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CN111441107A - Spinning solution for preparing carbon fiber material, flexible electrode material and preparation method - Google Patents

Spinning solution for preparing carbon fiber material, flexible electrode material and preparation method Download PDF

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CN111441107A
CN111441107A CN202010209387.7A CN202010209387A CN111441107A CN 111441107 A CN111441107 A CN 111441107A CN 202010209387 A CN202010209387 A CN 202010209387A CN 111441107 A CN111441107 A CN 111441107A
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赖超
孙闯
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Jiangsu Normal University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

本发明公开了一种用于制备碳纤维材料的纺丝液,包括:聚乙烯吡咯烷酮、冰乙酸、硅酸四乙酯、钛酸四丁酯以及有机溶剂。在前述基础上,本发明还公开了一种柔性电极材料以及柔性电极材料的制备方法。利用本发明的纺丝液制备的柔性电极材料具有空心结构,能够实现优良的机械性能与优异的电化学性能。

Figure 202010209387

The invention discloses a spinning solution for preparing carbon fiber material, which comprises polyvinylpyrrolidone, glacial acetic acid, tetraethyl silicate, tetrabutyl titanate and an organic solvent. On the basis of the foregoing, the present invention also discloses a flexible electrode material and a preparation method of the flexible electrode material. The flexible electrode material prepared by using the spinning solution of the present invention has a hollow structure, and can realize excellent mechanical properties and excellent electrochemical properties.

Figure 202010209387

Description

用于制备碳纤维材料的纺丝液、柔性电极材料以及制备方法Spinning solution for preparing carbon fiber material, flexible electrode material and preparation method

技术领域technical field

本发明涉及电极材料领域,具体涉及用于制备碳纤维材料的纺丝液、柔性电极材料以及制备方法。The invention relates to the field of electrode materials, in particular to a spinning solution for preparing carbon fiber materials, a flexible electrode material and a preparation method.

背景技术Background technique

在电极材料制备领域,现有的碳纤维材料制备工艺是通过烧结含碳量极高的有机高分子纤维实现,所制备的碳纤维材料表面极性低、表面官能团少、多为实心结构且大多为表现为超硬材料,更重要地是,实心结构的碳纤维材料无法保证电解液的完全浸润,阻碍了碳纤维材料在储能体系的应用。In the field of electrode material preparation, the existing carbon fiber material preparation process is realized by sintering organic polymer fibers with extremely high carbon content. The prepared carbon fiber materials have low surface polarity, few surface functional groups, mostly solid structures, and mostly expressive For superhard materials, more importantly, the solid structure of carbon fiber materials cannot guarantee the complete infiltration of electrolyte, which hinders the application of carbon fiber materials in energy storage systems.

目前,为了实现碳纤维材料的功能化,需要进一步对已制备的碳纤维材料表面进行官能团的修饰或其他功能性活性物质的二次负载。这使得碳纤维材料的实用化过程复杂化从而致使其无法实现在储能体系中有更多更好的发展。At present, in order to realize the functionalization of carbon fiber materials, it is necessary to further modify the surface of the prepared carbon fiber materials with functional groups or secondary loading of other functional active substances. This complicates the practical process of carbon fiber materials and makes it impossible to achieve more and better development in energy storage systems.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于至少提供一种用于制备碳纤维材料的纺丝液、柔性电极材料以及制备方法。利用本发明的纺丝液制备的柔性电极材料具有空心结构,能够实现优良的机械性能与优异的电化学性能。The purpose of the present invention is to provide at least one spinning solution for preparing carbon fiber material, flexible electrode material and preparation method. The flexible electrode material prepared by using the spinning solution of the present invention has a hollow structure, and can realize excellent mechanical properties and excellent electrochemical properties.

本发明通过如下技术方案实现:The present invention is achieved through the following technical solutions:

本发明的第一方面first aspect of the invention

本发明的第一方面提供了一种用于制备碳纤维材料的纺丝液,所述纺丝液包括:聚乙烯吡咯烷酮、催化剂、硅酸四乙酯、钛酸四丁酯以及有机溶剂。其中,所述催化剂为冰乙酸。A first aspect of the present invention provides a spinning solution for preparing carbon fiber materials, the spinning solution includes: polyvinylpyrrolidone, a catalyst, tetraethyl silicate, tetrabutyl titanate, and an organic solvent. Wherein, the catalyst is glacial acetic acid.

在一些实施例中,所述纺丝液中包含:聚乙烯吡咯烷酮,5-15重量份;催化剂,5-15重量份;硅酸四乙酯,15-25重量份;钛酸四丁酯,2-8重量份;有机溶剂40-60重量份。In some embodiments, the spinning solution comprises: polyvinylpyrrolidone, 5-15 parts by weight; catalyst, 5-15 parts by weight; tetraethyl silicate, 15-25 parts by weight; tetrabutyl titanate, 2-8 parts by weight; 40-60 parts by weight of organic solvent.

在一些实施例中,所述纺丝液中包含:聚乙烯吡咯烷酮,9-11重量份;催化剂,9-11重量份;硅酸四乙酯,18-22重量份;钛酸四丁酯,4-6重量份;有机溶剂,50-60重量份。In some embodiments, the spinning solution comprises: polyvinylpyrrolidone, 9-11 parts by weight; catalyst, 9-11 parts by weight; tetraethyl silicate, 18-22 parts by weight; tetrabutyl titanate, 4-6 parts by weight; organic solvent, 50-60 parts by weight.

在一些实施例中,所述纺丝液还包括纳米材料,所述纳米材料包括一维纳米材料和二维纳米材料中的至少一种;以100重量份的纺丝液为基准,所述纳米材料的添加量为是0.1-1重量份。In some embodiments, the spinning solution further includes nanomaterials, and the nanomaterials include at least one of one-dimensional nanomaterials and two-dimensional nanomaterials; based on 100 parts by weight of the spinning solution, the nanomaterials The addition amount of the material is 0.1-1 part by weight.

在一些实施例中,所述一维纳米材料至少包括碳纳米管与金属纳米线中的一种;所述金属纳米线为VIII、IB、IIIA族金属纳米线。优选地,金属纳米线可以是金、银、铜、镍、铂、钯、铝纳米线。In some embodiments, the one-dimensional nanomaterial includes at least one of carbon nanotubes and metal nanowires; the metal nanowires are group VIII, IB, and IIIA metal nanowires. Preferably, the metal nanowires may be gold, silver, copper, nickel, platinum, palladium, aluminum nanowires.

在一些实施例中,所述二维纳米材料至少包括氧化石墨烯、二维过渡金属碳化物以及二维过渡金属氮化物中的一种。In some embodiments, the two-dimensional nanomaterial includes at least one of graphene oxide, two-dimensional transition metal carbide, and two-dimensional transition metal nitride.

在一些实施例中,所述有机溶剂至少包括无水乙醇、N-甲基吡咯烷酮、二甲基甲酰胺以及二甲基乙酰胺中的一种。In some embodiments, the organic solvent includes at least one of absolute ethanol, N-methylpyrrolidone, dimethylformamide and dimethylacetamide.

本发明的第二方面Second aspect of the invention

本发明的第二方面提供了一种柔性电极材料,由本发明的第一方面所述的纺丝液制备。A second aspect of the present invention provides a flexible electrode material prepared from the spinning solution described in the first aspect of the present invention.

由于第一方面的纺丝液制备的纤维材料在纺丝后能够产生孔道结构,所以第二方面中的柔性电极材料是一种具有空心结构的亲锂三维柔性电极材料。Since the fiber material prepared from the spinning solution of the first aspect can generate a pore structure after spinning, the flexible electrode material of the second aspect is a lithiophilic three-dimensional flexible electrode material with a hollow structure.

本发明的第三方面Third aspect of the invention

在第一方面与第二方面的基础上,本发明的第三方面提供了一种柔性电极材料的制备方法,包括:On the basis of the first aspect and the second aspect, a third aspect of the present invention provides a preparation method of a flexible electrode material, comprising:

在有机溶剂中加入聚乙烯吡咯烷酮、冰乙酸搅拌均匀后,再加入硅酸四乙酯和钛酸四丁酯,制得纺丝液;After adding polyvinylpyrrolidone and glacial acetic acid to the organic solvent and stirring evenly, then adding tetraethyl silicate and tetrabutyl titanate to obtain spinning solution;

对所述纺丝液进行静电纺丝,制得纺丝纤维;Electrospinning the spinning solution to obtain spinning fibers;

将所述纺丝纤维进行活化水解,然后通入惰性气体并且于400-800℃的温度下烧结,制得所述柔性电极材料。The spun fibers are activated and hydrolyzed, and then passed into an inert gas and sintered at a temperature of 400-800° C. to prepare the flexible electrode material.

本发明的第四方面Fourth aspect of the present invention

在第三方面的基础上,本发明的第四方面提供了一种优选的柔性电极材料的制备方法,包括:On the basis of the third aspect, the fourth aspect of the present invention provides a preferred method for preparing a flexible electrode material, comprising:

在有机溶剂中加入聚乙烯吡咯烷酮、冰乙酸和纳米材料搅拌均匀后,再加入硅酸四乙酯和钛酸四丁酯,制得纺丝液;After adding polyvinylpyrrolidone, glacial acetic acid and nanomaterials to the organic solvent and stirring evenly, then adding tetraethyl silicate and tetrabutyl titanate to prepare spinning solution;

对所述纺丝液进行静电纺丝,制得纺丝纤维;Electrospinning the spinning solution to obtain spinning fibers;

将所述纺丝纤维进行活化水解,然后通入惰性气体并且于400-800℃的温度下烧结,制得所述柔性电极材料。The spun fibers are activated and hydrolyzed, and then passed into an inert gas and sintered at a temperature of 400-800° C. to prepare the flexible electrode material.

本发明的实施例至少具备以下有益效果:The embodiments of the present invention have at least the following beneficial effects:

1、本发明的一些实施例中制备的柔性电极材料具有空心结构,能够保证电解液的完全浸润,利用这种柔性电极材料制备的柔性电极材料具备优异的电化学性能。1. The flexible electrode material prepared in some embodiments of the present invention has a hollow structure, which can ensure complete infiltration of the electrolyte, and the flexible electrode material prepared by using this flexible electrode material has excellent electrochemical performance.

2、本发明的一些实施例制备的柔性电极材料中添加了纳米材料,通过改变纳米材料中一维或二维纳米材料本身的含量来设计纳米材料自身的柔韧性,进而提高柔性电极材料中纤维的机械性能。2. Nanomaterials are added to the flexible electrode materials prepared in some embodiments of the present invention, and the flexibility of the nanomaterials itself is designed by changing the content of the one-dimensional or two-dimensional nanomaterials in the nanomaterials, thereby improving the fibers in the flexible electrode materials. mechanical properties.

3、现有技术需要进一步对已制备的碳纤维材料表面进行官能团的修饰或其他功能性活性物质的二次负载,而本发明的一些实施例则无此步骤,缩减了制备柔性电极材料的工艺流程。3. In the prior art, the surface of the prepared carbon fiber material needs to be further modified with functional groups or the secondary loading of other functional active substances, while some embodiments of the present invention do not have this step, which reduces the process flow for preparing flexible electrode materials. .

附图说明Description of drawings

图1为实施例1中添加了碳纳米管的柔性电极材料中的碳纤维材料截面形貌示意图;1 is a schematic diagram of the cross-sectional morphology of the carbon fiber material in the flexible electrode material added with carbon nanotubes in Example 1;

图2为实施例8中添加了氧化石墨烯的柔性电极材料中的碳纤维材料截面形貌示意图;2 is a schematic diagram of the cross-sectional morphology of the carbon fiber material in the flexible electrode material added with graphene oxide in Example 8;

图3为实施例9中添加了碳化钛的柔性电极材料中的碳纤维材料截面形貌示意图;3 is a schematic diagram of the cross-sectional morphology of the carbon fiber material in the flexible electrode material with titanium carbide added in Example 9;

图4为现有技术的对比例1中电极材料中的碳纤维材料截面形貌示意图;4 is a schematic diagram of the cross-sectional morphology of the carbon fiber material in the electrode material in Comparative Example 1 of the prior art;

图5为实施例1制备的柔性电极材料的电化学性能测试结果图;Fig. 5 is the electrochemical performance test result diagram of the flexible electrode material prepared in Example 1;

图6为实施例8制备的柔性电极材料的电化学性能测试结果图;Fig. 6 is the electrochemical performance test result diagram of the flexible electrode material prepared in Example 8;

图7为实施例9制备的柔性电极材料的电化学性能测试结果图;Fig. 7 is the electrochemical performance test result diagram of the flexible electrode material prepared in Example 9;

图8为实施例1和11制备的电极的电化学性能测试对比结果图。FIG. 8 is a graph showing the comparison results of the electrochemical performance test of the electrodes prepared in Examples 1 and 11. FIG.

具体实施方式Detailed ways

以下结合附图对本发明的具体实施方式进行进一步的说明。The specific embodiments of the present invention will be further described below with reference to the accompanying drawings.

本发明的第一方面first aspect of the invention

本发明的第一方面提供了一种用于制备碳纤维材料材料的纺丝液,包括:A first aspect of the present invention provides a spinning solution for preparing carbon fiber material, comprising:

聚乙烯吡咯烷酮、冰乙酸、硅酸四乙酯、钛酸四丁酯以及有机溶剂。Polyvinylpyrrolidone, glacial acetic acid, tetraethyl silicate, tetrabutyl titanate and organic solvents.

其中,聚乙烯吡咯烷酮用于为该纤维材料提供碳源;Wherein, polyvinylpyrrolidone is used to provide carbon source for the fiber material;

有机溶剂用于使得各组分物质均匀分散,所述有机溶剂优选至少包括无水乙醇、N-甲基吡咯烷酮、二甲基甲酰胺以及二甲基乙酰胺中的一种。所述有机溶剂还可以是含卤代烃类溶剂、醇类、胺类、硝基烷烃及低分子脂肪酸等;The organic solvent is used to uniformly disperse the components, and the organic solvent preferably includes at least one of absolute ethanol, N-methylpyrrolidone, dimethylformamide and dimethylacetamide. The organic solvent can also be halogenated hydrocarbon solvents, alcohols, amines, nitroalkanes, low molecular fatty acids, etc.;

所述催化剂起催化作用,为硅酸四乙酯、钛酸四丁酯的水解提供酸性环境,加速硅酸四乙酯和钛酸四丁酯的水解;所述催化剂优选冰乙酸,酸度合适,便于调节用量。冰乙酸可以用盐酸、硫酸等酸性物质替换,但由于后两种酸的酸性更强,需要调节使用量。The catalyst plays a catalytic role, provides an acidic environment for the hydrolysis of tetraethyl silicate and tetrabutyl titanate, and accelerates the hydrolysis of tetraethyl silicate and tetrabutyl titanate; the catalyst is preferably glacial acetic acid, with suitable acidity, Easy to adjust dosage. Glacial acetic acid can be replaced with acidic substances such as hydrochloric acid and sulfuric acid, but since the latter two acids are more acidic, the dosage needs to be adjusted.

硅酸四乙酯用作SiO2的提供源,钛酸四丁酯用作TiO2的提供源。Tetraethyl silicate was used as a supply source of SiO 2 , and tetrabutyl titanate was used as a supply source of TiO 2 .

所述纺丝液的工作原理在于:纺丝液中加入了可水解的硅酸四乙酯、钛酸四丁酯原料,对纺丝液进行纺丝后产生的纤维材料可通过这两种物质的水解过程使得该纤维内部产生孔道结构。其中,该孔道结构的产生原理在于:硅酸四乙酯和钛酸四丁酯在酸性条件下遇水易水解,这两种物质的水解会由纤维中心向四周扩散,从而使得纤维产生多孔的结构。在加上纳米柔性材料的引入,进一步提高了纤维整体的柔韧性。The working principle of the spinning solution is as follows: hydrolyzable tetraethyl silicate and tetrabutyl titanate raw materials are added to the spinning solution, and the fiber material produced after spinning the spinning solution can pass through these two substances. The hydrolysis process produces a pore structure inside the fiber. Among them, the generation principle of the pore structure is: tetraethyl silicate and tetrabutyl titanate are easily hydrolyzed in water under acidic conditions, and the hydrolysis of these two substances will diffuse from the center of the fiber to the surrounding, so that the fiber produces a porous structure. structure. In addition to the introduction of nano-flexible materials, the overall flexibility of the fiber is further improved.

因此,利用本发明的纺丝液制备的碳纤维材料以及根据该碳纤维材料制备的柔性电机具有空心结构,能够实现优异的电化学性能。Therefore, the carbon fiber material prepared by using the spinning solution of the present invention and the flexible motor prepared according to the carbon fiber material have a hollow structure and can achieve excellent electrochemical performance.

进一步地,所述的纺丝液,所述纺丝液中包含:聚乙烯吡咯烷酮,5-15重量份;催化剂,5-15重量份;硅酸四乙酯,15-25重量份;钛酸四丁酯,2-8重量份;有机溶剂,40-60重量份。Further, the spinning solution includes: polyvinylpyrrolidone, 5-15 parts by weight; catalyst, 5-15 parts by weight; tetraethyl silicate, 15-25 parts by weight; titanic acid Tetrabutyl ester, 2-8 parts by weight; organic solvent, 40-60 parts by weight.

更优选地,所述纺丝液中包含:聚乙烯吡咯烷酮,9-11重量份;催化剂,9-11重量份;硅酸四乙酯,18-22重量份;钛酸四丁酯,4-6重量份;有机溶剂,50-60重量份。More preferably, the spinning solution contains: polyvinylpyrrolidone, 9-11 parts by weight; catalyst, 9-11 parts by weight; tetraethyl silicate, 18-22 parts by weight; tetrabutyl titanate, 4- 6 parts by weight; organic solvent, 50-60 parts by weight.

其中,所述的纺丝液各物质的最佳含量为:聚乙烯吡咯烷酮为10重量份;催化剂10重量份;硅酸四乙酯20重量份;钛酸四丁酯5重量份;有机溶剂55重量份时,纺丝液纤维相对具有更佳的效果。Wherein, the optimum content of each substance in the spinning solution is: 10 parts by weight of polyvinylpyrrolidone; 10 parts by weight of catalyst; 20 parts by weight of tetraethyl silicate; 5 parts by weight of tetrabutyl titanate; 55 parts by weight of organic solvent In parts by weight, spinning dope fibers have relatively better effects.

进一步地,所述纺丝液还包括纳米材料,所述纳米材料包括一维纳米材料和二维纳米材料中的至少一种。Further, the spinning solution further includes nanomaterials, and the nanomaterials include at least one of one-dimensional nanomaterials and two-dimensional nanomaterials.

纳米材料具有优良的机械性能,可以使得应用本发明的纺丝液制备的纤维材料具有良好的柔韧性,以实现进一步柔性电极材料的制备。在配制纺丝液时通过添加不同含量的一维或二维纳米材料或它们的组合,即可改变纳米材料的柔韧性,进而得以提高纤维的机械性能。优选地,,所述纺丝液还包括纳米材料,所述纳米材料包括一维纳米材料和二维纳米材料中的至少一种;以100重量份的纺丝液为基准,所述纳米材料的添加量为是0.1-1重量份。优选地,以100 重量份的纺丝液为基准,所述纳米材料的添加量为是0.1-0.5重量份,具体地是指在100重量份的纺丝液中额外加入0.1-0.5重量份的所述纳米材料。Nanomaterials have excellent mechanical properties, which can make the fiber materials prepared by using the spinning solution of the present invention have good flexibility, so as to realize the preparation of further flexible electrode materials. By adding different contents of one-dimensional or two-dimensional nanomaterials or their combination when preparing the spinning solution, the flexibility of the nanomaterials can be changed, thereby improving the mechanical properties of the fibers. Preferably, the spinning solution further includes nanomaterials, and the nanomaterials include at least one of one-dimensional nanomaterials and two-dimensional nanomaterials; based on 100 parts by weight of the spinning solution, the nanomaterials have The addition amount is 0.1-1 part by weight. Preferably, based on 100 parts by weight of spinning solution, the addition amount of the nanomaterials is 0.1-0.5 parts by weight, which specifically refers to adding 0.1-0.5 parts by weight to 100 parts by weight of spinning solution. the nanomaterials.

优选地,在所述的纺丝液中,所述一维纳米材料至少包括碳纳米管与金属纳米线中的一种。Preferably, in the spinning solution, the one-dimensional nanomaterial includes at least one of carbon nanotubes and metal nanowires.

其中,所述金属纳米线为VIII、IB、IIIA族金属纳米线。优选地,所述金属纳米线为含有金、银、铜、镍、铂、钯、铝的金属纳米线,能够使制得的碳纤维材料具有较好的机械性能。Wherein, the metal nanowires are group VIII, IB, and IIIA metal nanowires. Preferably, the metal nanowires are metal nanowires containing gold, silver, copper, nickel, platinum, palladium, and aluminum, so that the obtained carbon fiber material has better mechanical properties.

优选地,在所述的纺丝液中,所述二维纳米材料至少包括氧化石墨烯、二维过渡金属碳化物以及二维过渡金属氮化物中的一种。Preferably, in the spinning solution, the two-dimensional nanomaterial includes at least one of graphene oxide, two-dimensional transition metal carbide and two-dimensional transition metal nitride.

添加上述优选的一维纳米材料、二维纳米材料及其混合物,通过一维或二维纳米材料本身的柔韧性,能够提高所制备的纺丝纤维整体的机械性能。Adding the above-mentioned preferred one-dimensional nanomaterials, two-dimensional nanomaterials and mixtures thereof can improve the overall mechanical properties of the prepared spinning fibers through the flexibility of the one-dimensional or two-dimensional nanomaterials themselves.

本发明的第二方面Second aspect of the invention

本发明的第二方面提供了一种柔性电极材料,由本发明的第一方面所述的纺丝液制备。A second aspect of the present invention provides a flexible electrode material prepared from the spinning solution described in the first aspect of the present invention.

由于第一方面的纺丝液制备的纤维材料在纺丝后能够产生孔道结构,所以第二方面中的柔性电极材料是一种具有空心结构的亲锂三维柔性电极材料。Since the fiber material prepared from the spinning solution of the first aspect can generate a pore structure after spinning, the flexible electrode material of the second aspect is a lithiophilic three-dimensional flexible electrode material with a hollow structure.

本发明的第三方面Third aspect of the invention

在第一方面与第二方面的基础上,本发明的第三方面提供了一种柔性电极材料的制备方法,包括:On the basis of the first aspect and the second aspect, a third aspect of the present invention provides a preparation method of a flexible electrode material, comprising:

在有机溶剂中加入聚乙烯吡咯烷酮、冰乙酸搅拌均匀后,再加入硅酸四乙酯和钛酸四丁酯,制得纺丝液;After adding polyvinylpyrrolidone and glacial acetic acid to the organic solvent and stirring evenly, then adding tetraethyl silicate and tetrabutyl titanate to obtain spinning solution;

对所述纺丝液进行静电纺丝,制得纺丝纤维;Electrospinning the spinning solution to obtain spinning fibers;

将所述纺丝纤维进行活化水解,然后通入惰性气体并且于400-800℃的温度下烧结,制得所述柔性电极材料。The spun fibers are activated and hydrolyzed, and then passed into an inert gas and sintered at a temperature of 400-800° C. to prepare the flexible electrode material.

在上述的制备方法中,硅酸四乙酯和钛酸四丁酯在酸性条件下遇水易水解,硅酸四乙酯和钛酸四丁酯的水解会由纤维中心向四周扩散,从而使得纤维产生多孔的结构。另外,烧结过程中惰性气体的保护可保护纤维中碳的含量,赋予纤维的导电性。In the above-mentioned preparation method, tetraethyl silicate and tetrabutyl titanate are easily hydrolyzed in the presence of water under acidic conditions, and the hydrolysis of tetraethyl silicate and tetrabutyl titanate will diffuse from the center of the fiber to the surrounding, thereby making Fibers create a porous structure. In addition, the protection of the inert gas during sintering protects the carbon content of the fibers and imparts electrical conductivity to the fibers.

本发明的第四方面Fourth aspect of the present invention

在第三方面的基础上,本发明的第四方面提供了一种优选的柔性电极材料的制备方法,包括:在有机溶剂中加入聚乙烯吡咯烷酮、冰乙酸和纳米材料搅拌均匀后,再加入硅酸四乙酯和钛酸四丁酯,制得纺丝液;On the basis of the third aspect, the fourth aspect of the present invention provides a preferred method for preparing a flexible electrode material, comprising: adding polyvinylpyrrolidone, glacial acetic acid and nanomaterials into an organic solvent and stirring evenly, then adding silicon Tetraethyl acid and tetrabutyl titanate to obtain spinning solution;

其中,纳米材料需要在硅酸四乙酯和钛酸四丁酯之前加入有机溶剂中,若纳米材料与硅酸四乙酯、钛酸四丁酯同时加入有机溶剂中则会导致纳米材料在纺丝液中无法均匀分散,因为,硅酸四乙酯和钛酸四丁酯是两种较粘稠的有机物,加入后会使得溶剂较为粘稠,使得粉末状的纳米材料不能均匀分散;Among them, the nanomaterials need to be added to the organic solvent before tetraethyl silicate and tetrabutyl titanate. If the nanomaterials, tetraethyl silicate and tetrabutyl titanate are added to the organic solvent at the same time, the nanomaterials will be in spinning. The silk liquid cannot be uniformly dispersed, because tetraethyl silicate and tetrabutyl titanate are two kinds of viscous organic substances, which will make the solvent more viscous after adding, so that the powdery nanomaterials cannot be uniformly dispersed;

对所述纺丝液进行静电纺丝,制得纺丝纤维;静电纺丝为现有技术;Electrospinning the spinning solution to obtain spinning fibers; electrospinning is the prior art;

将所述纺丝纤维进行活化水解,然后通入惰性气体并且于400-800℃的温度下烧结,制得所述柔性电极材料。其中,所述活化水解通过将纺织纤维在空气中放置24h以上即可,无需催化剂,空气中的水蒸气便可以使其活化水解。在烧结过程中添加惰性气体,例如高纯氩气(99.999%的纯度),主要保护纤维中碳在烧结过程中的稳定,空气中碳会变成CO2气体;可保护制备的柔性电极材料中纤维的碳含量,赋予该纤维导电性。温度控制在400-800℃,有利于控制碳的石墨化程度,避免碳的石墨化程度过高。The spun fibers are activated and hydrolyzed, and then passed into an inert gas and sintered at a temperature of 400-800° C. to prepare the flexible electrode material. Wherein, the activated hydrolysis can be performed by placing the textile fibers in the air for more than 24 hours, and the water vapor in the air can activate and hydrolyze the fibers without a catalyst. Inert gas is added during the sintering process, such as high-purity argon (99.999% purity), which mainly protects the stability of the carbon in the fiber during the sintering process, and the carbon in the air will become CO2 gas; it can protect the fiber in the prepared flexible electrode material. The carbon content, which imparts electrical conductivity to the fiber. The temperature is controlled at 400-800°C, which is beneficial to control the degree of graphitization of carbon and avoid the degree of graphitization of carbon being too high.

在上述的制备方法中,硅酸四乙酯和钛酸四丁酯在酸性条件下遇水易水解,硅酸四乙酯和钛酸四丁酯的水解会由纤维中心向四周扩散,从而使得纤维产生多孔的结构;并且加入了纳米材料,使得纤维具有较佳的机械性能。另外,烧结过程中惰性气体的保护可保护纤维中碳的含量,赋予纤维的导电性。In the above-mentioned preparation method, tetraethyl silicate and tetrabutyl titanate are easily hydrolyzed in the presence of water under acidic conditions, and the hydrolysis of tetraethyl silicate and tetrabutyl titanate will diffuse from the center of the fiber to the surrounding, thereby making The fiber produces a porous structure; and nanomaterials are added to make the fiber have better mechanical properties. In addition, the protection of the inert gas during sintering protects the carbon content of the fibers and imparts electrical conductivity to the fibers.

实施例1Example 1

一种柔性电极材料的制备方法,包括:A preparation method of a flexible electrode material, comprising:

在有机溶剂中加入聚乙烯吡咯烷酮、冰乙酸和纳米材料搅拌均匀后,再加入硅酸四乙酯和钛酸四丁酯,制得纺丝液;After adding polyvinylpyrrolidone, glacial acetic acid and nanomaterials to the organic solvent and stirring evenly, then adding tetraethyl silicate and tetrabutyl titanate to prepare spinning solution;

对所述纺丝液进行静电纺丝,制得纺丝纤维;Electrospinning the spinning solution to obtain spinning fibers;

将所述纺丝纤维进行活化水解,然通入惰性气体并且于400-800℃的温度下烧结,制得所述柔性电极材料;The spun fibers are activated and hydrolyzed, and then passed in an inert gas and sintered at a temperature of 400-800° C. to obtain the flexible electrode material;

其中,以重量份计,所述聚乙烯吡咯烷酮、所述冰乙酸、所述硅酸四乙酯、所述钛酸四丁酯、所述有机溶剂分别加入10重量份、10重量份、20重量份、5重量份、55重量份;Wherein, in parts by weight, the polyvinylpyrrolidone, the glacial acetic acid, the tetraethyl silicate, the tetrabutyl titanate, and the organic solvent were added in 10 parts by weight, 10 parts by weight, and 20 parts by weight, respectively. parts, 5 parts by weight, 55 parts by weight;

所述有机溶剂为无水乙醇;Described organic solvent is dehydrated alcohol;

所述纺织液加入0.5重量份的纳米材料,所述纳米材料为一维纳米材料,具体为碳纳米管。The spinning solution is added with 0.5 parts by weight of nanomaterials, and the nanomaterials are one-dimensional nanomaterials, specifically carbon nanotubes.

实施例2Example 2

实施步骤与实施例一步骤相同,不同在于:The implementation steps are the same as those in the first embodiment, except that:

所述聚乙烯吡咯烷酮、所述冰乙酸、所述硅酸四乙酯、所述钛酸四丁酯、所述有机溶剂的添加量为:5重量份、15重量份、15重量份、8重量份、57 重量份;所述纳米材料的添加量为1重量份。The addition amounts of the polyvinylpyrrolidone, the glacial acetic acid, the tetraethyl silicate, the tetrabutyl titanate, and the organic solvent are: 5 parts by weight, 15 parts by weight, 15 parts by weight, 8 parts by weight parts, 57 parts by weight; the addition amount of the nanomaterial is 1 part by weight.

实施例3Example 3

实施步骤与实施例1步骤相同,不同在于:The implementation steps are the same as those in Example 1, except that:

所述聚乙烯吡咯烷酮、所述冰乙酸、所述硅酸四乙酯、所述钛酸四丁酯、所述纳米材料、所述有机溶剂的添加量为:15重量份、5重量份、25重量份、2重量份、53重量份;所述纳米材料的添加量为0.1重量份。The addition amounts of the polyvinylpyrrolidone, the glacial acetic acid, the tetraethyl silicate, the tetrabutyl titanate, the nanomaterial, and the organic solvent are: 15 parts by weight, 5 parts by weight, 25 parts by weight parts by weight, 2 parts by weight, 53 parts by weight; the addition amount of the nanomaterial is 0.1 part by weight.

实施例4Example 4

实施步骤与实施例1步骤相同,不同在于:The implementation steps are the same as those in Example 1, except that:

所述有机溶剂为二甲基甲酰胺。The organic solvent is dimethylformamide.

实施例5Example 5

实施步骤与实施例1步骤相同,不同在于:The implementation steps are the same as those in Example 1, except that:

所述有机溶剂为N-甲基吡咯烷酮。The organic solvent is N-methylpyrrolidone.

实施例6Example 6

实施步骤与实施例1步骤相同,不同在于:The implementation steps are the same as those in Example 1, except that:

所述催化剂采用盐酸替代冰乙酸。The catalyst uses hydrochloric acid instead of glacial acetic acid.

实施例7Example 7

实施步骤与实施例1步骤相同,不同在于:The implementation steps are the same as those in Example 1, except that:

所述纳米材料为一维纳米材料,具体为金属银纳米线。The nanomaterials are one-dimensional nanomaterials, specifically metallic silver nanowires.

实施例8Example 8

实施步骤与实施例1步骤相同,不同在于:The implementation steps are the same as those in Example 1, except that:

所述纳米材料为二维纳米材料,具体为氧化石墨烯。The nanomaterial is a two-dimensional nanomaterial, specifically graphene oxide.

实施例9Example 9

实施步骤与实施例1步骤相同,不同在于:The implementation steps are the same as those in Example 1, except that:

所述纳米材料为二维纳米材料,具体为二维过渡金属碳化物,更具体地为碳化钛。The nanomaterial is a two-dimensional nanomaterial, specifically a two-dimensional transition metal carbide, more specifically, titanium carbide.

实施例10Example 10

实施步骤与实施例1步骤相同,不同在于:The implementation steps are the same as those in Example 1, except that:

所述纳米材料为二维纳米材料,具体为二维过渡金属氮化物。The nanomaterials are two-dimensional nanomaterials, specifically two-dimensional transition metal nitrides.

实施例11Example 11

实施步骤与实施例1步骤相同,不同在于:The implementation steps are the same as those in Example 1, except that:

未添加所述纳米材料。The nanomaterials were not added.

对比例1Comparative Example 1

将二甲基乙酰胺与聚丙烯腈(PAN)混合后,制得纺丝液,对该纺丝液静电纺丝,制得电极材料,其中,二甲基乙酰胺与聚丙烯腈(PAN)的质量比为 88:12。After mixing dimethylacetamide and polyacrylonitrile (PAN), a spinning solution is prepared, and the spinning solution is electrospun to prepare an electrode material, wherein dimethylacetamide and polyacrylonitrile (PAN) The mass ratio is 88:12.

实验一:柔性电极材料空心结构测试实验Experiment 1: Test Experiment of Flexible Electrode Material Hollow Structure

采用Hitachi SU8010扫描电镜,对本发明的实施例1-11中制备的柔性电极材料以及对比例1中制备的电极材料进行扫描,记录所有电极材料中碳纤维材料截面形貌,结果如下:Using Hitachi SU8010 scanning electron microscope, the flexible electrode materials prepared in Examples 1-11 of the present invention and the electrode materials prepared in Comparative Example 1 were scanned, and the cross-sectional morphologies of carbon fiber materials in all electrode materials were recorded. The results are as follows:

表1碳纤维材料空心情况Table 1 Hollow case of carbon fiber material

实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4 实施例5Example 5 实施例6Example 6 空心hollow 空心hollow 空心hollow 空心hollow 空心hollow 空心hollow 实施例7Example 7 实施例8Example 8 实施例9Example 9 实施例10Example 10 实施例11Example 11 对比例1Comparative Example 1 空心hollow 空心hollow 空心hollow 空心hollow 空心hollow 实心 solid

根据上述表1中的结果可知,本发明的实施例1-11中的所有柔性电极材料中碳纤维材料截面都为空心结构,而现有技术的对比例1则为实心结构。说明相对于现有技术而言,本发明前述的各实施例制备的柔性电极材料具有良好的电化学性能。According to the results in Table 1 above, all the flexible electrode materials in Examples 1-11 of the present invention have a hollow structure in cross-section of the carbon fiber material, while Comparative Example 1 of the prior art has a solid structure. It is indicated that the flexible electrode materials prepared in the foregoing embodiments of the present invention have good electrochemical performance compared to the prior art.

此外,图1为实施例1中添加了碳纳米管(CNT)的柔性电极材料中的碳纤维材料截面形貌示意图,图2为实施例8中添加了氧化石墨烯的柔性电极材料中的碳纤维材料截面形貌示意图;图3为实施例9中添加了碳化钛的柔性电极材料中的碳纤维材料截面形貌示意图;图4为现有技术的对比例1中电极材料中的碳纤维材料截面形貌示意图。从图1至图4所示的结果中可以看出,本发明的实施例1、8、9中的所有柔性电极材料中碳纤维材料截面都为空心结构,而现有技术的对比例1则为实心结构。In addition, FIG. 1 is a schematic diagram of the cross-sectional morphology of the carbon fiber material in the flexible electrode material added with carbon nanotubes (CNT) in Example 1, and FIG. 2 is the carbon fiber material in the flexible electrode material added with graphene oxide in Example 8. Schematic diagram of the cross-sectional morphology; Figure 3 is a schematic diagram of the cross-sectional morphology of the carbon fiber material in the flexible electrode material added with titanium carbide in Example 9; Figure 4 is a schematic diagram of the cross-sectional morphology of the carbon fiber material in the electrode material in Comparative Example 1 of the prior art . It can be seen from the results shown in FIG. 1 to FIG. 4 that the carbon fiber material in all the flexible electrode materials in Examples 1, 8, and 9 of the present invention has a hollow structure in cross-section, while the comparative example 1 of the prior art is Solid structure.

实验二:柔性电极材料电化学性能实验Experiment 2: Electrochemical performance experiment of flexible electrode materials

采用LAND测试设备对由组装的电池进行电化学性能测试。具体实验过程如下:将柔性电极材料裁割为10mm直径的圆片,恒电流沉积定量的金属锂后,与NCM523匹配组装成全电池进行恒电流充放电测试。The electrochemical performance of the assembled cells was tested using LAND test equipment. The specific experimental process is as follows: the flexible electrode material is cut into 10mm diameter discs, and after constant current deposition of quantitative metal lithium, it is matched with NCM523 and assembled into a full battery for constant current charge-discharge test.

图5,图6,图7中下层黑线分别代表添加了氧化石墨烯(rGO)、MXene碳化钛、碳纳米管CNT纤维与锂复合后所组装电池的放电容量,灰色为空白对比。上层黑线为库伦效率,灰色为空白对比的库伦效率。Figure 5, Figure 6, and Figure 7, the lower black lines represent the discharge capacity of the assembled battery after adding graphene oxide (rGO), MXene titanium carbide, carbon nanotube CNT fibers and lithium composites, respectively, and the gray color is the blank comparison. The upper black line is the coulombic efficiency, and the gray is the coulombic efficiency of the blank contrast.

从图5至图7所示的结果中可以看出,采用本发明的实施例1、8、9所制得的柔性电极材料,具有更高的库伦效率,具有更好的电化学性能。It can be seen from the results shown in FIG. 5 to FIG. 7 that the flexible electrode materials prepared by using Examples 1, 8 and 9 of the present invention have higher coulombic efficiency and better electrochemical performance.

图8中下层黑线分别代表实施例1添加了碳纳米管CNT纤维与锂复合后所组装电池的放电容量,灰色为实施例11未添加纳米材料制备的柔性电池的放电容量。从图8所示的结果可以看出,实施例11未添加纳米材料所制得的柔性电极材料,其电化学性能稍差于实施例1。The black lines in the lower layer in Figure 8 represent the discharge capacity of the battery assembled in Example 1 with the addition of carbon nanotube CNT fibers and lithium, respectively, and the gray color is the discharge capacity of the flexible battery prepared in Example 11 without adding nanomaterials. It can be seen from the results shown in FIG. 8 that the electrochemical performance of the flexible electrode material prepared without adding nanomaterials in Example 11 is slightly worse than that in Example 1.

以上具体实施方式对本发明进行了详细的说明,但这些并非构成对本发明的限制。本发明的保护范围并不以上述实施方式为限,但凡本领域普通技术人员根据本发明所揭示内容所作的等效修饰或变化,皆应纳入权利要求书中记载的保护范围内。The above specific embodiments have described the present invention in detail, but these are not intended to limit the present invention. The protection scope of the present invention is not limited to the above-mentioned embodiments, but all equivalent modifications or changes made by those of ordinary skill in the art according to the contents disclosed in the present invention shall be included in the protection scope recorded in the claims.

Claims (10)

1.一种用于制备碳纤维材料的纺丝液,其特征在于,所述纺丝液包含:1. a spinning solution for preparing carbon fiber material, characterized in that, the spinning solution comprises: 聚乙烯吡咯烷酮、催化剂、硅酸四乙酯、钛酸四丁酯以及有机溶剂。Polyvinylpyrrolidone, catalyst, tetraethyl silicate, tetrabutyl titanate and organic solvent. 2.根据权利要求1所述的纺丝液,其特征在于,所述催化剂为冰乙酸。2. The spinning solution according to claim 1, wherein the catalyst is glacial acetic acid. 3.根据权利要求1所述的纺丝液,其特征在于,所述纺丝液中包含:3. spinning solution according to claim 1, is characterized in that, comprises in described spinning solution: 聚乙烯吡咯烷酮,5-15重量份;Polyvinylpyrrolidone, 5-15 parts by weight; 催化剂,5-15重量份;Catalyst, 5-15 parts by weight; 硅酸四乙酯,15-25重量份;Tetraethyl silicate, 15-25 parts by weight; 钛酸四丁酯,2-8重量份;Tetrabutyl titanate, 2-8 parts by weight; 有机溶剂,40-60重量份。Organic solvent, 40-60 parts by weight. 4.根据权利要求3所述的纺丝液,其特征在于,所述纺丝液中包含:4. The spinning solution according to claim 3, wherein the spinning solution comprises: 聚乙烯吡咯烷酮,9-11重量份;Polyvinylpyrrolidone, 9-11 parts by weight; 催化剂,9-11重量份;Catalyst, 9-11 parts by weight; 硅酸四乙酯,18-22重量份;Tetraethyl silicate, 18-22 parts by weight; 钛酸四丁酯,4-6重量份;Tetrabutyl titanate, 4-6 parts by weight; 有机溶剂,50-60重量份。Organic solvent, 50-60 parts by weight. 5.根据权利要求1所述的纺丝液,其特征在于,所述纺丝液还包括纳米材料,所述纳米材料包括一维纳米材料和二维纳米材料中的至少一种;以100重量份的纺丝液为基准,所述纳米材料的添加量为0.1-1重量份。5. The spinning solution according to claim 1, characterized in that, the spinning solution further comprises nanomaterials, and the nanomaterials comprise at least one of one-dimensional nanomaterials and two-dimensional nanomaterials; The amount of the nanomaterial added is 0.1-1 part by weight based on part of the spinning solution. 6.根据权利要求5所述的纺丝液,其特征在于,所述一维纳米材料至少包括碳纳米管与金属纳米线中的一种;所述金属纳米线为VIII、IB、IIIA族金属纳米线;6 . The spinning solution according to claim 5 , wherein the one-dimensional nanomaterial comprises at least one of carbon nanotubes and metal nanowires; the metal nanowires are metals from Groups VIII, IB, and IIIA. 7 . Nanowires; 所述二维纳米材料至少包括氧化石墨烯、二维过渡金属碳化物以及二维过渡金属氮化物中的一种。The two-dimensional nanomaterial includes at least one of graphene oxide, two-dimensional transition metal carbide and two-dimensional transition metal nitride. 7.根据权利要求1-6任一所述的纺丝液,其特征在于,所述有机溶剂至少包括无水乙醇、N-甲基吡咯烷酮、二甲基甲酰胺以及二甲基乙酰胺中的一种。7. The spinning solution according to any one of claims 1-6, wherein the organic solvent at least comprises dehydrated alcohol, N-methylpyrrolidone, dimethylformamide and dimethylacetamide. A sort of. 8.一种柔性电极材料,其特征在于,由权利要求1-7任一所述的纺丝液制备。8. A flexible electrode material, characterized in that, it is prepared from the spinning solution according to any one of claims 1-7. 9.一种柔性电极材料的制备方法,其特征在于,包括:9. A method for preparing a flexible electrode material, comprising: 在有机溶剂中加入聚乙烯吡咯烷酮、冰乙酸搅拌均匀后,再加入硅酸四乙酯和钛酸四丁酯,制得纺丝液;After adding polyvinylpyrrolidone and glacial acetic acid to the organic solvent and stirring evenly, then adding tetraethyl silicate and tetrabutyl titanate to obtain spinning solution; 对所述纺丝液进行静电纺丝,制得纺丝纤维;Electrospinning the spinning solution to obtain spinning fibers; 将所述纺丝纤维进行活化水解,然后通入惰性气体并且于400-800℃的温度下烧结,制得所述柔性电极材料。The spun fibers are activated and hydrolyzed, and then passed into an inert gas and sintered at a temperature of 400-800° C. to prepare the flexible electrode material. 10.一种柔性电极材料的制备方法,其特征在于,包括:10. A method for preparing a flexible electrode material, comprising: 在有机溶剂中加入聚乙烯吡咯烷酮、冰乙酸和纳米材料搅拌均匀后,再加入硅酸四乙酯和钛酸四丁酯,制得纺丝液;After adding polyvinylpyrrolidone, glacial acetic acid and nanomaterials to the organic solvent and stirring evenly, then adding tetraethyl silicate and tetrabutyl titanate to prepare spinning solution; 对所述纺丝液进行静电纺丝,制得纺丝纤维;Electrospinning the spinning solution to obtain spinning fibers; 将所述纺丝纤维进行活化水解,然后通入惰性气体并且于400-800℃的温度下烧结,制得所述柔性电极材料。The spun fibers are activated and hydrolyzed, and then passed into an inert gas and sintered at a temperature of 400-800° C. to prepare the flexible electrode material.
CN202010209387.7A 2020-03-23 2020-03-23 Spinning solution for preparing carbon fiber material, flexible electrode material and preparation method Pending CN111441107A (en)

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