WO2020107952A1 - 高效稳定的不锈钢基电解水催化电极，以及其制备方法和应用 - Google Patents

高效稳定的不锈钢基电解水催化电极，以及其制备方法和应用 Download PDF

Info

Publication number
WO2020107952A1
WO2020107952A1 PCT/CN2019/101359 CN2019101359W WO2020107952A1 WO 2020107952 A1 WO2020107952 A1 WO 2020107952A1 CN 2019101359 W CN2019101359 W CN 2019101359W WO 2020107952 A1 WO2020107952 A1 WO 2020107952A1
Authority
WO
WIPO (PCT)
Prior art keywords
stainless steel
catalytic electrode
electrolytic water
micro
nano
Prior art date
Application number
PCT/CN2019/101359
Other languages
English (en)
French (fr)
Other versions
WO2020107952A9 (zh
Inventor
钟敏霖
张红军
蔡明勇
Original Assignee
清华大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 清华大学 filed Critical 清华大学
Publication of WO2020107952A1 publication Critical patent/WO2020107952A1/zh
Publication of WO2020107952A9 publication Critical patent/WO2020107952A9/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present application belongs to the technical field of preparation of electrocatalytic materials, and in particular relates to a high-efficiency and stable stainless steel-based electrolytic water catalytic electrode, as well as its preparation method and application.
  • Fossil fuels and their derivatives have penetrated into all aspects of human daily life.
  • the normal operation of modern society is inseparable from the dependence on traditional fossil fuels.
  • the rapid economic development has intensified the consumption of fossil fuels. The greater the pressure on energy.
  • fossil fuels such as coal, oil, and natural gas, have limited reserves in the earth's crust and are also non-renewable. After all, they are sometimes exhausted by mining.
  • fossil fuels will adversely affect the human living environment during mining, refining and combustion.
  • the nitrogen oxides and sulfides emitted may form acid rain, and the emitted carbon dioxide will further exacerbate the greenhouse effect. Therefore, people invest huge human, material and financial resources to develop sustainable new technologies to provide green, cheap and renewable energy.
  • Hydrogen as a secondary energy with great development potential, has received more and more attention in scientific research and industrial fields.
  • the utilization forms are diverse and can be used for fuel cells or internal combustion engines; the production raw material can be water, with abundant reserves.
  • transition metals such as iron, cobalt, nickel, manganese (such as oxides, hydroxides, etc.) exhibited excellent electrocatalytic hydrogen evolution, oxygen evolution, and total water splitting performance.
  • Nickel-based nickel-based catalysts have been widely used in practical industrial alkaline electrolyzed water, but most of these catalysts are loaded on the electrode by electroplating, coating, etc., which are easy to peel off during long working hours and the catalytic performance declines. . Therefore, improving the stability of the catalyst is an urgent problem to be solved in the field of electrocatalytic material preparation.
  • iron is the second most abundant metal in the earth's crust and much larger than other transition metals.
  • the construction of iron-based catalysts can further reduce the cost of electrolyzed water.
  • the common 201, 304, and 316 stainless steels use Fe as the main element, and are also doped with Ni, Cr and other elements. They are potential catalytic materials for electrolytic water, but the catalytic performance of the original stainless steel is not ideal. To a certain extent, improve its catalytic performance.
  • the surface treatment mainly includes the following two types of methods: The first type of method is to introduce impurity elements P and Se on the surface of stainless steel, such as patent CN106486680A and patent CN106268876A.
  • the patent CN106486680A proposes a method for preparing a phosphating stainless steel electrolytic water catalytic material.
  • Patent CN106268876A proposes a method for preparing a selenized stainless steel electrolysis water catalytic material.
  • the stainless steel substrate and selenium powder or selenate are calcined at 500°C for 2 hours under the protection of argon to obtain a selenized stainless steel catalyst, which shows a good total solution Water performance.
  • the preparation process of this type of method is relatively simple, and the equipment requirements are low. However, toxic gases may be generated during the preparation process, which may pollute the environment.
  • the second method is to immerse the stainless steel in an oxidizing environment to form a surface oxide layer or a hydroxide layer, such as high-concentration NaOH (EnergyEnviron.Sci.,2015,8,2685-2697), sodium hypochlorite (ACSSustainableChem.Eng., 2017, 5,10072-10083).
  • the surface of the stainless steel treated in this way is enriched with Fe and Ni elements, and exhibits good electrocatalytic oxygen evolution performance, but the electrocatalytic hydrogen evolution performance is not good, so it cannot be used as an efficient total water splitting catalyst.
  • the purpose of the present application is to provide an efficient and stable stainless steel-based electrolyzed water catalytic electrode, as well as its preparation method and application.
  • the technical solution of the present application uses a pulse laser two-step patterned ablation composite method to first prepare a three-dimensional micro-concave array surface on a stainless steel substrate, and then prepare a nano-velvet structure on the surface to form a three-dimensional self-supporting micro-nano Compound multi-level structure, thereby obtaining highly efficient and stable electrolyzed water catalytic electrode.
  • the present application provides a stainless steel-based electrolytic water catalytic electrode, which includes a stainless steel substrate and a three-dimensional micro-concave array structure distributed on the stainless steel substrate. Micro-spheres of different sizes are randomly distributed on the surface of the array structure The surface of the ball is covered with nano-velvet structure.
  • the nano-fleece structure is a fluffy nano-fleece structure formed by randomly stacking very small nano-particles.
  • the array structure is a microscopic concave-convex square array.
  • the array period of the concave-convex array structure is about 20 ⁇ m to about 200 ⁇ m.
  • the array period refers to the size of the smallest unit in which the concave-convex array structure repeats periodically.
  • the concave-convex array structure includes a plurality of micro cones arranged in an array and protruding.
  • the height of the micrometer cone is about 20 ⁇ m to about 150 ⁇ m.
  • the diameter of the nanoparticle is from about 1 nm to about 100 nm.
  • the composition of the concave-convex array structure is stainless steel, and the composition of the nano-velvet structure is mainly ferric oxide.
  • the stainless steel substrate is a stainless steel sheet or plate, and the model number is 201, 304, or 316.
  • Another aspect of the present application provides a method for preparing a stainless steel-based electrolytic water catalytic electrode.
  • the method includes the following steps:
  • the surface of the stainless steel substrate is ablated by pulse laser patterning to form a three-dimensional microscopic concave-convex array structure
  • the nanosecond pulse laser is used to irradiate the surface of the stainless steel substrate with a concave-convex array structure in the atmospheric environment, so that the micro-spheres and the nano-velvet structure covering the surface of the concave-convex array are ablated to form a three-dimensional self-supporting micro-nano composite Multi-level structure.
  • the pulsed laser is a femtosecond, picosecond, or nanosecond laser
  • the patterned ablation is a vertical cross-scan mode
  • the scan pitch is 20-200 ⁇ m
  • the scan speed is 100- 2000mm/s.
  • step S1 the pulsed laser patterned ablation is performed in an atmospheric environment.
  • the pulse laser used in step S1 may be a high power and/or high energy density laser.
  • the average power of the pulsed laser used in step S1 ranges from 2W to 100W.
  • step S2 the ablation of the nanosecond laser is performed in a vertical cross-scanning manner, with a scanning pitch of 10 to 100 ⁇ m and a scanning speed of 20 to 1000 mm/s.
  • the average power of the nanosecond pulse laser used in step S2 is 5W to 60W.
  • the method further includes ultrasonic cleaning the three-dimensional self-supporting micro-nano composite multi-level structure in an organic solvent, for a time of, for example, 1 minute, and then blowing off the residual liquid with high-purity nitrogen, and Dry treatment.
  • Another aspect of the present application also provides an application of a catalytic electrode, which can be used for electrocatalytic hydrogen evolution, oxygen evolution, and total water splitting.
  • This application uses a pulse laser two-step patterned ablation composite method to prepare an electrolyzed water catalytic electrode with a micro-nano composite multi-level structure.
  • the surface structure on the substrate can be multi-scaled Regulation.
  • Changing the processing parameters of the high-energy-density pulsed laser in step S1 can adjust the height, period and other parameters of the three-dimensional microscopic concave-convex array structure on the micrometer scale; similarly, changing the processing parameters of the nanosecond pulse laser in step S2 can be Regulate the distribution and abundance of nano-velvety structures.
  • the micro-concavo-convex array can increase the specific surface area as a support for anchoring the nanostructure; the nano-fleece structure as a catalytically active material, showing the performance of electrolytic water.
  • nano-catalysts use a specific foam metal or carbon fiber cloth as a substrate, and cannot regulate the form and distribution of the microstructure on the surface of the substrate.
  • the present application breaks through such a bottleneck and chooses to prepare microstructures on a flat substrate to increase the specific surface area. By changing the laser processing parameters, the morphological distribution of the microstructures can be conveniently adjusted, thereby significantly optimizing the performance of the catalyst.
  • This application uses a laser preparation technology scheme, which can obtain a very strong nanostructure, thereby achieving excellent stability of the catalyst.
  • the instantaneous high-energy laser pulse is injected onto the surface of the substrate, the metal instantaneously vaporizes into a plasma, and contacts with air to oxidize, and then re-deposited under atmospheric pressure
  • a self-supporting, catalytically active oxide nanofleece structure is grown in situ.
  • Such nanostructures form a strong combination with the micro-concave array on the substrate, and finally obtain an integrated catalytic electrode in which the catalytically active material and the current collector coexist without any organic binder, and exhibit excellent structure in the performance test of electrolytic water stability.
  • pulsed laser ablation is an instantaneous non-equilibrium process, the oxidation reaction is inadequate, and there are a lot of oxygen defects in the resulting nano-fleece structure of the oxide, and the oxygen defects promote the electrolytic water performance of the oxide catalyst.
  • the present application introduces beneficial oxygen defects while preparing micro-nano structures, which is simple, easy to implement, efficient and convenient.
  • the raw material required for this application is only stainless steel, which is cheap and readily available and suitable for industrial applications.
  • this application uses industrial-grade pulse lasers combined with high-speed scanning galvanometers, which can efficiently prepare large-area products, which is very conducive to large-scale industrial production.
  • the stainless steel-based electrolytic water catalytic electrode of the present application has excellent water decomposition hydrogen production oxygen production performance and high stability, and has a wide range of application prospects.
  • the catalytic electrode can be used for electrocatalytic hydrogen evolution, oxygen evolution, and total water splitting, specifically, available It is widely used in industrial large-scale electrolysis of water and oxygen production, hydrogen for fuel cell vehicles, underwater equipment oxygen production, medical hydrogen production oxygen production, hydrogen water cup hydrogen production, plateau oxygen production, portable hydrogen production oxygen production equipment, etc.
  • FIGS. 1A, 1B and 1C are scans of microspheres and nanofleece structures distributed on the surface of a stainless steel-based three-dimensional micro-concave array prepared by a composite method of pulse laser two-step pattern ablation in Example 1 of the present application at different magnifications Electron micrograph.
  • Example 2 is an X-ray diffraction diagram of the stainless steel-based electrolytic water catalytic electrode prepared in Example 1 of the present application.
  • FIG. 3A is an oxygen evolution polarization curve of the stainless steel-based electrolytic water catalytic electrode in Example 1 of the present application
  • FIG. 3B is a Tafel curve of the stainless steel-based electrolytic water catalytic electrode in Example 1 of the present application.
  • FIG. 4 is an oxygen evolution stability curve of the stainless steel-based electrolytic water catalytic electrode in Example 1 of the present application.
  • FIG. 5A is a hydrogen evolution polarization curve of the stainless steel-based electrolytic water catalytic electrode in Example 1 of the present application
  • FIG. 5B is a hydrogen evolution polarization curve of the stainless steel-based electrolytic water catalytic electrode in Example 1 of the present application and its corresponding Tafel curve.
  • Fig. 6 is a polarization curve of total water dissociation of a stainless steel-based electrolytic water catalytic electrode in Example 1 of the present application.
  • FIG. 7 is a curve of total water dissociation stability of the stainless steel-based electrolytic water catalytic electrode in Example 1 of the present application.
  • 8A and 8B are scanning electron micrographs of microspheres and nanofleece structures distributed on the surface of a stainless steel-based three-dimensional microscopic concave-convex array prepared by a composite method of pulse laser two-step patterning ablation in Example 2 of the present application at different magnifications.
  • Example 9 is an oxygen evolution polarization curve of a stainless steel-based electrolytic water catalytic electrode in Example 2 of the present application.
  • the embodiments of the present application provide an efficient and stable stainless steel-based electrolyzed water catalytic electrode.
  • the electrolyzed water catalytic electrode is distributed on a stainless steel substrate with a three-dimensional micro-concavo-convex array structure. Micro-spheres of different sizes are randomly distributed on the surface of the concavo-convex array.
  • the surface is covered with nano-structures, which are fluffy nano-velvety structures formed by the disorderly accumulation of extremely small nano-particles.
  • the array structure may be a micro-concavo-convex square array, the array period may be 20-200 ⁇ m, the height of the micro-cone may be 20-150 ⁇ m; the diameter of the nano-particles may be about 1-100 nm.
  • the composition of the concave-convex array structure may be a stainless steel matrix, and the composition of the nano-velvet structure is mainly ferric oxide.
  • the embodiments of the present application also provide a method for preparing an efficient and stable stainless steel-based electrolytic water catalytic electrode, which includes the following steps:
  • the high-power pulse laser may be a femtosecond, picosecond, or nanosecond laser;
  • the nanosecond pulse laser is used to irradiate the surface of the stainless steel substrate with the concave and convex array structure in the atmospheric environment, and the micro-spheres and the nano fleece structure covering the surface of the concave and convex array are ablated by the vertical cross scanning method.
  • the sample was then ultrasonically cleaned in absolute ethanol for 1 minute, and then the residual liquid was blown off with high-purity nitrogen while drying.
  • Example 1 The first step of patterned ablation uses a femtosecond laser, and the second step uses a nanosecond laser to prepare an efficient and stable electrolytic water catalytic electrode, which includes the following steps:
  • the first pattern ablation on the surface of the stainless steel substrate using a femtosecond laser, where the laser wavelength is 1030nm, the pulse width is 800fs, the pulse repetition frequency is 200kHz, the average power is 20W, the scanning pattern is a vertical cross line, and the scanning interval It is 100 ⁇ m, and the scanning speed is 2000 mm/s.
  • the second pattern ablation using nano laser in which the laser wavelength is 1030nm, the pulse width is 100ns, the pulse repetition frequency is 60kHz, the average power is 20W, the scanning pattern is a vertical cross line, the scanning interval is 80 ⁇ m, the scanning speed 500mm/s.
  • the sample was ultrasonically cleaned in absolute ethanol for 1 minute, and then the residual liquid was blown off with high-purity nitrogen while drying.
  • the microspheres and nanofleece structures distributed on the surface of the resulting micro concave-convex array are shown in FIGS. 1A, 1B and 1C.
  • the reduced FIG. 1C is inserted and shows the location of the local area shown in FIG. 1C in FIG. 1A.
  • FIG. 2 The X-ray diffraction pattern of the prepared stainless steel-based electrolytic water catalytic electrode indicates that the matrix component is stainless steel and the nano-velvet structure component is ferric oxide.
  • the standard three-electrode system was used to test the electrocatalytic performance in 1M KOH solution.
  • the stainless steel-based catalytic electrode prepared by two-step laser ablation exhibits significantly improved oxygen evolution performance, and the overpotential with a current density of 10 mA/cm 2 decreases from 350 mV At 262mV, the Tafel slope decreased from 66.1mV/dec to 35.0mV/dec.
  • the catalytic electrode showed excellent oxygen evolution stability. After 120 hours of continuous testing, the current did not decay.
  • the catalytic electrode exhibits significantly improved hydrogen evolution performance, as shown in FIGS. 5A and 5B.
  • a total water-removal performance test was performed, as shown in FIGS. 6 and 7, which showed excellent total water-removal performance and stability.
  • Embodiment 2 Both steps of patterned ablation use nanosecond laser to prepare an efficient and stable electrolytic water catalytic electrode, including the following steps:
  • the first pattern ablation on the surface of the stainless steel substrate using a nanosecond laser where the laser wavelength is 1030nm, the pulse width is 500ns, the pulse repetition frequency is 90kHz, the average power is 36W, the scanning pattern is a vertical cross line, and the scanning interval It is 70 ⁇ m and the scanning speed is 1000mm/s.
  • the standard three-electrode system was used to test the electrocatalytic performance in 1M KOH solution. As shown in Fig. 9, compared with untreated stainless steel, the stainless steel-based catalytic electrode prepared by two-step laser ablation showed significantly improved oxygen evolution performance, and the overpotential with a current density of 10 mA/cm 2 was reduced from 350 mV to 270 mV.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

一种高效稳定的不锈钢基电解水催化电极及其制备方法，属于电催化材料制备技术领域。该电极是在不锈钢基体上分布有三维微米凹凸阵列结构，凹凸阵列表面随机分布有大小不一的微米球，微米球表面覆盖有极小的纳米颗粒无序堆积而成的蓬松纳米绒状结构。所述方法首先利用高功率脉冲激光图案化烧蚀不锈钢基材表面形成微米凹凸阵列结构，然后用纳秒脉冲激光烧蚀凹凸阵列表面形成纳米绒状结构，从而得到无需粘接剂的自支撑催化电极。该电极表现出优异的电催化析氢、析氧和全解水性能，其制备方法简单可控、可大面积制备，原料廉价易得，可用于燃料电池汽车用氢气、水下装备制氧、医用制氢制氧、氢水杯、高原制氧、便携式制氢制氧装备等广泛的应用领域。

Description

高效稳定的不锈钢基电解水催化电极，以及其制备方法和应用
相关申请
本申请要求2018年11月30日申请的，申请号为201811456430.9，名称为“一种高效稳定的不锈钢基电解水催化电极及其制备方法”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本申请属于电催化材料制备技术领域，具体涉及一种高效稳定的不锈钢基电解水催化电极，以及其制备方法和应用。
背景技术
化石燃料及其衍生品已经渗透到人类日常生活的方方面面，现代社会的正常运转离不开对传统化石燃料的依赖，经济的快速发展更是加剧了对化石燃料的消耗，因此，人类面临着越来越大的能源压力。一方面，化石燃料，如煤、石油、天然气等，在地壳中的储量是有限的，也是不可再生的，终究有被开采枯竭的时候。另一方面，化石燃料在开采提炼和燃烧使用过程中都会对人类生存环境产生不利影响，排放的氮氧化物和硫化物可能形成酸雨，排放的二氧化碳会进一步加剧温室效应。因此，人们投入巨大的人力、物力和财力发展可持续的新技术，以提供绿色、廉价和可再生的能源。
氢气作为一种很有发展潜力的二次能源，受到科研和工业领域越来越多的关注，其原因主要有：燃烧产物为水，环保无污染；很高的发热值，是汽油的3倍；利用形式多样，可用于燃料电池或内燃机等；生产原料可以是水，储量丰富。工业上制取氢气的方法主要有3种：甲烷/水蒸气重整、煤炭气化和电解水。前两种制取方法仍然完全依赖化石燃料，而且不可避免会产生大量的二氧化碳。而电解水可实现零排放，原料丰富，环境友好，是一种可持续的技术，吸引了研究者的广泛关注。已知最有效的电解水催化剂多为贵金属，其中析氢催化剂为Pt，析氧催化剂为RuO 2或IrO 2，但是贵金属储量低、成本高，限制了电解水的大规模应用。因此，寻求高效低成本的电解水催化剂成为了一项紧迫而富有挑战的任务。
研究发现，相对廉价的铁、钴、镍、锰等过渡金属的化合物(如氧化物、氢氧化物等)表现出了优良的电催化析氢、析氧和全解水性能。以镍为主的镍基催化剂在实际工业的碱 性电解水中得到了成熟应用，但是这样的催化剂多是以电镀、涂覆等方式负载于电极上，长时间工作过程中容易剥落，催化性能衰退。因此，提高催化剂稳定性是目前电催化材料制备领域一个亟待解决的问题。另外，铁是地壳中储量第二多的金属，远大于其他过渡金属，因此，构建以铁为主的催化剂可进一步降低电解水的成本。常见的201、304、316不锈钢就是以Fe作为主要元素，另外掺有Ni、Cr等元素，属于潜在的电解水催化材料，但原始不锈钢的催化性能并不理想，经过某些方法处理，可一定程度上提高其催化性能。表面处理主要有以下两类方法：第一类方法是在不锈钢表面引入杂质元素P、Se等，如专利CN106486680A、专利CN106268876A。例如专利CN106486680A提出一种磷化不锈钢电解水催化材料的制备方法，将不锈钢基底与次磷酸盐在氩气保护下500℃煅烧2小时，得到磷化不锈钢催化剂，表现出较好的全解水性能。专利CN106268876A提出一种硒化不锈钢电解水催化材料的制备方法，将不锈钢基底与硒粉或硒酸盐在氩气保护下500℃煅烧2小时，得到硒化不锈钢催化剂，表现出较好的全解水性能。这类方法制备过程相对简单，设备要求低，但制备过程中可能会产生有毒气体，污染环境，得到的产物难以有效调控，并且难以大面积制备方便应用于实际生产。第二类方法是将不锈钢浸泡于氧化环境中形成表面氧化层或氢氧化层，如高浓度NaOH(Energy Environ.Sci.,2015,8,2685-2697)、次氯酸钠(ACS Sustainable Chem.Eng.,2017,5,10072-10083)。这样处理过的不锈钢表面富集Fe、Ni元素，表现出良好的电催化析氧性能，但是电催化析氢性能并不好，因此不能作为高效的全解水催化剂。
综上所述，简单可控地制备大面积且高效稳定的电解水催化材料仍然是一个具有重大挑战的课题。
发明内容
本申请的目的是提供一种高效稳定的不锈钢基电解水催化电极，以及其制备方法和应用。
本申请的技术方案利用脉冲激光两步图案化烧蚀的复合方法，在不锈钢基底上先制备出三维微米凹凸阵列表面，再在该表面上制备出纳米绒状结构，形成三维自支撑的微纳复合多级结构，从而获得高效稳定的电解水催化电极。
本申请一方面提供一种不锈钢基电解水催化电极，包括不锈钢基体，以及在所述不锈钢基体上分布的三维微米凹凸阵列结构，凹凸阵列结构表面随机分布有大小不一的微米球，所述微米球表面覆盖有纳米绒状结构。
在其中一个实施例中，所述纳米绒状结构为极小的纳米颗粒无序堆积而成的蓬松纳米 绒状结构。
在其中一个实施例中，所述阵列结构为微米凹凸正方阵列。
在其中一个实施例中，所述凹凸阵列结构的阵列周期为约20μm～约200μm。所述阵列周期是指所述凹凸阵列结构以周期性重复的最小单元的尺寸。
在其中一个实施例中，所述凹凸阵列结构包括多个呈阵列排布且凸出的微米锥。
在其中一个实施例中，所述微米锥的高度为约20μm～约150μm。
在其中一个实施例中，所述纳米颗粒的直径为约1nm-约100nm。
在其中一个实施例中，所述凹凸阵列结构的成分为不锈钢，所述纳米绒状结构的成分主要为四氧化三铁。
在其中一个实施例中，所述不锈钢基体为不锈钢的片材或板材，型号为201、304或316等。
本申请另一方面提供一种不锈钢基电解水催化电极的制备方法，该方法包括如下步骤：
S1，利用脉冲激光图案化烧蚀不锈钢基材表面，形成三维微米凹凸阵列结构；
S2，采用纳秒脉冲激光在大气环境下辐照具有凹凸阵列结构的不锈钢基材表面，使凹凸阵列表面烧蚀出微米球和覆盖其表面的纳米绒状结构，形成三维自支撑的微纳复合多级结构。
在其中一个实施例中，步骤S1中，所述脉冲激光为飞秒、皮秒或纳秒激光，所述图案化烧蚀为垂直交叉扫描方式，扫描间距为20～200μm，扫描速度为100～2000mm/s。
在其中一个实施例中，步骤S1中，所述脉冲激光图案化烧蚀在大气环境中进行。
步骤S1采用的脉冲激光可以为高功率和/或高能量密度激光。在其中一个实施例中，步骤S1采用的脉冲激光的平均功率范围为2W至100W。
在其中一个实施例中，步骤S2中，所述纳秒激光的烧蚀按照垂直交叉扫描方式进行，扫描间距为10～100μm，扫描速度为20～1000mm/s。
在其中一个实施例中，步骤S2采用的纳秒脉冲激光的平均功率范围为5W至60W。
在其中一个实施例中，所述方法还包括将所述三维自支撑的微纳复合多级结构在有机溶剂中超声清洗，时间例如可以为1分钟，再用高纯氮气吹去残余液体，并干燥处理。
本申请另一方面还提供一种催化电极的应用，所述催化电极能够用于电催化析氢、析氧和全解水。
本申请采用脉冲激光两步图案化烧蚀的复合方法来制备具有微纳复合多级结构的电解水催化电极，借助脉冲激光微纳加工的可编程性，可对基体上的表面结构实现多尺度调控。改变步骤S1高能密度脉冲激光的加工参数，在微米尺度上，可以调控三维微米凹凸 阵列结构的高度、周期等参数；同样地，改变步骤S2纳秒脉冲激光的加工参数，在纳米尺度上，可以调控纳米绒状结构的分布形态和丰富程度。其中，微米凹凸阵列可以增加比表面积，作为支撑，用来锚定纳米结构；纳米绒状结构则作为催化活性材料，表现出电解水性能。
相关技术中纳米催化剂很多都是采用特定的泡沫金属或碳纤维布作为基体，并不能调控基体表面微米结构的形式及分布。本申请突破了这样的瓶颈，选择在平板基底上制备微米结构，以此来增大比表面积，通过改变激光加工参数，可便捷地调控微米结构的形态分布，从而显著优化催化剂的性能。
本申请采用激光制备技术方案，可以得到非常牢固的纳米结构，从而实现催化剂优异的稳定性。在本申请步骤S2的纳秒脉冲激光图案化烧蚀过程中，瞬时高能的激光脉冲注入到基体表面，金属瞬间气化成等离子体，并与空气接触发生氧化，然后在大气压力作用下重新沉积到基体表面，从而原位生长出自支撑的、具有催化活性的氧化物纳米绒状结构。这样的纳米结构与基体上的微米凹凸阵列形成牢固的结合，最终得到催化活性材料与集流体共存的一体化催化电极，无需任何有机粘接剂，并且在电解水性能测试中表现出优异的结构稳定性。同时，脉冲激光烧蚀是一个瞬时非平衡的过程，氧化反应不充分，最终得到的氧化物纳米绒状结构中存在大量的氧缺陷，而氧缺陷对氧化物催化剂的电解水性能良好促进作用。与现有技术相比，本申请在制备微纳米结构的同时引入有益的氧缺陷，简单易行，高效便捷。
本申请需要的原料仅为不锈钢，廉价易得，适合于工业化应用。另外，本申请采用工业级的脉冲激光器，结合高速扫描振镜，可高效制备大面积产品，非常有利于大规模工业化生产。
本申请不锈钢基电解水催化电极具有优异的水分解制氢制氧性能和高稳定性，应用前景十分广泛，所述催化电极能够用于电催化析氢、析氧和全解水，具体地，可用于工业大规模电解水制氢制氧、燃料电池汽车用氢气、水下装备制氧、医用制氢制氧、氢水杯制氢、高原制氧、便携式制氢制氧装备等广泛的应用领域。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据公开的附图获得其他的附图。
图1A、图1B和图1C是本申请实施例1利用脉冲激光两步图案化烧蚀的复合方法制备的不锈钢基三维微米凹凸阵列表面分布的微米球和纳米绒状结构不同放大倍率下的扫描电镜照片。
图2是本申请实施例1中制备的不锈钢基电解水催化电极的X射线衍射图。
图3A是本申请实施例1中不锈钢基电解水催化电极的析氧极化曲线；图3B是本申请实施例1中不锈钢基电解水催化电极的塔菲尔曲线。
图4是本申请实施例1中不锈钢基电解水催化电极的析氧稳定性曲线。
图5A是本申请实施例1中不锈钢基电解水催化电极的析氢极化曲线；图5B是本申请实施例1中不锈钢基电解水催化电极的析氢极化曲线及其相应的塔菲尔曲线。
图6是本申请实施例1中不锈钢基电解水催化电极的全解水极化曲线。
图7是本申请实施例1中不锈钢基电解水催化电极的全解水稳定性曲线。
图8A和图8B是本申请实施例2利用脉冲激光两步图案化烧蚀的复合方法制备的不锈钢基三维微米凹凸阵列表面分布的微米球和纳米绒状结构不同放大倍率下的扫描电镜照片。
图9是本申请实施例2中不锈钢基电解水催化电极的析氧极化曲线。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请实施例提供一种高效稳定的不锈钢基电解水催化电极，所述电解水催化电极是在不锈钢基体上分布有三维微米凹凸阵列结构，凹凸阵列表面随机分布有大小不一的微米球，其表面覆盖有纳米结构，所述纳米结构为极小的纳米颗粒无序堆积而成的蓬松纳米绒状结构。
所述阵列结构可以为微米凹凸正方阵列，阵列周期可以为20～200μm，所述微米锥的高度可以为20～150μm；所述纳米颗粒的直径可以为1-100nm左右。所述凹凸阵列结构的成分可以为不锈钢基体，所述纳米绒状结构的成分主要为四氧化三铁。
本申请实施例还提供一种高效稳定的不锈钢基电解水催化电极的制备方法，包括如下步骤：
S1，利用高功率脉冲激光图案化烧蚀不锈钢基材表面，按照垂直交叉扫描方式，形成 三维微米凹凸阵列结构，所述高功率脉冲激光可以为飞秒、皮秒或纳秒激光；
S2，采用纳秒脉冲激光在大气环境下辐照具有凹凸阵列结构的不锈钢基材表面，同样按照垂直交叉扫描方式，使凹凸阵列表面烧蚀出微米球和覆盖其表面的纳米绒状结构，形成三维自支撑的微纳复合多级结构，随后将样品放在无水乙醇中超声清洗1分钟，再用高纯氮气吹去残余液体，同时干燥处理。
下面举出几个具体的实施例，以便更好地理解本申请。
下述实例中所述的材料、试剂等，如无特殊说明，均可从商业途径获得。
实施例1：第一步图案化烧蚀采用飞秒激光、第二步采用纳秒激光制备高效稳定的电解水催化电极，包括以下步骤：
S0，将不锈钢片材裁剪为尺寸10×20×0.3mm 3的小片基体，撕掉保护膜。
S1，采用飞秒激光在不锈钢基体表面进行第一次图案化烧蚀，其中激光波长为1030nm，脉冲宽度为800fs，脉冲重复频率为200kHz，平均功率为20W，扫描图案为垂直交叉线，扫描间距为100μm，扫描速度为2000mm/s。
S2，采用纳米激光进行第二次图案化烧蚀，其中激光波长为1030nm，脉冲宽度为100ns，脉冲重复频率为60kHz，平均功率为20W，扫描图案为垂直交叉线，扫描间距为80μm，扫描速度为500mm/s。随后将样品放在无水乙醇中超声清洗1分钟，再用高纯氮气吹去残余液体，同时干燥处理。所得微米凹凸阵列表面分布的的微米球和纳米绒状结构如图1A、图1B和图1C所示。图1A中右上角插入了缩小的图1C并显示了图1C显示的局部区域在图1A中所处的位置。请参阅图2，制备的不锈钢基电解水催化电极的X射线衍射图说明基体成分为不锈钢，纳米绒状结构的成分为四氧化三铁。
采用标准的三电极体系在1M KOH溶液中进行电催化性能测试。如图3A、图3B所示，相比于未处理的不锈钢，两步激光烧蚀制备的不锈钢基催化电极表现出显著提升的析氧性能，电流密度为10mA/cm 2的过电位从350mV降为262mV，塔菲尔斜率由66.1mV/dec降为35.0mV/dec。如图4所示，所述催化电极表现出优异的析氧稳定性，持续测试120小时后，电流无衰减。同样地，所述催化电极表现出显著提升的析氢性能，如图5A、图5B所示。分别以所述的催化电极作为阳极和阴极，进行全解水性能测试，如图6、图7所示，表现出优异的全解水性能和稳定性。
实施例2：两步图案化烧蚀均采用纳秒激光制备高效稳定的电解水催化电极，包括以下步骤：
1)将不锈钢片材裁剪为尺寸10×20×0.3mm 3的小片基体，撕掉保护膜。
2)采用纳秒激光在不锈钢基体表面进行第一次图案化烧蚀，其中激光波长为1030nm， 脉冲宽度为500ns，脉冲重复频率为90kHz，平均功率为36W，扫描图案为垂直交叉线，扫描间距为70μm，扫描速度为1000mm/s。
3)采用纳米激光进行第二次图案化烧蚀，其中激光波长为1064nm，脉冲宽度为250ns，脉冲重复频率为100kHz，平均功率为50W，扫描图案为垂直交叉线，扫描间距为30μm，扫描速度为1000mm/s。随后将样品放在无水乙醇中超声清洗1分钟，再用高纯氮气吹去残余液体，同时干燥处理。所得微米凹凸阵列表面分布的微米球和纳米绒状结构如图8A、图8B所示。
采用标准的三电极体系在1M KOH溶液中进行电催化性能测试。如图9所示，相比于未处理的不锈钢，两步激光烧蚀制备的不锈钢基催化电极表现出显著提升的析氧性能，电流密度为10mA/cm 2的过电位从350mV降为270mV。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (13)

  1. 一种不锈钢基电解水催化电极，其特征在于，包括不锈钢基体，以及在所述不锈钢基体表面分布的三维微米凹凸阵列结构，所述凹凸阵列结构表面随机分布有大小不一的微米球，所述微米球表面覆盖有纳米绒状结构。
  2. 如权利要求1所述的不锈钢基电解水催化电极，其特征在于，所述纳米绒状结构为纳米颗粒无序堆积而成的蓬松纳米绒状结构。
  3. 如权利要求1所述的不锈钢基电解水催化电极，其特征在于，所述阵列结构为微米凹凸正方阵列。
  4. 如权利要求1所述的不锈钢基电解水催化电极，其特征在于，所述凹凸阵列结构的阵列周期为约20μm～约200μm。
  5. 如权利要求1所述的不锈钢基电解水催化电极，其特征在于，所述凹凸阵列结构包括多个呈阵列排布且凸出的微米锥。
  6. 如权利要求5所述的不锈钢基电解水催化电极，其特征在于，所述微米锥的高度为约20μm～约150μm。
  7. 如权利要求1所述的不锈钢基电解水催化电极，其特征在于，所述纳米颗粒的直径为约1nm-约100nm。
  8. 如权利要求1所述的不锈钢基电解水催化电极，其特征在于，所述阵列结构的成分为不锈钢，所述纳米绒状结构的成分主要为四氧化三铁。
  9. 如权利要求1所述的不锈钢基电解水催化电极，其特征在于，所述不锈钢为201不锈钢、304不锈钢和316不锈钢中的一种或多种。
  10. 一种不锈钢基电解水催化电极的制备方法，包括如下步骤：
    S1，利用脉冲激光图案化烧蚀不锈钢基材表面，形成三维微米凹凸阵列结构；
    S2，采用纳秒脉冲激光在大气环境下辐照具有所述凹凸阵列结构的所述不锈钢基材表面，使所述凹凸阵列结构表面形成微米球和覆盖所述微米球表面的纳米绒状结构，形成三维自支撑的微纳复合多级结构。
  11. 根据权利要求10所述的不锈钢基电解水催化电极的制备方法，其特征在于，步骤S1中所述脉冲激光为飞秒、皮秒或纳秒激光，所述图案化烧蚀为垂直交叉扫描方式，扫描间距为20～200μm，扫描速度为100～2000mm/s。
  12. 根据权利要求10所述的不锈钢基电解水催化电极的制备方法，其特征在于，步骤S2中所述纳秒激光的烧蚀按照垂直交叉扫描方式进行，扫描间距为10～100μm，扫描 速度为20～1000mm/s。
  13. 一种如权利要求1-9任一项所述的催化电极或者如权利要求10-12任一项所述的制备方法得到的催化电极的应用，其特征在于，所述催化电极能够用于电催化析氢、析氧和全解水。
PCT/CN2019/101359 2018-11-30 2019-08-19 高效稳定的不锈钢基电解水催化电极，以及其制备方法和应用 WO2020107952A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811456430.9A CN109440125A (zh) 2018-11-30 2018-11-30 一种不锈钢基电解水催化电极及其制备方法
CN201811456430.9 2018-11-30

Publications (2)

Publication Number Publication Date
WO2020107952A1 true WO2020107952A1 (zh) 2020-06-04
WO2020107952A9 WO2020107952A9 (zh) 2020-07-30

Family

ID=65555187

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/101359 WO2020107952A1 (zh) 2018-11-30 2019-08-19 高效稳定的不锈钢基电解水催化电极，以及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN109440125A (zh)
WO (1) WO2020107952A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109440125A (zh) * 2018-11-30 2019-03-08 清华大学 一种不锈钢基电解水催化电极及其制备方法
CN109999851A (zh) * 2019-04-30 2019-07-12 苏州科技大学 硒化不锈钢材料及其制备方法与应用
CN110808355B (zh) * 2019-11-08 2020-12-08 西安交通大学 一种超快激光水下加工微纳米复合结构铜箔集流体的方法
CN114094115A (zh) * 2021-10-13 2022-02-25 中国长江三峡集团有限公司 柱状铜阵列集流体及其制备方法和应用
CN114964601B (zh) * 2022-05-24 2024-05-14 深圳市一鸣新材料有限公司 一种用于电池内部的压力变化实时监测装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110147205A1 (en) * 2009-12-21 2011-06-23 Daniel Guay Method and system for producing electrocatalytic coatings and electrodes
CN106268876A (zh) * 2016-11-07 2017-01-04 济南大学 硒化不锈钢泡沫电解水催化材料的制备及应用
CN106486680A (zh) * 2016-11-07 2017-03-08 济南大学 一种磷化不锈钢电解水催化材料的制备方法
CN109440125A (zh) * 2018-11-30 2019-03-08 清华大学 一种不锈钢基电解水催化电极及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103627883B (zh) * 2013-11-07 2015-04-22 清华大学 一种用皮秒脉冲激光调控金属表面吸光性能的方法
CN106624369A (zh) * 2016-10-14 2017-05-10 清华大学 一种快速制备氧化物多级纳米结构的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110147205A1 (en) * 2009-12-21 2011-06-23 Daniel Guay Method and system for producing electrocatalytic coatings and electrodes
CN106268876A (zh) * 2016-11-07 2017-01-04 济南大学 硒化不锈钢泡沫电解水催化材料的制备及应用
CN106486680A (zh) * 2016-11-07 2017-03-08 济南大学 一种磷化不锈钢电解水催化材料的制备方法
CN109440125A (zh) * 2018-11-30 2019-03-08 清华大学 一种不锈钢基电解水催化电极及其制备方法

Also Published As

Publication number Publication date
WO2020107952A9 (zh) 2020-07-30
CN109440125A (zh) 2019-03-08

Similar Documents

Publication Publication Date Title
WO2020107952A1 (zh) 高效稳定的不锈钢基电解水催化电极，以及其制备方法和应用
Pan et al. The photocatalytic overall water splitting hydrogen production of g-C3N4/CdS hollow core–shell heterojunction via the HER/OER matching of Pt/MnOx
Gong et al. Perspective of hydrogen energy and recent progress in electrocatalytic water splitting
Kumar et al. New trends in the development of heterogeneous catalysts for electrochemical CO2 reduction
Gao et al. High-entropy oxides for catalysis: Status and perspectives
Xie et al. Degradation of refractory organic compounds by photocatalytic fuel cell with solar responsive WO3/FTO photoanode and air-breathing cathode
Li et al. Ultrafast fabrication of Cu oxide micro/nano-structures via laser ablation to promote oxygen evolution reaction
KR101724690B1 (ko) 양극산화를 통한 철-니켈 기반 물분해 촉매전극 제조방법 및 이에 따라 제조된 물 분해 촉매전극
Li et al. Porous ceramic nanofibers as new catalysts toward heterogeneous reactions
CN108671944B (zh) 一种镍钼氧化物@镍钼硫化物@泡沫镍复合纳米材料及其制备方法与应用
Sun et al. Amorphous MnCO3/C double layers decorated on BiVO4 photoelectrodes to boost nitrogen reduction
CN108505058B (zh) 一种用于提高全解水催化活性的双金属共掺杂复合材料
CN107557806B (zh) 一种覆盖于Co-Mo-O上的Co-O高效复合析氢电极及其制备方法
CN104998642A (zh) 醇类燃料电池阳极催化剂Pd-MnO2/GNRs的制备方法
CN106624369A (zh) 一种快速制备氧化物多级纳米结构的方法
Su et al. 3D coral-like Fe doped NiCo2S4 cathode for stable high-efficiency photoelectrochemical tetracycline degradation and simultaneous energy recovery
Baibars et al. Boosted electrolytic hydrogen production at tailor-tuned nano-dendritic Ni-doped Co foam-like catalyst
Liao et al. Carbon dots dominated photoelectric surface in titanium dioxide nanotube/nitrogen-doped carbon dot/gold nanocomposites for improved photoelectrochemical water splitting
Li et al. One-step fabrication of Cu2O-Cu catalytic electrodes with regular porous array by ultra-fast laser scanning
CN104888769A (zh) 一种直接甲醇燃料电池用炭载钯银纳米复合催化剂的制备方法
Wang et al. Recent progress of carbon-based electrocatalytic materials in Lithium-based batteries
Yan et al. Biaxial strain-induced trions in artificial onion-like MoSe2 for promoting photocatalytic hydrogen evolution
CN106745525B (zh) 金属复合材料、其制备方法及应用
CN111841609A (zh) 一种Cu2O/C3N4/TiO2异质结可见光催化剂及其制备方法
Roshanravan et al. Mini-Review on Graphene Quantum Dots as an electro-catalyst in fuel cell

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19888450

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19888450

Country of ref document: EP

Kind code of ref document: A1