CN114614027A - Preparation method of CoFe-S @3D-S-NCNT electrode and quasi-solid zinc-air battery - Google Patents

Preparation method of CoFe-S @3D-S-NCNT electrode and quasi-solid zinc-air battery Download PDF

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CN114614027A
CN114614027A CN202210150723.4A CN202210150723A CN114614027A CN 114614027 A CN114614027 A CN 114614027A CN 202210150723 A CN202210150723 A CN 202210150723A CN 114614027 A CN114614027 A CN 114614027A
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孙小华
赵大福
刘秋恒
孙盼盼
吕小伟
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Abstract

CoFe‑S@3D‑S‑NCNT电极的制备方法和准固态锌‑空气电池。本发明涉及可充放电准固态锌‑空气电池技术领域,具体为电极的制备方法和包含该电极的准固态锌‑空气电池。通过以钴盐、铁盐、2‑甲基咪唑为反应原料,室温下生长得到CoFe‑MOF纳米片后经CVD退火碳化得CoFe@3D‑NCNT微纳米材料;然后在硫化钠溶液中进行水热反应,得到具有3D微纳米分级结构、高催化活性和较好疏水性的CoFe‑S@3D‑S‑NCNT微纳米复合材料。将所制备的CoFe‑S@3D‑S‑NCNT复合材料作为阴极,与锌阳极和准固态电解质组装成具有三明治结构的准固态锌‑空气电池。该电池具有理想的充放电性能,开路电压高达1.479V,放电峰值功率密度高达460mW/cm2,具有优异的充放电稳定性,可循环225周次以上。Preparation method of CoFe-S@3D-S-NCNT electrode and quasi-solid-state zinc-air battery. The invention relates to the technical field of rechargeable quasi-solid-state zinc-air batteries, in particular to a preparation method of an electrode and a quasi-solid-state zinc-air battery comprising the electrode. By using cobalt salt, iron salt and 2-methylimidazole as reaction raw materials, CoFe-MOF nanosheets were grown at room temperature and then carbonized by CVD annealing to obtain CoFe@3D-NCNT micro-nano materials; then hydrothermally in sodium sulfide solution reaction to obtain CoFe-S@3D-S-NCNT micro-nano composites with 3D micro-nano hierarchical structure, high catalytic activity and good hydrophobicity. The as-prepared CoFe‑S@3D‑S‑NCNT composite was used as a cathode, which was assembled with a zinc anode and a quasi-solid electrolyte to form a quasi-solid-state zinc-air battery with a sandwich structure. The battery has ideal charge-discharge performance, the open circuit voltage is as high as 1.479V, the discharge peak power density is as high as 460mW/cm 2 , it has excellent charge-discharge stability, and can be cycled for more than 225 cycles.

Description

CoFe-S@3D-S-NCNT电极的制备方法和准固态锌-空气电池Preparation method of CoFe-S@3D-S-NCNT electrode and quasi-solid-state zinc-air battery

技术领域technical field

本发明涉及准固态可充电锌-空电池制备技术领域,空气阴极侧具体涉及新能源材料的制备技术领域。The invention relates to the technical field of preparation of quasi-solid rechargeable zinc-air batteries, and the air cathode side specifically relates to the technical field of preparation of new energy materials.

背景技术Background technique

准固态锌-空气电池具有能量密度高、便携、体积小、成本低、安全、环保等优点,具有很好应用前景。然而准固态锌-空气电池的峰值功率密度低,稳定性较差,实现实际应用仍是一个巨大的挑战。空气电极作为准固态锌-空气电池的核心部件,对电池的能量存储密度、放电峰值功率密度以及电池的循环寿命都有着重要影响。因此,开发高催化活性、高稳定性、高反应动力学的阴极电催化材料及空气电极对推动高性能准固态锌-空气电池的实际应用具有重要意义,也会产生显著的经济价值和社会效益。目前可穿戴电子设备的发展使准固态锌-空气电池备受关注,这要求电池在保持高性能的同时具有便携性,故而电池的设计需要同时关注其电化学性能和结构稳定性。Quasi-solid-state zinc-air batteries have the advantages of high energy density, portability, small size, low cost, safety, and environmental protection, and have good application prospects. However, the low peak power density and poor stability of quasi-solid-state Zn-air batteries remain a huge challenge for practical applications. As the core component of quasi-solid-state zinc-air batteries, the air electrode has an important impact on the energy storage density, discharge peak power density, and cycle life of the battery. Therefore, the development of cathode electrocatalytic materials and air electrodes with high catalytic activity, high stability, and high reaction kinetics is of great significance to promote the practical application of high-performance quasi-solid-state zinc-air batteries, and will also produce significant economic and social benefits. . The current development of wearable electronic devices has attracted much attention to quasi-solid-state zinc-air batteries, which require the battery to maintain high performance while being portable. Therefore, the design of the battery needs to pay attention to both its electrochemical performance and structural stability.

铂碳、氧化钌、氧化铱是目前为止对ORR和OER最有效的电催化剂。然而,这样的贵金属材料价格昂贵,也对燃料氧化分子的免疫力差。并且制备的一体化电极材料无法兼具高双功能活性,组装的准固态锌-空气电池性能不足。无论面临何种挑战,开发一种高效、耐用的电催化剂是非常重要的。因而,本发明中的阴极材料旨在制备出一种经济、高效的双功能电催化剂——经硫化后的钴铁合金纳米粒子包覆在氮掺杂的碳纳米管材料,其中钴铁硫化物起着催化氧析出反应(OER)的功能、氮掺杂碳纳米管催化ORR反应的功能,此外这种碳纳米管结构材料的形貌结构、导电能力、表面组分缺陷亦能相互协同促进催化反应的进行。制备的阴极催化剂、锌阳极与电解质组成三明治结构的准固态锌-空气电池。通过这种简便的方法制备出具有高双功能活性、高功率密度、较优异的稳定性的粉体空气电极材料应用于准固态锌-空气电池还没有被报道。Platinum-carbon, ruthenium oxide, and iridium oxide are by far the most effective electrocatalysts for ORR and OER. However, such precious metal materials are expensive and also have poor immunity to fuel oxidizing molecules. Moreover, the prepared integrated electrode material cannot have both high bifunctional activity, and the assembled quasi-solid-state zinc-air battery has insufficient performance. Regardless of the challenge, it is important to develop an efficient and durable electrocatalyst. Therefore, the cathode material in the present invention aims to prepare an economical and efficient bifunctional electrocatalyst—the sulfided cobalt-iron alloy nanoparticles are wrapped in nitrogen-doped carbon nanotube materials, wherein cobalt-iron sulfide plays the role of It has the function of catalyzing the oxygen evolution reaction (OER) and the function of nitrogen-doped carbon nanotubes catalyzing the ORR reaction. In addition, the morphology, structure, electrical conductivity and surface component defects of this carbon nanotube structure material can also cooperate with each other to promote the catalytic reaction. conduct. The prepared cathode catalyst, zinc anode and electrolyte form a sandwich-structured quasi-solid-state zinc-air battery. The preparation of powder air electrode materials with high bifunctional activity, high power density, and excellent stability by this facile method has not been reported for quasi-solid-state zinc-air batteries.

发明内容SUMMARY OF THE INVENTION

为解决上述问题,本发明提供一种CoFe-S@3D-S-NCNT微纳米复合材料及其制备方法和应用。该材料具有高的双功能活性,与锌阳极、电解质组装的具有三明治结构的准固态锌-空气电池具有优异的峰值功率密度和较好的循环稳定性。In order to solve the above problems, the present invention provides a CoFe-S@3D-S-NCNT micro-nano composite material and a preparation method and application thereof. The material has high bifunctional activity, and the quasi-solid-state zinc-air battery with sandwich structure assembled with zinc anode and electrolyte has excellent peak power density and good cycle stability.

本发明的技术方案之一,一种CoFe-S@3D-S-NCNT微纳米复合材料,三维碳基底原位生长CoFe合金碳纳米管的具有3D微纳米复合结构材料。CoFe-S@3D-S-NCN微纳米复合材料具有3D微纳米分级结构和较好疏水性,将由CoFe-S@3D-S-NCNT微纳米复合材料制备的空气阴极、锌阳极和准固态电解质组成具有三明治结构的准固态锌-空气电池,其具有高峰值功率密度和高循环稳定性。One of the technical solutions of the present invention is a CoFe-S@3D-S-NCNT micro-nano composite material, a material with a 3D micro-nano composite structure for in-situ growth of CoFe alloy carbon nanotubes on a three-dimensional carbon substrate. CoFe-S@3D-S-NCN micro-nanocomposite has 3D micro-nano hierarchical structure and good hydrophobicity. Air cathode, zinc anode and quasi-solid electrolyte prepared by CoFe-S@3D-S-NCNT micro-nanocomposite A quasi-solid-state zinc-air battery with a sandwich structure is formed, which exhibits high peak power density and high cycle stability.

本发明的技术方案之二,上述CoFe-S@3D-S-NCNT微纳米复合材料的制备方法,包括以下步骤:以钴盐、铁盐、2-甲基咪唑为反应原料,得到CoFe-MOF纳米片后经CVD退火碳化得CoFe@3D-NCNT微纳米材料;然后在硫化钠水溶液中进行水热反应,得到CoFe@3D-NCNT表面覆盖钴硫化物、钴铁硫化物的CoFe-S@3D-S-NCNT微纳米复合材料。The second technical solution of the present invention, the preparation method of the above-mentioned CoFe-S@3D-S-NCNT micro-nano composite material, includes the following steps: using cobalt salt, iron salt and 2-methylimidazole as reaction raw materials to obtain CoFe-MOF After the nanosheets were annealed and carbonized by CVD, CoFe@3D-NCNT micro-nanomaterials were obtained; and then the hydrothermal reaction was carried out in an aqueous sodium sulfide solution to obtain CoFe-S@3D coated with cobalt sulfide and cobalt iron sulfide on the surface of CoFe@3D-NCNT. -S-NCNT micro-nano composites.

进一步地,具体包括以下步骤:Further, the following steps are specifically included:

(1)CoFe-MOF纳米片的制备:钴盐、铁盐水溶液和2-甲基咪唑水溶液组成的混合溶液中陈化后离心清洗干燥得CoFe-MOF;(1) Preparation of CoFe-MOF nanosheets: the mixed solution composed of cobalt salt, iron salt aqueous solution and 2-methylimidazole aqueous solution is aged, centrifugally washed and dried to obtain CoFe-MOF;

(2) CoFe@3D-NCNT的制备:在三聚氰胺存在的条件下将CoFe-MOF纳米片在混氢氛围中进行退火得CoFe@3D-NCNT纳米材料;(2) Preparation of CoFe@3D-NCNT: CoFe@3D-NCNT nanomaterials were obtained by annealing CoFe-MOF nanosheets in a mixed hydrogen atmosphere in the presence of melamine;

(3)CoFe-S@3D-S-NCNT的制备:CoFe@3D-NCNT纳米材料浸没于硫化钠溶液中进行水热反应后洗涤干燥得CoFe-S@3D-S-NCNT。(3) Preparation of CoFe-S@3D-S-NCNT: CoFe@3D-NCNT nanomaterials were immersed in sodium sulfide solution for hydrothermal reaction, washed and dried to obtain CoFe-S@3D-S-NCNT.

进一步地,所述步骤(1)中,钴盐可为硝酸钴、氯化钴、醋酸钴,其水溶液的浓度为5-20g/L,铁盐可为氯化铁,硝酸铁,醋酸铁,其水溶液的浓度为0.5-2g/L ,2-甲基咪唑水溶液的浓度为20-50g/L;搅拌时间2-6h,干燥温度60℃,干燥时间10h。Further, in the step (1), the cobalt salt can be cobalt nitrate, cobalt chloride, cobalt acetate, the concentration of its aqueous solution is 5-20g/L, and the iron salt can be ferric chloride, ferric nitrate, ferric acetate, The concentration of its aqueous solution is 0.5-2g/L, the concentration of 2-methylimidazole aqueous solution is 20-50g/L; the stirring time is 2-6h, the drying temperature is 60°C, and the drying time is 10h.

进一步地,所述步骤(2)具体包括:将CoFe-MOF纳米片放置在管式气氛炉炉管下游,三聚氰胺置于上游,置于氩气+氢气氛围中进行煅烧,然后0.5~2小时内升高温度至700~900℃继续保温1~2小时,自然降温后,得到CoFe@3D-NCNT;Further, the step (2) specifically includes: placing the CoFe-MOF nanosheets in the downstream of the tubular atmosphere furnace tube, placing the melamine upstream, and calcining in an argon+hydrogen atmosphere, and then within 0.5 to 2 hours Raise the temperature to 700-900 °C for 1-2 hours, and cool down naturally to obtain CoFe@3D-NCNT;

所述的氩气与氢气的混合气氛中,氩气为85-95%,氢气为5-15%。优选方案为氩气与氢气的混合气氛中,氩气为95%,氢气为5%。In the mixed atmosphere of argon and hydrogen, argon is 85-95%, and hydrogen is 5-15%. A preferred solution is that in a mixed atmosphere of argon and hydrogen, 95% argon and 5% hydrogen.

三聚氰胺与钴盐、铁盐的质量比为0.05-0.2:5-20:5-20。高温气氛下,三聚氰胺中的铵根离子与气氛中少量氢气具有还原性,会将CoFe-MOF中的金属离子还原成金属合金,金属合金在有碳源的存在下催化生长成碳纳米管。The mass ratio of melamine to cobalt salt and iron salt is 0.05-0.2:5-20:5-20. Under the high temperature atmosphere, the ammonium ions in melamine and a small amount of hydrogen in the atmosphere have reducing properties, which will reduce the metal ions in the CoFe-MOF to metal alloys, and the metal alloys catalyze growth into carbon nanotubes in the presence of carbon sources.

进一步地,所述步骤(3)中:硫化钠溶液浓度为10-20g/L;水热反应温度100-140℃,水热反应时间6-18h。Further, in the step (3): the concentration of the sodium sulfide solution is 10-20g/L; the hydrothermal reaction temperature is 100-140°C, and the hydrothermal reaction time is 6-18h.

硫化钠溶液中的硫离子在水热环境下会三维碳骨架中的部分金属颗粒形成硫化物,并且也与碳纳米管中的部分合金也形成硫化物,这使得其催化性能得到显著改善。The sulfide ions in the sodium sulfide solution can form sulfides with some metal particles in the three-dimensional carbon framework in a hydrothermal environment, and also form sulfides with some alloys in carbon nanotubes, which makes its catalytic performance significantly improved.

本发明的技术方案之三,上述CoFe-S@3D-S-NCNT微纳米复合材料在准固态锌-空气电池空气电极中的应用。The third technical solution of the present invention is the application of the above-mentioned CoFe-S@3D-S-NCNT micro-nano composite material in the air electrode of a quasi-solid zinc-air battery.

本发明的技术方案之四,一种准固态锌-空气电池空气电极,将上述的CoFe-S@3D-S-NCNT微纳米复合材料中加入乙醇、萘酚溶液其比例为(800~1000μL):(40~100μL),超声混合40~80min,得到催化剂墨水,将催化剂墨水滴加到碳纸或碳布上,50℃下烘干,得到准固态可充锌-空气电池空气电极。The fourth technical solution of the present invention is a quasi-solid-state zinc-air battery air electrode. The above-mentioned CoFe-S@3D-S-NCNT micro-nano composite material is added with ethanol and naphthol solution in a ratio of (800-1000 μL) : (40-100 μL), ultrasonically mixed for 40-80 min to obtain catalyst ink, drop the catalyst ink on carbon paper or carbon cloth, and dry at 50°C to obtain a quasi-solid rechargeable zinc-air battery air electrode.

本发明的技术方案之五,一种准固态锌-空气电池阳极材料为锌片、锌箔、锌带、碳布碳纸等原位电镀锌的其中一种。In the fifth technical solution of the present invention, a quasi-solid-state zinc-air battery anode material is one of in-situ electro-galvanizing, such as zinc flakes, zinc foils, zinc strips, and carbon cloth and carbon paper.

本发明的技术方案之六,一种准固态锌-空气电池的准固态电解质材料为PVA电解质、PaNa电解质、生物纤维素膜电解质、丙烯酸凝胶电解质的其中一种。In the sixth technical solution of the present invention, a quasi-solid electrolyte material of a quasi-solid zinc-air battery is one of PVA electrolyte, PaNa electrolyte, biological cellulose membrane electrolyte, and acrylic gel electrolyte.

本发明的技术方案之七,一种准固态锌-空气电池,CoFe-S@3D-S-NCNT纳米复合材料的碳纸作为阴极电极,锌阳极电极,电解质凝胶制成,得到CoFe-S@3D-S-NCNT微纳米复合材料的准固态锌-空气电池。The seventh technical solution of the present invention is a quasi-solid zinc-air battery, which is made of CoFe-S@3D-S-NCNT nanocomposite carbon paper as a cathode electrode, a zinc anode electrode, and an electrolyte gel to obtain CoFe-S Quasi-solid-state zinc-air batteries of @3D-S-NCNT micro-nanocomposites.

与现有技术相比,本发明的有益效果:Compared with the prior art, the beneficial effects of the present invention:

CoFe-S@3D-S-NCNT三维微纳米复合材料具有碳纳米管原位生长在三维碳骨架的复合结构,产品形貌均匀,这种微结构具有一定的疏水性,钴铁硫化物有较好的OER性能,碳纳米管的ORR性能优异,该复合材料结合了三者的优点,拥有高的双功能活性。由于疏水性的提高,在电解质中能接触到更多空气,使得其放电极化显著提升,进一步提升材料的功率密度。The CoFe-S@3D-S-NCNT three-dimensional micro-nano composite material has a composite structure in which carbon nanotubes grow in-situ on a three-dimensional carbon skeleton, and the product has a uniform morphology. This microstructure has a certain degree of hydrophobicity. Good OER performance and excellent ORR performance of carbon nanotubes, the composite material combines the advantages of the three and possesses high bifunctional activity. Due to the increase in hydrophobicity, more air can be contacted in the electrolyte, so that the discharge polarization is significantly improved, and the power density of the material is further improved.

本发明所述的CoFe-S@3D-S-NCNT三维微纳米复合材料空气电极的制备方法具有可重复性高、合成过程简单、易控制等优点。将所制备的CoFe-S@3D-S-NCNT微纳米复合材料用作阴极、锌阳极和准固态电解质材料组成的准固态锌-空气电池具有高双功能活性、高功率密度、高稳定性;应用于可充准固态锌-空气电池空气电极,功率密度为460mWcm2,225次循环的长时间稳定性。The preparation method of the CoFe-S@3D-S-NCNT three-dimensional micro-nano composite material air electrode according to the present invention has the advantages of high repeatability, simple synthesis process, easy control and the like. The as-prepared CoFe-S@3D-S-NCNT micro-nanocomposite material is used as a quasi-solid-state zinc-air battery composed of a cathode, a zinc anode and a quasi-solid electrolyte material with high bifunctional activity, high power density, and high stability; Applied to the air electrode of rechargeable solid-state zinc-air battery, the power density is 460mWcm 2 , and the long-term stability of 225 cycles.

附图说明Description of drawings

图1是实施例1中制备的产物的XRD图谱,其中:横坐标X是衍射角度(2θ),纵坐标Y是相对衍射强度。Fig. 1 is the XRD pattern of the product prepared in Example 1, wherein: the abscissa X is the diffraction angle (2θ), and the ordinate Y is the relative diffraction intensity.

图2是实施例1中制备的产物的TEM图,a图中的物象为Co9S8、Co和非晶碳材料,b图中的物象为Co8FeS8和Co7Fe3Figure 2 is a TEM image of the product prepared in Example 1, the objects in a picture are Co 9 S 8 , Co and amorphous carbon materials, and the objects in b picture are Co 8 FeS 8 and Co 7 Fe 3 .

图3是实施例1中制备的CoFe-S@3D-S-NCNT微纳米复合材料形貌图(5μm)。FIG. 3 is a topography (5 μm) of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in Example 1. FIG.

图4是实施例1中制备的CoFe-S@3D-S-NCNT微纳米复合材料形貌图(2μm)。FIG. 4 is a topography (2 μm) of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in Example 1. FIG.

图5是实施例1中步骤(2)制备的CoFe@3D-NCNT材料形貌图。FIG. 5 is a topography diagram of the CoFe@3D-NCNT material prepared in step (2) in Example 1. FIG.

图6是实施例1中制备的CoFe-S@3D-S-NCNT微纳米复合材料疏水性图。6 is a hydrophobicity diagram of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in Example 1.

图7是实施例1中制备的CoFe-S@3D-S-NCNT微纳米复合材料ORR性能图。7 is a graph of the ORR performance of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in Example 1.

图8是实施例1中制备的CoFe-S@3D-S-NCNT微纳米复合材料OER性能图。FIG. 8 is a graph showing the OER performance of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in Example 1.

图9是实施例1中制备的CoFe-S@3D-S-NCNT微纳米复合材料ORR稳定性测试性能图。FIG. 9 is a performance diagram of the ORR stability test of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in Example 1. FIG.

图10是实施例1中制备的PaNa准固态电解质图。FIG. 10 is a diagram of the PaNa quasi-solid electrolyte prepared in Example 1. FIG.

图11是实施例1中制备CoFe-S@3D-S-NCN微T纳米复合材料的可充锌空电池的开路电压图。11 is an open circuit voltage diagram of a rechargeable zinc-air battery prepared with CoFe-S@3D-S-NCN micro-T nanocomposite in Example 1.

图12是实施例1中制备的CoFe-S@3D-S-NCN微T纳米复合材料的可充锌空电池的放电极化曲线性能结果。12 is the discharge polarization curve performance results of the rechargeable zinc-air battery of the CoFe-S@3D-S-NCN micro-T nanocomposite prepared in Example 1.

图13是实施例1中制备的CoFe-S@3D-S-NCNT微纳米复合材料的可充锌空电池的循环性能结果。13 is the cycle performance results of the rechargeable zinc-air battery of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in Example 1.

图14是实施例1中制备的CoFe-S@3D-S-NCNT微纳米复合材料的可充锌空电池点亮LED灯图。14 is a diagram of the rechargeable zinc-air battery of the CoFe-S@3D-S-NCNT micro-nano composite prepared in Example 1 lighting up an LED light.

具体实施方式Detailed ways

现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。Various exemplary embodiments of the present invention will now be described in detail, which detailed description should not be construed as a limitation of the invention, but rather as a more detailed description of certain aspects, features, and embodiments of the invention.

应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。It should be understood that the terms described in the present invention are only used to describe particular embodiments, and are not used to limit the present invention. Additionally, for numerical ranges in the present disclosure, it should be understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in that stated range is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present invention without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the present invention. The description and examples of the present application are only exemplary.

关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。As used herein, "comprising," "including," "having," "containing," and the like, are open-ended terms, meaning including but not limited to.

实施例1Example 1

(1)CoFe-MOF的制备(1) Preparation of CoFe-MOF

将0.582g硝酸钴(Co(NO3)2·6H2O)与0.06g四水氯化亚铁(FeCl2·4H2O)溶解在40mL的去离子水中,将其与溶解了1.32g 2-甲基咪唑(2-MIM)的40mL去离子水混合,室温下老化4小时,将其紫色溶液在6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥12小时。Dissolve 0.582g cobalt nitrate (Co(NO 3 ) 2 6H 2 O) and 0.06g ferrous chloride tetrahydrate (FeCl 2 4H 2 O) in 40 mL of deionized water, and dissolve 1.32 g 2 -Methylimidazole (2-MIM) was mixed with 40 mL of deionized water, aged at room temperature for 4 hours, the purple solution was washed several times with deionized water and ethanol at 6500 rpm, and dried at 80°C for 12 hours.

(2) CoFe@3D-NCNT的制备(2) Preparation of CoFe@3D-NCNT

将制备的CoFe-MOF的紫色粉体放置在瓷舟下游,三聚氰胺置于上游,将瓷舟放入管式炉中煅烧,煅烧气氛为95%氩气+5%氢气,煅烧温度为800℃,升温时间为176分钟,保温时间为1小时,等管式炉自然降温后,得到CoFe@3D-NCNT纳米材料。The prepared CoFe-MOF purple powder was placed downstream of the porcelain boat, and melamine was placed upstream, and the porcelain boat was placed in a tube furnace for calcination. The calcination atmosphere was 95% argon + 5% hydrogen, and the calcination temperature was 800 °C. The heating time was 176 minutes, and the holding time was 1 hour. After the tube furnace cooled down naturally, the CoFe@3D-NCNT nanomaterials were obtained.

(3) CoFe-S@3D-S-NCNT的制备(3) Preparation of CoFe-S@3D-S-NCNT

将0.7g硫化钠超声溶解于40mL去离子水中,转移至反应釜,把步骤(2)合成的CoFe@3D-NCNT黑色粉体浸入该溶液,在120℃下水热反应10小时,冷却至室温,6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥,得到最终产物CoFe-S@3D-S-NCNT纳米复合材料。0.7 g of sodium sulfide was ultrasonically dissolved in 40 mL of deionized water, transferred to a reactor, the CoFe@3D-NCNT black powder synthesized in step (2) was immersed in the solution, hydrothermally reacted at 120 ° C for 10 hours, cooled to room temperature, Centrifugal washing with deionized water and ethanol at 6500 rpm for several times, and drying at 80 °C, the final product CoFe-S@3D-S-NCNT nanocomposite was obtained.

对于本实施例中XRD测试结果表明:如图1所示,其横坐标X是衍射角度(2θ),纵坐标Y是相对衍射强度,其衍射峰对应于C峰,Co峰,CoFe合金的峰。至于未出现硫化物,是因为水域硫化程度较弱,XRD的探测能力有限,未能发现。The XRD test results in this example show that: as shown in Figure 1, the abscissa X is the diffraction angle (2θ), the ordinate Y is the relative diffraction intensity, and the diffraction peaks correspond to the C peak, the Co peak, and the peak of the CoFe alloy. . As for the absence of sulfides, it is because the degree of sulfide in the waters is weak, and the detection ability of XRD is limited and cannot be found.

对于本实施例中TEM测试结果表明:如图2所示,在TEM中发现了Co9S8,Co,非晶C材料,Co7Fe3和Co8FeS8,证明水热硫化成功使得合金向硫化物的转变For this example, the TEM test results show that: as shown in Figure 2, Co 9 S 8 , Co, amorphous C materials, Co 7 Fe 3 and Co 8 FeS 8 were found in the TEM, proving that the successful hydrothermal vulcanization makes the alloy transition to sulfide

对于本实施例中制备的纳米复合材料作场发射扫描电镜分析,得到的电镜照片如图3-5所示;其中图3-4为制备的CoFe-S@3D-S-NCNT微纳米复合材料分别在5μm、3μm比例下的形貌图,图5为步骤(2)制备的CoFe@3D-NCNT微纳米材料形貌图;可以看到,三维碳骨架上原位生长碳纳米管的这种微纳米复合结构,本实施例制备的CoFe-S@3D-S-NCNT微纳米复合材料形貌均匀,具有典型的疏水结构。The nanocomposite prepared in this example is analyzed by field emission scanning electron microscope, and the obtained electron microscope photo is shown in Fig. 3-5; Fig. 3-4 is the prepared CoFe-S@3D-S-NCNT micro-nano composite material Figure 5 shows the morphology of the CoFe@3D-NCNT micro-nano material prepared in step (2); it can be seen that the in-situ growth of carbon nanotubes on the three-dimensional carbon framework Micro-nano composite structure, the CoFe-S@3D-S-NCNT micro-nano composite material prepared in this example has a uniform morphology and a typical hydrophobic structure.

取本实施例中制备的CoFe-S@3D-S-NCNT微纳米复合材料,充分研磨后,依次加入乙醇、萘酚溶液其比例为(800~1000μL):(40~100μL),超声混合40~80min,得到催化剂墨水,将催化剂墨水滴加到面积为1平方厘米碳纸或碳布上, 50℃下烘干,得到准固态可充锌-空气电池空气电极。Take the CoFe-S@3D-S-NCNT micro-nano composite material prepared in this example, and after sufficient grinding, add ethanol and naphthol solution in sequence in the ratio of (800-1000 μL): (40-100 μL), and ultrasonically mix 40 ~80min to obtain catalyst ink, drop the catalyst ink on carbon paper or carbon cloth with an area of 1 square centimeter, and dry at 50°C to obtain a quasi-solid rechargeable zinc-air battery air electrode.

对制备的CoFe-S@3D-S-NCNT微纳米复合材料进行疏水性测试,直接将负载有CoFe-S@3D-S-NCNT微纳米复合材料的碳纸进行测试,如图6所示,可以看出,其疏水角具有151°,这证明了CoFe-S@3D-S-NCNT微纳米复合材料的疏水性优,疏水性较好的材料在放电极化中占有优势,因为放电极化需要大量的氧气使得反应正向进行。The prepared CoFe-S@3D-S-NCNT micro-nanocomposite was tested for hydrophobicity, and the carbon paper loaded with CoFe-S@3D-S-NCNT micro-nanocomposite was directly tested, as shown in Figure 6. It can be seen that its hydrophobic angle is 151°, which proves the excellent hydrophobicity of CoFe-S@3D-S-NCNT micro-nanocomposite, and the material with better hydrophobicity dominates the discharge polarization because the discharge polarization A large amount of oxygen is required for the reaction to proceed in the forward direction.

对制备的CoFe-S@3D-S-NCNT微纳米复合材料进行ORR性能测试,如图7所示,可以看出其具有0.855V的较高的半波电位,接近6mA/cm2的极限电流密度,说明其具有优异的ORR活性。The ORR performance test of the prepared CoFe-S@3D-S-NCNT micro-nanocomposite is carried out, as shown in Figure 7, it can be seen that it has a high half-wave potential of 0.855V, which is close to the limiting current of 6mA/ cm2 density, indicating that it has excellent ORR activity.

对制备的CoFe-S@3D-S-NCNT微纳米复合材料进行OER性能测试,如图8所示,可以看出其在10mA/cm2的过电位只有很小的310mV,足以说明优异的OER性能。The OER performance test of the prepared CoFe-S@3D-S-NCNT micro-nanocomposite, as shown in Figure 8, it can be seen that its overpotential at 10mA/cm 2 is only a small 310mV, which is enough to show the excellent OER performance.

对制备的CoFe-S@3D-S-NCNT微纳米复合材料进行ORR稳定性测试,如图9所示,可以看出其在经过7200s的稳定性测试后,其电流密度仍然可以保持在初始电流的96%,证明其具有良好的稳定性。The ORR stability test was carried out on the prepared CoFe-S@3D-S-NCNT micro-nanocomposite, as shown in Figure 9, it can be seen that after the stability test for 7200s, its current density can still be maintained at the initial current 96%, proving that it has good stability.

对准固态电池进行组装,将抛光的锌片作为阳极,PaNa(聚丙烯酸钠)电解质,负载有CoFe-S@3D-S-NCNT微纳米复合材料的碳纸做为阴极,组装成具有三明治结构的准固态锌-空气电池。The solid-state battery was assembled with polished zinc sheet as anode, PaNa (sodium polyacrylate) electrolyte, and carbon paper loaded with CoFe-S@3D-S-NCNT micro-nano composite material as cathode, and assembled into a sandwich structure quasi-solid-state zinc-air battery.

图10所示,其为PaNa电解质,可以看出是具有果冻状的凝胶状的物质。As shown in FIG. 10, it is a PaNa electrolyte, and it can be seen that it has a jelly-like gel-like substance.

对制备的CoFe-S@3D-S-NCNT微纳米复合材料的准固态锌-空气电池进行放电极化性能测试,结果如图12所示,可以看出,在测试时间内,其开路电压可以稳定在1.479V,可以看出,其具有较大的开路电压。The discharge polarization performance of the prepared CoFe-S@3D-S-NCNT micro-nanocomposite quasi-solid zinc-air battery was tested. The results are shown in Figure 12. It can be seen that within the test time, its open circuit voltage can be Stable at 1.479V, it can be seen that it has a large open circuit voltage.

对制备的CoFe-S@3D-S-NCNT微纳米复合材料的准固态锌-空气电池进行放电极化性能测试,结果如图13,其放电功能正常,最大功率密度为460mW/cm 2 ,表明由本发明方法制备的CoFe-S@3D-S-NCNT微纳米复合材料组装具有三明治结构的准固态锌-空气电池具有较高的能量转换效率。The discharge polarization performance of the prepared CoFe-S@3D-S-NCNT micro-nano composite quasi-solid zinc-air battery was tested. The results are shown in Figure 13. The discharge function is normal and the maximum power density is 460mW/cm 2 , indicating that The CoFe-S@3D-S-NCNT micro-nano composite material prepared by the method of the present invention assembles a quasi-solid-state zinc-air battery with a sandwich structure, which has high energy conversion efficiency.

对制备的CoFe-S@3D-S-NCNT微纳米复合材料的准固态锌-空气电池进行循环性能检测,进行循环充放电,结果如图13所示,在连续工作225个循环之前,电池性能仍保持稳定,表明由本发明方法制备的CoFe-S@3D-S-NCNT微纳米复合材料组装的可充锌空电池具有较好的电池循环稳定性。The cycle performance of the prepared CoFe-S@3D-S-NCNT micro-nanocomposite quasi-solid-state zinc-air battery was tested, and the cycle charge and discharge were carried out. The results are shown in Figure 13. Before 225 cycles of continuous operation, the battery performance It remains stable, indicating that the rechargeable zinc-air battery assembled by the CoFe-S@3D-S-NCNT micro-nanocomposite prepared by the method of the present invention has better battery cycle stability.

图14所示,可以看出,两个由CoFe-S@3D-S-NCNT微纳米复合材料为阴极材料,PaNa电解质,锌片组成的的准固态锌-空气电池制备的CoFe-S@3D-S-NCNT微纳米复合材料的准固态锌-空气电池可以点亮LED(3V)灯。As shown in Fig. 14, it can be seen that two CoFe-S@3D quasi-solid-state zinc-air batteries composed of CoFe-S@3D-S-NCNT micro-nanocomposite as cathode material, PaNa electrolyte, and zinc flakes - Quasi-solid-state zinc-air batteries of S-NCNT micro-nanocomposites can light up LED (3V) lamps.

实施例2Example 2

(1)CoFe-MOF的制备(1) Preparation of CoFe-MOF

将0.582g硝酸钴(Co(NO3)2·6H2O)与0.06g四水氯化亚铁(FeCl2·4H2O)溶解在40mL的去离子水中,将其与溶解了1.32g 2-甲基咪唑(2-MIM)的40mL去离子水混合,室温下老化4小时,将其紫色溶液在6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥12小时。Dissolve 0.582g cobalt nitrate (Co(NO 3 ) 2 6H 2 O) and 0.06g ferrous chloride tetrahydrate (FeCl 2 4H 2 O) in 40 mL of deionized water, and dissolve 1.32 g 2 -Methylimidazole (2-MIM) was mixed with 40 mL of deionized water, aged at room temperature for 4 hours, the purple solution was washed several times with deionized water and ethanol at 6500 rpm, and dried at 80°C for 12 hours.

(2) CoFe@3D-NCNT的制备(2) Preparation of CoFe@3D-NCNT

将制备的CoFe-MOF的紫色粉体放置在瓷舟下游,三聚氰胺置于上游,将瓷舟放入管式炉中煅烧,煅烧气氛为95%氩气+5%氢气 ,煅烧温度为800℃,升温时间为176分钟,保温时间为1小时,等管式炉自然降温后,得到CoFe@3D-NCNT纳米材料。The prepared CoFe-MOF purple powder was placed downstream of the porcelain boat, and melamine was placed upstream, and the porcelain boat was placed in a tube furnace for calcination. The calcination atmosphere was 95% argon + 5% hydrogen, and the calcination temperature was 800 °C. The heating time was 176 minutes, and the holding time was 1 hour. After the tube furnace cooled down naturally, the CoFe@3D-NCNT nanomaterials were obtained.

(3) CoFe-S@3D-S-NCNT的制备(3) Preparation of CoFe-S@3D-S-NCNT

将0.7g硫化钠超声溶解于40mL去离子水中,转移至反应釜,把步骤(2)合成的CoFe@3D-NCNT黑色粉体浸入该溶液,在120℃下水热反应5小时,冷却至室温,6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥,得到最终产物CoFe-S@3D-S-NCNT纳米复合材料。0.7 g of sodium sulfide was ultrasonically dissolved in 40 mL of deionized water, transferred to a reactor, the CoFe@3D-NCNT black powder synthesized in step (2) was immersed in the solution, hydrothermally reacted at 120 ° C for 5 hours, cooled to room temperature, Centrifugal washing with deionized water and ethanol at 6500 rpm for several times, and drying at 80 °C, the final product CoFe-S@3D-S-NCNT nanocomposite was obtained.

实施例3Example 3

(1)CoFe-MOF的制备(1) Preparation of CoFe-MOF

将0.582g硝酸钴(Co(NO3)2·6H2O)与0.06g四水氯化亚铁(FeCl2·4H2O)溶解在40mL的去离子水中,将其与溶解了1.32g 2-甲基咪唑(2-MIM)的40mL去离子水混合,室温下老化4小时,将其紫色溶液在6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥12小时。Dissolve 0.582g cobalt nitrate (Co(NO 3 ) 2 6H 2 O) and 0.06g ferrous chloride tetrahydrate (FeCl 2 4H 2 O) in 40 mL of deionized water, and dissolve 1.32 g 2 -Methylimidazole (2-MIM) was mixed with 40 mL of deionized water, aged at room temperature for 4 hours, the purple solution was washed several times with deionized water and ethanol at 6500 rpm, and dried at 80°C for 12 hours.

(2) CoFe@3D-NCNT的制备(2) Preparation of CoFe@3D-NCNT

将制备的CoFe-MOF的紫色粉体放置在瓷舟下游,三聚氰胺置于上游,将瓷舟放入管式炉中煅烧,煅烧气氛为95%氩气+5%氢气 ,煅烧温度为800℃,升温时间为176分钟,保温时间为1小时,等管式炉自然降温后,得到CoFe@3D-NCNT微纳米材料。The prepared CoFe-MOF purple powder was placed downstream of the porcelain boat, and melamine was placed upstream, and the porcelain boat was placed in a tube furnace for calcination. The calcination atmosphere was 95% argon + 5% hydrogen, and the calcination temperature was 800 °C. The heating time was 176 minutes, and the holding time was 1 hour. After the tube furnace cooled down naturally, the CoFe@3D-NCNT micro-nano material was obtained.

(3) CoFe-S@3D-S-NCNT的制备(3) Preparation of CoFe-S@3D-S-NCNT

将0.7g硫化钠超声溶解于40mL去离子水中,转移至反应釜,把步骤(2)合成的CoFe@3D-NCNT黑色粉体浸入该溶液,在120℃下水热反应15小时,冷却至室温,6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥,得到最终产物CoFe-S@3D-S-NCNT微纳米复合材料。0.7 g of sodium sulfide was ultrasonically dissolved in 40 mL of deionized water, transferred to a reaction kettle, the CoFe@3D-NCNT black powder synthesized in step (2) was immersed in the solution, hydrothermally reacted at 120 ° C for 15 hours, cooled to room temperature, Centrifugal washing with deionized water and ethanol at 6500 rpm for several times, and drying at 80 °C, the final product CoFe-S@3D-S-NCNT micro-nano composite was obtained.

将实施例2-3制备的纳米复合材料进行性能验证,实施例2制备的纳米复合材料,其ORR半波电位为0.84V,OER过电位为350mV,实施例3制备的纳米复合材料,其ORR半波电位为0.83V,OER过电位为330mV,结果发现水热时间为10小时制备的产品具有更优异的双功能活性。The performance of the nanocomposite prepared in Example 2-3 was verified. The nanocomposite prepared in Example 2 had an ORR half-wave potential of 0.84V and an OER overpotential of 350mV. The nanocomposite prepared in Example 3 had an ORR of 0.84V. The half-wave potential was 0.83 V, and the OER overpotential was 330 mV. It was found that the product prepared with a hydrothermal time of 10 hours had better bifunctional activity.

实施例4Example 4

(1)CoFe-MOF的制备(1) Preparation of CoFe-MOF

将0.582g硝酸钴(Co(NO3)2·6H2O)与0.06g四水氯化亚铁(FeCl2·4H2O)溶解在40mL的去离子水中,将其与溶解了1.32g 2-甲基咪唑(2-MIM)的40mL去离子水混合,室温下老化4小时,将其紫色溶液在6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥12小时。Dissolve 0.582g cobalt nitrate (Co(NO 3 ) 2 6H 2 O) and 0.06g ferrous chloride tetrahydrate (FeCl 2 4H 2 O) in 40 mL of deionized water, and dissolve 1.32 g 2 -Methylimidazole (2-MIM) was mixed with 40 mL of deionized water, aged at room temperature for 4 hours, the purple solution was washed several times with deionized water and ethanol at 6500 rpm, and dried at 80°C for 12 hours.

(2) CoFe@3D-NCNT的制备(2) Preparation of CoFe@3D-NCNT

将制备的CoFe-MOF的紫色粉体放置在瓷舟下游,三聚氰胺置于上游,将瓷舟放入管式炉中煅烧,煅烧气氛为95%氩气+5%氢气 ,煅烧温度700℃,升温时间为176分钟,保温时间为1小时,等管式炉自然降温后,得到CoFe@3D-NCNT纳米材料。The prepared CoFe-MOF purple powder was placed downstream of the porcelain boat, melamine was placed upstream, and the porcelain boat was placed in a tube furnace for calcination. The time was 176 minutes, and the holding time was 1 hour. After the tube furnace cooled down naturally, the CoFe@3D-NCNT nanomaterials were obtained.

(3) CoFe-S@3D-S-NCNT的制备(3) Preparation of CoFe-S@3D-S-NCNT

将0.7g硫化钠超声溶解于40mL去离子水中,转移至反应釜,把步骤(2)合成的CoFe@3D-NCNT黑色粉体浸入该溶液,在120℃下水热反应10小时,冷却至室温,6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥,得到最终产物CoFe-S@3D-S-NCNT纳米复合材料。0.7 g of sodium sulfide was ultrasonically dissolved in 40 mL of deionized water, transferred to a reactor, the CoFe@3D-NCNT black powder synthesized in step (2) was immersed in the solution, hydrothermally reacted at 120 ° C for 10 hours, cooled to room temperature, Centrifugal washing with deionized water and ethanol at 6500 rpm for several times, and drying at 80 °C, the final product CoFe-S@3D-S-NCNT nanocomposite was obtained.

实施例5Example 5

(1)CoFe-MOF的制备(1) Preparation of CoFe-MOF

将0.582g硝酸钴(Co(NO3)2·6H2O)与0.06g四水氯化亚铁(FeCl2·4H2O)溶解在40mL的去离子水中,将其与溶解了1.32g 2-甲基咪唑(2-MIM)的40mL去离子水混合,室温下老化4小时,将其紫色溶液在6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥12小时。Dissolve 0.582g cobalt nitrate (Co(NO 3 ) 2 6H 2 O) and 0.06g ferrous chloride tetrahydrate (FeCl 2 4H 2 O) in 40 mL of deionized water, and dissolve 1.32 g 2 -Methylimidazole (2-MIM) was mixed with 40 mL of deionized water, aged at room temperature for 4 hours, the purple solution was washed several times with deionized water and ethanol at 6500 rpm, and dried at 80°C for 12 hours.

(2) CoFe@3D-NCNT的制备(2) Preparation of CoFe@3D-NCNT

将制备的CoFe-MOF的紫色粉体放置在瓷舟下游,三聚氰胺置于上游,将瓷舟放入管式炉中煅烧,煅烧气氛为95%氩气+5%氢气 ,煅烧温度900℃,升温时间为176分钟,保温时间为1小时,等管式炉自然降温后,得到CoFe@3D-NCNT纳米材料。The prepared CoFe-MOF purple powder was placed downstream of the porcelain boat, and melamine was placed upstream, and the porcelain boat was placed in a tube furnace for calcination. The time was 176 minutes, and the holding time was 1 hour. After the tube furnace cooled down naturally, the CoFe@3D-NCNT nanomaterials were obtained.

(3) CoFe-S@3D-S-NCNT的制备(3) Preparation of CoFe-S@3D-S-NCNT

将0.7g硫化钠超声溶解于40mL去离子水中,转移至反应釜,把步骤(2)合成的CoFe@3D-NCNT黑色粉体浸入该溶液,在120℃下水热反应10小时,冷却至室温,6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥,得到最终产物CoFe-S@3D-S-NCNT纳米复合材料。0.7 g of sodium sulfide was ultrasonically dissolved in 40 mL of deionized water, transferred to a reactor, the CoFe@3D-NCNT black powder synthesized in step (2) was immersed in the solution, hydrothermally reacted at 120 ° C for 10 hours, cooled to room temperature, Centrifugal washing with deionized water and ethanol at 6500 rpm for several times, and drying at 80 °C, the final product CoFe-S@3D-S-NCNT nanocomposite was obtained.

实施例6Example 6

(1)CoFe-MOF的制备(1) Preparation of CoFe-MOF

将0.582g硝酸钴(Co(NO3)2·6H2O)与0.06g四水氯化亚铁(FeCl2·4H2O)溶解在40mL的去离子水中,将其与溶解了1.32g 2-甲基咪唑(2-MIM)的40mL去离子水混合,室温下老化4小时,将其紫色溶液在6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥12小时。Dissolve 0.582g cobalt nitrate (Co(NO 3 ) 2 6H 2 O) and 0.06g ferrous chloride tetrahydrate (FeCl 2 4H 2 O) in 40 mL of deionized water, and dissolve 1.32 g 2 -Methylimidazole (2-MIM) was mixed with 40 mL of deionized water, aged at room temperature for 4 hours, the purple solution was washed several times with deionized water and ethanol at 6500 rpm, and dried at 80°C for 12 hours.

(2) CoFe@3D-NCNT的制备(2) Preparation of CoFe@3D-NCNT

将制备的CoFe-MOF的紫色粉体放置在瓷舟下游,三聚氰胺置于上游,将瓷舟放入管式炉中煅烧,煅烧气氛为氩气,煅烧温度800℃,升温时间为176分钟,保温时间为1小时,等管式炉自然降温后,得到CoFe@3D-NCNT纳米材料。The prepared CoFe-MOF purple powder was placed downstream of the porcelain boat, melamine was placed upstream, the porcelain boat was placed in a tube furnace for calcination, the calcination atmosphere was argon, the calcination temperature was 800 °C, the heating time was 176 minutes, and the The time was 1 hour, and after the tube furnace was cooled down naturally, CoFe@3D-NCNT nanomaterials were obtained.

(3) CoFe-S@3D-S-NCNT的制备(3) Preparation of CoFe-S@3D-S-NCNT

将0.7g硫化钠超声溶解于40mL去离子水中,转移至反应釜,把步骤(2)合成的CoFe@3D-NCNT黑色粉体浸入该溶液,在120℃下水热反应10小时,冷却至室温,6500转的转速下去离子水和乙醇离心冲洗数次,80℃干燥,得到最终产物CoFe-S@3D-S-NCNT纳米复合材料。0.7 g of sodium sulfide was ultrasonically dissolved in 40 mL of deionized water, transferred to a reactor, the CoFe@3D-NCNT black powder synthesized in step (2) was immersed in the solution, hydrothermally reacted at 120 ° C for 10 hours, cooled to room temperature, Centrifugal washing with deionized water and ethanol at 6500 rpm for several times, and drying at 80 °C, the final product CoFe-S@3D-S-NCNT nanocomposite was obtained.

经过同实施例1相同的实验验证,结果显示,实施例2制备的材料用于可充锌空电池电极的制备时,其峰值功率密度在360 mW/cm2,其循环稳定性在180周次以上;实施例3制备的材料用于可充锌空电池电极的制备时,其峰值功率密度在380 mW/cm2,其循环稳定性在150周次以上;实施例4制备的材料用于可充锌空电池电极的制备时,其峰值功率密度在240 mW/cm2,其循环稳定性在110周次以上;实施例5制备的材料用于可充锌空电池电极的制备时,其峰值功率密度在240 mW/cm2,其循环稳定性在140周次以上;实施例6制备的材料用于可充锌空电池电极的制备时,其峰值功率密度在120 mW/cm2,其循环稳定性在100周次以上,实施例2-6制备的材料用于可充锌空电池电极的制备时,均较好的功率密度和较好的循环稳定性。After the same experimental verification as in Example 1, the results show that when the material prepared in Example 2 is used for the preparation of electrodes for rechargeable zinc-air batteries, its peak power density is 360 mW/cm 2 , and its cycle stability is 180 cycles. Above; when the material prepared in Example 3 is used for the preparation of rechargeable zinc-air battery electrodes, its peak power density is 380 mW/cm 2 , and its cycle stability is over 150 cycles; the material prepared in Example 4 is used for rechargeable zinc-air battery electrodes. When the electrode of rechargeable zinc-air battery is prepared, its peak power density is 240 mW/cm 2 , and its cycle stability is more than 110 cycles; when the material prepared in Example 5 is used for the preparation of electrode of rechargeable zinc-air battery, its peak value When the power density is 240 mW/cm 2 , its cycle stability is over 140 cycles; when the material prepared in Example 6 is used for the preparation of electrodes for rechargeable zinc-air batteries, its peak power density is 120 mW/cm 2 , and its cycle time is 120 mW/cm 2 . The stability is more than 100 cycles. When the materials prepared in Examples 2-6 are used for the preparation of electrodes for rechargeable zinc-air batteries, they all have better power density and better cycle stability.

对比例1Comparative Example 1

同实施例1,区别在于,步骤(1)中的未引入铁元素,只是单纯的Co-MOF。Same as Example 1, the difference is that no iron element is introduced in step (1), only pure Co-MOF.

对制备的材料进行催化活性测试、放电极化测试,其ORR半波电位为0.82V,OER过电位为390mV,其峰值功率密度为375 mW/cm2,结果显示:单纯的Co-MOF经退火硫化后,其电化学性能下降。The prepared materials were tested for catalytic activity and discharge polarization. The ORR half-wave potential was 0.82V, the OER overpotential was 390mV, and the peak power density was 375 mW/cm 2 . The results showed that the pure Co-MOF was annealed. After vulcanization, its electrochemical performance decreased.

对比例2Comparative Example 2

同实施例1,区别在于,步骤(2)中的煅烧过程不引入三聚氰胺为碳源直接升温到800°,然后保温时间为1小时。With Embodiment 1, the difference is that the calcination process in the step (2) does not introduce melamine as a carbon source and directly heats up to 800°, and then the holding time is 1 hour.

对制备的材料进行形貌、循环稳定性、催化活性测试,放电极化测试,其ORR半波电位为0.73V,OER过电位为430mV,其峰值功率密度为140 mW/cm2,其循环稳定性在85周次,结果显示:不引入三聚氰胺为碳源煅烧后,CoFe-MOF纳米片上不会原位生长碳纳米管,使得电化学性能下降,组装的准固态锌-空气电池功率密度较差。The morphology, cycling stability, catalytic activity and discharge polarization test of the prepared materials showed that the ORR half-wave potential was 0.73V, the OER overpotential was 430mV, and the peak power density was 140 mW/cm 2 , and the cycle was stable. The results show that: after calcination without introducing melamine as the carbon source, carbon nanotubes will not grow in situ on the CoFe-MOF nanosheets, which reduces the electrochemical performance and the assembled quasi-solid-state zinc-air battery has poor power density .

对比例3Comparative Example 3

同实施例1,区别在于,省略步骤(3)。Same as Embodiment 1, the difference is that step (3) is omitted.

对制备的材料进行催化活性测试、循环稳定性、放电极化测试,其ORR半波电位为0.78V,OER过电位为370mV,其峰值功率密度为340 mW/cm2,其循环稳定性在100周次,结果显示:无硫化的产品,双功能活性下降,组装的可充锌空电池功率密度较差。The prepared materials were tested for catalytic activity, cycle stability, and discharge polarization. The ORR half-wave potential was 0.78V, the OER overpotential was 370mV, the peak power density was 340 mW/cm 2 , and the cycle stability was 100 V. Weekly, the results showed that the bifunctional activity of the non-vulcanized product decreased, and the power density of the assembled rechargeable zinc-air battery was poor.

上述结果表明,本发明方法所制备得到的CoFe-S@3D-S-NCNT纳米复合材料具有高的双功能催化活性,将该材料应用于准固态锌-空气电池,具有优异的功率密度和较好的循环稳定性,本发明促进了对可充锌-空气电池空气电极的研究,这对于高性能准固态锌-空气电池空气电极材料的发展起到了一定的推动作用。The above results show that the CoFe-S@3D-S-NCNT nanocomposite prepared by the method of the present invention has high bifunctional catalytic activity. Good cycle stability, the invention promotes the research on the air electrode of rechargeable zinc-air battery, which plays a certain role in promoting the development of high-performance quasi-solid-state zinc-air battery air electrode material.

以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the present invention. within.

Claims (10)

1.CoFe-S@3D-S-NCNT微纳米复合材料的制备方法,其特征在于,包括以下步骤:1. The preparation method of CoFe-S@3D-S-NCNT micro-nano composite material, is characterized in that, comprises the following steps: (1)CoFe-MOF纳米片的制备:钴盐、铁盐水溶液和2-甲基咪唑水溶液组成的混合溶液中陈化后离心清洗干燥得CoFe-MOF;(1) Preparation of CoFe-MOF nanosheets: the mixed solution composed of cobalt salt, iron salt aqueous solution and 2-methylimidazole aqueous solution is aged, centrifugally washed and dried to obtain CoFe-MOF; (2) CoFe@3D-NCNT的制备:在三聚氰胺存在的条件下将CoFe-MOF微纳米片在氩气与氢气的混合气氛中进行退火得CoFe@3D-NCNT微纳米材料;(2) Preparation of CoFe@3D-NCNT: CoFe@3D-NCNT micro-nano materials were obtained by annealing CoFe-MOF micro-nano sheets in a mixed atmosphere of argon and hydrogen in the presence of melamine; (3)CoFe-S@3D-S-NCNT的制备:CoFe@3D-NCNT微纳米材料浸没于硫化钠溶液中进行水热反应后洗涤干燥得CoFe-S@3D-S-NCNT。(3) Preparation of CoFe-S@3D-S-NCNT: CoFe@3D-NCNT micro-nanomaterial was immersed in sodium sulfide solution for hydrothermal reaction, washed and dried to obtain CoFe-S@3D-S-NCNT. 2.根据权利要求1所述的CoFe-S@3D-S-NCNT微纳米复合材料的制备方法,其特征在于,所述步骤(1)中,钴盐包括硝酸钴、氯化钴、或醋酸钴,其水溶液的浓度为5-20g/L;铁盐包括氯化铁、硝酸铁、或醋酸铁,其水溶液的浓度为0.5-2g/L;2-甲基咪唑水溶液的浓度为20-50g/L。2. the preparation method of CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, is characterized in that, in described step (1), cobalt salt comprises cobalt nitrate, cobalt chloride or acetic acid Cobalt, the concentration of its aqueous solution is 5-20g/L; the iron salt includes ferric chloride, ferric nitrate, or ferric acetate, and the concentration of its aqueous solution is 0.5-2g/L; the concentration of 2-methylimidazole aqueous solution is 20-50g /L. 3.根据权利要求1所述的CoFe-S@3D-S-NCNT微纳米复合材料的制备方法,其特征在于,氩气与氢气的混合气氛中,氩气为85-95%,氢气为5-15%。3. the preparation method of CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, is characterized in that, in the mixed atmosphere of argon and hydrogen, argon is 85-95%, and hydrogen is 5 -15%. 4.根据权利要求1所述的CoFe-S@3D-S-NCNT微纳米复合材料的制备方法,其特征在于,氩气与氢气的混合气氛中,氩气为95%,氢气为5%。4. the preparation method of CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, is characterized in that, in the mixed atmosphere of argon and hydrogen, argon is 95%, and hydrogen is 5%. 5.根据权利要求1所述的CoFe-S@3D-S-NCNT微纳米复合材料的制备方法,其特征在于,三聚氰胺与钴盐、铁盐的质量比为0.05-0.2:5-20:5-20。5. The preparation method of CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, wherein the mass ratio of melamine to cobalt salt and iron salt is 0.05-0.2:5-20:5 -20. 6.根据权利要求1所述的CoFe-S@3D-S-NCNT微纳米复合材料的制备方法,其特征在于,所述步骤(2)是将CoFe-MOF纳米片放置在管式气氛炉炉管下游,三聚氰胺置于上游,置于氩气与氢气氛围中,0.5~2小时内升高温度至700~900℃继续保温1~2小时,自然降温后,得到CoFe@3D-NCNT。6. the preparation method of CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, is characterized in that, described step (2) is to place CoFe-MOF nano sheet on tubular atmosphere furnace furnace Downstream of the tube, melamine was placed upstream, placed in an atmosphere of argon and hydrogen, and the temperature was raised to 700-900 °C within 0.5-2 hours, and the temperature was maintained for 1-2 hours. After natural cooling, CoFe@3D-NCNT was obtained. 7.根据权利要求1所述的CoFe-S@3D-S-NCNT微纳米复合材料的制备方法,其特征在于,所述步骤(3)中:硫化钠溶液浓度为10-20g/L。7. The preparation method of CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, is characterized in that, in described step (3): sodium sulfide solution concentration is 10-20g/L. 8.根据权利要求1所述的CoFe-S@3D-S-NCNT微纳米复合材料的制备方法,其特征在于,所述步骤(3)中:水热反应温度100-140℃,水热反应时间6-18h。8. The preparation method of CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, wherein in the step (3): a hydrothermal reaction temperature of 100-140° C., a hydrothermal reaction Time 6-18h. 9.一种包含权利要求1-8任一项CoFe-S@3D-S-NCNT微纳米复合材料的准固态可充锌-空气电池空气电极,其特征在于,CoFe-S@3D-S-NCNT微纳米复合材料中加入乙醇、萘酚溶液中超声分散得到催化剂墨水,将催化剂墨水滴加到碳纸或碳布上,烘干,得到准固态可充锌-空气电池空气电极。9. A quasi-solid rechargeable zinc-air battery air electrode comprising any one of claims 1-8 CoFe-S@3D-S-NCNT micro-nano composite material, characterized in that CoFe-S@3D-S- Add ethanol and naphthol solution to the NCNT micro-nano composite material by ultrasonic dispersion to obtain a catalyst ink, drop the catalyst ink on carbon paper or carbon cloth, and dry to obtain a quasi-solid rechargeable zinc-air battery air electrode. 10.一种准固态锌-空气电池,包含权利要求1-8任一项CoFe-S@3D-S-NCNT微纳米复合材料所制备的空气电极作为阴极电极;锌片、锌箔、锌带、碳布或碳纸原位沉积的锌电极的任意一种作为阳极电极;PVA电解质、PaNa电解质、生物纤维素膜电解质、丙烯酸凝胶电解质中的任意一种作为凝胶电解质经组装得到准固态锌-空气电池。10. A quasi-solid-state zinc-air battery, comprising the air electrode prepared by the CoFe-S@3D-S-NCNT micro-nano composite material of any one of claims 1-8 as a cathode electrode; zinc sheet, zinc foil, zinc ribbon , any one of the zinc electrodes deposited in situ by carbon cloth or carbon paper is used as the anode electrode; any one of the PVA electrolyte, PaNa electrolyte, biocellulose membrane electrolyte, and acrylic gel electrolyte is assembled as a gel electrolyte to obtain a quasi-solid state Zinc-air battery.
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