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CN114974908B - Communicating tubular nitrogen-doped carbon material and preparation method and application thereof - Google Patents

Communicating tubular nitrogen-doped carbon material and preparation method and application thereof Download PDF

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CN114974908B
CN114974908B CN202210463618.6A CN202210463618A CN114974908B CN 114974908 B CN114974908 B CN 114974908B CN 202210463618 A CN202210463618 A CN 202210463618A CN 114974908 B CN114974908 B CN 114974908B
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carbon material
doped carbon
nitrogen
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CN114974908A (en
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潘红飞
张海宁
唐浩林
薛松林
刘进
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Foshan Xianhu Laboratory
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • Y02E60/13Energy storage using capacitors

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
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  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

本发明属于碳材料技术领域,公开了一种连通管状氮掺杂碳材料及其制备方法和应用。本发明提供的连通管状氮掺杂碳材料具有三维网络结构,其内部具有多个管状结构,管状结构之间相互连通,管状结构的端部具有开口并与外界相互连通,其比表面积为1000‑1300m2·g‑1,在1A·g‑1的恒电流充放电、‑1~0V(vs.HgO/Hg)条件下,放电比电容可达到302.1F·g‑1,具备良好的电容性能;本发明提供的自支撑柔性膜电极,具有面积较大,无需金属集流体支撑,断裂强度可达2.77MPa,断裂伸长率可达3.89%的优点;将本发明自支撑柔性膜电极组装成的离子液体双电层超级电容器具有良好的工作电压与能量密度。

The present invention belongs to the technical field of carbon materials, and discloses a connected tubular nitrogen-doped carbon material and a preparation method and application thereof. The connected tubular nitrogen-doped carbon material provided by the present invention has a three-dimensional network structure, wherein a plurality of tubular structures are provided inside the material, the tubular structures are interconnected, the ends of the tubular structures have openings and are interconnected with the outside world, and the specific surface area is 1000-1300m 2 ·g ‑1 , and the discharge specific capacitance can reach 302.1F·g ‑1 under the conditions of constant current charge and discharge of 1A·g ‑1 and ‑1~0V (vs.HgO/Hg), and has good capacitance performance; the self-supporting flexible membrane electrode provided by the present invention has the advantages of large area, no need for metal current collector support, fracture strength of up to 2.77MPa, and elongation at break of up to 3.89%; the ionic liquid double-layer supercapacitor assembled by the self-supporting flexible membrane electrode of the present invention has good operating voltage and energy density.

Description

一种连通管状氮掺杂碳材料及其制备方法和应用A connected tubular nitrogen-doped carbon material and its preparation method and application

技术领域Technical Field

本发明属于碳材料技术领域,特别涉及一种连通管状氮掺杂碳材料及其制备方法和应用。The invention belongs to the technical field of carbon materials, and in particular relates to a connected tubular nitrogen-doped carbon material and a preparation method and application thereof.

背景技术Background Art

超级电容器具有可以进行多次快速充放电以提供高瞬时能量的优势,是一种非常有潜力的环境友好型的储能器件。更短的充电和放电时间以及更长的寿命使得超级电容器能够作为优秀的能量循环再生系统,即电荷物理存储在电极表面,理论上系统内无化学反应,可以维持数百万次电荷存储机制的循环。此外,超级电容器设计的目的是实现更高的功率密度,但实际中却受其有限的能量密度和低的电位窗口等问题影响而难以实现,且能够低温运行并具有合理性能的超级电容器对于其在室外的应用至关重要。Supercapacitors have the advantage of being able to perform multiple rapid charge and discharge cycles to provide high instantaneous energy, and are a very promising environmentally friendly energy storage device. Shorter charge and discharge times and longer lifespans allow supercapacitors to serve as excellent energy recycling systems, i.e., charges are physically stored on the electrode surface. Theoretically, there is no chemical reaction in the system, and the charge storage mechanism can be maintained for millions of cycles. In addition, supercapacitors are designed to achieve higher power density, but in practice this is difficult to achieve due to problems such as limited energy density and low potential window, and supercapacitors that can operate at low temperatures and have reasonable performance are essential for their outdoor applications.

多孔碳材料是传统超级电容器碳基电极材料中具有代表性的一种,为了提高超级电容器电极材料的能量密度且在低温下具有合理的性能,最常用的策略是使用硬模板法制备多孔碳材料。其中碳前驱体和硬模板(通常是SiO2纳米颗粒)的混合物通过高温无氧热解碳化,然后去除硬模板。然而使用硬模板法直接制备所生成的孔隙大多相对独立,其电容性能较差,不适合在大电流下工作,这明显与超级电容器快速获得/释放能量的优点和工作方式相悖。为了形成一个多孔之间相互连接的结构,通常会利用KOH等物质在高温下的活性对多孔碳材料孔壁进行刻蚀,增加材料内部微孔数量。但是,使用KOH对碳材料进行刻蚀,通常需要二次煅烧过程,这往往会导致产量严重下降。Porous carbon materials are a representative type of traditional carbon-based electrode materials for supercapacitors. In order to improve the energy density of supercapacitor electrode materials and have reasonable performance at low temperatures, the most commonly used strategy is to prepare porous carbon materials using a hard template method. A mixture of a carbon precursor and a hard template (usually SiO2 nanoparticles) is carbonized by high-temperature oxygen-free pyrolysis, and then the hard template is removed. However, the pores generated by direct preparation using the hard template method are mostly relatively independent, and their capacitance performance is poor, which is not suitable for working under large currents. This is obviously contrary to the advantages and working methods of supercapacitors that quickly obtain/release energy. In order to form a porous structure that is interconnected, the activity of substances such as KOH at high temperatures is usually used to etch the pore walls of porous carbon materials to increase the number of micropores inside the material. However, etching carbon materials using KOH usually requires a secondary calcination process, which often leads to a serious decrease in yield.

发明内容Summary of the invention

本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出连通管状氮掺杂碳材料及其制备方法和应用,本发明提供的连通管状氮掺杂碳材料,其内部具有多个管状结构,且管状结构之间相互连通,具有良好的电容性能。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a connected tubular nitrogen-doped carbon material and a preparation method and application thereof. The connected tubular nitrogen-doped carbon material provided by the present invention has a plurality of tubular structures inside, and the tubular structures are interconnected, and has good capacitance performance.

本发明的第一方面提供一种连通管状氮掺杂碳材料,所述连通管状氮掺杂碳材料具有三维网络结构,所述连通管状氮掺杂碳材料的内部具有多个管状结构,所述管状结构之间相互连通,所述管状结构的端部具有开口并与外界相互连通。The first aspect of the present invention provides a connected tubular nitrogen-doped carbon material, which has a three-dimensional network structure. The interior of the connected tubular nitrogen-doped carbon material has multiple tubular structures, which are interconnected, and the ends of the tubular structures have openings and are interconnected with the outside.

本发明的第二方面提供本发明所述连通管状氮掺杂碳材料的制备方法,包括以下步骤:A second aspect of the present invention provides a method for preparing the interconnected tubular nitrogen-doped carbon material of the present invention, comprising the following steps:

取具有三维网络结构的纳米棒作为模板;Nanorods with a three-dimensional network structure are used as templates;

将所述钛酸盐纳米棒和造孔剂、聚合物单体、引发剂、交联剂和溶剂混合,进行聚合反应,得到聚合物前驱体(TiRDs/P-VIm/KNO3);The titanate nanorods are mixed with a pore-forming agent, a polymer monomer, an initiator, a cross-linking agent and a solvent to carry out a polymerization reaction to obtain a polymer precursor (TiRDs/P-VIm/KNO 3 );

将所述聚合物前驱体进行煅烧,去除模板,得到所述连通管状氮掺杂碳材料(NPHTCK)。The polymer precursor is calcined to remove the template, thereby obtaining the interconnected tubular nitrogen-doped carbon material (NPHTC K ).

优选地,所述模板的制备方法,包括以下步骤:Preferably, the method for preparing the template comprises the following steps:

将二氧化钛与碱液混合,进行水热反应,得到钛酸盐纳米棒;所述碱液为氢氧化钾或氢氧化钠溶液,所述氢氧化钠溶液的浓度为6~10mol·L-1;在所述将二氧化钛与碱液混合后的溶液中,所述二氧化钛的浓度为0.02~0.1g·mL-1,所述水热反应的温度为150~180℃,时间为24~48h。Titanium dioxide is mixed with alkali solution and subjected to hydrothermal reaction to obtain titanate nanorods; the alkali solution is potassium hydroxide or sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 6-10 mol·L -1 ; in the solution obtained by mixing titanium dioxide and alkali solution, the concentration of titanium dioxide is 0.02-0.1 g·mL -1 , the temperature of the hydrothermal reaction is 150-180°C, and the time is 24-48 hours.

优选地,所述造孔剂包括硝酸钾、硝酸钠或氯化铵中的一种,所述聚合物单体包括1-乙烯基咪唑、乙烯基吡咯烷酮或乙烯基吡啶中的一种,所述引发剂包括4,4′-偶氮二氰基戊酸、过硫酸钾或偶氮二异丁基脒盐酸盐中的一种,所述交联剂包括N,N′-亚甲基双丙烯酰胺、二乙烯基苯或二异氰酸酯中的一种,所述溶剂包括水、N,N-二甲基甲酰胺或二甲基亚砜中的一种;所述模板、所述造孔剂和所述聚合物单体的质量比为(0.5~1.25):(0.5~1.5):2.6。Preferably, the pore-forming agent includes one of potassium nitrate, sodium nitrate or ammonium chloride, the polymer monomer includes one of 1-vinylimidazole, vinyl pyrrolidone or vinyl pyridine, the initiator includes one of 4,4′-azobiscyanovaleric acid, potassium persulfate or azobisisobutylamidine hydrochloride, the cross-linking agent includes one of N,N′-methylenebisacrylamide, divinylbenzene or diisocyanate, and the solvent includes one of water, N,N-dimethylformamide or dimethyl sulfoxide; the mass ratio of the template, the pore-forming agent and the polymer monomer is (0.5-1.25):(0.5-1.5):2.6.

优选地,所述聚合反应的温度为70℃~80℃,聚合时间为1h~1.5h。Preferably, the polymerization reaction temperature is 70° C. to 80° C., and the polymerization time is 1 h to 1.5 h.

优选地,所述煅烧的温度为700℃~900℃,时间为1h~3h。Preferably, the calcination temperature is 700° C. to 900° C., and the calcination time is 1 h to 3 h.

本发明的第三方面提供本发明所述连通管状氮掺杂碳材料在超级电容器中的应用。The third aspect of the present invention provides the use of the interconnected tubular nitrogen-doped carbon material of the present invention in a supercapacitor.

基于上述应用,本发明提供了一种自支撑柔性膜电极,包括本发明所述的连通管状氮掺杂碳材料和助剂。Based on the above application, the present invention provides a self-supporting flexible membrane electrode, comprising the interconnected tubular nitrogen-doped carbon material and an additive as described in the present invention.

优选地,所述助剂包括导电剂、成膜剂和溶剂;所述导电剂包括乙炔黑或科琴黑,所述成膜剂包括聚偏二氟乙烯、聚甲基丙烯酸甲酯或聚四氟乙烯中的一种,所述溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮或二甲基亚砜中的一种。Preferably, the auxiliary agent includes a conductive agent, a film-forming agent and a solvent; the conductive agent includes acetylene black or Ketjen black, the film-forming agent includes one of polyvinylidene fluoride, polymethyl methacrylate or polytetrafluoroethylene, and the solvent includes one of N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide.

优选地,所述连通管状氮掺杂碳材料和所述导电剂的质量之和占所述连通管状氮掺杂碳材料、所述导电剂和所述成膜剂的质量之和的20%~40%。Preferably, the sum of the masses of the interconnected tubular nitrogen-doped carbon material and the conductive agent accounts for 20% to 40% of the sum of the masses of the interconnected tubular nitrogen-doped carbon material, the conductive agent and the film-forming agent.

优选地,所述自支撑柔性膜电极的厚度为70~80μm。Preferably, the thickness of the self-supporting flexible membrane electrode is 70-80 μm.

本发明所述自支撑柔性膜电极的制备方法,包括以下步骤:The method for preparing the self-supporting flexible membrane electrode of the present invention comprises the following steps:

将所述连通管状氮掺杂碳材料和所述助剂配制成浆料,再倒入模具中,干燥,得到所述自支撑柔性膜电极(SFME)。The interconnected tubular nitrogen-doped carbon material and the auxiliary agent are prepared into a slurry, which is then poured into a mold and dried to obtain the self-supporting flexible membrane electrode (SFME).

优选地,所述自支撑柔性膜电极的制备方法,包括以下步骤:Preferably, the method for preparing the self-supporting flexible membrane electrode comprises the following steps:

将所述连通管状氮掺杂碳材料和所述乙炔黑按照质量比为(4-2):1混合后作为碳基材料,再将碳基材料与所述聚偏二氟乙烯、所述N,N-二甲基甲酰胺混合配制成浆料,然后将浆料平铺于聚四氟乙烯模具中,烘干溶剂成膜,得到自支撑柔性膜电极。The interconnected tubular nitrogen-doped carbon material and the acetylene black are mixed in a mass ratio of (4-2):1 to form a carbon-based material, and then the carbon-based material is mixed with the polyvinylidene fluoride and the N,N-dimethylformamide to form a slurry. The slurry is then spread flat on a polytetrafluoroethylene mold, and the solvent is dried to form a film to obtain a self-supporting flexible membrane electrode.

相对于现有技术,本发明的有益效果如下:Compared with the prior art, the beneficial effects of the present invention are as follows:

本发明提供的连通管状氮掺杂碳材料的比表面积为1000-1300m2·g-1,在100mV·s-1扫速下的循环伏安曲线表现为具有双电层电容特性的类矩形,在1A·g-1的恒电流充放电、-1~0V(vs.HgO/Hg)条件下,放电比电容可达到302.1F·g-1,具备良好的电容性能。The interconnected tubular nitrogen-doped carbon material provided by the present invention has a specific surface area of 1000-1300m 2 ·g -1 , and a cyclic voltammetry curve at a scan rate of 100mV·s -1 exhibits a quasi-rectangular shape with double-layer capacitance characteristics. Under constant current charge and discharge conditions of 1A·g -1 and -1 to 0V (vs.HgO/Hg), the discharge specific capacitance can reach 302.1F·g -1 , and has good capacitance performance.

基于本发明连通管状氮掺杂碳材料制备的自支撑柔性膜电极,具有面积较大(可达10×10cm),无需金属集流体支撑,断裂强度可达2.77MPa,断裂伸长率可达3.89%的优点,在室温(约25℃)下的工作电压区间为0~3V;将本发明自支撑柔性膜电极组装成的离子液体双电层超级电容器具有良好的工作电压与能量密度,在1A·g-1、0~3V条件下,比电容可达到35F·g-1,在功率密度为1500W·kg-1时的能量密度可达到43.8W·kg-1The self-supporting flexible membrane electrode prepared based on the interconnected tubular nitrogen-doped carbon material of the present invention has the advantages of a large area (up to 10×10 cm), no need for metal current collector support, a breaking strength of up to 2.77 MPa, and a breaking elongation of up to 3.89%. The working voltage range at room temperature (about 25°C) is 0 to 3V; the ionic liquid double-layer supercapacitor assembled with the self-supporting flexible membrane electrode of the present invention has good working voltage and energy density. Under the conditions of 1A·g -1 and 0 to 3V, the specific capacitance can reach 35F·g -1 , and the energy density can reach 43.8W·kg-1 when the power density is 1500W·kg - 1 .

本发明的连通管状氮掺杂碳材料以及自支撑柔性膜电极的制备方法简单,操作方便,易于大规模、大面积生产。The preparation method of the interconnected tubular nitrogen-doped carbon material and the self-supporting flexible membrane electrode of the present invention is simple, easy to operate, and easy to produce on a large scale and over a large area.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为本发明实施例1的TiRDs和TiRDs/P-VIm/KNO3的SEM图。FIG. 1 is a SEM image of TiRDs and TiRDs/P-VIm/KNO 3 of Example 1 of the present invention.

图2为本发明实施例1的NPHTCK的SEM图。FIG. 2 is a SEM image of NPHTC K of Example 1 of the present invention.

图3为本发明实施例1-4的NPHTCK在100mV·s-1下的CV曲线和1A·g-1时的充放电曲线。FIG3 is a CV curve of NPHTC K of Examples 1-4 of the present invention at 100 mV·s -1 and a charge-discharge curve at 1 A·g -1 .

图4为实施例1、9和10的NPHTCK在1A·g-1时的充放电曲线。FIG4 is the charge and discharge curves of NPHTC K of Examples 1, 9 and 10 at 1 A·g -1 .

图5为实施例11的SFME的SEM图,其中a和b为其表面图,c和d为其在液氮中淬断后所形成的断面图。FIG. 5 is a SEM image of the SFME of Example 11, wherein a and b are surface images thereof, and c and d are cross-sectional images thereof after quenching in liquid nitrogen.

图6为实施例11-14的SFME的成型图。FIG. 6 is a diagram showing the formation of SFME of Examples 11-14.

图7为实施例11-13的SFME的抗拉强度和断裂延伸率图。FIG. 7 is a graph of tensile strength and elongation at break for SFMEs of Examples 11-13.

图8为实施例11-13所组装的电容器的电化学性能测试图。FIG8 is a graph showing the electrochemical performance of the capacitors assembled in Examples 11-13.

具体实施方式DETAILED DESCRIPTION

为了让本领域技术人员更加清楚明白本发明所述技术方案,现列举以下实施例进行说明。需要指出的是,以下实施例对本发明要求的保护范围不构成限制作用。In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

以下实施例中所用的原料、试剂如无特殊说明,均可从常规商业途径得到,或者可以通过现有已知方法得到。Unless otherwise specified, the raw materials and reagents used in the following examples can be obtained from conventional commercial sources or by existing known methods.

实施例1Example 1

一种连通管状氮掺杂碳材料的制备方法,包括以下步骤:A method for preparing a connected tubular nitrogen-doped carbon material comprises the following steps:

(1)将1g粒径为25nm的二氧化钛粉末加入到50mL、浓度为10mol·L-1的氢氧化钠溶液中,搅拌0.5小时后置于反应釜中,于180℃下进行水热反应24小时,再将反应产物用去离子水洗至中性,然后置于冻干机进行冷冻干燥后,研磨成白色粉末,得到钛酸盐纳米棒(TiRDs),作为模板备用;(1) 1 g of titanium dioxide powder with a particle size of 25 nm was added to 50 mL of a sodium hydroxide solution with a concentration of 10 mol·L -1 , stirred for 0.5 hours, and then placed in a reactor for hydrothermal reaction at 180° C. for 24 hours. The reaction product was then washed with deionized water until neutral, and then placed in a freeze dryer for freeze drying, and then ground into a white powder to obtain titanate nanorods (TiRDs), which were used as templates for later use;

(2)将0.75g的TiRDs、1.25g的硝酸钾、2.6g的1-乙烯基咪唑、0.0375g的4,4′-偶氮二氰基戊酸以及0.0425g的N,N′-亚甲基双丙烯酰胺加入到装有10mL去离子水的烧瓶中,超声、搅拌各0.5小时,再使用液氮将混合溶液进行冻融脱气三次后,置于80℃的油浴锅中聚合反应1.5小时,然后将聚合得到的白色固体进行冷冻干燥,得到聚合物前驱体(TiRDs/P-VIm/KNO3);(2) 0.75 g of TiRDs, 1.25 g of potassium nitrate, 2.6 g of 1-vinylimidazole, 0.0375 g of 4,4′-azobiscyanovaleric acid and 0.0425 g of N,N′-methylenebisacrylamide were added to a flask containing 10 mL of deionized water, and ultrasonicated and stirred for 0.5 hours respectively. The mixed solution was then freeze-thawed and degassed three times with liquid nitrogen, and then placed in an oil bath at 80°C for polymerization reaction for 1.5 hours. The white solid obtained by polymerization was then freeze-dried to obtain a polymer precursor (TiRDs/P-VIm/KNO 3 );

(3)将TiRDs/P-VIm/KNO3在氩气气氛中、800℃下煅烧2小时,将煅烧后的产物倒入氢氟酸溶液中浸泡48小时以去除模板,再用去离子水洗至中性,烘干得到连通管状氮掺杂碳材料(NPHTCK)。(3) TiRDs/P-VIm/KNO 3 was calcined at 800 °C for 2 h in an argon atmosphere, and the calcined product was poured into a hydrofluoric acid solution and soaked for 48 h to remove the template, then washed with deionized water until neutral, and dried to obtain a connected tubular nitrogen-doped carbon material (NPHTC K ).

图1a为实施例1中所制备的TiRDs的SEM图,可以明显地看出所有的TiRDs长度均为微米级别,但直径大小不一,几十纳米至几百纳米均有分布。图1b为实施例1中所制备的TiRDs/P-VIm/KNO3的SEM图,由于TiRDs尺寸较大,可以在TiRDs/PVIm-N/KNO3的表面观察到包裹于聚合物内部的呈现出堆积状态的棒状结构,表明交联聚合物可以在保持模板三维堆积结构的前提下有效地将模板固定在其内部。Figure 1a is a SEM image of the TiRDs prepared in Example 1. It can be clearly seen that all TiRDs are of micrometer length, but the diameters vary from tens of nanometers to hundreds of nanometers. Figure 1b is a SEM image of the TiRDs/P-VIm/KNO 3 prepared in Example 1. Due to the large size of TiRDs, a stacked rod-like structure wrapped in the polymer can be observed on the surface of TiRDs/PVIm-N/KNO 3 , indicating that the cross-linked polymer can effectively fix the template inside it while maintaining the three-dimensional stacking structure of the template.

图2a为NPHTCK的SEM图,在对TiRDs/PVIm-N/KNO3进行煅烧碳化并除去TiRDs模板之后,材料的三维空间结构与间隙依然清晰可见,与煅烧之前的基本保持一致,表明材料在经过高温煅烧及后续处理过程中可以有效地保留堆积结构与模板形貌。值得注意的是,在材料边缘处可以明显观察到管状结构的端部为开口状态,表明NPHTCK内部保留的管状结构通道可以有效地与外界交互。此外,从图2b中的高倍率SEM图可以看出,管状结构之间为相互连接、贯通的状态,而非以单根碳纳米管的形式独立存在。Figure 2a is a SEM image of NPHTC K. After calcining and carbonizing TiRDs/PVIm-N/KNO 3 and removing the TiRDs template, the three-dimensional spatial structure and gaps of the material are still clearly visible, which is basically consistent with that before calcination, indicating that the material can effectively retain the stacking structure and template morphology during high-temperature calcination and subsequent treatment. It is worth noting that it can be clearly observed that the ends of the tubular structure are open at the edge of the material, indicating that the tubular structure channels retained inside NPHTC K can effectively interact with the outside world. In addition, it can be seen from the high-magnification SEM image in Figure 2b that the tubular structures are interconnected and interpenetrated, rather than existing independently in the form of a single carbon nanotube.

实施例2-4Embodiment 2-4

实施例2-4与实施例1的区别仅在于步骤(2)中所使用的TiRDs的用量不同,具体为:实施例2所使用的TiRDs为0.5g,实施例3所使用的TiRDs为1g,实施例4所使用的TiRDs为1.25g,其他组分、使用量和制备方法均同实施例1。The difference between Examples 2-4 and Example 1 is only that the amount of TiRDs used in step (2) is different, specifically: 0.5 g of TiRDs is used in Example 2, 1 g of TiRDs is used in Example 3, and 1.25 g of TiRDs is used in Example 4. The other components, usage amounts and preparation methods are the same as those in Example 1.

不同的TiRDs用量对NPHTCK性能的影响Effects of different TiRDs dosage on NPHTC K performance

对比实施例1-4(实施例1制备的NPHTCK记为NPHTCK-0.75,实施例2制备的NPHTCK记为NPHTCK-0.5,实施例3制备的NPHTCK记为NPHTCK-1,实施例4制备的NPHTCK记为NPHTCK-1.25),根据室温(25℃)下三电极系统中的循环伏安(CV)曲线(图3a)可以看出,四种不同TiRDs用量所制备的NPHTCK样品在100mV·s-1扫速下的CV曲线均表现为具有双电层电容特性的类矩形。同时,不同样品的CV曲线的大小和形状又有所区别,说明不同的TiRDs用量对NPHTCK的性能确实有影响。为了具体地评估各个样品的电容性能,对其进行了1A·g-1的恒电流充放电(GCD)测试,如图3b所示,可以看出,所有样品在-1~0V(vs.HgO/Hg)均呈现出符合双电层电容器特性的较为对称的三角形GCD曲线。根据公式计算得出NPHTCK-0.5(实施例2)、NPHTCK-0.75(实施例1)、NPHTCK-1(实施例3)和NPHTCK-1.25(实施例4)的放电比电容分别为272、302.1、277.4和251.4F·g-1,其中在TiRDs与1-乙烯基咪唑的质量比为0.75:2.6时所制得的NPHTCK拥有最佳的电容性能,即实施例1中所制备的NPHTCK性能最佳。Comparative Examples 1-4 (NPHTC K prepared in Example 1 is recorded as NPHTC K -0.75, NPHTC K prepared in Example 2 is recorded as NPHTC K -0.5, NPHTC K prepared in Example 3 is recorded as NPHTC K -1, and NPHTC K prepared in Example 4 is recorded as NPHTC K -1.25), according to the cyclic voltammetry (CV) curve (Figure 3a) in the three-electrode system at room temperature (25°C), it can be seen that the CV curves of the NPHTC K samples prepared by four different TiRDs dosages at a scan rate of 100mV·s -1 are all rectangular with double-layer capacitance characteristics. At the same time, the size and shape of the CV curves of different samples are different, indicating that different TiRDs dosages do have an effect on the performance of NPHTC K. In order to specifically evaluate the capacitance performance of each sample, a constant current charge and discharge (GCD) test of 1A·g- 1 was performed on it. As shown in Figure 3b, it can be seen that all samples show a relatively symmetrical triangular GCD curve that conforms to the characteristics of a double-layer capacitor at -1 to 0V (vs.HgO/Hg). According to the formula, the discharge specific capacitances of NPHTCK-0.5 (Example 2), NPHTCK-0.75 (Example 1), NPHTCK-1 (Example 3) and NPHTCK-1.25 (Example 4) are 272, 302.1, 277.4 and 251.4F·g -1 , respectively. Among them, the NPHTC K prepared when the mass ratio of TiRDs to 1-vinylimidazole is 0.75:2.6 has the best capacitance performance, that is, the NPHTC K prepared in Example 1 has the best performance.

实施例5-8Embodiment 5-8

实施例5-8与实施例1的区别仅在于步骤(2)中所使用的硝酸钾的用量不同,具体为:实施例5所使用的硝酸钾为0.5g,实施例6所使用的硝酸钾为0.75g,实施例7所使用的硝酸钾为1g,实施例8所使用的硝酸钾为1.5g,其他组分、使用量和制备方法均同实施例1。The difference between Examples 5-8 and Example 1 is only that the amount of potassium nitrate used in step (2) is different, specifically: the potassium nitrate used in Example 5 is 0.5 g, the potassium nitrate used in Example 6 is 0.75 g, the potassium nitrate used in Example 7 is 1 g, and the potassium nitrate used in Example 8 is 1.5 g. The other components, usage amounts and preparation methods are the same as those in Example 1.

不同的硝酸钾用量对NPHTCK性能的影响Effect of different potassium nitrate dosage on the performance of NPHTC K

对比实施例5-8,在硝酸钾用量为0.5g、0.75g、1g和1.5g时,所制得的样品的放电比电容分别为248.5、260、283和269F·g-1,表明随着硝酸钾用量的增加,NPHTCK的内部联通结构和微孔增加,电容性能提升;而过量的硝酸钾则会对NPHTCK过度刻蚀,造成孔结构的合并与破坏,使得NPHTCK的电容性能下降。其中,在硝酸钾与1-乙烯基咪唑的质量比为1.25:2.6时所制备得到的NPHTCK拥有最佳的电容性能,即实施例1中所制备的NPHTCK性能最佳。Comparative Examples 5-8, when the amount of potassium nitrate is 0.5g, 0.75g, 1g and 1.5g, the discharge specific capacitance of the prepared samples is 248.5, 260, 283 and 269F·g -1 , respectively, indicating that with the increase of the amount of potassium nitrate, the internal interconnected structure and micropores of NPHTC K increase, and the capacitance performance is improved; while excessive potassium nitrate will over-etch NPHTC K , causing the merging and destruction of the pore structure, so that the capacitance performance of NPHTC K decreases. Among them, the NPHTC K prepared when the mass ratio of potassium nitrate to 1-vinylimidazole is 1.25:2.6 has the best capacitance performance, that is, the NPHTC K prepared in Example 1 has the best performance.

实施例9-10Examples 9-10

实施例9-10与实施例1的区别仅在于步骤(3)中的煅烧温度不同,具体为:实施例9的煅烧温度为700℃,实施例10的煅烧温度为900℃,其他组分、使用量和制备方法均同实施例1。The difference between Examples 9-10 and Example 1 is only the calcination temperature in step (3), specifically: the calcination temperature of Example 9 is 700°C, and the calcination temperature of Example 10 is 900°C. The other components, usage amounts and preparation methods are the same as those of Example 1.

不同的煅烧温度对NPHTCK性能的影响Effect of different calcination temperatures on the properties of NPHTC K

图4为实施例1、9和10中在不同的煅烧温度下所制备的NPHTCK材料在1A·g-1的电流密度下的GCD曲线。其中700℃和900℃时的放电比电容为266.3F·g-1和280.6F·g-1,均低于800℃时的302.1F·g-1。这是由于硝酸钾的加入可以明显增加材料的比表面积以及微孔含量,从而有效提高材料的电容性能。而随着煅烧温度的升高,硝酸钾的刻蚀效果增强,材料的石墨化程度提高,电容性能提高;但过高的煅烧温度,会导致硝酸钾对碳材料过度刻蚀,对材料的骨架和结构造成破坏,并且材料中N掺杂量下降,导致电容性能反而下降。因此,制备NPHTCK材料的最适宜煅烧温度为800℃,即实施例1中所制备的NPHTCK性能最佳。Figure 4 is the GCD curve of the NPHTC K material prepared at different calcination temperatures in Examples 1, 9 and 10 at a current density of 1A·g -1 . The discharge specific capacitance at 700°C and 900°C is 266.3F·g -1 and 280.6F·g -1 , both lower than 302.1F·g -1 at 800°C. This is because the addition of potassium nitrate can significantly increase the specific surface area and micropore content of the material, thereby effectively improving the capacitance performance of the material. As the calcination temperature increases, the etching effect of potassium nitrate is enhanced, the degree of graphitization of the material is improved, and the capacitance performance is improved; but too high a calcination temperature will cause potassium nitrate to over-etch the carbon material, damage the skeleton and structure of the material, and the N doping amount in the material decreases, resulting in a decrease in capacitance performance. Therefore, the most suitable calcination temperature for preparing the NPHTC K material is 800°C, that is, the NPHTC K prepared in Example 1 has the best performance.

实施例11Embodiment 11

一种自支撑柔性膜电极的制备方法,包括以下步骤:A method for preparing a self-supporting flexible membrane electrode comprises the following steps:

将0.12g的NPHTCK与0.03g的乙炔黑混合后(碳基材料),再与0.35g的聚偏二氟乙烯混合,倒入10mL的N,N-二甲基甲酰胺溶液中,搅拌配制成具有一定流动性以及粘度的浆料,并将其倒入聚四氟乙烯模具(10×10cm)中,置于50℃烘箱中烘干12小时,取出膜得到自支撑柔性膜电极(SFME-30wt%);其中,碳基材料的质量占碳基材料与聚偏二氟乙烯的质量之和的30%,即碳基材料的质量占比为30%。0.12 g of NPHTC K was mixed with 0.03 g of acetylene black (carbon-based material), and then mixed with 0.35 g of polyvinylidene fluoride, poured into 10 mL of N,N-dimethylformamide solution, stirred to prepare a slurry with certain fluidity and viscosity, and poured into a polytetrafluoroethylene mold (10×10 cm), placed in a 50°C oven for drying for 12 hours, and the film was taken out to obtain a self-supporting flexible membrane electrode (SFME-30wt%); wherein the mass of the carbon-based material accounts for 30% of the sum of the mass of the carbon-based material and polyvinylidene fluoride, that is, the mass of the carbon-based material accounts for 30%.

实施例12-14Examples 12-14

实施例12-14与实施例11的区别仅在于碳基材料的质量占比不同,具体为:实施例12(NPHTCK、乙炔黑和聚偏二氟乙烯的质量分别为:0.08g、0.02g和0.4g,碳基材料的质量占比为20%,得到的自支撑柔性膜电极记为SFME-20wt%),实施例13(NPHTCK、乙炔黑和聚偏二氟乙烯的质量分别为:0.16g、0.04g和0.3g,碳基材料的质量占比为40%,得到的自支撑柔性膜电极记为SFME-40wt%),实施例14(NPHTCK、乙炔黑和聚偏二氟乙烯的质量分别为:0.2g、0.05g和0.25g,碳基材料的质量占比为50%,得到的自支撑柔性膜电极记为SFME-50wt%),其他组分、使用量和制备方法均同实施例11。The difference between Examples 12-14 and Example 11 is only that the mass proportion of carbon-based materials is different, specifically: Example 12 (the masses of NPHTC K , acetylene black and polyvinylidene fluoride are: 0.08g, 0.02g and 0.4g respectively, the mass proportion of carbon-based materials is 20%, and the obtained self-supporting flexible membrane electrode is recorded as SFME-20wt%), Example 13 (the masses of NPHTC K , acetylene black and polyvinylidene fluoride are: 0.16g, 0.04g and 0.3g respectively, the mass proportion of carbon-based materials is 40%, and the obtained self-supporting flexible membrane electrode is recorded as SFME-40wt%), Example 14 (the masses of NPHTC K , acetylene black and polyvinylidene fluoride are: 0.2g, 0.05g and 0.25g respectively, the mass proportion of carbon-based materials is 50%, and the obtained self-supporting flexible membrane electrode is recorded as SFME-50wt%), and the other components, usage amounts and preparation methods are the same as Example 11.

图5为实施例11中所制备的自支撑柔性膜电极的SEM图,其中图5a和图5b为其表面,图5c和图5d为其在液氮中淬断后所形成的断面。从图5a中可以明显看出实施例11中所制备的自支撑柔性膜电极(SFME-30wt%)是堆积成型的膜,其中还保留有加热烘干过程中溶解于浆料的气体溢出所形成的气孔,符合浇筑法制备薄膜的特点。增加放大倍数后,如图5b所示,可以明显看到NPHTCK的管状结构,并且呈现出被聚偏二氟乙烯包裹的状态,从而形成薄膜。图5c的断面图表明SFME-30wt%为丰富的多孔薄膜,气孔和NPHTCK的管状结构通道也能够在放大倍数更高的图5d中清晰地观察到。Figure 5 is a SEM image of the self-supporting flexible membrane electrode prepared in Example 11, wherein Figures 5a and 5b are its surfaces, and Figures 5c and 5d are the cross-sections formed after it is quenched in liquid nitrogen. It can be clearly seen from Figure 5a that the self-supporting flexible membrane electrode (SFME-30wt%) prepared in Example 11 is a stacked film, in which pores formed by the overflow of the gas dissolved in the slurry during the heating and drying process are retained, which conforms to the characteristics of preparing thin films by the casting method. After increasing the magnification, as shown in Figure 5b, the tubular structure of NPHTC K can be clearly seen, and it appears to be wrapped by polyvinylidene fluoride to form a thin film. The cross-sectional view of Figure 5c shows that SFME-30wt% is a rich porous film, and the pores and tubular structure channels of NPHTC K can also be clearly observed in Figure 5d with a higher magnification.

不同质量占比的碳基材料对自支撑柔性膜电极机械性能的影响Effects of different mass proportions of carbon-based materials on the mechanical properties of self-supporting flexible membrane electrodes

对比实施例11-14,根据具有不同质量占比碳基材料的浆料倒入模具烘干后还未脱模时的图片(图6)可以判断,当碳材料质量比小于40wt%时,可以通过浇筑烘干的方式在模具中形成较为平整且完整的薄膜;当碳材料质量比为40%时,成型的膜仅可以部分地取下,表明此时膜的机械性能已经下降;当碳材料的质量比为50wt%时,相对的聚偏二氟乙烯的量较低,不足以支撑形成完整的薄膜,在未脱模时就已经碎裂,无法成膜。Comparative Examples 11-14, according to the pictures (Figure 6) of the slurry with different mass proportions of carbon-based materials poured into the mold after drying but not demolding, it can be judged that when the mass ratio of the carbon material is less than 40wt%, a relatively flat and complete film can be formed in the mold by pouring and drying; when the mass ratio of the carbon material is 40%, the formed film can only be partially removed, indicating that the mechanical properties of the film have decreased at this time; when the mass ratio of the carbon material is 50wt%, the relative amount of polyvinylidene fluoride is low, which is insufficient to support the formation of a complete film, and it has been broken before demolding, and cannot form a film.

图7为实施例11-13不同质量占比的碳基材料所制备的SFME-20wt%、SFME-30wt%和SFME-40wt%的抗拉强度和断裂延伸率图,测试时将薄膜裁剪为7×1cm的矩形,标距为30mm,拉伸速率为5mm·min-1。从图7中曲线可知,SFME-40wt%的机械强度最差,其断裂强度为0.59mPa,断裂伸长率为0.88%;SFME-20wt%次之,断裂强度为1.78mPa,断裂伸长率为1.41%;而三者中,SFME-30wt%的机械性能较为优异,断裂强度为2.77mPa,断裂伸长率为3.89%。综上,SFME-30wt%拥有较为优异的机械性能。FIG7 is a graph showing the tensile strength and elongation at break of SFME-20wt%, SFME-30wt% and SFME-40wt% prepared from carbon-based materials with different mass proportions in Examples 11-13. During the test, the film was cut into a rectangle of 7×1cm, the gauge length was 30mm, and the tensile rate was 5mm·min -1 . From the curve in FIG7, it can be seen that SFME-40wt% has the worst mechanical strength, with a fracture strength of 0.59mPa and a fracture elongation of 0.88%; SFME-20wt% is second, with a fracture strength of 1.78mPa and a fracture elongation of 1.41%; and among the three, SFME-30wt% has relatively excellent mechanical properties, with a fracture strength of 2.77mPa and a fracture elongation of 3.89%. In summary, SFME-30wt% has relatively excellent mechanical properties.

不同质量占比的碳基材料对自支撑柔性膜电极电性能的影响Effects of different mass proportions of carbon-based materials on the electrical properties of self-supporting flexible membrane electrodes

将实施例11-13不同质量占比的碳基材料所制备的SFME-20wt%、SFME-30wt%和SFME-40wt%分别裁剪为Φ14mm的圆形电极片作为电极,2mol·L-1的1-乙基-3-甲基咪唑四氟硼酸盐(EMIMBF4)/无水乙腈(acetonitrile,ACN)作为电解液,玻璃纤维隔膜(Φ16mm)作为隔膜,垫片和扣式电池壳(CR2016)组装成扣式离子液体双电层超级电容器(SC-IL),测试其电容性能。SFME-20wt%, SFME-30wt% and SFME-40wt% prepared with carbon-based materials of different mass proportions in Examples 11-13 were cut into circular electrode sheets of Φ14 mm as electrodes, 2 mol·L -1 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4)/anhydrous acetonitrile (ACN) as electrolyte, glass fiber diaphragm (Φ16 mm) as diaphragm, gasket and button battery shell (CR2016) were assembled into button ionic liquid double-layer supercapacitors (SC-IL), and their capacitance performance was tested.

根据图8a中室温下的线性扫描伏安(LSV)曲线可以看出,在不使用金属集流体制备电极的情况下,室温下,所有器件的LSV曲线的起始电位非常接近,均为3V左右,说明直接使用SFME组装的SC-IL具有良好的电化学稳定性以及工作电压。图8b记录了上述器件的奈奎斯特(Nyquist)曲线,可以发现,随着碳材料的质量占比从20wt%增加至40wt%,所组装的电容器器件的阻抗显著减小,说明膜电极中碳材料的质量占比增加可以有效地降低器件的阻抗。此外,使用SFME-30wt%和SFME-40wt%时,Nyquist曲线的低频区域均为几乎垂直于横轴的曲线,说明使用这两种膜电极所组装的SC-IL内部具有较为优异的离子扩散能力。根据LSV曲线的起始电位,在0~3V的电压范围内分别对三种器件进行CV和GCD测试。在图8c中可以明显看出,室温下,扫速为100mV·s-1时,使用SFME-30wt%和SFME-40wt%所组装的电容器的CV曲线是较为标准的类矩形;而使用SFME-20wt%作为电极时,由于聚偏二氟乙烯的绝缘特性,CV曲线为非类矩形,且更加细窄、尖锐,进一步说明SFME-20wt%所组装的SC-IL电容性能不理想。由图8d中的GCD曲线计算得知,室温下,当电流密度为1A·g-1时,使用所制备的SFME-20wt%、SFME-30wt%和SFME-40wt%作为电极所组装的SC-IL的比电容分别为22.7、35和31F·g-1,换算后三种器件在功率密度为1500w·kg-1时的能量密度分别为28.4、43.8和38.8wh·kg-1According to the linear sweep voltammetry (LSV) curve at room temperature in Figure 8a, it can be seen that when the metal current collector is not used to prepare the electrode, the starting potential of the LSV curve of all devices at room temperature is very close, all about 3V, indicating that the SC-IL assembled directly using SFME has good electrochemical stability and working voltage. Figure 8b records the Nyquist curve of the above device. It can be found that as the mass proportion of carbon material increases from 20wt% to 40wt%, the impedance of the assembled capacitor device decreases significantly, indicating that the increase in the mass proportion of carbon material in the membrane electrode can effectively reduce the impedance of the device. In addition, when SFME-30wt% and SFME-40wt% are used, the low-frequency region of the Nyquist curve is almost perpendicular to the horizontal axis, indicating that the SC-IL assembled using these two membrane electrodes has a relatively excellent ion diffusion capacity. According to the starting potential of the LSV curve, CV and GCD tests were performed on the three devices in the voltage range of 0 to 3V. It can be clearly seen in Figure 8c that at room temperature, when the scan rate is 100mV·s -1 , the CV curves of the capacitors assembled using SFME-30wt% and SFME-40wt% are relatively standard rectangular; while when SFME-20wt% is used as the electrode, due to the insulating properties of polyvinylidene fluoride, the CV curve is non-rectangular, narrower and sharper, further indicating that the capacitance performance of the SC-IL assembled using SFME-20wt% is not ideal. Calculated from the GCD curve in Figure 8d, at room temperature, when the current density is 1A·g -1 , the specific capacitances of the SC-IL assembled using the prepared SFME-20wt%, SFME-30wt% and SFME-40wt% as electrodes are 22.7, 35 and 31F·g -1 , respectively. After conversion, the energy densities of the three devices at a power density of 1500w·kg -1 are 28.4, 43.8 and 38.8wh·kg -1 , respectively.

结合SFME的机械性能可知,室温下,SFME-30wt%是一种可以大面积成膜的拥有较好机械性能的膜电极,并且在使用SFME-30wt%组装离子液体扣式双电层超级电容器时,器件拥有较小的阻抗和优异的电容性能。因此,碳基材料的质量占比为30%为制备自支撑柔性膜电极配制浆料时的最佳配比。Combined with the mechanical properties of SFME, it can be seen that at room temperature, SFME-30wt% is a membrane electrode with good mechanical properties that can be formed on a large area, and when SFME-30wt% is used to assemble ionic liquid button double-layer supercapacitors, the device has a small impedance and excellent capacitance performance. Therefore, a mass proportion of 30% carbon-based materials is the best ratio for preparing slurry for preparing self-supporting flexible membrane electrodes.

以上对本发明的较佳实施方式进行了具体说明,但本发明创造并不限于所述实施例,熟悉本领域的技术人员在不违背本发明精神的前提下还可作出种种的等同变型或替换,这些等同的变型或替换均包含在本申请权利要求所限定的范围内。The preferred embodiments of the present invention are specifically described above, but the invention is not limited to the embodiments. Those skilled in the art may make various equivalent modifications or substitutions without violating the spirit of the invention. These equivalent modifications or substitutions are all included in the scope defined by the claims of this application.

Claims (4)

1.一种自支撑柔性膜电极,其特征在于,由连通管状氮掺杂碳材料和助剂组成,无需金属集流体支撑;1. A self-supporting flexible membrane electrode, characterized in that it is composed of interconnected tubular nitrogen-doped carbon materials and additives, and does not require metal current collector support; 所述助剂包括导电剂、成膜剂和溶剂;所述导电剂包括乙炔黑或科琴黑,所述成膜剂包括聚偏二氟乙烯、聚甲基丙烯酸甲酯或聚四氟乙烯中的一种,所述溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮或二甲基亚砜中的一种;The auxiliary agent includes a conductive agent, a film-forming agent and a solvent; the conductive agent includes acetylene black or Ketjen black, the film-forming agent includes one of polyvinylidene fluoride, polymethyl methacrylate or polytetrafluoroethylene, and the solvent includes one of N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide; 所述连通管状氮掺杂碳材料和所述导电剂的质量之和占所述连通管状氮掺杂碳材料、所述导电剂和所述成膜剂的质量之和的20%~40%;The sum of the masses of the interconnected tubular nitrogen-doped carbon material and the conductive agent accounts for 20% to 40% of the sum of the masses of the interconnected tubular nitrogen-doped carbon material, the conductive agent and the film-forming agent; 所述连通管状氮掺杂碳材料具有三维网络结构,所述连通管状氮掺杂碳材料的内部具有多个管状结构,所述管状结构之间相互连通,所述管状结构的端部具有开口并与外界相互连通;The interconnected tubular nitrogen-doped carbon material has a three-dimensional network structure, the interior of the interconnected tubular nitrogen-doped carbon material has a plurality of tubular structures, the tubular structures are interconnected, and the ends of the tubular structures have openings and are interconnected with the outside; 所述连通管状氮掺杂碳材料通过包括以下步骤的制备方法制备:The interconnected tubular nitrogen-doped carbon material is prepared by a preparation method comprising the following steps: 取具有三维网络结构的钛酸盐纳米棒作为模板;Titanate nanorods with a three-dimensional network structure are used as templates; 将钛酸盐纳米棒和造孔剂、聚合物单体、引发剂、交联剂和溶剂混合,进行聚合反应,得到聚合物前驱体;The titanate nanorods are mixed with a pore-forming agent, a polymer monomer, an initiator, a cross-linking agent and a solvent to carry out a polymerization reaction to obtain a polymer precursor; 将所述聚合物前驱体进行煅烧,去除模板,得到所述连通管状氮掺杂碳材料;calcining the polymer precursor and removing the template to obtain the interconnected tubular nitrogen-doped carbon material; 所述造孔剂包括硝酸钾、硝酸钠或氯化铵中的一种,所述聚合物单体包括1-乙烯基咪唑、乙烯基吡咯烷酮或乙烯基吡啶中的一种,所述引发剂包括4,4′-偶氮二氰基戊酸、过硫酸钾或偶氮二异丁基脒盐酸盐中的一种,所述交联剂包括N,N′-亚甲基双丙烯酰胺、二乙烯基苯或二异氰酸酯中的一种,所述溶剂包括水、N,N-二甲基甲酰胺或二甲基亚砜中的一种;所述模板、所述造孔剂和所述聚合物单体的质量比为0.75:1.25:2.6。The pore-forming agent includes one of potassium nitrate, sodium nitrate or ammonium chloride, the polymer monomer includes one of 1-vinylimidazole, vinyl pyrrolidone or vinyl pyridine, the initiator includes one of 4,4′-azobiscyanovaleric acid, potassium persulfate or azobisisobutylamidine hydrochloride, the cross-linking agent includes one of N,N′-methylenebisacrylamide, divinylbenzene or diisocyanate, and the solvent includes one of water, N,N-dimethylformamide or dimethyl sulfoxide; the mass ratio of the template, the pore-forming agent and the polymer monomer is 0.75:1.25:2.6. 2.根据权利要求1所述的自支撑柔性膜电极,其特征在于,所述模板的制备方法,包括以下步骤:2. The self-supporting flexible membrane electrode according to claim 1, characterized in that the method for preparing the template comprises the following steps: 将二氧化钛与碱液混合,进行水热反应,得到钛酸盐纳米棒;所述碱液为氢氧化钾或氢氧化钠溶液,所述氢氧化钠溶液的浓度为6~10mol·L-1;在所述将二氧化钛与碱液混合后的溶液中,所述二氧化钛的浓度为0.02~0.1g·mL-1,所述水热反应的温度为150~180℃,时间为24~48h。Titanium dioxide is mixed with alkali solution and subjected to hydrothermal reaction to obtain titanate nanorods; the alkali solution is potassium hydroxide or sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 6-10 mol·L -1 ; in the solution obtained by mixing titanium dioxide and alkali solution, the concentration of titanium dioxide is 0.02-0.1 g·mL -1 , the temperature of the hydrothermal reaction is 150-180°C, and the time is 24-48 hours. 3.根据权利要求1所述的自支撑柔性膜电极,其特征在于,所述煅烧的温度为700℃~900℃,时间为1h~3h。3. The self-supporting flexible membrane electrode according to claim 1 is characterized in that the calcination temperature is 700°C to 900°C and the time is 1h to 3h. 4.权利要求1所述的自支撑柔性膜电极的制备方法,其特征在于,包括以下步骤:4. The method for preparing the self-supporting flexible membrane electrode according to claim 1, characterized in that it comprises the following steps: 将所述连通管状氮掺杂碳材料和所述助剂配制成浆料,再倒入模具中,干燥,得到所述自支撑柔性膜电极。The interconnected tubular nitrogen-doped carbon material and the auxiliary agent are prepared into a slurry, which is then poured into a mold and dried to obtain the self-supporting flexible membrane electrode.
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