WO2023092630A1 - 一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极及其制备方法 - Google Patents

一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极及其制备方法 Download PDF

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WO2023092630A1
WO2023092630A1 PCT/CN2021/135199 CN2021135199W WO2023092630A1 WO 2023092630 A1 WO2023092630 A1 WO 2023092630A1 CN 2021135199 W CN2021135199 W CN 2021135199W WO 2023092630 A1 WO2023092630 A1 WO 2023092630A1
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electrode
ethylenedioxythiophene
poly
dimensional porous
flexible composite
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PCT/CN2021/135199
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English (en)
French (fr)
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谢世磊
林家瑾
杨小曼
张敏
赵鹏
程发良
谢东
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东莞理工学院
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8853—Electrodeposition

Definitions

  • the invention relates to the field of energy storage, in particular to a three-dimensional porous cobalt nitride-poly(3,4-ethylenedioxythiophene) flexible composite electrode and a preparation method thereof.
  • Lithium-ion batteries are currently widely used in flexible electronic devices due to their high energy density and output voltage.
  • the shortage of lithium resources has seriously increased the cost of lithium-ion batteries.
  • wearable devices are often in direct contact with the human body, which puts higher requirements on the electrolyte and electrode materials used in energy storage devices.
  • the electrolytes used in lithium-ion batteries are often highly flammable and toxic, which require high rigidity and large volume to ensure the safety of the battery. Therefore, there is an urgent need to develop flexible energy storage devices with higher energy density and higher safety.
  • the rechargeable zinc-air battery has many characteristics such as large discharge capacity, low production cost, stable discharge performance, safe use, no pollution, high power use, and easy-to-obtain, abundant and renewable materials. , has received great attention, and has shown great application potential in portable electronic devices, communication systems and other fields.
  • zinc-air batteries still face problems such as low power density, poor high-rate discharge capacity retention, and difficulty in meeting the needs of modern electronic equipment in terms of service life and safety performance.
  • the air electrode is one of the most important components of the zinc-air battery.
  • the surface of the air electrode sequentially undergoes the reaction of water oxidation to generate oxygen (OER) and the reduction reaction of oxygen (ORR). Therefore, the air electrode for Zn-air battery requires the bifunctional catalyst used to have good catalytic activity for both ORR and OER.
  • the commonly used air electrode materials are mainly noble metal materials such as platinum and ruthenium, which have problems such as high cost, poor stability, and low activity. Therefore, the design and preparation of high-activity, low-cost bifunctional catalysts is very important and meaningful.
  • these powder materials often need to be coated, dried and other complex, multi-step processes before they can be used in batteries.
  • the electrode substrate materials used for coating are often not flexible, which limits the use of this material in the field of flexible energy storage. Therefore, it is necessary to develop composite electrodes with high activity, low cost, high stability and flexibility.
  • a three-dimensional porous cobalt nitride-poly(3,4-ethylenedioxythiophene) flexible composite electrode which has high electrocatalytic performance for catalytic reduction of oxygen and catalytic water oxidation active.
  • the zinc-air battery assembled with the flexible composite electrode has good capacity and cycle stability. Also provided is a method for preparing an efficient and stable three-dimensional porous cobalt nitride-poly(3,4-ethylenedioxythiophene) flexible composite electrode.
  • a method for preparing a three-dimensional porous cobalt nitride-poly(3,4-ethylenedioxythiophene) flexible composite electrode comprising the following steps: S1. Cleaning of substrate material: a certain area of flexible conductive substrate is washed in organic solvent and Ultrasonic cleaning in deionized water for 20 minutes. S2. Preparation of Co(OH)F: Dissolve cobalt nitrate hexahydrate, ammonium fluoride and urea in 20 mL of deionized water, stir and dissolve to obtain a mixed solution. Subsequently, the mixed solution and the above-mentioned cleaned flexible conductive substrate were transferred to a high-temperature reactor, and reacted at 120° C. for 3-9 hours.
  • step S3 Washed several times with distilled water and ethanol and dried overnight. S3. Put the above-mentioned dried materials in a porcelain boat, and then put them into a high-temperature furnace for firing to obtain fired materials. S4. Using the fired material in step S3 as a working electrode, a three-electrode system is used to electrodeposit to obtain a three-dimensional porous cobalt nitride/poly(3,4-ethylenedioxythiophene) flexible composite electrode.
  • the organic solvent is one of acetone, ethanol, and methanol.
  • the flexible conductive substrate is one of nickel foam, copper foam, copper foil, copper sheet, titanium foil, titanium sheet, and conductive carbon cloth.
  • a further improvement to the above technical solution is that in the step S3, ammonia gas is continuously fed during the firing process, and then the temperature is raised to 400°C at a rate of 5°C/min, kept for 1-3h, and then cooled to room temperature.
  • the counter electrode of the three-electrode system is an inert electrode Pt sheet
  • the reference electrode is a silver/silver chloride electrode
  • the counter electrode can also be a Pt mesh.
  • the reference electrode can also be one of a hydrogen electrode, a Hg/HgO electrode, a calomel electrode, and a mercury/mercurous sulfate electrode.
  • the three-electrode system further includes an electrodeposition electrolyte.
  • the electrodeposition electrolyte includes 10.639g/L lithium perchlorate, 20.187g/L sodium dodecyl sulfate, and 4.265g/L 3,4-ethylenedioxythiophene monomer.
  • a further improvement to the above technical solution is that, in the three-electrode system, the electrodeposition potential is 1.0 volts, and the electrodeposition time is 10-240s.
  • a three-dimensional porous cobalt nitride-poly(3,4-ethylenedioxythiophene) flexible composite electrode uses the above preparation method be made of.
  • the preparation method of the invention is simple and easy to implement, and the hydrothermal temperature and ammonia treatment conditions are simple.
  • the surface coating of the prepared electrode material only needs to use electrochemical deposition technology, and the deposition voltage is less than 1.5 volts, which is safe and convenient.
  • the prepared electrode material has high stability, simple and convenient recycling, many cycles, and high flexibility, which can be used for flexible electrodes and flexible batteries.
  • Fig. 1 is the X-ray diffraction spectrum of CoN and CoN/PEDOT composite material of the present invention.
  • Figure 2 is a scanning electron microscope image of CoN flexible electrode material.
  • Figure 3 is a scanning electron microscope image of the CoN/PEDOT flexible electrode material.
  • Figure 4 is a comparison of the activities of (a) catalytic oxygen reduction and (b) catalytic water oxidation of flexible CoN and CoN/PEDOT composites.
  • Figure 5 is a comparison of the performance of zinc-air batteries made of flexible CoN and CoN/PEDOT composites.
  • a method for preparing a three-dimensional porous cobalt nitride-poly(3,4-ethylenedioxythiophene) flexible composite electrode comprising the following steps: 1. Cleaning of substrate material: a certain area of flexible conductive substrate is washed in an organic solvent and removed Ultrasonic cleaning with ionized water for 20 minutes to remove most of the oil and solid impurities on the flexible conductive carbon cloth; wherein the organic solvent can be polar or non-polar solvents such as acetone, ethanol, and methanol.
  • the flexible substrate can be flexible metal materials such as nickel foam (copper), copper foil (sheet), titanium foil (sheet); 2.
  • Co(OH)F 0.3492g cobalt nitrate hexahydrate, 0.1184g ammonium fluoride and 0.1802g of urea was dissolved in 20mL of deionized water, and fully stirred and dissolved to obtain a mixed solution. Subsequently, the mixed solution and the above-mentioned cleaned flexible conductive substrate were transferred to a high-temperature reactor, and reacted at 120° C. for 3-9 hours. Repeated washing with distilled water and ethanol several times and then drying overnight; 3. Place the above-mentioned dried materials in a porcelain boat, and then put them into a high-temperature furnace for firing.
  • the counter electrode is an inert electrode Pt sheet
  • the reference electrode is a silver/silver chloride electrode (Ag/AgCl electrode).
  • the electrodeposition electrolyte contains 10.639g/L lithium perchlorate, 20.187g/L sodium dodecyl sulfate, and 4.265g/L 3,4-ethylenedioxythiophene monomer; the electrodeposition potential is 1.0 volts, Electrodeposition time is 10 ⁇ 240s.
  • the counter electrode used in the three-electrode system can be metal Pt materials such as Pt sheet, Pt mesh, or graphite electrode with a purity greater than 99.9%;
  • the reference electrode can be Ag/AgCl electrode, or other reference electrodes , such as hydrogen electrode, Hg/HgO, calomel electrode, mercury/mercurous sulfate electrode and other reference electrodes, the potential between different electrodes can be converted by Nernst equation.
  • Example 1 1. Take a 2*3 cm 2 conductive carbon cloth, ultrasonically clean it in ethanol and deionized water for 20 minutes, and then take it out for use.
  • the material obtained in the above step is used as the working electrode, and a three-electrode system is used to electrodeposit to obtain a three-dimensional porous cobalt nitride/poly(3,4-ethylenedioxythiophene) flexible composite electrode.
  • the counter electrode is an inert electrode Pt sheet
  • the reference electrode is a silver/silver chloride electrode.
  • the electrodeposition electrolyte contains 10.639g/L lithium perchlorate, 20.187g/L sodium dodecyl sulfate, and 4.265g/L 3,4-ethylenedioxythiophene monomer; the electrodeposition potential is 1.0 volts, The electrodeposition time is 120s.
  • Example 2 1. Take a 2*3 cm 2 conductive carbon cloth, ultrasonically clean it in ethanol and deionized water for 20 minutes, and then take it out for use.
  • Electrodeposition electrolyte contains 10.639g/L lithium perchlorate, 20.187g/L sodium dodecyl sulfate, 4,265g/L 3,4-ethylenedioxythiophene monomer; electrodeposition potential is 1.0 volts , The electrodeposition time is 120s.
  • Example 3 1. Take a 2*3 cm 2 conductive carbon cloth, ultrasonically clean it in ethanol and deionized water for 20 minutes, and then take it out for use.
  • Electrodeposition electrolyte contains 10.639g/L lithium perchlorate, 20.187g/L sodium dodecyl sulfate, 4,265g/L 3,4-ethylenedioxythiophene monomer; electrodeposition potential is 1.0 volts , The electrodeposition time is 120s.
  • Example 4 1. Take a 2*3cm 2 conductive carbon cloth, ultrasonically clean it in ethanol and deionized water for 20 minutes, and then take it out for use.
  • Electrodeposition electrolyte contains 10.639g/L lithium perchlorate, 20.187g/L sodium dodecyl sulfate, 4,265g/L 3,4-ethylenedioxythiophene monomer; electrodeposition potential is 1.0 volts , The electrodeposition time is 120s.
  • Example 5 1. Take a 2*3 cm 2 conductive carbon cloth, ultrasonically clean it in ethanol and deionized water for 20 minutes, and then take it out for use.
  • Electrodeposition electrolyte contains 10.639g/L lithium perchlorate, 20.187g/L sodium dodecyl sulfate, 4,265g/L 3,4-ethylenedioxythiophene monomer; electrodeposition potential is 1.0 volts , The electrodeposition time is 120s.
  • Example 6 1. Take a 2*3cm 2 conductive carbon cloth, ultrasonically clean it in ethanol and deionized water for 20 minutes, and then take it out for use.
  • Electrodeposition electrolyte contains 10.639g/L lithium perchlorate, 20.187g/L sodium dodecyl sulfate, 4,265g/L 3,4-ethylenedioxythiophene monomer; electrodeposition potential is 1.0 volts , The electrodeposition time is 60s.
  • Example 7 1. Take a 2*3cm 2 conductive carbon cloth, ultrasonically clean it in ethanol and deionized water for 20 minutes, and then take it out for use.
  • Electrodeposition electrolyte contains 10.639g/L lithium perchlorate, 20.187g/L sodium dodecyl sulfate, 4,265g/L 3,4-ethylenedioxythiophene monomer; electrodeposition potential is 1.0 volts , The electrodeposition time is 240s.
  • Example 2-7 After the same experimental verification as in Example 1, the results show that the material prepared in Example 2-7 also has good electrocatalytic water oxidation, catalytic oxygen reduction activity, and high cycle stability of zinc-air batteries.
  • Comparative example 1 1. Take a 2*3cm 2 conductive carbon cloth, ultrasonically clean it in ethanol and deionized water for 20 minutes, and then take it out for use.
  • step (4) is omitted.
  • the morphology, cycle stability, and specific capacity tests of the prepared materials showed that the surface of the flexible electrode material is free of poly(3,4-ethylenedioxythiophene)-coated electrodes, the electrocatalytic life of the electrode, and the cycle stability of the zinc-air battery sex decline.
  • Fig. 1 is the X-ray diffraction spectrum of CoN and CoN/PEDOT composite material. It can be seen from Figure 1 that the CoN material was obtained; and after the surface was coated with PEDOT, the structure of CoN did not change.
  • the CoN prepared on the flexible carbon cloth material is a nano-needle material through hydrothermal and subsequent ammonia heat treatment; the CoN obtained by using the above material as the substrate and electrochemical deposition
  • the surface of the /PEDOT composite becomes rough and has a porous structure.
  • the flexible CoN material has good catalytic activity for oxygen reduction and water oxidation.
  • the half-wave potential of CoN materials for catalyzing oxygen reduction is about 0.890 V vs. RHE; the voltage required to catalyze the oxidation of water to oxygen with a current density of 10 mA cm-2 is 1.469 V vs. RHE.
  • the three-dimensional porous CoN/PEDOT composites prepared by coating a layer of PEDOT on the surface of flexible CoN and CoN/PEDOT composites have catalytic oxygen reduction and catalytic water oxidation activities close to those of flexible CoN composites: half-wave catalytic oxygen reduction
  • the potential is about 0.895 V vs. RHE, and the voltage required for the oxidation current to reach a current density of 10 mA cm-2 is 1.493 V vs. RHE.
  • Figure 5 is a comparison of the performance of zinc-air batteries made of flexible CoN and CoN/PEDOT composites.
  • the discharge voltage of the flexible CoN material decreased significantly after about 25 hours of cycling, and the charge voltage increased significantly.
  • the CoN/PEDOT composite material has good cycle charge-discharge stability, and its charge-discharge voltage does not change significantly during the 65-hour cycle.

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Abstract

提供一种三维多孔氮化钴-聚(3,4-乙烯二氧噻吩)柔性复合电极及其制备方法，该三维多孔氮化钴-聚(3,4-乙烯二氧噻吩)柔性复合电极材料对于氧气的催化还原、催化水氧化具有很高的电催化活性；以该三维多孔氮化钴-聚(3,4-乙烯二氧噻吩)柔性复合电极组装的锌-空气电池具有良好的容量以及循环稳定性。

Description

一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极及其制备方法
相关申请的交叉引用。
本申请要求于2021年11月29日提交中国专利局，申请号为202111436831.X，发明名称为“一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及能源储存领域，特别是涉及一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极及其制备方法。
 背景技术
随着可弯曲、折叠的便携式/可穿戴电子设备的快速发展，人们对于柔性储能器件的需求也不断的增加。锂离子电池由于其具有较高的能量密度和输出电压，目前广泛的应用于柔性电子设备。然而，锂资源短缺严重的提高了锂离子电池的成本。此外，可穿戴设备往往与人体直接接触，这对储能设备所使用的电解质和电极材料提出了更高的要求。锂离子电池使用的电解质往往具有较高的可燃性和毒性，其需要高刚性和较大的体积来保证电池的安全性。因而，人们亟需开发得到具有更高能量密度和安全性更高的的柔性储能器件。
可充电的锌空电池作为一种新型绿色储能器件，拥有放电容量大、生产成本低、放电性能稳定、使用安全、无污染、可大功率使用及材料易得、丰富且可再生等诸多特点，受到了人们极大的关注，并在便携式电子设备、通讯系统等领域显示出巨大的应用潜力。但目前锌空气电池仍然面临着功率密度低、大倍率放电容量保持率差、使用寿命和安全性能难以满足现代电子设备的需求等问题。
 技术问题
空气电极作为锌空气电池中最重要的组成部分之一，在充放电过程当中，空气电极表面依次发生水氧化产生氧气的反应（OER）和氧气的还原反应（ORR）。因此，锌空电池用的空气电极要求所使用的双功能催化剂同时具有良好的ORR和OER催化活性。目前常用的空气电极材料主要是铂钌等贵金属材料，具有成本高、稳定差、活性较低等问题。因而，高活性、低成本的双功能催化剂的设计和制备是十分重要和有意义的。此外，这些粉末材料在使用时往往需要先进行涂布、烘干等复杂、多步工艺之后才可以得到电池中可以使用的电极。此外，由于工艺的限制，涂布使用的电极基底材料往往不具有柔性的特点，限制了这次材料在柔性储能领域的使用。因此，需要开发得到具有高活性、低成本、高稳定以及具有柔性特征的复合电极。
 技术解决方案
根据本申请的各种实施例，提供一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极，该电极对于氧气的催化还原、催化水氧化具有较高的电催化活性。以该柔性复合电极组装的锌-空气电池具有良好的容量以及循环稳定性。还提供一种高效稳定的三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法。
一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，包括如下步骤：S1、基底材料的清洗：将一定面积的柔性导电基底，分别在有机溶剂和去离子水中超声清洗20分钟。S2、Co(OH)F的制备：将六水合硝酸钴、氟化铵和尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至高温反应釜，将120℃反应3~9h。用蒸馏水和乙醇反复洗涤数遍后干燥过夜。S3、将上述干燥后的材料放置在瓷舟中，然后放入高温炉中烧制，得到烧制后的材料。S4、以步骤S3中的烧制后的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。
对上述技术方案的进一步改进为，在所述步骤S1中，所述有机溶剂为丙酮、乙醇、甲醇中的一种。
对上述技术方案的进一步改进为，在所述步骤S1中，所述柔性导电基底为泡沫镍、泡沫铜、铜箔、铜片、钛箔、钛片、导电碳布中的一种。
对上述技术方案的进一步改进为，在所述步骤S3中，在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持1~3h，之后冷却到室温。
对上述技术方案的进一步改进为，在所述步骤S4中，所述三电极体系的对电极为惰性电极Pt片，参比电极为银/氯化银电极。
对上述技术方案的进一步改进为，所述对电极还可以为Pt网。
对上述技术方案的进一步改进为，所述参比电极还可为氢电极、Hg/HgO电极、甘汞电极、汞/硫酸亚汞电极中的一种。
对上述技术方案的进一步改进为，所述三电极体系还包括电沉积电解液。所述电沉积电解液包括10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4.265g/L的3,4-乙烯二氧噻吩单体。
对上述技术方案的进一步改进为，在所述三电极体系中，电沉积电势为1.0伏，电沉积时间为10~240s。
一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极，所述三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极使用上述的制备方法制得。
 有益效果
本发明的制备方法简单、易行，水热温度和氨气处理条件简单。制得的电极材料表面包覆仅需要使用电化学沉积技术，沉积电压小于1.5伏，安全便捷。制得的电极材料具有很高的稳定性，循环利用简单方便，可循环次数多，同时还具有较高的柔性，可以用于柔性电极、柔性电池。
 附图说明
为了更好地描述和说明这里公开的那些发明的实施例和/或示例，可以参考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的任何一者的范围的限制。
图1为本发明的CoN和CoN/PEDOT复合材料的X-射线衍射谱图。
图2为CoN 柔性电极材料的扫描电镜图。
图3为CoN/PEDOT柔性电极材料的扫描电镜图。
图4为柔性CoN和CoN/PEDOT复合材料的（a）催化氧气还原、（b）催化水氧化的活性对比图。
图5为柔性CoN和CoN/PEDOT复合材料的锌-空气电池性能对比图。
 本发明的实施方式
为了便于理解本发明，下面将对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，包括如下步骤：1、基底材料的清洗：将一定面积的柔性导电基底，在有机溶剂和去离子水的分别超声清洗20分钟，以去除柔性导电碳布上的大部分油污、固体杂质等；其中，有机溶剂可以是丙酮、乙醇、甲醇等极性或非极性溶剂。柔性基底可以是泡沫镍（铜）、铜箔（片）、钛箔（片）等柔性金属材料；2、Co(OH)F的制备：将0.3492g六水合硝酸钴、0.1184g氟化铵和0.1802g尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至高温反应釜，将120℃反应3~9h。用蒸馏水和乙醇反复洗涤数遍后干燥过夜；3、将上述干燥后的材料放置在瓷舟中，然后放入高温炉中烧制。在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持1~3h，之后冷却到室温；4、以上一步得到的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。
在三电极体系中，对电极为惰性电极Pt片，参比电极为银/氯化银电极（Ag/AgCl电极）。电沉积电解液包含10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4.265g/L的3,4-乙烯二氧噻吩单体；电沉积电势为1.0伏，电沉积时间为10~240s。其中，三电极体系中使用的对电极可以为Pt片、Pt网等金属Pt材料，也可以为纯度大于99.9%的石墨电极；参比电极可以为Ag/AgCl电极，也可以为其他参比电极，例如氢电极、Hg/HgO、甘汞电极、汞/硫酸亚汞电极等参比电极，不同电极之间的电势可以通过能斯特方程换算。
实施例1：1、取2*3 cm 2的导电碳布，在乙醇和去离子水中分别超声清洗20分钟后取出备用。
2、将0.3492g六水合硝酸钴、0.1184g氟化铵和0.1802g尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至30mL高温反应釜，将120℃反应6h。用蒸馏水和乙醇反复洗涤上述反应后的导电碳布数遍后干燥过夜。
3、将上一步得到的材料放置在瓷舟中，然后放入高温炉中烧制。在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持2h，之后冷却到室温。
4、以上一步得到的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。其中，三电极体系中对电极为惰性电极Pt片，参比电极为银/氯化银电极。电沉积电解液包含10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4.265g/L的3,4-乙烯二氧噻吩单体；电沉积电势为1.0伏，电沉积时间为120s。
实施例2：1、取2*3 cm 2的导电碳布，在乙醇和去离子水中分别超声清洗20分钟后取出备用。
2、将0.3492g六水合硝酸钴、0.1184g氟化铵和0.1802g尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至30mL高温反应釜，将120℃反应3h。用蒸馏水和乙醇反复洗涤上述反应后的导电碳布数遍后干燥过夜。
3、将上一步得到的材料放置在瓷舟中，然后放入高温炉中烧制。在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持2h，之后冷却到室温。
4、以上一步得到的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。其中，三电极体系中对电极为惰性电极Pt片，参比电极为银/氯化银电极。电沉积电解液包含10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4、265g/L的3,4-乙烯二氧噻吩单体；电沉积电势为1.0伏，电沉积时间为120s。
实施例3：1、取2*3 cm 2的导电碳布，在乙醇和去离子水中分别超声清洗20分钟后取出备用。
2、将0.3492g六水合硝酸钴、0.1184g氟化铵和0.1802g尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至30mL高温反应釜，将120℃反应9h。用蒸馏水和乙醇反复洗涤上述反应后的导电碳布数遍后干燥过夜。
3、将上一步得到的材料放置在瓷舟中，然后放入高温炉中烧制。在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持2h，之后冷却到室温。
4、以上一步得到的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。其中，三电极体系中对电极为惰性电极Pt片，参比电极为银/氯化银电极。电沉积电解液包含10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4、265g/L的3,4-乙烯二氧噻吩单体；电沉积电势为1.0伏，电沉积时间为120s。
实施例4：1、取2*3cm 2的导电碳布，在乙醇和去离子水中分别超声清洗20分钟后取出备用。
2、将0.3492g六水合硝酸钴、0.1184g氟化铵和0.1802g尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至30mL高温反应釜，将120℃反应6h。用蒸馏水和乙醇反复洗涤上述反应后的导电碳布数遍后干燥过夜。
3、将上一步得到的材料放置在瓷舟中，然后放入高温炉中烧制。在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持1h，之后冷却到室温。
4、以上一步得到的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。其中，三电极体系中对电极为惰性电极Pt片，参比电极为银/氯化银电极。电沉积电解液包含10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4、265g/L的3,4-乙烯二氧噻吩单体；电沉积电势为1.0伏，电沉积时间为120s。
实施例5：1、取2*3 cm 2的导电碳布，在乙醇和去离子水中分别超声清洗20分钟后取出备用。
2、将0.3492g六水合硝酸钴、0.1184g氟化铵和0.1802g尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至30mL高温反应釜，将120℃反应6h。用蒸馏水和乙醇反复洗涤上述反应后的导电碳布数遍后干燥过夜。
3、将上一步得到的材料放置在瓷舟中，然后放入高温炉中烧制。在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持3h，之后冷却到室温。
4、以上一步得到的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。其中，三电极体系中对电极为惰性电极Pt片，参比电极为银/氯化银电极。电沉积电解液包含10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4、265g/L的3,4-乙烯二氧噻吩单体；电沉积电势为1.0伏，电沉积时间为120s。
实施例6：1、取2*3cm 2的导电碳布，在乙醇和去离子水中分别超声清洗20分钟后取出备用。
2、将0.3492g六水合硝酸钴、0.1184g氟化铵和0.1802g尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至30mL高温反应釜，将120℃反应6h。用蒸馏水和乙醇反复洗涤上述反应后的导电碳布数遍后干燥过夜。
3、将上一步得到的材料放置在瓷舟中，然后放入高温炉中烧制。在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持2h，之后冷却到室温。
4、以上一步得到的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。其中，三电极体系中对电极为惰性电极Pt片，参比电极为银/氯化银电极。电沉积电解液包含10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4、265g/L的3,4-乙烯二氧噻吩单体；电沉积电势为1.0伏，电沉积时间为60s。
实施例7：1、取2*3cm 2的导电碳布，在乙醇和去离子水中分别超声清洗20分钟后取出备用。
2、将0.3492g六水合硝酸钴、0.1184g氟化铵和0.1802g尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至30mL高温反应釜，将120℃反应6h。用蒸馏水和乙醇反复洗涤上述反应后的导电碳布数遍后干燥过夜。
3、将上一步得到的材料放置在瓷舟中，然后放入高温炉中烧制。在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持2h，之后冷却到室温。
4、以上一步得到的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。其中，三电极体系中对电极为惰性电极Pt片，参比电极为银/氯化银电极。电沉积电解液包含10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4、265g/L的3,4-乙烯二氧噻吩单体；电沉积电势为1.0伏，电沉积时间为240s。
经过同实施例1相同的实验验证，结果显示，实施例2‑7制备的材料同样具有良好的电催化水氧化、催化氧气还原活性，以及较高的锌空电池循环稳定性。
对比例1：1、取2*3cm 2的导电碳布，在乙醇和去离子水中分别超声清洗20分钟后取出备用。
2、将0.3492g六水合硝酸钴、0.1184g氟化铵和0.1802g尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液。随后，将混合溶液和上述清洗后的柔性导电基底转移至30mL高温反应釜，将120℃反应6h。用蒸馏水和乙醇反复洗涤上述反应后的导电碳布数遍后干燥过夜。
3、将上一步得到的材料放置在瓷舟中，然后放入高温炉中烧制。在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持2h，之后冷却到室温。
对比例1与实施例1的不同之处在于，省略步骤(4)。对制备的材料进行形貌、循环稳定性、比容量测试，结果显示：柔性电极材料表面无聚（3,4-乙烯二氧噻吩）包覆的电极，电极电催化寿命、锌空电池循环稳定性下降。
图1为CoN和CoN/PEDOT复合材料的X-射线衍射谱图。由图1可知，得到了CoN材料；以及在表面包覆PEDOT之后，CoN的结构未发生变化。
如图2~3所示，通过水热以及后续氨气热处理的方式，在柔性碳布材料上制备得到的CoN为纳米针状材料；以上述材料为基底，通过电化学沉积之后，到的CoN/PEDOT复合材料表面变得粗糙，具有多孔结构。
图4所示，柔性CoN材料具有良好的催化氧气还原和催化水氧化的活性。CoN材料催化氧气还原的半波电位约为0.890 V vs. RHE；催化水氧化为氧气，且氧化电流达到电流密度为10 mA cm-2时所需的电压为 1.469 V vs. RHE。并且，在柔性CoN和CoN/PEDOT复合材料表面包覆一层PEDOT制备得到的三维多孔CoN/PEDOT复合材料的催化氧气还原和催化水氧化的活性与柔性CoN复合材料接近：催化氧气还原的半波电位约为0.895 V vs. RHE，氧化电流达到电流密度为10 mA cm-2时所需的电压为 1.493 V vs. RHE。
图5为柔性CoN和CoN/PEDOT复合材料的锌-空气电池性能对比图。柔性CoN材料在约25小时循环后放电电压显著降低，充电电压明显上升。而CoN/PEDOT复合材料具有良好的循环充放电稳定性，在长达65个小时的循环过程中，其充放电电压均未发生明显的变化。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，其特征在于，包括如下步骤：S1、基底材料的清洗：将一定面积的柔性导电基底，分别在有机溶剂和去离子水中超声清洗20分钟；S2、Co(OH)F的制备：将六水合硝酸钴、氟化铵和尿素溶于20mL去离子水中，充分搅拌溶解得到混合溶液；随后，将混合溶液和上述清洗后的柔性导电基底转移至高温反应釜，将120℃反应3~9h；用蒸馏水和乙醇反复洗涤数遍后干燥过夜；S3、将上述干燥后的材料放置在瓷舟中，然后放入高温炉中烧制，得到烧制后的材料；S4、以步骤S3中的烧制后的材料为工作电极，采用三电极体系，电沉积得到三维多孔氮化钴/聚（3,4-乙烯二氧噻吩）柔性复合电极。
  2. 根据权利要求1所述的三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，其特征在于，在所述步骤S1中，所述有机溶剂为丙酮、乙醇、甲醇中的一种。
  3. 根据权利要求1所述的三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，其特征在于，在所述步骤S1中，所述柔性导电基底为泡沫镍、泡沫铜、铜箔、铜片、钛箔、钛片、导电碳布中的一种。
  4. 根据权利要求1所述的三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，其特征在于，在所述步骤S3中，在烧制过程中持续通入氨气，然后以5℃/min升温速率升至400℃，保持1~3h，之后冷却到室温。
  5. 根据权利要求1所述的三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，其特征在于，在所述步骤S4中，所述三电极体系的对电极为惰性电极Pt片，参比电极为银/氯化银电极。
  6. 根据权利要求5所述的三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，其特征在于，所述对电极还可以为Pt网。
  7. 根据权利要求5所述的三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，其特征在于，所述参比电极还可为氢电极、Hg/HgO电极、甘汞电极、汞/硫酸亚汞电极中的一种。
  8. 根据权利要求1所述的三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，其特征在于，所述三电极体系还包括电沉积电解液；所述电沉积电解液包括10.639g/L的高氯酸锂、20.187g/L的十二烷基硫酸钠，4.265g/L的3,4-乙烯二氧噻吩单体。
  9. 根据权利要求1所述的三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极的制备方法，其特征在于，在所述三电极体系中，电沉积电势为1.0伏，电沉积时间为10~240s。
  10. 一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极，其特征在于，所述三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极使用如权利要求1-9任一项所述的制备方法制得。
PCT/CN2021/135199 2021-11-29 2021-12-02 一种三维多孔氮化钴-聚（3,4-乙烯二氧噻吩）柔性复合电极及其制备方法 WO2023092630A1 (zh)

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