CN112023946A - A kind of preparation method of self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst - Google Patents

A kind of preparation method of self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst Download PDF

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CN112023946A
CN112023946A CN202010936550.XA CN202010936550A CN112023946A CN 112023946 A CN112023946 A CN 112023946A CN 202010936550 A CN202010936550 A CN 202010936550A CN 112023946 A CN112023946 A CN 112023946A
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孙剑辉
孙蓓蕾
禹崇菲
陈如艳
张雅楠
吴宇涵
李冰宇
刘瑜辉
董淑英
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Abstract

The invention provides a preparation method of a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst, which comprises the following steps: pretreating the original foam nickel to obtain purified foam nickel; dissolving nickel nitrate hexahydrate, ferric nitrate nonahydrate and urea in deionized water according to a preset proportion to obtain a mixed solution; the concentration of cations in the mixed solution is 40-45 mmol/L, and the concentration of urea is 130-150 mmol/L; carrying out a primary hydrothermal reaction on the mixed solution to obtain NiFe LDH/NF; putting NiFe LDH/NF into thioacetamide solution to carry out secondary hydrothermal reaction to obtain NiFe LDH-Sx/NF; wherein x = any number from 1 to 8. According to the preparation method of the self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst provided by the invention, the electrocatalyst shows excellent catalytic activity of oxygen evolution reaction under an alkaline condition, and a nickel-iron double hydroxide nanosheet structure directly grown on foamed nickel is beneficial to electron transfer, the catalytic surface area is increased, the catalytic active sites are improved, and the diffusion of the oxygen evolution reaction is facilitated.

Description

一种自支撑镍铁层状双氢氧化物硫化物电催化剂的制备方法A kind of preparation method of self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst

技术领域technical field

本发明涉及电催化材料技术领域，特别是涉及一种自支撑镍铁层状双氢氧化物硫化物电催化剂的制备方法。The invention relates to the technical field of electrocatalytic materials, in particular to a preparation method of a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst.

背景技术Background technique

氢能具有良好的能量转换效率、高能量密度、零二氧化碳排放和环境相容性，被认为是替代传统化石燃料的理想选择。电解水技术是基于电化学分解水的原理，利用可持续太阳能、风能转化为电能，进而将水驱动分解成氢气和氧气，被认为是一种高效的和可持续产氢的途径。Hydrogen energy has good energy conversion efficiency, high energy density, zero carbon dioxide emissions, and environmental compatibility, and is considered an ideal alternative to traditional fossil fuels. Water electrolysis technology is based on the principle of electrochemical water splitting, which utilizes sustainable solar and wind energy to convert into electricity, and then drives water to be split into hydrogen and oxygen. It is considered to be an efficient and sustainable way to produce hydrogen.

层状双氢氧化物（Layer double hydroxides，LDHs）因具有比表面积大、化学性质多样、结构开放等优点备受关注。对于析氧反应（OER），LDH片上的金属原子可以提供丰富的暴露活性位点，特别是LDH独特的阴离子交换性能和易分层性使得LDH的工程纳米组装更容易增强OER性能。常见的Ni基层状氢氧化物为双过渡金属（Fe、Co、Mn等）元素组合形成的层状双氢氧化物（如NiFe LDH、NiCo LDH和 NiMn LDH等），这些层状双氢氧化物被证实具有可以与商业RuO2相媲美的优越性能，其中成分可调、层状结构的NiFe-LDH基催化剂被认为是碱性溶液中性能比较好的非贵金属氧化物电催化剂之一。Layered double hydroxides (LDHs) have attracted much attention due to their large specific surface area, diverse chemical properties, and open structure. For the oxygen evolution reaction (OER), the metal atoms on the LDH sheet can provide abundant exposed active sites, especially the unique anion exchange properties and easy delamination of LDH make the engineered nanoassembly of LDH easier to enhance the OER performance. Common Ni-based layered hydroxides are layered double hydroxides (such as NiFe LDH, NiCo LDH and NiMn LDH, etc.) formed by the combination of double transition metal (Fe, Co, Mn, etc.) elements. These layered double hydroxides The NiFe-LDH-based catalyst with tunable composition and layered structure has been confirmed to have superior performance comparable to that of commercial RuO2, which is considered to be one of the better non-noble metal oxide electrocatalysts in alkaline solution.

现有针对现有OER催化剂资源稀缺、价格昂贵、电流密度低、过电位高、稳定性差、合成方法繁杂等问题。The existing OER catalysts have the problems of scarcity of resources, high price, low current density, high overpotential, poor stability, and complicated synthesis methods.

发明内容SUMMARY OF THE INVENTION

本发明的一个目的是要提供一种操作简单、可工业化的自支撑镍铁层状双氢氧化物硫化物电催化剂的制备方法。An object of the present invention is to provide a method for preparing a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst with simple operation and industrialization.

本发明一个进一步的目的是要提高自支撑镍铁层状双氢氧化物硫化物电催化剂的催化性能。A further object of the present invention is to improve the catalytic performance of the self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst.

特别地，本发明提供了一种自支撑镍铁层状双氢氧化物硫化物电催化剂的制备方法，该制备方法包括如下步骤：In particular, the present invention provides a preparation method of a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst, the preparation method comprising the following steps:

对原始泡沫镍进行预处理得到净化泡沫镍；Pretreatment of original nickel foam to obtain purified nickel foam;

按照预设比例将六水合硝酸镍、九水合硝酸铁和尿素溶于去离子水中得到混合液；其中，混合液的阳离子的浓度为40~45 mmol/L，尿素的浓度为130~150 mmol/L；According to the preset ratio, nickel nitrate hexahydrate, ferric nitrate nonahydrate and urea are dissolved in deionized water to obtain a mixed solution; wherein, the concentration of cations in the mixed solution is 40-45 mmol/L, and the concentration of urea is 130-150 mmol/L. L;

将混合液进行一次水热反应，得到NiFe LDH/NF；The mixed solution is subjected to a hydrothermal reaction to obtain NiFe LDH/NF;

将NiFe LDH/NF置于硫代乙酰胺溶液中进行二次水热反应得到NiFe LDH-Sx/NF；其中，x=1至8中的任意数字。The NiFe LDH/NF was placed in a thioacetamide solution for secondary hydrothermal reaction to obtain NiFe LDH-Sx/NF; wherein, x=any number from 1 to 8.

优选地，六水合硝酸镍、九水合硝酸铁和尿素的摩尔比为2：1：10。Preferably, the molar ratio of nickel nitrate hexahydrate, ferric nitrate nonahydrate and urea is 2:1:10.

优选地，混合液的阳离子的浓度为42 mmol/L，尿素的浓度为140 mmol/L。Preferably, the concentration of cations in the mixed solution is 42 mmol/L, and the concentration of urea is 140 mmol/L.

优选地，硫代乙酰胺溶液的溶度为0.1 mmol/mL。Preferably, the solubility of the thioacetamide solution is 0.1 mmol/mL.

优选地，预处理的步骤为：Preferably, the step of preprocessing is:

将原始泡沫镍依次浸入丙酮、盐酸溶液中并分别进行超声处理；The original nickel foam is immersed in acetone and hydrochloric acid solution and ultrasonically treated respectively;

再依次用去离子水、乙醇冲洗；Rinse with deionized water and ethanol in turn;

干燥后得到净化泡沫镍。After drying, purified nickel foam is obtained.

优选地，一次水热反应的条件为：Preferably, the condition of a hydrothermal reaction is:

温度为100~140℃，时间为10~12h。The temperature is 100~140℃, and the time is 10~12h.

优选地，二次水热反应的条件为：Preferably, the condition of the secondary hydrothermal reaction is:

温度为100~140℃，时间为7~9h。。The temperature is 100~140℃, and the time is 7~9h. .

优选地，NiFe LDH-Sx/NF中的x的值与二次水热反应的反应时间存在线性对应关系。Preferably, there is a linear correspondence between the value of x in NiFe LDH-Sx/NF and the reaction time of the secondary hydrothermal reaction.

优选地，自支撑镍铁层状双氢氧化物硫化物电催化剂为纳米片状结构。Preferably, the self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst has a nanosheet structure.

本发明提供的自支撑镍铁层状双氢氧化物硫化物电催化剂的制备方法，以泡沫镍为基底的自支撑镍铁层状双氢氧化物硫化物电催化剂具有高效的析氧反应（OER）催化性能。因泡沫镍具有导电率高、比表面积大、多孔结构等优点，将催化材料直接生长到泡沫镍上，不仅可以作为镍源用于材料合成，而且利于气泡的释放和电解质的渗透，导致电子更好的转移，从而有效提高催化剂的催化活性。The preparation method of the self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst provided by the present invention, the self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst based on foamed nickel has an efficient oxygen evolution reaction (OER ) catalytic performance. Because nickel foam has the advantages of high conductivity, large specific surface area, porous structure, etc., the direct growth of catalytic materials on nickel foam can not only be used as a nickel source for material synthesis, but also facilitate the release of bubbles and the penetration of electrolytes, resulting in more electrons. good transfer, thereby effectively improving the catalytic activity of the catalyst.

进一步地，该自支撑镍铁层状双氢氧化物硫化物电催化剂在碱性条件下显示出优异的析氧反应催化活性，当电流密度达到50mA/cm2时，析氧过电位仅为289mV，这种高效的析氧反应催化性能可归因于硫的掺入进一步促进催化活性和导电性的提高，并且直接生长在泡沫镍上的镍铁双氢氧化物纳米片结构，不仅有利于电子转移、催化表面积增大，而且纳米片状结构更有利于与电解液充分接触，使纳米片表面和边缘的催化活性位点得到提高，这样更利于析氧反应的扩散。Further, the self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst shows excellent catalytic activity for oxygen evolution reaction under alkaline conditions. When the current density reaches 50 mA/cm2, the oxygen evolution overpotential is only 289 mV. This efficient oxygen evolution reaction catalytic performance can be attributed to the incorporation of sulfur which further promotes the improvement of catalytic activity and electrical conductivity, and the nickel-iron double hydroxide nanosheet structure directly grown on nickel foam is not only beneficial for electron transfer , The catalytic surface area is increased, and the nano-sheet structure is more conducive to full contact with the electrolyte, so that the catalytic active sites on the surface and edge of the nano-sheet are improved, which is more conducive to the diffusion of the oxygen evolution reaction.

最后，本发明的电催化剂为非贵金属材料，所用原料易于采购和制备，资源丰富且价格低廉，制备成本低，且制备过程简单易操作，对设备要求不高，可大规模生产用于工业化。Finally, the electrocatalyst of the present invention is a non-precious metal material, the raw materials used are easy to purchase and prepare, the resources are abundant, the price is low, the preparation cost is low, the preparation process is simple and easy to operate, the equipment requirements are not high, and it can be produced on a large scale for industrialization.

根据下文对本发明具体实施例的详细描述，本领域技术人员将会更加明了本发明的上述以及其他目的、优点和特征。The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments of the present invention.

附图说明Description of drawings

后文将参照附图以示例性而非限制性的方式详细描述本发明的一些具体实施例。附图中相同的附图标记标示了相同或类似的部件或部分。本领域技术人员应该理解，这些附图未必是按比例绘制的。附图中：Hereinafter, some specific embodiments of the present invention will be described in detail by way of example and not limitation with reference to the accompanying drawings. The same reference numbers in the figures designate the same or similar parts or parts. It will be understood by those skilled in the art that the drawings are not necessarily to scale. In the attached picture:

图1是各个实施例和对比例制备的电催化剂的X射线衍射（XRD）图谱；Fig. 1 is the X-ray diffraction (XRD) pattern of the electrocatalyst prepared by each embodiment and comparative example;

图2是图1中一个实施例制得的镍铁层状双氢氧化物硫化物电催化剂的扫描电镜（SEM）图片；Fig. 2 is the scanning electron microscope (SEM) picture of the nickel-iron layered double hydroxide sulfide electrocatalyst prepared by an embodiment in Fig. 1;

图3是各个实施例和对比例中镍铁层状双氢氧化物硫化物电催化剂的析氧极化曲线。FIG. 3 is the oxygen evolution polarization curves of the nickel-iron layered double hydroxide sulfide electrocatalysts in various examples and comparative examples.

具体实施方式Detailed ways

下面结合实施例对本发明作进一步说明。显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The present invention will be further described below in conjunction with the examples. Obviously, the described embodiments are some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

在电解水技术中，电催化水裂解反应过程中，阳极侧发生的析氧反应（OER）是一个四电子转移耦合反应，阴极侧发生析氢反应（HER），通过HER反应和OER反应可持续地、大规模地生产氢，然而，在这一过程中，由于OER反应动力学相比HER更加缓慢，需要更高的过电位来克服动力学障碍，以降低电压进而加速催化反应过程。In the water electrolysis technology, during the electrocatalytic water splitting reaction, the oxygen evolution reaction (OER) at the anode side is a four-electron transfer coupled reaction, and the hydrogen evolution reaction (HER) at the cathode side occurs sustainably through the HER reaction and the OER reaction. However, in this process, since the OER reaction kinetics is slower than that of HER, a higher overpotential is required to overcome the kinetic barrier to lower the voltage and accelerate the catalytic reaction process.

本发明提供了一种自支撑镍铁层状双氢氧化物硫化物电催化剂的制备方法，该制备方法包括如下步骤：The invention provides a preparation method of a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst, the preparation method comprising the following steps:

步骤1，对原始泡沫镍进行预处理得到净化泡沫镍。In step 1, the raw nickel foam is pretreated to obtain purified nickel foam.

具体地，将原始泡沫镍剪成2cm*3cm，厚度为0.5mm。上述原始泡沫镍依次浸入丙酮、3mol/L盐酸溶液中并分别进行超声处理，超声时间为15分钟左右；再依次用去离子水、乙醇冲洗3-5次（中间可适当超声），以去除表面杂质；在真空干燥箱内进行干燥，干燥温度为60℃，干燥时间为8~12 h，干燥后得到净化泡沫镍。Specifically, the original nickel foam was cut into 2cm*3cm, and the thickness was 0.5mm. The above-mentioned raw nickel foam is immersed in acetone and 3mol/L hydrochloric acid solution and ultrasonically treated respectively, and the ultrasonic time is about 15 minutes; then rinsed with deionized water and ethanol for 3-5 times in turn (the middle can be ultrasonically appropriate) to remove the surface. Impurities; dried in a vacuum drying oven, the drying temperature was 60 °C, and the drying time was 8-12 h, and purified nickel foam was obtained after drying.

因泡沫镍具有导电率高、比表面积大、多孔结构等优点，将催化材料直接生长到泡沫镍上，不仅可以作为镍源用于材料合成，而且利于气泡的释放和电解质的渗透，导致电子更好的转移，从而有效提高催化剂的催化活性。Because nickel foam has the advantages of high conductivity, large specific surface area, porous structure, etc., the direct growth of catalytic materials on nickel foam can not only be used as a nickel source for material synthesis, but also facilitate the release of bubbles and the penetration of electrolytes, resulting in more electrons. good transfer, thereby effectively improving the catalytic activity of the catalyst.

步骤2，按照预设比例将六水合硝酸镍、九水合硝酸铁和尿素溶于去离子水中得到混合液。Step 2: Dissolve nickel nitrate hexahydrate, ferric nitrate nonahydrate and urea in deionized water according to a preset ratio to obtain a mixed solution.

具体地，六水合硝酸镍、九水合硝酸铁和尿素的摩尔比为2：1：10，混合于去离子水中，使得混合液的阳离子的浓度为40~45 mmol/L，尿素的浓度为130~150 mmol/L；磁力搅拌15分钟后得到均匀的澄清溶液。在具体实施例中，混合液的阳离子的浓度可以但不限于选择40 mmol/L、42 mmol/L和45 mmol/L，尿素的浓度可以但不限于选择130mmol/L、140mmol/L和150 mmol/L。尿素作为碱源，在后续的水热反应过程中提供碱性环境使镍、铁沉积生产氢氧化物。Specifically, the molar ratio of nickel nitrate hexahydrate, ferric nitrate nonahydrate and urea was 2:1:10, mixed in deionized water, so that the concentration of the cation of the mixed solution was 40 to 45 mmol/L, and the concentration of urea was 130 mmol/L. ~150 mmol/L; a homogeneous clear solution was obtained after 15 min of magnetic stirring. In a specific embodiment, the concentration of the cation of the mixed solution can be selected but not limited to 40 mmol/L, 42 mmol/L and 45 mmol/L, and the concentration of urea can be selected but not limited to 130 mmol/L, 140 mmol/L and 150 mmol/L /L. Urea is used as an alkali source to provide an alkaline environment in the subsequent hydrothermal reaction process to deposit nickel and iron to produce hydroxide.

步骤3，将混合液进行一次水热反应，得到NiFe LDH/NF。In step 3, the mixed solution is subjected to a hydrothermal reaction to obtain NiFe LDH/NF.

具体地，将混合液倒入内含净化泡沫镍（2cm*3cm）的不锈钢高压反应釜的内衬中，封闭高压反应釜，将其放入100~140℃烘箱中加热10~12h，进行一次水热反应，一次水热反应的温度可以但不限于选择100℃、110℃、120℃、130℃和140℃，加热时间可以但限于选择10h、11h和12h。反应后冷却至室温后，取出反应后的泡沫镍并依次用去离子水和无水乙醇冲洗3-5次，然后放入60℃的真空干燥箱内干燥6~8 h，冷却至室温，取出得到NiFe LDH/NF。Specifically, the mixed solution was poured into the lining of a stainless steel autoclave containing purified nickel foam (2cm*3cm), the autoclave was closed, and the autoclave was placed in a 100-140°C oven for 10-12 hours for once For hydrothermal reaction, the temperature of a hydrothermal reaction can be selected but not limited to 100°C, 110°C, 120°C, 130°C and 140°C, and the heating time can be selected but not limited to 10h, 11h and 12h. After the reaction was cooled to room temperature, the reacted nickel foam was taken out and washed with deionized water and anhydrous ethanol for 3-5 times in turn, then placed in a vacuum drying box at 60 °C to dry for 6-8 h, cooled to room temperature, and taken out. NiFe LDH/NF is obtained.

步骤4，将NiFe LDH/NF置于硫代乙酰胺溶液中进行二次水热反应得到NiFe LDH-Sx/NF；其中，x=1至8中的任意数字。In step 4, NiFe LDH/NF is placed in a thioacetamide solution to carry out a secondary hydrothermal reaction to obtain NiFe LDH-Sx/NF; wherein, x=any number from 1 to 8.

具体地，将3mmol硫代乙酰胺溶于30ml去离子水中，磁力搅拌1小时后得到均匀的澄清溶液，然后倒入内含NiFe LDH/NF（2cm*3cm）的不锈钢高压反应釜的内衬中，封闭高压反应釜，将其放入100~140度烘箱中分别加热1~8 h进行二次水热反应。一次水热反应的温度可以但不限于选择100℃、110℃、120℃、130℃和140℃，加热时间可以但限于选择1~8 中的任意整数或小数。反应后冷却至室温后，取出泡沫镍并依次用去离子水和无水乙醇冲洗3-5次，然后放入60℃真空干燥箱内6~8h，最后取出，得到NiFe LDH-Sx/NF。上述自支撑镍铁层状双氢氧化物硫化物电催化剂NiFe LDH-Sx/NF为纳米片状结构Specifically, 3 mmol of thioacetamide was dissolved in 30 ml of deionized water, and a uniform clear solution was obtained after magnetic stirring for 1 hour, and then poured into the lining of a stainless steel autoclave containing NiFe LDH/NF (2cm*3cm). , closed the autoclave, put it into a 100-140 degree oven and heated for 1-8 h respectively for secondary hydrothermal reaction. The temperature of the first hydrothermal reaction can be, but not limited to, 100°C, 110°C, 120°C, 130°C, and 140°C, and the heating time can be, but limited to, any integer or decimal from 1 to 8. After the reaction was cooled to room temperature, the nickel foam was taken out and washed with deionized water and absolute ethanol for 3-5 times in turn, then placed in a vacuum drying oven at 60 °C for 6-8 h, and finally taken out to obtain NiFe LDH-Sx/NF. The above-mentioned self-supporting nickel-iron layered double hydroxide-sulfide electrocatalyst NiFe LDH-Sx/NF is nanosheet-like structure

其中，NF代表Ni Foam即泡沫镍，整体含义代表在泡沫镍上生长的镍铁层状双氢氧化物硫化物。在该反应过程中使用硫代乙酰胺提供硫源，使镍铁层状双氢氧化物转化为硫化物，使材料表面***糙，以达到提高材料活性位点，增强析氧反应性能的目的。Among them, NF stands for Ni Foam, that is, foamed nickel, and the overall meaning represents the nickel-iron layered double hydroxide sulfide grown on the foamed nickel. In the reaction process, thioacetamide is used to provide a sulfur source, so that the nickel-iron layered double hydroxide is converted into sulfide, and the surface of the material is roughened, so as to achieve the purpose of improving the active site of the material and enhancing the performance of the oxygen evolution reaction.

最后，NiFe LDH-Sx/NF中的x的值与二次水热反应的反应时间存在线性对应关系，x=1至8中的任意数字。Finally, there is a linear correspondence between the value of x in NiFe LDH-Sx/NF and the reaction time of the secondary hydrothermal reaction, with x = any number from 1 to 8.

以下各个实施例为具体实施例。The following embodiments are specific examples.

对比例1Comparative Example 1

（1）泡沫镍的预处理：(1) Pretreatment of nickel foam:

将原始泡沫镍剪成2cm*3cm，厚度为0.5mm。上述原始泡沫镍依次浸入丙酮、3mol/L盐酸溶液中并分别进行超声处理，超声时间为15分钟左右；再依次用去离子水、乙醇冲洗3-5次（中间可适当超声），以去除表面杂质；在真空干燥箱内进行干燥，干燥温度为60℃，干燥时间为8~12 h，干燥后得到净化泡沫镍以备用。 Cut the original nickel foam into 2cm*3cm with a thickness of 0.5mm. The above-mentioned raw nickel foam is immersed in acetone and 3mol/L hydrochloric acid solution and ultrasonically treated respectively, and the ultrasonic time is about 15 minutes; then rinsed with deionized water and ethanol for 3-5 times in turn (the middle can be ultrasonically appropriate) to remove the surface. Impurities; dry in a vacuum drying oven, the drying temperature is 60 °C, and the drying time is 8-12 h. After drying, purified nickel foam is obtained for use.

（2）一次水热反应：(2) A hydrothermal reaction:

六水合硝酸镍、九水合硝酸铁和尿素的摩尔比为2：1：10，混合于去离子水中，使得混合液的阳离子的浓度为40~45 mmol/L，尿素的浓度为130~150 mmol/L；磁力搅拌15分钟后得到均匀的澄清溶液。尿素作为碱源，在后续的水热反应过程中提供碱性环境使镍、铁沉积生产氢氧化物。The molar ratio of nickel nitrate hexahydrate, ferric nitrate nonahydrate and urea is 2:1:10, mixed in deionized water, so that the concentration of cations in the mixed solution is 40~45 mmol/L, and the concentration of urea is 130~150 mmol /L; a homogeneous clear solution was obtained after 15 minutes of magnetic stirring. Urea is used as an alkali source to provide an alkaline environment in the subsequent hydrothermal reaction process to deposit nickel and iron to produce hydroxide.

将混合液倒入内含净化泡沫镍（2cm*3cm）的不锈钢高压反应釜的内衬中，封闭高压反应釜，将其放入120℃烘箱中加热12h，进行一次水热反应。反应后冷却至室温后，取出反应后的泡沫镍并依次用去离子水和无水乙醇冲洗3-5次，然后放入60℃的真空干燥箱内干燥6~8 h，冷却至室温，取出得到NiFe LDH/NF。The mixture was poured into the lining of a stainless steel autoclave containing purified nickel foam (2cm*3cm), the autoclave was closed, and the autoclave was heated for 12h in a 120°C oven to conduct a hydrothermal reaction. After the reaction was cooled to room temperature, the reacted nickel foam was taken out and washed with deionized water and anhydrous ethanol for 3-5 times in turn, then placed in a vacuum drying box at 60 °C to dry for 6-8 h, cooled to room temperature, and taken out. NiFe LDH/NF is obtained.

（3）析氧反应（OER）催化性能测试：(3) Oxygen evolution reaction (OER) catalytic performance test:

析氧反应性能测试均是在CHI660E电化学工作站上完成的。配置1mol/L的KOH作为电解液，将电解液加入三电极体系电解槽中，以铂片作为对电极，以银/氯化银作为参比电极，以制备的电催化剂（将泡沫镍剪成1cm*1cm）作为工作电极，在测试之前，将1mol/L的KOH电解液以适当的速率通入氮气30分钟，然后将各电极与电化学工作站相连，先经过循环伏安法在一定电压范围内施加20个循环对电极进行活化处理，然后以5mv/s的扫速在0~0.9V电压范围内进行线性扫描极化曲线测试，测得电化学数据并进行处理。结果显示，当电流密度为50mA/cm2时，过电位为410mV。The oxygen evolution reaction performance tests were all completed on a CHI660E electrochemical workstation. Configure 1mol/L KOH as the electrolyte, add the electrolyte into the three-electrode system electrolytic cell, use the platinum sheet as the counter electrode, and use the silver/silver chloride as the reference electrode to prepare the electrocatalyst (cut nickel foam into 1cm*1cm) as the working electrode. Before the test, 1mol/L KOH electrolyte was passed into nitrogen gas at an appropriate rate for 30 minutes, and then each electrode was connected to the electrochemical workstation. The electrodes were activated for 20 cycles, and then the linear scanning polarization curve test was performed at a scanning speed of 5mv/s in the voltage range of 0~0.9V, and the electrochemical data were measured and processed. The results show that the overpotential is 410mV when the current density is 50mA/ cm2 .

实施例1Example 1

在实施例1中，泡沫镍的预处理和一次水热反应的过程与对比例1相同，在此不赘述，其区别在于二次水热反应，具体过程如下：将3mmol硫代乙酰胺溶于30ml去离子水中，磁力搅拌1小时后得到均匀的澄清溶液，然后倒入内含一次水热反应得到的NiFe LDH/NF（2cm*3cm）的不锈钢高压反应釜的内衬中，封闭高压反应釜，将其放入120℃烘箱中分别加热1 h进行二次水热反应。一次水热反应的温度可以但不限于选择100℃、110℃、120℃、130℃和140℃，加热时间可以但限于选择7h、8h和9h。反应后冷却至室温后，取出泡沫镍并依次用去离子水和无水乙醇冲洗3-5次，然后放入60℃真空干燥箱内6~8h，最后取出，得到NiFe LDH-S1/NF。In embodiment 1, the process of the pretreatment of foamed nickel and a hydrothermal reaction is the same as that of Comparative Example 1, which is not repeated here, and the difference lies in the secondary hydrothermal reaction, and the specific process is as follows: 3mmol thioacetamide is dissolved in 30ml of deionized water, magnetically stirred for 1 hour to obtain a uniform clear solution, then poured into the lining of a stainless steel autoclave containing NiFe LDH/NF (2cm*3cm) obtained by a hydrothermal reaction, and closed the autoclave , put them into a 120 °C oven and heated for 1 h respectively for the secondary hydrothermal reaction. The temperature of the first hydrothermal reaction can be selected but not limited to 100°C, 110°C, 120°C, 130°C and 140°C, and the heating time can be selected but limited to 7h, 8h and 9h. After the reaction was cooled to room temperature, the nickel foam was taken out and washed with deionized water and anhydrous ethanol for 3-5 times in turn, then placed in a vacuum drying oven at 60 °C for 6-8 hours, and finally taken out to obtain NiFe LDH-S1/NF.

析氧反应（OER）催化性能测试与对比例1中的测试方法相同，结果显示，当电流密度为50mA/cm2时，过电位为351mV。The oxygen evolution reaction (OER) catalytic performance was tested in the same way as in Comparative Example 1, and the results showed that the overpotential was 351mV when the current density was 50mA/ cm2 .

实施例2Example 2

在实施例2中，泡沫镍的预处理、一次水热反应和二次水热反应的过程与实施例1相同，在此不赘述，其区别在于二次水热反应的条件，在该实施例中，二次水热反应的条件为加热温度为120℃、反应时间为4h，最终得到NiFe LDH-S4/NF。In Example 2, the processes of the pretreatment, primary hydrothermal reaction and secondary hydrothermal reaction of the nickel foam are the same as those in Example 1, which will not be repeated here. The difference lies in the conditions of the secondary hydrothermal reaction. Among them, the conditions of the secondary hydrothermal reaction were that the heating temperature was 120 °C and the reaction time was 4 h, and finally NiFe LDH-S4/NF was obtained.

析氧反应（OER）催化性能测试与对比例1中的测试方法相同，结果显示，当电流密度为50mA/cm2时，过电位为315mV。The oxygen evolution reaction (OER) catalytic performance was tested in the same way as in Comparative Example 1, and the results showed that the overpotential was 315mV when the current density was 50mA/ cm2 .

实施例3Example 3

在实施例3中，泡沫镍的预处理、一次水热反应和二次水热反应的过程与实施例1相同，在此不赘述，其区别在于二次水热反应的条件，在该实施例中，二次水热反应的条件为加热温度为120℃、反应时间为8h，最终得到NiFe LDH-S8/NF。In Example 3, the processes of the pretreatment, primary hydrothermal reaction and secondary hydrothermal reaction of the nickel foam are the same as those in Example 1, which will not be repeated here, and the difference lies in the conditions of the secondary hydrothermal reaction. The conditions of the secondary hydrothermal reaction were that the heating temperature was 120 °C and the reaction time was 8 h, and finally NiFe LDH-S8/NF was obtained.

析氧反应（OER）催化性能测试与对比例1中的测试方法相同，结果显示，当电流密度为50mA/cm2时，过电位为289 mV。The oxygen evolution reaction (OER) catalytic performance was tested in the same way as in Comparative Example 1 , and the results showed that the overpotential was 289 mV when the current density was 50 mA/cm.

对比例2：Comparative Example 2:

在对比例2中，泡沫镍的预处理、一次水热反应和二次水热反应的过程与实施例1相同，在此不赘述，其区别在于二次水热反应的条件，在该实施例中，二次水热反应的条件为加热温度为120℃、反应时间为12h，最终得到NiFe LDH-S12/NF。In Comparative Example 2, the processes of the pretreatment, primary hydrothermal reaction and secondary hydrothermal reaction of the nickel foam are the same as those in Example 1, which will not be repeated here. The difference lies in the conditions of the secondary hydrothermal reaction. The conditions of the secondary hydrothermal reaction were that the heating temperature was 120 °C and the reaction time was 12 h, and finally NiFe LDH-S12/NF was obtained.

析氧反应（OER）催化性能测试与对比例1中的测试方法相同，结果显示，当电流密度为50mA/cm2时，过电位为340 mV。The oxygen evolution reaction (OER) catalytic performance was tested in the same way as in Comparative Example 1 , and the results showed that the overpotential was 340 mV when the current density was 50 mA/cm.

图1为上述各个实施例与对比例制备得到的催化剂的X-射线衍射（XRD）图谱，从图1中可知，实施例1至3和对比例2中，镍铁层状双氢氧化物硫化物比镍铁层状双氢氧化物多出的峰较好的证实了第二次水热反应过程中硫代乙酰胺作为硫源的反应成功，并且随着硫化时间增大，峰值增强。Figure 1 shows the X-ray diffraction (XRD) patterns of the catalysts prepared in the above-mentioned examples and comparative examples. It can be seen from Figure 1 that in Examples 1 to 3 and Comparative Example 2, the nickel-iron layered double hydroxide sulfide The more peaks of thioacetamide than nickel-iron layered double hydroxides better confirm the successful reaction of thioacetamide as the sulfur source during the second hydrothermal reaction, and the peaks increase with the increase of vulcanization time.

图2为实施例3所制备的NiFe LDH-S8/NF催化剂的扫描电镜 （SEM）图，从图中分析可知，本发明提供的二次水热法制备的自支撑镍铁层状双氢氧化物硫化物电催化剂为纳米片状结构，并且表面略粗糙，该纳米片状结构可以使催化活性位点增多，提高电子之间的转移，增强析氧反应性能。Figure 2 is a scanning electron microscope (SEM) image of the NiFe LDH-S8/NF catalyst prepared in Example 3. From the analysis of the figure, it can be seen that the self-supporting nickel-iron layered double hydroxide prepared by the secondary hydrothermal method provided by the present invention The sulfide electrocatalyst has a nano-sheet structure with a slightly rough surface. The nano-sheet structure can increase the number of catalytic active sites, improve the transfer between electrons, and enhance the performance of the oxygen evolution reaction.

图3为上述各个实施例和对比例中镍铁层状双氢氧化物硫化物电催化剂的析氧极化曲线。从该析氧极化曲线分析可知，当电流密度为50mA/cm2时，实施例3中NiFe LDH-S8/NF对应的过电位最低，为289mV，因此其析氧性能最好。对比例1中由于没有二次水热反应，对比例2中由于二次水热反应时间过长，均导致其制得的电催化剂的析氧性能较差。3 is the oxygen evolution polarization curve of the nickel-iron layered double hydroxide sulfide electrocatalyst in each of the above examples and comparative examples. From the analysis of the oxygen evolution polarization curve, it can be seen that when the current density is 50 mA/cm 2 , the overpotential corresponding to NiFe LDH-S8/NF in Example 3 is the lowest, which is 289 mV, so its oxygen evolution performance is the best. Since there is no secondary hydrothermal reaction in Comparative Example 1, and the secondary hydrothermal reaction time in Comparative Example 2 is too long, the electrocatalyst prepared by the electrocatalyst has poor oxygen evolution performance.

本发明提供的自支撑镍铁层状双氢氧化物硫化物电催化剂的制备方法，以泡沫镍为基底的自支撑镍铁层状双氢氧化物硫化物电催化剂具有高效的析氧反应（OER）催化性能。因泡沫镍具有导电率高、比表面积大、多孔结构等优点，将催化材料直接生长到泡沫镍上，不仅可以作为镍源用于材料合成，而且利于气泡的释放和电解质的渗透，导致电子更好的转移，从而有效提高催化剂的催化活性。The invention provides a preparation method of a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst, and the self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst based on foamed nickel has an efficient oxygen evolution reaction (OER ) catalytic performance. Due to the advantages of high conductivity, large specific surface area, and porous structure of nickel foam, the direct growth of catalytic materials on nickel foam can not only be used as a nickel source for material synthesis, but also facilitate the release of bubbles and the penetration of electrolytes, resulting in more electrons. good transfer, thereby effectively improving the catalytic activity of the catalyst.

进一步地，该自支撑镍铁层状双氢氧化物硫化物电催化剂在碱性条件下显示出优异的析氧反应催化活性，当电流密度达到50mA/cm2时，析氧过电位仅为289mV，这种高效的析氧反应催化性能可归因于硫的掺入进一步促进催化活性和导电性的提高，并且直接生长在泡沫镍上的镍铁双氢氧化物纳米片结构，不仅有利于电子转移、催化表面积增大，而且纳米片状结构更有利于与电解液充分接触，使纳米片表面和边缘的催化活性位点得到提高，这样更利于析氧反应的扩散。Further, the self-supporting nickel-iron layered double hydroxide-sulfide electrocatalyst shows excellent catalytic activity for oxygen evolution reaction under alkaline conditions, and the oxygen evolution overpotential is only 289mV when the current density reaches 50 mA/ cm2 . , this efficient oxygen evolution reaction catalytic performance can be attributed to the incorporation of sulfur further promoting the improvement of catalytic activity and electrical conductivity, and the nickel-iron double hydroxide nanosheet structure directly grown on the nickel foam, which is not only beneficial for electronic The transfer and catalytic surface area increases, and the nanosheet structure is more conducive to full contact with the electrolyte, so that the catalytically active sites on the surface and edge of the nanosheet are improved, which is more conducive to the diffusion of the oxygen evolution reaction.

最后，本发明的电催化剂为非贵金属材料，所用原料易于采购和制备，资源丰富且价格低廉，制备成本低，且制备过程简单易操作，对设备要求不高，可大规模生产用于工业化。Finally, the electrocatalyst of the present invention is a non-precious metal material, the raw materials used are easy to purchase and prepare, the resources are abundant, the price is low, the preparation cost is low, the preparation process is simple and easy to operate, the equipment requirements are not high, and it can be produced on a large scale for industrialization.

至此，本领域技术人员应认识到，虽然本文已详尽示出和描述了本发明的多个示例性实施例，但是，在不脱离本发明精神和范围的情况下，仍可根据本发明公开的内容直接确定或推导出符合本发明原理的许多其他变型或修改。因此，本发明的范围应被理解和认定为覆盖了所有这些其他变型或修改。By now, those skilled in the art will recognize that, although various exemplary embodiments of the present invention have been illustrated and described in detail herein, the present invention may still be implemented in accordance with the present disclosure without departing from the spirit and scope of the present invention. The content directly determines or derives many other variations or modifications consistent with the principles of the invention. Accordingly, the scope of the present invention should be understood and deemed to cover all such other variations or modifications.

Claims (9)

1. A preparation method of a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst is characterized by comprising the following steps of:
pretreating the original foam nickel to obtain purified foam nickel;
dissolving nickel nitrate hexahydrate, ferric nitrate nonahydrate and urea in deionized water according to a preset proportion to obtain a mixed solution; wherein the concentration of the positive ions of the mixed solution is 40-45 mmol/L, and the concentration of the urea is 130-150 mmol/L;
carrying out a primary hydrothermal reaction on the mixed solution to obtain NiFe LDH/NF;
putting the NiFe LDH/NF into a thioacetamide solution for secondary hydrothermal reaction to obtain NiFe LDH-Sx/NF; wherein x = any number from 1 to 8.
2. The method of preparing a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst according to claim 1, wherein the molar ratio of nickel nitrate hexahydrate, iron nitrate nonahydrate and urea is 2: 1: 10.
3. the method of preparing a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst according to claim 1,
the concentration of the positive ions of the mixed solution is 42 mmol/L, and the concentration of the urea is 140 mmol/L.
4. The method of preparing a self-supporting nickel iron layered double hydroxide sulfide electrocatalyst according to claim 1, characterized in that the thioacetamide solution has a solubility of 0.1 mmol/mL.
5. The method of preparing a self-supporting nickel iron layered double hydroxide sulfide electrocatalyst according to claim 1, characterized in that: the pretreatment steps are as follows:
sequentially immersing the original foamed nickel into acetone and hydrochloric acid solution and respectively carrying out ultrasonic treatment;
washing with deionized water and ethanol in sequence;
and drying to obtain the purified foam nickel.
6. The method for preparing self-supporting layered nickel iron double hydroxide sulfide electrocatalyst according to claim 1, characterized in that the conditions of the primary hydrothermal reaction are:
the temperature is 100-140 ℃ and the time is 10-12 h.
7. The method for preparing a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst according to claim 1, characterized in that the conditions of the secondary hydrothermal reaction are:
the temperature is 100-140 ℃ and the time is 7-9 h.
8. The method of preparing a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst according to claim 1,
and the value of x in the NiFe LDH-Sx/NF has a linear corresponding relation with the reaction time of the secondary hydrothermal reaction.
9. The method of preparing a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst according to claim 1,
the self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst is of a nano flaky structure.
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