WO2025256097A1 - 一种电催化剂及其制备方法、电极、电解装置和应用 - Google Patents

一种电催化剂及其制备方法、电极、电解装置和应用

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Publication number
WO2025256097A1
WO2025256097A1 PCT/CN2024/141212 CN2024141212W WO2025256097A1 WO 2025256097 A1 WO2025256097 A1 WO 2025256097A1 CN 2024141212 W CN2024141212 W CN 2024141212W WO 2025256097 A1 WO2025256097 A1 WO 2025256097A1
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Prior art keywords
electrocatalyst
carbon
electrode
based substrate
nickel
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PCT/CN2024/141212
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English (en)
French (fr)
Inventor
李小杰
邓晨
闵洛夫
黄鹏辉
陈明
李泽彪
秦丹倪
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Petrochina Shenzhen New Energy Research Institute Co Ltd
Petrochina Co Ltd
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Petrochina Shenzhen New Energy Research Institute Co Ltd
Petrochina Co Ltd
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Publication of WO2025256097A1 publication Critical patent/WO2025256097A1/zh
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Anticipated expiration legal-status Critical

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    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • 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

  • This application belongs to the field of water electrolysis for hydrogen production technology, specifically relating to an electrocatalyst and its preparation method, electrode, electrolysis device and application.
  • Electrocatalytic hydrogen production is one of the green hydrogen production methods, and the activity of the electrocatalyst is a key factor determining the hydrogen production efficiency.
  • HER hydrogen evolution reaction
  • noble metal-based catalysts, especially Pt-based catalysts exhibit good performance and low overpotential; however, their high price limits their practical application.
  • transition metal disulfide compounds such as NiS2 and CoS2
  • HER transition metal alternative catalysts in the HER process.
  • the performance of MS2 still has significant room for improvement, especially in terms of hydrogen evolution overpotential.
  • This application provides an electrocatalyst to address the problems of high hydrogen evolution overpotential and poor stability in existing hydrogen evolution electrocatalysts.
  • This application provides a method for preparing the above-mentioned electrocatalyst, which is simple, easy to implement, low in cost, and easy to industrialize.
  • This application provides an electrode that can reduce hydrogen evolution overpotential and has good stability.
  • This application provides an electrolysis apparatus, including the above-described electrocatalyst, the electrocatalyst prepared by the above-described preparation method, or an electrode.
  • This application also provides an electrolysis method in which the above-described electrocatalyst, the electrocatalyst prepared by the above-described preparation method, or the electrode participates in the electrolysis of water, thereby reducing the hydrogen evolution overpotential.
  • the carbon-based substrate has a three-dimensional porous structure.
  • the mass ratio of the metallic nickel to the nickel disulfide is (90-99):(1-10).
  • the mass ratio of the coating layer to the carbon-based substrate is (1-10):(90-99).
  • this application provides a method for preparing the electrocatalyst described in the first aspect, comprising the following steps:
  • the electrode precursor includes a carbon-based substrate and nickel disulfide loaded on at least a portion of the surface of the carbon-based substrate, wherein the carbon-based substrate has a three-dimensional porous structure.
  • the reduction potential of the electrocatalytic reduction treatment is -400 to -1200 mV; and/or,
  • the reduction time for the electrocatalytic reduction treatment is 10–100 min.
  • the counter electrode also includes a counter electrode and a reference electrode; the counter electrode, the reference electrode, and the electrode precursor together constitute a three-electrode system placed in the alkaline electrolyte; wherein, the counter electrode is a carbon rod, and the reference electrode is a saturated calomel electrode.
  • this application provides an electrode comprising the electrocatalyst described in the first aspect or the electrocatalyst obtained by the preparation method described in the second aspect.
  • this application provides an electrolysis apparatus, comprising the electrocatalyst described in the first aspect, the electrocatalyst obtained by the preparation method of the second aspect, or the electrode of the third aspect.
  • this application provides an electrolysis method in which the electrocatalyst described in the first aspect, the electrocatalyst obtained by the preparation method described in the second aspect, or the electrode described in the third aspect participates in the electrolysis reaction of water.
  • the electrocatalyst provided in this application utilizes the porous structure of a carbon-based substrate to provide a larger specific surface area to increase the coating amount and provide more catalytic active sites. Furthermore, through the synergistic effect of the carbon-based substrate and the metallic nickel and nickel trisulfide supported on its surface, a locally negatively charged region can be formed, providing more active sites for hydrogen adsorption. This can greatly improve catalytic activity, reduce hydrogen evolution overpotential, and enhance the stability of the electrocatalyst.
  • Figure 1 is a SEM image of Ni(OH) 2 @CC prepared in Example 1 of this application;
  • Figure 2 is a magnified SEM image of Ni(OH) 2 @CC prepared in Example 1 of this application;
  • Figure 4 is a magnified SEM image of NiS2 @CC prepared in Example 1 of this application;
  • Figure 5 is a TEM image of NiS2 @CC prepared in Example 1 of this application.
  • Figure 6 is a SEM image of Ni/ Ni3S2 @ CC prepared in Example 1 of this application;
  • Figure 7 is a magnified SEM image of Ni/ Ni3S2 @ CC prepared in Example 1 of this application;
  • Figure 8 is a TEM image of Ni/ Ni3S2 @ CC prepared in Example 1 of this application;
  • Figure 9 is an XPS comparison diagram of Ni/ Ni3S2 @ CC prepared in Example 1 of this application and NiS2 @CC prepared in Comparative Example 1;
  • Figure 10 is a comparison of the polarization curves of Ni/ Ni3S2 @ CC obtained in some embodiments of this application;
  • Figure 11 is a comparison of the polarization curves of Ni/ Ni3S2 @ CC obtained in some embodiments of this application;
  • Figure 12 is a comparison diagram of the overpotentials of Ni/ Ni3S2 @ CC prepared in some embodiments of this application.
  • this application provides an electrocatalyst, comprising a carbon-based substrate and a coating layer supported on at least a portion of the surface of the carbon-based substrate;
  • the carbon-based substrate has a three-dimensional porous structure
  • the coating consists of metallic nickel and nickel disulfide.
  • This application does not limit the specific type of carbon-based substrate. Any carbon-based conductive substrate with a three-dimensional porous structure is acceptable. Optionally, it includes carbon fiber cloth, carbon paper, etc.
  • the electrocatalyst provided in this application comprises a carbon-based substrate and a coating layer supported on at least a portion of the surface of the carbon-based substrate. Because the carbon-based substrate has a three-dimensional porous structure, it can increase the specific surface area of the coating layer, thereby increasing the number of active sites on the electrocatalyst. Since the coating layer comprises metallic nickel and nickel disulfide, wherein metallic nickel and nickel disulfide exist in amorphous or polycrystalline forms respectively, they form interlaced grain boundaries. These interfaces between different crystal forms can provide a large number of high-quality active sites. Simultaneously, the bonding of negatively charged sulfur elements with transition metal nickel can form locally negatively charged regions.
  • These regions can further provide active sites for hydrogen adsorption, accelerate the water dissociation process, and thus contribute to the formation of active sites for the hydrogen evolution reaction of the electrocatalyst, further enhancing catalytic performance.
  • the activation energy in the catalytic process can be greatly reduced, improving catalytic performance and reducing the overpotential of hydrogen evolution.
  • the electrocatalyst provided in this application utilizes the porous structure of a carbon-based substrate to provide a larger specific surface area to increase the coating amount and provide more catalytic active sites. Furthermore, through the synergistic effect of the carbon-based substrate and the metallic nickel and nickel trisulfide supported on its surface, a locally negatively charged region can be formed, providing more active sites for hydrogen adsorption. This can greatly improve catalytic activity, reduce hydrogen evolution overpotential, and enhance the stability of the electrocatalyst.
  • the mass ratio of metallic nickel to nickel disulfide is (90-99):(1-10).
  • the mass ratio of metallic nickel to nickel disulfide in the coating layer has a close influence on the performance of the electrocatalyst.
  • the inventors discovered that when the mass ratio of metallic nickel to nickel disulfide is (90-99):(1-10), the hardness and strength of the electrocatalyst can be improved, thereby further enhancing its stability.
  • the mass ratio of the coating layer to the carbon-based substrate is (1-10):(90-99).
  • the mass relationship between the carbon-based substrate and the coating layer supported on at least part of its surface affects the performance of the electrocatalyst. Therefore, by further limiting the mass ratio of the coating layer to the carbon-based substrate, the stability of the electrocatalyst can be further improved, its specific surface area can be increased, and the hydrogen evolution overpotential can be reduced.
  • the electrode precursor was placed in an alkaline electrolyte and subjected to electrocatalytic reduction to obtain an electrocatalyst.
  • the electrode precursor includes a carbon-based substrate and nickel disulfide loaded on at least a portion of the surface of the carbon-based substrate, wherein the carbon-based substrate has a three-dimensional porous structure.
  • an electrode precursor comprising a carbon-based substrate and nickel disulfide supported on at least a portion of the surface of the carbon-based substrate is placed in an alkaline electrolyte and subjected to electrocatalytic reduction treatment.
  • the nickel disulfide supported on at least a portion of the surface of the carbon-based substrate undergoes in-situ reconstruction reaction to generate metallic nickel and nickel trisulfide, thus obtaining an electrocatalyst.
  • the reaction formula for the electrocatalytic reduction treatment can be referred to as Equation (1): NiS 2 +O 2 ⁇ Ni+Ni 3 S 2 +SO 2 formula (1)
  • the carbon-based substrate has a three-dimensional porous structure, which can increase the specific surface area of the coating layer and increase the active sites of the electrocatalyst.
  • the preparation method provided in this application can reconstitute nickel disulfide loaded on at least a portion of the surface of a carbon-based substrate into metallic nickel and nickel trisulfide in situ, forming a coating layer including a carbon-based substrate and a coating layer including metallic nickel and nickel trisulfide loaded on at least a portion of the surface of the carbon-based substrate.
  • the method is simple, easy to implement, reduces manufacturing costs, and is conducive to industrialization.
  • the alkaline electrolyte includes at least one of potassium hydroxide or sodium hydroxide; wherein the molar concentration of the alkaline electrolyte is 0.9 to 1.1 mol/L, and the parameter can be further limited to 1 mol/L; by further limiting the type and concentration of the alkaline electrolyte, the cathodic reduction can be further promoted and the ion transport rate can be improved.
  • the electrode precursor is prepared by the following steps:
  • the first raw material system including carbon-based substrate, nickel source, urea and ammonium salt, is placed in deionized water for first hydrothermal treatment to obtain a first precursor loaded with nickel hydroxide;
  • the second raw material system including the first precursor and the sulfur-containing compound, is placed in deionized water for a second hydrothermal treatment to obtain an electrode precursor loaded with nickel disulfide.
  • step (1) the reaction formula for the first hydrothermal treatment can be referred to as shown in formula (2): Ni(NO 3 ) 2 +CO(NH 2 ) 2 +H 2 O ⁇ Ni(OH) 2 +NH 4 NO 3 +CO 2 Formula (2)
  • step (3) the reaction formula for the second hydrothermal treatment can be referred to as shown in formula (3): Ni(OH) 2 +C 2 H 5 NS+H 2 O ⁇ NiS 2 +C 2 H 5 O 2 +NH 3 ⁇ H 2 O Formula (3)
  • the temperature of the first hydrothermal treatment is 100–140°C, and the time is 4–8 hours;
  • the second hydrothermal treatment is carried out at a temperature of 140–180°C for 14–19 hours.
  • the molar ratio of nickel source, urea, and ammonium salt is (0.3–0.4):(1.6–1.8):1;
  • the nickel source is selected from at least one of nickel nitrate, nickel chloride, or nickel sulfate; the ammonium salt is selected from at least one of ammonium fluoride, ammonium chloride, or ammonium sulfate.
  • the mass ratio of the sulfur-containing compound to the first precursor is (0.01–0.07):1;
  • the sulfur-containing compound can be an inorganic sulfur-containing compound, including at least one of sulfur powder, sodium sulfide, thiourea and sodium thiosulfate, or an organic sulfur-containing compound, including at least one of carbon disulfide and thioacetamide.
  • step (1) after the first hydrothermal treatment, there are also sequential washing and drying treatments; wherein, the washing treatment includes washing the first precursor in deionized water and anhydrous ethanol in sequence, repeating the operation 2 to 3 times; the drying treatment includes drying in a vacuum drying oven at 50 to 70°C for 10 to 15 hours to remove the detergent; optionally, the first hydrothermal treatment is carried out in a hydrothermal reactor made of polytetrafluoroethylene material.
  • step (2) after the second hydrothermal reaction, a washing treatment and a drying treatment are performed in sequence; wherein, the washing treatment includes washing the electrode precursor in deionized water and anhydrous ethanol in sequence, repeating the operation 2 to 3 times; the drying treatment includes drying in a vacuum drying oven at 50 to 70°C for 8 to 10 hours to remove the detergent; optionally, the second hydrothermal treatment is carried out in a hydrothermal reactor made of polytetrafluoroethylene material.
  • a pretreatment before step (1), includes washing the carbon-based substrate precursor in deionized water and anhydrous ethanol in sequence, and then drying it in a vacuum oven to obtain the carbon-based substrate.
  • the reduction potential of the electrocatalytic reduction treatment is -400 to -1200 mV; the reduction time of the electrocatalytic reduction treatment is 10-100 min.
  • the reduction potential and reduction time of electrocatalytic reduction treatment affect the products of in-situ reconstruction of nickel disulfide, namely, the ratio of metallic nickel to nickel trisulfide and the specific surface area of the electrocatalyst. Therefore, by further limiting the reduction potential and reduction time, it is beneficial to better control the full progress of electrocatalytic reduction, further improve the catalytic activity of the electrocatalyst, reduce the hydrogen evolution overpotential, and improve stability; wherein, the reduction potential is the potential relative to the reversible hydrogen electrode (RHE);
  • RHE reversible hydrogen electrode
  • the reduction potential can be further defined as -800 to -1000 mV vs. RHE, and the reduction time as 30 to 70 min; further still, the reduction potential can be -850 to -950 mV vs. RHE.
  • the counter electrode also includes a counter electrode and a reference electrode; the counter electrode, the reference electrode, and the electrode precursor together constitute a three-electrode system placed in an alkaline electrolyte; wherein, the counter electrode is a carbon rod and the reference electrode is a saturated calomel.
  • the electrode precursor undergoes electrocatalytic reduction, a counter electrode and a reference electrode are also required.
  • the counter electrode is a carbon rod and the reference electrode is saturated calomel, which can better reconstruct nickel disulfide in the electrode precursor in situ to produce metallic nickel and nickel trisulfide, and further improve the catalytic activity of the electrocatalyst, reduce the hydrogen evolution overpotential, and improve stability.
  • this application provides an electrode comprising the electrocatalyst of the first aspect or the electrocatalyst obtained by the preparation method of the second aspect.
  • This application provides an electrode that can reduce hydrogen evolution overpotential and has good stability.
  • this application provides an electrolysis apparatus, including an electrocatalyst as described in the first aspect, an electrocatalyst obtained by the preparation method of the second aspect, or an electrode as described in the third aspect.
  • this application also provides an electrolysis method in which the electrocatalyst of the first aspect or the electrocatalyst obtained by the preparation method of the second aspect or the electrode of the third aspect participates in the electrolysis reaction of water.
  • This application also provides an electrolysis method in which the above-described electrocatalyst, the electrocatalyst prepared by the above-described preparation method, or the electrode participates in the electrolysis of water, thereby reducing the hydrogen evolution overpotential.
  • the carbon fiber cloth was washed in deionized water and anhydrous ethanol in sequence, and dried in a vacuum oven to obtain pretreated carbon fiber cloth; 4 mmol of nickel nitrate was dissolved in 30 mL of deionized water and stirred evenly at room temperature using a magnetic stirrer; 20 mL of urea and 12 mmol of ammonium fluoride were dissolved in 20 mL of deionized water, and the two solutions were mixed to obtain 50 mL of mixed solution, which was poured into the inner liner of a 100 mL hydrothermal reactor.
  • a piece of carbon fiber cloth of 1 cm ⁇ 1.5 cm was added to the hydrothermal reactor; the first hydrothermal treatment was carried out at 120 °C for 6 h; after cooling to room temperature, the carbon fiber cloth was taken out, washed 3 times with deionized water and 3 times with anhydrous ethanol, and dried in a 60 °C oven for 12 h to obtain the first precursor loaded with nickel hydroxide, denoted as Ni(OH) 2 @CC;
  • NiS2 @CC was placed in a 1 mol/L KOH solution as the working electrode, a saturated calomel electrode and a carbon rod. NiS2 @CC was electrocatalytically reduced for 50 min at a reduction potential of -900 mV (vs. RHE) using a constant voltage amperometry mode. After cleaning the working electrode, the electrocatalyst was obtained and denoted as Ni/ Ni3S2 @ CC .
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that carbon paper is used as the carbon-based substrate.
  • the difference between this embodiment and Embodiment 1 is that the reduction processing time is 10 minutes.
  • the difference between this embodiment and Embodiment 1 is that the reduction processing time is 100 minutes.
  • the difference between this embodiment and Embodiment 1 is that the reduction processing time is 120 minutes.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the reduction potential is -300mV.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the reduction potential is -500mV.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the reduction potential is -700mV.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the reduction potential is -1100mV.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the reduction potential is -1300mV.
  • step (3) is not performed, that is, the in-situ reconstruction process is not carried out.
  • Example 1 The difference between this comparative example and Example 1 is that FTO conductive glass is used as the substrate.
  • Example 1 The materials prepared in Example 1 and Comparative Example 1 were characterized by SEM, TEM and XPS, and the results are shown in Figures 1 to 9.
  • Figure 1 is a SEM image of Ni(OH) 2 @CC prepared in Example 1 of this application. As can be seen from the figure, the nickel hydroxide nanosheets are relatively uniform, and the length and width of the nanosheets are about 5-10 ⁇ m.
  • Figure 2 is a magnified view of a portion of Figure 1. As can be seen from the figure, the thickness of the nickel hydroxide nanosheets is approximately 10-70 nm.
  • Figure 3 is a SEM image of NiS2 @CC prepared in Example 1 of this application.
  • the electrode precursor NiS2 @CC has some pores. This may be because the thioacetamide in step (2) rapidly forms H2S with water under high temperature conditions.
  • the acidic H2S reduces the surface bonding force of Ni(OH) 2 with a planar dense structure when it is converted into particulate NiS2 , thus leading to the formation of pores.
  • FIG 4 is a partial enlarged view of Figure 3.
  • NiS2 @CC is formed by bonding together nanoblocks with a diameter of approximately 20-150 nm.
  • FIG. 5 is a TEM image of NiS2 @CC prepared in Example 1 of this application. It can also be seen that NiS2 is a sheet structure composed of nano cubes.
  • Figure 6 is a SEM image of Ni/ Ni3S2 @ CC prepared in Example 1 of this application. After electrocatalytic reduction treatment at a potential of -900mV for about 50 minutes, the originally granular NiS2 was transformed into a flower-like structure.
  • Figure 7 is a magnified view of a portion of Figure 6. As can be seen from the figure, the petals are composed of a large number of ultrathin nanosheet structures.
  • Figure 8 is a TEM image of Ni/ Ni3S2 @ CC prepared in Example 1 of this application. It can also be seen that the reconstructed Ni/ Ni3S2 is an ultrathin sheet structure.
  • Figure 9 shows the XPS diagrams of Ni/ Ni3S2 @ CC prepared in Example 1 of this application and NiS2 @CC prepared in Comparative Example 1. A comparison reveals that the main chemical structure of Comparative Example 1 is NiS2 , while the main chemical structure of Example 1 is Ni and Ni3S2 .
  • the electrocatalysts prepared in the above examples and comparative examples were placed in a 1M KOH solution at 25°C in a three-electrode system.
  • the polarization potential curves of the electrodes were measured when the polarization current density reached -150 mA/ cm2 , and the results are shown in Figures 10 and 11.
  • Figure 12 is a comparison diagram of the overpotentials of some embodiments.
  • the electrocatalyst provided in this application utilizes the porous structure of a carbon-based substrate to provide a larger specific surface area to increase the coating amount and provide more catalytic active sites. Furthermore, through the synergistic effect of the carbon-based substrate and the metallic nickel and nickel trisulfide supported on its surface, a locally negatively charged region can be formed, providing more active sites for hydrogen adsorption. This can greatly improve catalytic activity, reduce hydrogen evolution overpotential, and enhance the stability of the electrocatalyst.

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Abstract

本申请提供一种电催化剂及其制备方法、电极、电解装置和应用，该电催化剂包括碳基基底和负载在碳基基底至少部分表面的包覆层；其中，碳基基底具有三维多孔结构；包覆层包括金属镍和二硫化三镍；利用碳基基底的多孔结构，提供更大的比表面积以提高包覆量，提供了更多的催化活性位点，并且通过碳基基底与负载在其表面的金属镍与二硫化三镍的协同作用，能够形成局部带负电的区域，为氢吸附提供更多的活性位点，能够大大提高催化活性，降低析氢过电位，提高电催化剂的稳定性。

Description

一种电催化剂及其制备方法、电极、电解装置和应用
本申请要求于2024年6月13日提交中国专利局、申请号为CN 2024107644925、申请名称为“一种电催化剂及其制备方法、电极、电解装置和应用”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
本申请属于电解水制氢技术领域，具体涉及一种电催化剂及其制备方法、电极、电解装置和应用。
背景技术
能源作为支持社会发展的重要基石，其中，以氢气为代表的新能源则是未来能源的立足点之一。其中，电催化制氢是绿色制氢方法之一，在该过程中，电催化剂的活性是决定产氢效率的关键因素。在析氢反应(HER)中，贵金属基催化剂，尤其是Pt基催化剂展现出良好的性能以及较低的过电势，然而其高昂的价格限制了其实际应用范围。
因此，非贵金属基催化剂的开发显得尤为重要。近年来，二硫化过渡金属化合物(MS2)，如NiS2、CoS2成为HER过程中重要的贵金属替代催化剂。然而，相对于Pt基催化剂的综合性能，MS2的性能发挥还有巨大的提升空间，尤其在析氢过电位方面还有待提高。
因此，学界采用了杂原子掺杂工程、异质结工程、缺陷工程以及非晶化工程等一系列措施来提升MS2的HER性能。然而，这些措施的实现都需要更高的制备成本，并且制得的电催化剂存在不稳定的问题，限制了未来工业体系的实际应用。
基于此，现有技术中的析氢电催化剂仍存在析氢过电位较高、稳定性较差的问题。
发明内容
本申请提供了一种电催化剂，用于解决现有技术中析氢电催化剂的析氢过电位较高、稳定性较差的问题。
本申请提供了一种上述电催化剂的制备方法，方法简单易行，成本低，易于实现产业化。
本申请提供了一种电极，能够降低析氢过电位，具有良好的稳定性。
本申请提供了一种电解装置，包括上述的电催化剂、上述制备方法制得的电催化剂或电极。
本申请还提供了一种电解方法，利用上述的电催化剂、上述制备方法制得的电催化剂或电极参与水的电解，能够降低析氢过电位。
第一方面，本申请提供一种电催化剂，包括碳基基底和负载在所述碳基基底至少部分表面的包覆层；
其中，所述碳基基底具有三维多孔结构；
所述包覆层包括金属镍和二硫化三镍。
进一步地，所述包覆层包括片层结构，所述片层结构的长度为15～25nm，宽度为15～25nm，厚度为2～7nm。
进一步地，所述金属镍与所述二硫化三镍的质量比为(90～99)：(1～10)。
进一步地，所述包覆层与所述碳基基底的质量比为(1～10)：(90～99)。
第二方面，本申请提供一种第一方面所述的电催化剂的制备方法，其中，包括以下步骤：
将电极前驱体置于碱性电解液中，对所述电极前驱体进行电催化还原处理，得到所述电催化剂；
其中，所述电极前驱体包括碳基基底和负载在所述碳基基底至少部分表面的二硫化镍，所述碳基基底具有三维多孔结构。
进一步地，所述电催化还原处理的还原电位为-400～-1200mV；和/或，
所述电催化还原处理的还原时间为10～100min。
进一步地，还包括对电极和参比电极；所述对电极与所述参比电极以及所述电极前驱体共同构成三电极体系置于所述碱性电解液中；其中，对电极为碳棒，参比电极为饱和甘汞。
第三方面，本申请提供一种电极，包括第一方面所述的电催化剂或第二方面所述的制备方法得到的电催化剂。
第四方面，本申请提供一种电解装置，包括第一方面所述的电催化剂或第二方面的制备方法得到的电催化剂或第三方面的电极。
第五方面，本申请提供一种电解方法，使第一方面所述的电催化剂或第二方面所述的制备方法得到的电催化剂或第三方面所述的电极参与水的电解反应。
本申请提供的电催化剂，利用碳基基底的多孔结构，提供更大的比表面积以提高包覆量，提供了更多的催化活性位点，并且通过碳基基底与负载在其表面的金属镍与二硫化三镍的协同作用，能够形成局部带负电的区域，为氢吸附提供更多的活性位点，能够大大提高催化活性，降低析氢过电位，提高电催化剂的稳定性。
附图说明
图1为本申请实施例1制得的Ni(OH)2@CC的SEM图；
图2为本申请实施例1制备得到的Ni(OH)2@CC的SEM放大图；
图3为本申请实施例1制备得到的NiS2@CC的SEM图；
图4为本申请实施例1制备得到的NiS2@CC的SEM放大图；
图5为本申请实施例1制备得到的NiS2@CC的TEM图；
图6为本申请实施例1制备得到的Ni/Ni3S2@CC的SEM图；
图7为本申请实施例1制备得到的Ni/Ni3S2@CC的SEM放大图；
图8为本申请实施例1制备得到的Ni/Ni3S2@CC的TEM图；
图9为本申请实施例1制备得到的Ni/Ni3S2@CC与对比例1制备得到的NiS2@CC的XPS对比图；
图10为本申请部分实施例制得的Ni/Ni3S2@CC的极化曲线对比图；
图11为本申请部分实施例制得的Ni/Ni3S2@CC的极化曲线对比图；
图12为本申请部分实施例制得的Ni/Ni3S2@CC的过电位对比图。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚，下面将结合本申请的实施例，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。
第一方面，本申请提供一种电催化剂，包括碳基基底和负载在碳基基底至少部分表面的包覆层；
其中，碳基基底具有三维多孔结构；
包覆层包括金属镍和二硫化三镍。
本申请不限定碳基基底的具体种类，凡是具有三维多孔结构的碳基导电基底均可，可选地，包括碳纤维布、碳纸等；
本申请提供的电催化剂包括碳基基底和负载在碳基基底至少部分表面的包覆层，由于碳基基底具有三维多孔结构，能够提高包覆层的比表面积，增加电催化剂的活性位点；由于包覆层包括金属镍和二硫化三镍，其中，金属镍和二硫化三镍各自以非晶或多晶形式存在，会形成交错的晶界，这些不同晶形之间交错的界面可提供较多高质量的活性位点；同时，通过带负电的硫元素与过渡金属镍键合能够形成局部带负电的区域，这些区域可以进一步为氢吸附提供活性位点，加速水的解离过程，从而有助于形成电催化剂析氢反应的活性位点，进一步增强催化性能；而且通过金属镍与二硫化三镍以及碳基基底在催化过程中的协同作用，可以大大降低催化过程中的活化能，提高催化性能，降低析氢的过电位。
本申请提供的电催化剂，利用碳基基底的多孔结构，提供更大的比表面积以提高包覆量，提供更多的催化活性位点，并且通过碳基基底与负载在其表面的金属镍与二硫化三镍的协同作用，能够形成局部带负电的区域，为氢吸附提供更多的活性位点，能够大大提高催化活性，降低析氢过电位，提高电催化剂的稳定性。
进一步地，包覆层包括片层结构，片层结构的长度为15～25nm，宽度为15～25nm，厚度为2～7nm。
其中，包覆层包括片层结构，片层结构包括金属镍和二硫化三镍，其中，多个片层结构堆叠排列能够在碳基基底至少部分表面形成花瓣状形貌；申请人发现，形成片层结构更有利于增加电催化剂的比表面积，增加催化活性位点，并且当片层结构的长度为15～25nm，宽度为15～25nm，厚度为2～7nm时，能够进一步地降低析氢过电位，且更有利于稳定性得到改善。
在本申请一具体实施方式中，金属镍与二硫化三镍的质量比为(90～99)：(1～10)。
能够理解，包覆层中金属镍与二硫化三镍的质量比对电催化剂的性能有密切影响，发明人通过付出创造性劳动发现，当金属镍与二硫化三镍的质量比为(90～99)：(1～10)时，能够提高电催化剂的硬度和强度，进一步地提高其稳定性。
在另一具体实施方式中，包覆层与碳基基底的质量比为(1～10)：(90～99)。
同样，碳基基底与负载在其至少部分表面的包覆层的质量关系影响到电催化剂的性能，因此，通过进一步限定包覆层与碳基基底的质量比，能够进一步提高电催化剂的稳定性，提高其比表面积，降低析氢过电位。
第二方面，本申请提供一种第一方面的电催化剂的制备方法，包括以下步骤：
将电极前驱体置于碱性电解液中，对电极前驱体进行电催化还原处理，得到电催化剂；
其中，电极前驱体包括碳基基底和负载在碳基基底至少部分表面的二硫化镍，碳基基底具有三维多孔结构。
具体地，将包括碳基基底和负载在碳基基底至少部分表面的二硫化镍的电极前驱体置于碱性电解液中，对电极前驱体进行电催化还原处理，此时负载在碳基基底至少部分表面的二硫化镍原位重构反应生成金属镍和二硫化三镍，得到电催化剂，电催化还原处理的反应式可以参照式(1)所示：
NiS2+O2→Ni+Ni3S2+SO2            式(1)
其中，碳基基底具有三维多孔结构，能够提高包覆层的比表面积，增加电催化剂的活性位点。
本申请提供的制备方法，能够将负载在碳基基底至少部分表面的二硫化镍原位重构成金属镍与二硫化三镍，形成包括碳基基底和负载在碳基基底至少部分表面的包括金属镍和二硫化三镍的包覆层；方法简单，易于实现，降低了制造成本，利于实现产业化。
在一具体实施例中，碱性电解液包括氢氧化钾或氢氧化钠中的至少一种；其中，碱性电解液的摩尔浓度为0.9～1.1mol/L，参数还可以进一步限定为1mol/L；通过进一步限定碱性电解液的种类和浓度，能够进一步促进阴极还原的充分进行，提高离子传输速率。
本申请不限定电极前驱体的来源，可选地，电极前驱体通过以下步骤制得：
(1)将包括碳基基底、镍源、尿素和铵盐的第一原料体系置于去离子水中进行第一水热处理，得到负载氢氧化镍的第一前驱体；
(2)将包括第一前驱体与含硫化合物的第二原料体系置于去离子水中进行第二水热处理，得到负载二硫化镍的电极前驱体。
其中，步骤(1)中，第一水热处理的反应式可以参照式(2)所示：
Ni(NO3)2+CO(NH2)2+H2O→Ni(OH)2+NH4NO3+CO2    式(2)
步骤(3)中，第二水热处理的反应式可以参照式(3)所示：
Ni(OH)2+C2H5NS+H2O→NiS2+C2H5O2+NH3·H2O    式(3)
具体地，第一水热处理的温度为100～140℃，时间为4～8h；
第二水热处理的温度为140～180℃，时间为14～19h；
镍源、尿素及铵盐的摩尔比为(0.3～0.4)：(1.6～1.8)：1；
其中，镍源选自硝酸镍、氯化镍或硫酸镍中的至少一种；铵盐选自氟化铵、氯化铵或硫酸铵中的至少一种；
含硫化合物与第一前驱体的质量比为(0.01～0.07)：1；
可选地，含硫化合物可以为无机含硫化合物，包括硫粉、硫化钠、硫脲和硫代硫酸钠中的至少一种，也可以为有机含硫化合物，包括二硫化碳和硫代乙酰胺中的至少一种。
进一步地，步骤(1)中，第一水热处理之后还包括依次进行的洗涤处理和烘干处理；其中，洗涤处理包括对第一前驱体依次于去离子水及无水乙醇中洗涤，重复操作2～3次；烘干处理包括在50～70℃的真空干燥箱中进行烘干10～15h，用以除去洗涤剂；可选地，第一水热处理在聚四氟乙烯材料的水热釜中进行。
进一步地，步骤(2)中，第二水热反应之后还包括依次进行的洗涤处理和烘干处理；其中，洗涤处理包括将电极前驱体依次于去离子水及无水乙醇中洗涤，重复操作2～3次；烘干处理包括在50～70℃的真空干燥箱中进行烘干8～10h，用以除去洗涤剂；可选地，第二水热处理在聚四氟乙烯材料的水热釜中进行。
在一具体实施方式中，步骤(1)前，还包括预处理；预处理包括将碳基基底前体依次于去离子水及无水乙醇中进行洗涤后，置于真空烘箱中进行烘干，得到碳基基底。
进一步地，电催化还原处理的还原电位为-400～-1200mV；电催化还原处理的还原时间为10-100min。
发明人发现，电催化还原处理的还原电位和还原时间会影响二硫化镍原位重构的产物，即影响金属镍和二硫化三镍的比例以及电催化剂的比表面积等，因此，通过进一步限定还原电位和还原时间，有利于更好的控制电催化还原的充分进行，进一步地提高电催化剂的催化活性，降低析氢过电位并且改善稳定性；其中，还原电位为相对于可逆氢电极(RHE)的电位；
可选地，还可以进一步限定还原电位为-800～-1000mVvs.RHE，还原时间为30～70min；再进一步地，还原电位为-850～-950mVvs.RHE。
具体地，还包括对电极和参比电极；对电极与参比电极以及电极前驱体共同构成三电极体系置于碱性电解液中；其中，对电极为碳棒，参比电极为饱和甘汞。
能够理解，电极前驱体进行电催化还原处理时还需要对电极和参比电极，电极前驱体作为工作电极与对电极和参比电极共同构成三电极体系；其中，对电极为碳棒，参比电极为饱和甘汞，能够更好的将电极前驱体中的二硫化镍原位重构生产金属镍和二硫化三镍，并且进一步地提高电催化剂的催化活性，降低析氢过电位并且改善稳定性。
第三方面，本申请提供一种电极，包括第一方面的电催化剂或第二方面的制备方法得到的电催化剂。
本申请提供了一种电极，能够降低析氢过电位，具有良好的稳定性。
第四方面，本申请提供一种电解装置，包括第一方面的电催化剂或第二方面的制备方法得到的电催化剂或第三方面的电极。
第五方面，本申请还提供一种电解方法，使第一方面的电催化剂或第二方面的制备方法得到的电催化剂或第三方面的电极参与水的电解反应。
本申请还提供了一种电解方法，利用上述的电催化剂、上述制备方法制得的电催化剂或电极参与水的电解，能够降低析氢过电位。
以下，通过具体实施例对本申请提供的一种电催化剂进行详细的介绍。
实施例1
(1)将碳纤维布依次于去离子水及无水乙醇中进行洗涤，置于真空烘箱中进行烘干，得到预处理后的碳纤维布；取4mmol的硝酸镍溶入30mL的去离子水中，使用磁力搅拌器在常温下搅拌均匀；取20mL的去离子水溶解20mmol的尿素和12mmol的氟化铵，两溶液混合得到的50mL的混合溶液，倒入100mL的水热釜内胆中，在水热釜中加入一块1cm×1.5cm的碳纤维布；在120℃条件下进行第一水热处理6h；冷却至室温后取出碳纤维布，用去离子水洗3次，无水乙醇洗涤3次，并放入60℃烘箱中干燥12h，得到负载氢氧化镍的第一前驱体，记为Ni(OH)2@CC；
(2)取0.05g的硫代乙酰胺溶解在40mL的去离子水中，转移到聚四氟乙烯水热釜中，将2g Ni(OH)2@CC浸没其中，并置于160℃的烘箱中进行第二水热处理16h；待冷却后，分别使用去离子水和乙醇清洗3次，放入60℃真空干燥箱中烘干9h，得到负载二硫化镍的电极前驱体，记为NiS2@CC；
(3)将NiS2@CC作为工作电极、饱和甘汞电极以及碳棒置于1mol/L的KOH溶液中，使用恒压的安培计时模式，在-900mV(vs.RHE)的还原电位下对NiS2@CC进行电催化还原处理50min，将工作电极清洗后，得到电催化剂，记为Ni/Ni3S2@CC。
实施例2
本实施例与实施例1的区别在于：采用碳纸作为碳基基底。
实施例3
本实施例与实施例1的区别在于：还原处理时间为10min。
实施例4
本实施例与实施例1的区别在于：还原处理时间为100min。
实施例5
本实施例与实施例1的区别在于：还原处理时间为120min。
实施例6
本实施例与实施例1的区别在于：还原电位为-300mV。
实施例7
本实施例与实施例1的区别在于：还原电位为-500mV。
实施例8
本实施例与实施例1的区别在于：还原电位为-700mV。
实施例9
本实施例与实施例1的区别在于：还原电位为-1100mV。
实施例10
本实施例与实施例1的区别在于：还原电位为-1300mV。
对比例1
本对比例与实施例1的区别在于：不进行步骤(3)，即不经过原位重构过程。
对比例2
本对比例与实施例1的区别在于：采用FTO导电玻璃作为基底。
试验例1
对上述实施例1和对比例1中制得的材料进行SEM表征、TEM表征和XPS表征，得到图1～图9；
图1为本申请实施例1制得的Ni(OH)2@CC的SEM图，由图可知，氢氧化镍纳米片较为均匀，纳米片长宽大约5-10μm；
图2为图1的局部放大图，由图可知，氢氧化镍纳米片厚度大约为10-70nm；
图3为本申请实施例1制得的NiS2@CC的SEM图，由图可知，电极前驱体NiS2@CC具有部分孔洞，可能由于步骤(2)中的硫代乙酰胺在高温条件下与水快速形成H2S，酸性的H2S使得具有平面致密结构的Ni(OH)2在转换为颗粒状NiS2时，表面结合力降低，从而导致了孔洞生成；
图4为图3的局部放大图，由图可知NiS2@CC是由直径大约为20-150nm的纳米块粘连而成的；
图5为本申请实施例1制备得到的NiS2@CC的TEM图，同样可以发现，NiS2为纳米方块组成的片层结构；
图6为本申请实施例1制备得到的Ni/Ni3S2@CC的SEM图，在-900mV的电位下经过约50分钟的电催化还原处理后，原本颗粒状的NiS2转变为花状；
图7为图6的局部放大图，由图可见，花瓣为大量的超薄纳米片层结构；
图8为本申请实施例1制备得到的Ni/Ni3S2@CC的TEM图，同样可以发现重构后所得的Ni/Ni3S2为超薄的片层结构；
图9为本申请实施例1制备得到的Ni/Ni3S2@CC的XPS图，以及对比例1制备得到的NiS2@CC的XPS图。二者对比可知，对比例1的主要化学结构为NiS2，而实施例1的主要化学结构为Ni与Ni3S2。
试验例2
取上述实施例及对比例制备得到的电催化剂在25℃，1M KOH溶液中，三电极体系下，测量极化电流密度从0达到-150mA/cm2时的电极的极化电位曲线，得到图10与图11；
计算极化电位与析氢标准电位之差的绝对值，得到过电位，其中，析氢标准电位为0V，图12为部分实施例的过电位对比图。
上述测试结果如表1所示；
表1

本申请提供的电催化剂，利用碳基基底的多孔结构，提供更大的比表面积以提高包覆量，提供了更多的催化活性位点，并且通过碳基基底与负载在其表面的金属镍与二硫化三镍的协同作用，能够形成局部带负电的区域，为氢吸附提供更多的活性位点，能够大大提高催化活性，降低析氢过电位，提高电催化剂的稳定性。
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。

Claims (11)

  1. 一种电催化剂，其中，包括碳基基底和负载在所述碳基基底至少部分表面的包覆层；
    所述碳基基底具有三维多孔结构；
    所述包覆层包括金属镍和二硫化三镍。
  2. 根据权利要求1所述的电催化剂，其中，所述包覆层包括片层结构，所述片层结构的长度为15～25nm，宽度为15～25nm，厚度为2～7nm。
  3. 根据权利要求1或2所述的电催化剂，其中，所述金属镍与所述二硫化三镍的质量比为(90～99)：(1～10)。
  4. 根据权利要求1-3任一项所述的电催化剂，其中，所述包覆层与所述碳基基底的质量比为(1～10)：(90～99)。
  5. 一种权利要求1-4任一项所述的电催化剂的制备方法，其中，包括以下步骤：
    将电极前驱体置于碱性电解液中，对所述电极前驱体进行电催化还原处理，得到所述电催化剂；
    其中，所述电极前驱体包括碳基基底和负载在所述碳基基底至少部分表面的二硫化镍，所述碳基基底具有三维多孔结构。
  6. 根据权利要求5所述的制备方法，其中，所述电催化还原处理的还原电位为-400～-1200mV。
  7. 根据权利要求5或6所述的制备方法，其中，所述电催化还原处理的还原时间为10～100min。
  8. 根据权利要求5或6或7所述的制备方法，其中，还包括对电极和参比电极；所述对电极与所述参比电极以及所述电极前驱体共同构成三电极体系置于所述碱性电解液中；其中，对电极为碳棒，参比电极为饱和甘汞。
  9. 一种电极，其中，包括权利要求1-4任一项所述的电催化剂或权利要求5-8任一项所述的制备方法得到的电催化剂。
  10. 一种电解装置，其中，包括权利要求1-4任一项所述的电催化剂或权利要求5-8任一项所述的制备方法得到的电催化剂或权利要求9所述的电极。
  11. 一种电解方法，其中，使权利要求1-4任一项所述的电催化剂或权利要求5-8任一项所述的制备方法得到的电催化剂或权利要求9所述的电极参与水的电解反应。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825127A (zh) * 2020-07-07 2020-10-27 江苏大学 一种金属镍基纳米材料的制备方法及其应用
CN116377504A (zh) * 2023-06-01 2023-07-04 中石油深圳新能源研究院有限公司 析氢析氧催化剂及其制备方法和电解装置及其电极

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825127A (zh) * 2020-07-07 2020-10-27 江苏大学 一种金属镍基纳米材料的制备方法及其应用
CN116377504A (zh) * 2023-06-01 2023-07-04 中石油深圳新能源研究院有限公司 析氢析氧催化剂及其制备方法和电解装置及其电极

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QIAN HAO; WU BAOXIN; NIE ZHONGWU; LIU TIANTIAN; LIU PENG; HE HAO; WU JIANGHONG; CHEN ZHAOYONG; CHEN SHUGUANG: "A flexible Ni3S2/Ni@CC electrode for high-performance battery-like supercapacitor and efficient oxygen evolution reaction", CHEMICAL ENGENEERING JOURNAL, vol. 420, 15 September 2020 (2020-09-15), AMSTERDAM, NL , pages 1 - 9, XP086636122, ISSN: 1385-8947, DOI: 10.1016/j.cej.2020.127646 *

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