thermal conductivity of 1400W/(m K).
  • the mechanical curve is shown in Figure 5Random GF.
  • the dried graphene oxide fiber is subjected to chemical reduction of hydroiodic acid and heat treatment at 2700 degrees to obtain the final graphene fiber.
  • the graphene fiber prepared under this condition has a strength of 2GPa, a modulus of 650GPa, and a thermal conductivity of 1490W/(m K).
  • This comparative example is the same as the embodiment 8, the difference is that: the rotating speed of the rotor is 500rpm, forming a helical structure.
  • the dried graphene oxide fiber is subjected to chemical reduction of hydroiodic acid and heat treatment at 2700 degrees to obtain the final graphene fiber.
  • the graphene fiber prepared under this condition has a strength of 1.8GPa, a modulus of 500GPa, and a thermal conductivity of 1360W/(m K).

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Abstract

一种具有特定截面形态特征的气凝胶纤维及其制备方法与装置，所述气凝胶纤维的截面二维纳米片的排列的形态是可调控的，该调控方法如下：在湿法纺丝的同时，于纺丝液流体喷出前增加旋转流场装置，旋转流场使得二维纳米片在旋转剪切作用下在凝胶纤维截面方向形成特定的片层排列的形态，将具有特定形态截面结构的凝胶纤维在冷冻干燥的条件下制备得到具有特定形态结构(同心圆和螺旋线)的氧化石墨烯气凝胶纤维。将这种同心圆结构的水凝胶纤维进行干燥致密化、拉伸、还原，得到高模量与高导热的石墨烯纤维，相比于现有的石墨烯纤维，其导热率和模量得到提升。

Description

具有特定截面形态特征的气凝胶纤维及其制备方法与装置 技术领域
本发明涉及纳米材料领域，特别是一种具有特定截面形态特征的气凝胶纤维及其制备方法与装置。
背景技术
气凝胶纤维是一种结合了气凝胶和纤维两种材料优异特性的新兴材料，是指将湿法纺丝制备的凝胶纤维经过冷冻干燥或常压干燥等条件得到的具有轻质、高比表面积、高孔隙率的纤维品种。二维片状分子是以单原子层为厚度的一种具有巨大的宽厚比的分子，以石墨烯为例，其具有极高的拉伸强度、杨氏模量，高的导电率，以及室温下最高的导热率。以二维片状分子为组装单元制备的气凝胶纤维除了典型的高孔隙率等特性外，还具有更加优异的力学-电学-热学性能。
然而目前，对于这种以二维纳米片组装的气凝胶纤维的研究仅仅停留在可以成功制备的起点上，对于气凝胶纤维内部结构的调控尚未有方法提出，尤其是针对二维纳米片在空间上存在二维的各向异性，其在纤维内部不仅存在轴向的取向，二维纳米片在纤维周向截面方向排列仍然是无序排列的状态。二位纳米片在气凝胶纤维周向截面方向排列的无序性势必会导致气凝胶纤维的耐压缩性能下降，影响气凝胶纤维在实际生活中的应用，同时未加调控的截面方向排列形态还会影响到高导电高导热的二维纳米片之间电子和声子的有效传递，影响气凝胶纤维的传导性能。因此寻找一种有效精确调控气凝胶纤维内部二维片排列的有序性的策略成为一大研究方向。通过精确调控气凝胶纤维内部二维纳米片的排列，可以制备具有特定截面形态特征的气凝胶纤维，从而推进气凝胶纤维的现实应用。
2011年浙江大学高超课题组发明了一种以单层石墨烯为组装单元的宏观石墨烯纤维，开创了以天然石墨为原料制备碳质纤维的新路径。目前纯石墨烯纤维在导热率方面表现出优异的特性，远高于传统的碳纤维，然而石墨烯纤维的机械性能表现平平，尽管其单丝力学强度目前可以达到3.4GPa，但是其模量仍未突破400GPa，这与传统碳纤维中模量与导热同时改善的规律不符，即石墨烯纤维的导热率远超传统碳纤维，但是其模量却低于传统碳纤维。
高导热与高模量在传统碳纤维中是同时改善的两项关键指标，通常与纤维的取向度与密度紧密相关。目前来看，石墨烯纤维的取向度已经可以达到90％以上，然而，石墨烯纤维由单层石墨烯直接组装而成，石墨烯为典型的二维大分子结构，其折叠排列的有序性最终决定了石墨烯纤维的密度，因此改善石墨 烯纤维中二维石墨烯片排列的有序性，将改善石墨烯纤维的密度，从而制备得到高模量和高导热的石墨烯纤维。
发明内容
为了克服上述现有的技术短板，本发明提供了一种具有特定截面形态特征的气凝胶纤维及其制备方法与装置，并获得了高模量与高导热的石墨烯纤维。
本申请针对二维平面纳米片，基于二维平面纳米片特有的巨大宽厚比，使其具有良好的溶致液晶现象；基于二维平面纳米片特有的大分子，使其液晶的动力学稳定性良好，二维平面纳米片液晶纺丝液经过旋转流场后，形成具有特定结构的水凝胶纤维。这种凝胶纤维经过冷冻干燥后，得到具有特定截面形态的气凝胶纤维。将水凝胶纤维经过干燥致密化后可以得到初生的氧化石墨烯纤维，将这种氧化石墨烯初生纤维进行塑化拉伸、化学还原和热处理，可得到高模量和高导热的石墨烯纤维。
一方面，本发明一种具有特定截面形态特征的气凝胶纤维，由二维纳米片构成，纤维截面呈同心圆片层排列或呈放射型螺旋线片层排列。
上述气凝胶纤维的制备方法为：将二维纳米片的分散液挤出到凝固浴中，凝固后进行结构固定，得到具有特定截面形态特征的气凝胶纤维；挤出速度包括沿着挤出方向的轴向速度和垂直于所述轴向速度的周向旋转速度。
进一步地，所述周向速度是通过在二维纳米片的分散液中引入周向旋转剪切力带来的。
进一步地，所述二维纳米片为氧化石墨烯、石墨烯、Mxene、二硫化钼、蒙脱土具有二维各向异性的纳米片及多种混合二维纳米片。
进一步地，所述二维纳米片的分散液的浓度大于1mg/g。
本发明还涉及一种制备具有特定截面形态特征的气凝胶纤维的装置，至少包括一挤出装置、一凝固浴和一冷冻干燥系统；所述挤出装置包括纺丝管，所述纺丝管内具有周向旋转剪切力。
进一步地，所述纺丝管内具有一转子，所述转子位于纺丝管轴心位置。
进一步地，所述纺丝管中的转子沿其轴心旋转。
另一方面，本发明还提供一种高模量与高导热的石墨烯纤维，由石墨烯二维纳米片构成，纤维截面呈同心圆片层排列，所述石墨烯二位纳米片沿轴向取向排列；所述石墨烯片构成多个轴向长度在200nm以上，径向长度在100nm以上的石墨晶体；石墨烯纤维密度大于等于1.9g/cm 3。
本发明还涉及上述石墨烯纤维的制备方法，该方法为：将氧化石墨烯二维纳米片的分散液挤出到凝固浴中，干燥后得到初生的氧化石墨烯纤维；然后依 次进行塑化拉伸、化学还原和热处理，得到高模量和高导热的石墨烯纤维；其中，挤出速度包括沿着挤出方向的轴向速度和垂直于所述轴向速度的周向旋转速度。
进一步地，所述周向速度是通过在二维纳米片的分散液中引入周向旋转剪切力带来的。
进一步地，所述氧化石墨烯二维纳米片的分散液为氧化石墨烯的水相分散液、DMF相分散液、DMAc相分散液、DMSO相分散液，凝固浴为乙酸乙酯、二氯甲烷、乙酸、乙醇、异丙醇、三氯甲烷、丙酮等及其混合凝固浴，或为高价盐的水溶液凝固浴，所述高价盐为氯化钙，氯化亚铁或硫酸铁。
进一步地，塑化拉伸是指：将纤维浸没在塑化剂中进行拉伸，所述塑化剂选自：丙三醇、丙二醇、乙二醇、三乙二醇、丙酮、异丙醇、乙酸、甲醇、四乙二醇、五乙二醇、盐酸、稀硫酸、有机胺等或其混合塑化剂。
进一步地，化学还原所采用的试剂为氢碘酸、水合肼、抗坏血酸钠、氯化亚锡等，热处理温度为1300-3000摄氏度。
最后，本发明还提供上述纤维在传感、相变储能、催化能源中的应用。
本发明的有益效果在于：
1)通过精确调控气凝胶纤维内部二维纳米片的排列，可以制备具有特定截面形态特征的气凝胶纤维，解决气凝胶纤维内部二维纳米片无法精确调控片层排列的难题，从而提高气凝胶纤维的力学性能和传导性能，推进气凝胶纤维的现实应用。
2)本发明通过构建特定结构的石墨烯纤维结构，提高了纤维内部石墨烯片排列的有序性，从而提高最终热处理石墨烯纤维的密度，使石墨烯在热处理过程中结晶度明显提高，晶体尺寸明显增大，大大提升了石墨烯纤维的导热率和模量。
附图说明
图1为自制的旋转挤出纺丝装置示意图。
图2为旋转挤出装置里的转子结构。
图3为不同石墨烯液晶纺丝液浓度与不同转子转速下制备的氧化石墨烯气凝胶纤维的截面形态。
图4为典型的三种氧化石墨烯气凝胶纤维的截面形态，包括a为无序分布截面结构；b为同心圆的截面结构；c为螺旋线的截面结构。
图5为石墨烯纤维的力学曲线，Concentric GF为同心圆分布的凝胶纤维经过凝固干燥和热处理后的石墨烯纤维；Random GF为无序分布的凝胶纤维经过 凝固干燥和热处理后的石墨烯纤维。
具体实施方式
对比例1
(1)将浓度为6mg/g的水相氧化石墨烯液晶纺丝液以0.2mL/min速度挤入直径为500μm的圆形纺丝管中，挤入纺丝管时，液晶纺丝液经过旋转转子的装置，转子转速为0rpm，此时氧化石墨烯液晶纺丝液未经过转子转动的剪切作用；
(2)接着继续将氧化石墨烯液晶纺丝液挤入3wt％氯化钙水溶液的凝固浴中，凝固后得到氧化石墨烯凝胶纤维，凝胶纤维经过浸泡去离子水3次，将多余的游离钙离子清洗干净；
(3)将氧化石墨烯凝胶纤维在-80摄氏度的冰箱中冷冻一小时，接着放入冷冻干燥机中进行冷冻干燥，干燥后得到氧化石墨烯气凝胶纤维。
制备得到的氧化石墨烯气凝胶纤维的截面形貌如图4a所示。
实施例1
(1)将浓度为6mg/g的水相氧化石墨烯液晶纺丝液以0.2mL/min速度挤入直径为500μm的圆形纺丝管中，挤入纺丝管时，液晶纺丝液经过旋转转子的装置，转子转速为100rpm，此时氧化石墨烯液晶纺丝液经过转子转动的剪切作用，形成了同心圆的排列结构；
(2)接着继续将同心圆排列的氧化石墨烯液晶纺丝液挤入3wt％氯化钙水溶液的凝固浴中，凝固后得到氧化石墨烯凝胶纤维，凝胶纤维经过浸泡去离子水3次，将多余的游离钙离子清洗干净；
(3)将氧化石墨烯凝胶纤维在-80摄氏度的冰箱中冷冻一小时，接着放入冷冻干燥机中进行冷冻干燥，干燥后得到氧化石墨烯气凝胶纤维。
制备得到的氧化石墨烯气凝胶纤维的截面形貌如图4b所示。这是由于氧化石墨烯是一种大分子，液晶在动力学上的稳定性较好，使其经过旋转流场后的特定结构可以得到保持，最终经过旋转流场后石墨烯大分子的排列结构得以延续至氧化石墨烯气凝胶纤维和相应的石墨烯气凝胶纤维。
在此实施例1的基础上，调控氧化石墨烯的浓度和转子速度，结果见图3。气凝胶纤维的截面形态主要由氧化石墨烯液晶纺丝液的浓度与转子转速决定。氧化石墨烯溶液的浓度决定其是否可形成液晶，作为本领域公知常识，氧化石墨烯溶液的浓度在0.1wt％以上即可形成液晶。当浓度固定时，转子转速提高，氧化石墨烯气凝胶纤维截面先呈同心圆结构，进一步提高转速时，纤维截面呈螺旋线结构。调控氧化石墨烯浓度来形成液晶为本领域公知常识，本领域技术 人员可根据上述转速的规律调控凝胶纤维的截面形貌。
实施例2
(1)将浓度为6mg/g的水相氧化石墨烯液晶纺丝液以0.2mL/min速度挤入直径为500μm的圆形纺丝管中，挤入纺丝管时，液晶纺丝液经过旋转转子的装置，转子转速为500rpm，此时氧化石墨烯液晶纺丝液经过转子转动的剪切作用，形成了螺旋线的排列结构；
(2)接着继续将螺旋线排列的氧化石墨烯液晶纺丝液挤入3wt％氯化钙水溶液的凝固浴中，凝固后得到氧化石墨烯凝胶纤维，凝胶纤维经过浸泡去离子水3次，将多余的游离钙离子清洗干净；
(3)将氧化石墨烯凝胶纤维在-80摄氏度的冰箱中冷冻一小时，接着放入冷冻干燥机中进行冷冻干燥，干燥后得到氧化石墨烯气凝胶纤维。
制备得到的氧化石墨烯气凝胶纤维的截面形貌如图4c所示。
实施例3
(1)将浓度为8mg/g的水相氧化石墨烯液晶纺丝液以0.2mL/min速度挤入直径为300μm的圆形纺丝管中，挤入纺丝管时，液晶纺丝液经过旋转转子的装置，转子转速为50rpm，此时氧化石墨烯液晶纺丝液经过转子转动的剪切作用，形成了同心圆的排列结构；
(2)接着继续将同心圆排列的氧化石墨烯液晶纺丝液挤入3wt％氯化亚铁水溶液的凝固浴中，凝固后得到氧化石墨烯凝胶纤维，凝胶纤维经过浸泡去离子水3次，将多余的游离二价铁离子清洗干净；
(3)将清洗干净的氧化石墨烯凝胶纤维浸泡在1％的抗坏血酸钠水溶液中，加热至80摄氏度，还原12小时后，得到化学还原的石墨烯凝胶纤维，并经过去离子水置换清晰；
(4)将制备的石墨烯凝胶纤维在-120摄氏度的液氮环境中冷冻一小时，接着放入冷冻干燥机中进行冷冻干燥，干燥后得到石墨烯气凝胶纤维。
(5)将干燥的具有同心圆排列的石墨烯气凝胶纤维在氩气环境下进行2800摄氏度的热处理，最终得到纯石墨烯气凝胶纤维。
经测试，制备的热处理后的石墨烯气凝胶纤维具有较高的导热率，达到15W/(m K)，相比之下，无序排列的石墨烯气凝胶纤维的导热率仅有不足10W/(m K)，高导热的石墨烯气凝胶纤维框架可以用于热、电、光响应的功能性材料。
实施例4
(1)将浓度为6mg/g的Mxene纺丝液以0.2mL/min速度挤入直径为500μm的圆形纺丝管中，挤入纺丝管时，纺丝液经过旋转转子的装置，转子转速为 200rpm，此时纺丝液经过转子转动的剪切作用，形成了同心圆的排列结构；
(2)接着继续将同心圆排列的Mxene纺丝液挤入6wt％氯化铵水溶液的凝固浴中，凝固后得到Mxene凝胶纤维，凝胶纤维经过浸泡去离子水混合清洗液3次，将多余的游离离子清洗干净；
(3)将Mxene凝胶纤维在-80摄氏度的冰箱中冷冻一小时，接着放入冷冻干燥机中进行冷冻干燥，干燥后得到Mxene气凝胶纤维。
实施例5
(1)将浓度为6mg/g的水相氧化石墨烯液晶纺丝液以0.2mL/min速度挤入直径为500μm的圆形纺丝管中，挤入纺丝管时，纺丝管在外部机械作用下进行旋转，使得液晶纺丝液在纺丝管旋转作用下，氧化石墨烯二维纳米片经历周向的旋转剪切作用，形成同心圆的排列结构；
(2)接着继续将同心圆排列的氧化石墨烯液晶纺丝液挤入3wt％氯化钙水溶液的凝固浴中，凝固后得到氧化石墨烯凝胶纤维，凝胶纤维经过浸泡去离子水3次，将多余的游离钙离子清洗干净；
(3)将氧化石墨烯凝胶纤维在-80摄氏度的冰箱中冷冻一小时，接着放入冷冻干燥机中进行冷冻干燥，干燥后得到氧化石墨烯气凝胶纤维。
实施例6
(1)将浓度为10mg/g的氧化石墨烯和蒙脱土纺丝液以0.2mL/min速度挤入直径为500μm的圆形纺丝管中，挤入纺丝管时，纺丝液经过旋转转子的装置，转子转速为400rpm，此时纺丝液经过转子转动的剪切作用，形成了螺旋线的排列结构；
(2)接着继续将螺旋线排列的纺丝液挤入4wt％氯化钙水溶液的凝固浴中，凝固后得到氧化石墨烯和蒙脱土的混合凝胶纤维，凝胶纤维经过浸泡去离子水混合清洗液3次，将多余的游离离子清洗干净；
(3)将氧化石墨烯和蒙脱土的混合凝胶纤维在液氮环境下冷冻一小时，接着放入冷冻干燥机中进行冷冻干燥，干燥后得到氧化石墨烯和蒙脱土的混合气凝胶纤维。
实施例7
(1)将浓度为6mg/g的DMF相氧化石墨烯液晶纺丝液以0.2mL/min速度挤入直径为100μm的圆形纺丝管中，挤入纺丝管前，液晶纺丝液经过旋转转子的装置，转子转速为100rpm，此时氧化石墨烯液晶被旋转转子转动带动为同心圆的结构，如图2所示；
(2)接着继续将同心圆结构的氧化石墨烯液晶纺丝液挤入乙酸乙酯的凝固 浴中，干燥后得到初生的氧化石墨烯纤维；
(3)将初生的氧化石墨烯纤维浸泡在乙酸中浸泡塑化，对塑化的氧化石墨烯纤维进行塑化拉伸，拉伸率为30％，然后保持当前长度进行干燥；
(4)干燥后的氧化石墨烯纤维进行氢碘酸的化学还原及2700度的热处理，得到高模量与高导热的石墨烯纤维。
经过力学测试，从同心圆凝胶纤维制备的石墨烯纤维强度达3GPa，模量为833GPa，导热率达到1590W/(m K)。力学曲线如图5Concentric GF所示。
对比例2
本对比例同实施例7，区别在于：挤入无转子的纺丝管中
(1)将浓度为6mg/g的DMF相氧化石墨烯液晶纺丝液以0.2mL/min速度挤入流道直径为100μm的圆形纺丝管中，纺丝管中不具有转子，此时氧化石墨烯液晶未旋转流场带动成同心圆的结构，为典型未加控制的无序分布状态；
(2)接着继续将无序分布的氧化石墨烯液晶纺丝液挤入乙酸乙酯的凝固浴中，干燥后得到初生的氧化石墨烯纤维；
(3)将初生的氧化石墨烯纤维浸泡在乙酸中浸泡塑化，对塑化的氧化石墨烯纤维进行塑化拉伸，拉伸率为30％，然后保持当前长度进行干燥；
(4)干燥后的氧化石墨烯纤维进行氢碘酸的化学还原及2700度的热处理，得到由无序分布的凝胶纤维制备的石墨烯纤维。
经过力学测试，这种没有微纤化的石墨烯纤维强度为3.1GPa，模量为343GPa，导热率为1400W/(m K)。力学曲线如图5Random GF所示。
实施例8
(1)将浓度为8mg/g的DMF相氧化石墨烯液晶纺丝液以0.2mL/min速度挤入直径为100μm的圆形纺丝管中，挤入纺丝管前，液晶纺丝液经过旋转转子的装置，转子转速为50rpm，此时氧化石墨烯液晶被旋转转子转动带动为同心圆的结构；
(2)接着继续将同心圆结构的氧化石墨烯液晶纺丝液挤入乙酸乙酯的凝固浴中，干燥后得到初生的氧化石墨烯纤维；
(3)将初生的氧化石墨烯纤维浸泡在乙醇中浸泡塑化，对塑化的氧化石墨烯纤维进行塑化拉伸，拉伸率为10％，然后保持当前长度进行干燥；
(4)干燥后的氧化石墨烯纤维进行氢碘酸的化学还原及2700度的热处理，得到最终的石墨烯纤维。
经过力学测试，该条件下制备的石墨烯纤维强度达2GPa，模量为650GPa，导热率达到1490W/(m K)。
实施例9
本对比例同实施例8，区别在于：转子转速为500rpm，形成螺旋线结构。
(1)将浓度为8mg/g的DMF相氧化石墨烯液晶纺丝液以0.2mL/min速度挤入直径为100μm的圆形纺丝管中，挤入纺丝管前，液晶纺丝液经过旋转转子的装置，转子转速为500rpm，此时氧化石墨烯液晶被旋转转子转动带动为螺旋线的结构；
(2)接着继续将螺旋线结构的氧化石墨烯液晶纺丝液挤入乙酸乙酯的凝固浴中，干燥后得到初生的氧化石墨烯纤维；
(3)将初生的氧化石墨烯纤维浸泡在乙醇中浸泡塑化，对塑化的氧化石墨烯纤维进行塑化拉伸，拉伸率为10％，然后保持当前长度进行干燥；
(4)干燥后的氧化石墨烯纤维进行氢碘酸的化学还原及2700度的热处理，得到最终的石墨烯纤维。
经过力学测试，该条件下制备的石墨烯纤维强度达1.8GPa，模量为500GPa，导热率达到1360W/(m K)。

Claims (15)

  1. 一种具有特定截面形态特征的气凝胶纤维，其特征在于，由二维纳米片构成，纤维截面呈同心圆片层排列或呈放射型螺旋线片层排列。
  2. 如权利要求1所述的气凝胶纤维的制备方法，其特征在于，该方法为：将二维纳米片的分散液挤出到凝固浴中，凝固后进行结构固定，得到具有特定截面形态特征的气凝胶纤维；挤出速度包括沿着挤出方向的轴向速度和垂直于所述轴向速度的周向旋转速度。
  3. 根据权利要求2所述的方法，其特征在于，所述周向速度是通过在二维纳米片的分散液中引入周向旋转剪切力带来的。
  4. 根据权利要求2所述的方法，其特征在于，所述二维纳米片为氧化石墨烯、石墨烯、Mxene、二硫化钼、蒙脱土具有二维各向异性的纳米片及多种混合二维纳米片。
  5. 根据权利要求2所述的方法，其特征在于，所述二维纳米片的分散液的浓度大于1mg/g。
  6. 一种制备具有特定截面形态特征的气凝胶纤维的装置，其特征在于，至少包括一挤出装置、一凝固浴和一冷冻干燥系统；所述挤出装置包括纺丝管，所述纺丝管内具有周向旋转剪切力。
  7. 根据权利要求6所述的装置，其特征在于，所述纺丝管内具有一转子，所述转子位于纺丝管轴心位置。
  8. 根据权利要求6所述的装置，其特征在于，所述纺丝管中的转子沿其轴心旋转。
  9. 一种高模量与高导热的石墨烯纤维，其特征在于，由石墨烯二维纳米片构成，纤维截面呈同心圆片层排列，所述石墨烯二维纳米片沿轴向取向排列；所述石墨烯片构成多个轴向长度在200nm以上，径向长度在100nm以上的石墨晶体；石墨烯纤维密度大于等于1.9g/cm 3。
  10. 如权利要求9所述的石墨烯纤维的制备方法，其特征在于，将氧化石墨烯二维纳米片的分散液挤出到凝固浴中，干燥后得到初生的氧化石墨烯纤维；然后依次进行塑化拉伸、化学还原和热处理，得到高模量和高导热的石墨烯纤维；其中，挤出速度包括沿着挤出方向的轴向速度和垂直于所述轴向速度的周向旋转速度。
  11. 根据权利要求10所述的方法，其特征在于，所述周向速度是通过在二维纳米片的分散液中引入周向旋转剪切力带来的。
  12. 根据权利要求10所述的方法，其特征在于，所述氧化石墨烯二维纳米片 的分散液为氧化石墨烯的水相分散液、DMF相分散液、DMAc相分散液、DMSO相分散液，凝固浴为乙酸乙酯、二氯甲烷、乙酸、乙醇、异丙醇、三氯甲烷、丙酮等及其混合凝固浴，或为高价盐的水溶液凝固浴，所述高价盐为氯化钙/氯化亚铁、硫酸铁等。
  13. 根据权利要求10所述的方法，其特征在于，塑化拉伸是指：将纤维浸没在塑化剂中进行拉伸，所述塑化剂选自：丙三醇、丙二醇、乙二醇、三乙二醇、丙酮、异丙醇、乙酸、甲醇、四乙二醇、五乙二醇、盐酸、稀硫酸、有机胺等或其混合塑化剂。
  14. 根据权利要求10所述的方法，其特征在于，化学还原所采用的试剂为氢碘酸、水合肼、抗坏血酸钠、氯化亚锡等，热处理温度为1300-3000摄氏度。
  15. 权利要求1～14任一项所述的纤维在传感、相变储能、催化能源、结构材料中的应用。
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