CN115261915B - Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof - Google Patents

Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof Download PDF

Info

Publication number
CN115261915B
CN115261915B CN202211039239.0A CN202211039239A CN115261915B CN 115261915 B CN115261915 B CN 115261915B CN 202211039239 A CN202211039239 A CN 202211039239A CN 115261915 B CN115261915 B CN 115261915B
Authority
CN
China
Prior art keywords
source
cobalt
nickel
aqueous solution
solution containing
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CN202211039239.0A
Other languages
Chinese (zh)
Other versions
CN115261915A (en
Inventor
乔靓
陈雄
刘淑杰
张维锦
李筱霏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun University
Original Assignee
Changchun University
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 Changchun University filed Critical Changchun University
Priority to CN202211039239.0A priority Critical patent/CN115261915B/en
Publication of CN115261915A publication Critical patent/CN115261915A/en
Application granted granted Critical
Publication of CN115261915B publication Critical patent/CN115261915B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/089—Alloys
    • 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
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

本发明采用CFP作为基底，以避免使用粘结剂，从而避免使用粘结剂降低制备的所述催化剂的催化性能；先后在CFP表面原位沉积CoS2和NiCo2S4，避免CoS2的团聚，暴露更多的活性催化位点，其中CoS2析氢和析氧动力学过程较快，导电性能优异，双金属硫化物NiCo2S4本身存在丰富的氧化还原电对，CoS2和NiCo2S4复合形成异质结，从而加速电子在电催化过程中的转移速率，且在形成所述异质结时还会产生缺陷和空位，提供了更多的催化活性位点，进一步提高电催化性能，CoS2和NiCo2S4的协同效应得到充分利用，显著提高了制备得到的所述含钴和镍的复合电催化剂的析氢、析氧和电解水催化性能。

Figure 202211039239

The present invention uses CFP as a substrate to avoid the use of binders, thereby avoiding the use of binders to reduce the catalytic performance of the prepared catalyst; successively deposit CoS 2 and NiCo 2 S 4 on the surface of CFP in situ to avoid the agglomeration of CoS 2 , to expose more active catalytic sites, among which CoS 2 has faster hydrogen evolution and oxygen evolution kinetics, excellent electrical conductivity, and bimetallic sulfide NiCo 2 S 4 itself has abundant redox pairs, CoS 2 and NiCo 2 S 4 Recombination to form a heterojunction, thereby accelerating the transfer rate of electrons in the electrocatalytic process, and defects and vacancies will also be generated when the heterojunction is formed, providing more catalytic active sites and further improving the electrocatalytic performance , the synergistic effect of CoS 2 and NiCo 2 S 4 is fully utilized, which significantly improves the catalytic performance of hydrogen evolution, oxygen evolution and electrolysis of water of the prepared composite electrocatalyst containing cobalt and nickel.

Figure 202211039239

Description

一种含钴和镍的复合电催化剂及其制备方法和应用A kind of composite electrocatalyst containing cobalt and nickel and its preparation method and application

技术领域technical field

本发明涉及催化材料技术领域，尤其涉及一种含钴和镍的复合电催化剂及其制备方法和应用。The invention relates to the technical field of catalytic materials, in particular to a composite electrocatalyst containing cobalt and nickel, a preparation method and application thereof.

背景技术Background technique

随着人类社会的快速发展，能源短缺问题和环境污染问题日益成为社会关注的热点问题，这也促使人们高度重视生态环境保护及能源的可持续发展。目前，人类能源供给逐渐从化石能源向太阳能、潮汐能、风能等无污染可持续的绿色能源转变。然而，这些绿色能源也存在一些不足之处，如容易受到天气、时间和地域的影响，无法持续稳定供给，难以满足人类生产生活的需求。而氢能在使用过程中无污染，能量密度高，其供应形式比其他绿色能源更稳定，已经成为最具有应用前景的绿色能源之一。With the rapid development of human society, the problem of energy shortage and environmental pollution has increasingly become a hot issue of social concern, which also prompts people to attach great importance to ecological environment protection and sustainable development of energy. At present, human energy supply is gradually shifting from fossil energy to non-polluting and sustainable green energy such as solar energy, tidal energy, and wind energy. However, these green energies also have some shortcomings, such as being easily affected by weather, time and geography, unable to sustain a stable supply, and difficult to meet the needs of human production and life. Hydrogen energy is pollution-free during use, has high energy density, and its supply form is more stable than other green energy sources. It has become one of the most promising green energy sources.

氢气的制取手段有很多种，主要有甲烷蒸汽转化法、天然气制氢法以及电解水制氢法。工业上主要采取甲烷蒸汽转化法和天然气制氢法，但是在制取过程中会产生温室气体二氧化碳。在电解水制备氢气过程中，阴极和阳极分别发生还原反应和氧化反应，只有氢气和氧气生成，制备方法更绿色更环保，另一产物氧气在医疗保健、国防工业等方面也有着广泛的运用。There are many ways to produce hydrogen, mainly including steam reforming of methane, hydrogen production from natural gas and hydrogen production from electrolysis of water. The industry mainly adopts methane steam reforming method and natural gas hydrogen production method, but the greenhouse gas carbon dioxide will be produced in the production process. In the process of electrolyzing water to produce hydrogen, the cathode and the anode undergo reduction and oxidation reactions respectively, and only hydrogen and oxygen are produced. The preparation method is greener and more environmentally friendly. The other product, oxygen, is also widely used in medical care and defense industries.

使用电解水法制取氢气和氧气的过程中，需要克服一定的能量势垒。在电解水过程中引入催化剂是解决这一问题的有效手段。目前，商业上使用较多的催化剂为Pt、Pd和Ru等贵金属催化剂，然而贵金属在地壳中的储量相对较低且成本相对高昂，这严重阻碍了电解水制氢和制氧的广泛推广和应用。因此，提供一种电催化性能高效且成本低的电解水催化剂是现有技术亟需解决的问题。In the process of producing hydrogen and oxygen by electrolysis of water, a certain energy barrier needs to be overcome. Introducing catalysts during water electrolysis is an effective means to solve this problem. At present, noble metal catalysts such as Pt, Pd, and Ru are commonly used commercially. However, the reserves of noble metals in the earth’s crust are relatively low and the cost is relatively high, which seriously hinders the widespread promotion and application of hydrogen and oxygen production by electrolysis of water. . Therefore, it is an urgent problem to be solved in the prior art to provide an electrolytic water catalyst with high electrocatalytic performance and low cost.

发明内容Contents of the invention

本发明的目的在于提供一种含钴和镍的复合电催化剂及其制备方法和应用，本发明提供的制备方法，原料来源广泛，成本低廉，制备的含钴和镍的复合电催化剂，在析氢反应、析氧反应和电解水方面都表现出优异的电催化性能。The purpose of the present invention is to provide a composite electrocatalyst containing cobalt and nickel and its preparation method and application. The preparation method provided by the present invention has a wide range of raw material sources and low cost. Reaction, oxygen evolution reaction and water electrolysis all exhibit excellent electrocatalytic performance.

为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

本发明提供了一种含钴和镍的复合电催化剂的制备方法，包括以下步骤：The invention provides a method for preparing a composite electrocatalyst containing cobalt and nickel, comprising the following steps:

(1)将碳纤维纸进行亲水性处理，得到预处理的碳纤维纸；(1) Carry out hydrophilic treatment to carbon fiber paper to obtain pretreated carbon fiber paper;

(2)将所述步骤(1)得到的预处理的碳纤维纸浸渍到含钴源和硫源的水溶液中，然后进行水热反应，得到二硫化钴/碳纤维纸；(2) impregnating the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source and a sulfur source, and then carrying out a hydrothermal reaction to obtain cobalt disulfide/carbon fiber paper;

(3)将所述步骤(2)得到的二硫化钴/碳纤维纸浸渍到含钴源、镍源和硫源的水溶液中，然后进行水热反应，得到含钴和镍的复合电催化剂。(3) Immerse the cobalt disulfide/carbon fiber paper obtained in the step (2) into an aqueous solution containing a cobalt source, a nickel source and a sulfur source, and then perform a hydrothermal reaction to obtain a composite electrocatalyst containing cobalt and nickel.

优选地，所述步骤(1)中亲水性处理为电化学处理、热处理氧化、液相处理、等离子体处理、微波处理中的一种。Preferably, the hydrophilic treatment in the step (1) is one of electrochemical treatment, thermal oxidation, liquid phase treatment, plasma treatment and microwave treatment.

优选地，所述步骤(2)中含钴源和硫源的水溶液中钴源和所述步骤(3)中含钴源、镍源和硫源的水溶液中的钴源独立地为CoCl2·6H2O和Co(NO3)2·6H2O中的一种或两种。Preferably, the cobalt source in the aqueous solution containing cobalt source and sulfur source in the step (2) and the cobalt source in the aqueous solution containing cobalt source, nickel source and sulfur source in the step (3) are independently CoCl 2 . One or both of 6H 2 O and Co(NO 3 ) 2 ·6H 2 O.

优选地，所述步骤(2)中含钴源和硫源的水溶液中钴源的浓度为3.75×10-2～4.60×10-2mmol/mL。Preferably, the concentration of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) is 3.75×10 -2 to 4.60×10 -2 mmol/mL.

优选地，所述步骤(2)中水热反应的温度为160～200℃，所述水热反应的时间为16～20h。Preferably, the temperature of the hydrothermal reaction in the step (2) is 160-200° C., and the time of the hydrothermal reaction is 16-20 h.

优选地，所述步骤(2)中含钴源和硫源的水溶液中的钴源和所述步骤(3)中含钴源、镍源和硫源的水溶液中的镍源的物质的量之比为1:(0.15～5.5)。Preferably, the amount of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) and the amount of the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source in the step (3) The ratio is 1:(0.15～5.5).

优选地，所述步骤(3)中浸渍的温度为室温，所述浸渍的时间为20～40min。Preferably, the impregnation temperature in the step (3) is room temperature, and the impregnation time is 20-40 minutes.

优选地，所述步骤(3)中水热反应的温度为170～190℃，所述水热反应的时间为8～12h。Preferably, the temperature of the hydrothermal reaction in the step (3) is 170-190° C., and the time of the hydrothermal reaction is 8-12 hours.

本发明还提供了上述技术方案所述制备方法制备得到的含钴和镍的复合电催化剂，包括碳纤维纸、原位生长在碳纤维纸表面的二硫化钴纳米颗粒、原位生长在碳纤维纸和二硫化钴纳米颗粒表面的四硫化二钴合镍微米球。The present invention also provides a composite electrocatalyst containing cobalt and nickel prepared by the preparation method described in the above technical solution, including carbon fiber paper, cobalt disulfide nanoparticles grown on the surface of carbon fiber paper in situ, and cobalt disulfide nanoparticles grown on carbon fiber paper and disulfide in situ. Cobalt tetrasulfide nickel microspheres on the surface of cobalt sulfide nanoparticles.

本发明还提供了上述技术方案所述制备方法制备得到的含钴和镍的复合电催化剂或上述技术方案所述含钴和镍的复合电催化剂在电解水中的应用。The present invention also provides the composite electrocatalyst containing cobalt and nickel prepared by the preparation method described in the above technical solution or the application of the composite electrocatalyst containing cobalt and nickel described in the above technical solution in the electrolysis of water.

本发明提供了一种含钴和镍的复合电催化剂的制备方法，首先将碳纤维纸CFP进行亲水性处理，使CFP表面具有极性，并引入丰富的含氧基团，提高其表面活性，利于后续水热反应中过渡金属硫化物在CFP表面的生长，得到预处理的碳纤维纸，然后依次经浸渍和水热反应，在预处理的碳纤维纸上原位沉积二硫化钴CoS2，得到二硫化钴/碳纤维纸，再依次经浸渍和水热反应，得到含钴和镍的复合电催化剂即NiCo2S4/CoS2/CFP电催化剂。本发明采用CFP作为基底，避免了粘结剂的使用，从而避免使用粘结剂降低制备的所述催化剂的催化性能；先后利用水热合成方法在CFP表面原位沉积过渡金属硫化物CoS2和NiCo2S4，简单高效，避免CoS2的团聚，暴露更多的活性催化位点，其中CoS2具有金属性，析氢和析氧动力学过程较快，导电性能优异，双金属硫化物NiCo2S4本身存在丰富的氧化还原电对，具有出色的电催化性能；且在水热反应形成NiCo2S4的过程中，CoS2同时和生成的NiCo2S4复合成异质结，从而加速电子在电催化过程中的转移速率，协同提高电催化性能；并且在形成所述异质结时还会产生一定的缺陷和空位，这些缺陷和空位提供了更多的催化活性位点，进一步提高所述催化剂的电催化性能，使得CoS2和NiCo2S4的协同效应得到充分利用，显著提高了制备得到的所述含钴和镍的复合电催化剂的析氢、析氧和电解水催化性能，且本申请中使用的原料来源广泛，成本低。实施例的结果显示，实施例1制备的NiCo2S4/CoS2/CFP电催化剂在析氢和析氧性能测试中都具有优异的电催化性能，且具有优异的电解水催化性能；在电流密度为10mA cm-2时，实施例1制备的NiCo2S4/CoS2/CFP电催化剂的析氢过电位为244mV，Tafel斜率为151mV dec-1；在电流密度为50mA cm-2时，实施例1制备的NiCo2S4/CoS2/CFP电催化剂的析氧过电位为367mV，Tafel斜率为120mV dec-1；在电流密度为10mA cm-2时，实施例1制备的NiCo2S4/CoS2/CFP电催化剂的电解水的电位为1.61V。The invention provides a method for preparing a composite electrocatalyst containing cobalt and nickel. First, the carbon fiber paper CFP is subjected to hydrophilic treatment to make the surface of the CFP polar, and to introduce abundant oxygen-containing groups to improve its surface activity. It is conducive to the growth of transition metal sulfides on the surface of CFP in the subsequent hydrothermal reaction, and the pretreated carbon fiber paper is obtained, and then sequentially impregnated and hydrothermally reacted, cobalt disulfide CoS 2 is deposited on the pretreated carbon fiber paper in situ, and two Cobalt sulfide/carbon fiber paper, followed by impregnation and hydrothermal reaction to obtain a composite electrocatalyst containing cobalt and nickel, namely NiCo 2 S 4 /CoS 2 /CFP electrocatalyst. The present invention adopts CFP as substrate, has avoided the use of binding agent, thereby avoids the catalytic performance of described catalyst that uses binding agent to reduce preparation; Utilizes hydrothermal synthesis method to deposit transition metal sulfide CoS in situ on the surface of CFP successively and NiCo 2 S 4 , simple and efficient, avoids the agglomeration of CoS 2 and exposes more active catalytic sites. Among them, CoS 2 is metallic, with fast hydrogen and oxygen evolution kinetics and excellent electrical conductivity. Bimetallic sulfide NiCo 2 S 4 itself has abundant redox couples, which has excellent electrocatalytic performance; and in the process of hydrothermal reaction to form NiCo 2 S 4 , CoS 2 simultaneously recombines with the generated NiCo 2 S 4 to form a heterojunction, thus accelerating The transfer rate of electrons in the electrocatalytic process synergistically improves the electrocatalytic performance; and certain defects and vacancies will be generated when the heterojunction is formed, these defects and vacancies provide more catalytic active sites, further improving The electrocatalytic performance of the catalyst makes full use of the synergistic effect of CoS2 and NiCo2S4 , significantly improving the hydrogen evolution, oxygen evolution and electrolytic water catalytic performance of the prepared composite electrocatalyst containing cobalt and nickel, And the source of raw material used in this application is extensive, and cost is low. The results of the examples show that the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1 has excellent electrocatalytic performance in hydrogen evolution and oxygen evolution performance tests, and has excellent electrolytic water catalytic performance; When the current density is 10mA cm -2 , the hydrogen evolution overpotential of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1 is 244mV, and the Tafel slope is 151mV dec -1 ; when the current density is 50mA cm -2 , the embodiment The oxygen evolution overpotential of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in 1 is 367mV, and the Tafel slope is 120mV dec -1 ; when the current density is 10mA cm -2 , the NiCo 2 S 4 /CFP prepared in Example 1 The electrolysis potential of CoS 2 /CFP electrocatalyst is 1.61V.

附图说明Description of drawings

图1为本发明实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂的XRD图；Figure 1 is the XRD pattern of CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts prepared in Example 1 of the present invention, and NiCo 2 S 4 /CFP electrocatalysts prepared in Comparative Example;

图2为本发明实施例1制备的NiCo2S4/CoS2/CFP电催化剂的SEM图；Fig. 2 is the SEM image of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1 of the present invention;

图3为实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂的析氢性能测试的LSV曲线图；Fig. 3 is the CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1, and the LSV curve diagram of the hydrogen evolution performance test of the NiCo 2 S 4 /CFP electrocatalyst prepared in Comparative Example;

图4为实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂的析氢性能测试的Tafel斜率图；Fig. 4 is the Tafel slope diagram of the hydrogen evolution performance test of CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts prepared in Example 1, and NiCo 2 S 4 /CFP electrocatalysts prepared in Comparative Example;

图5为实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂的析氧性能测试的LSV曲线图；Fig. 5 is the CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1, and the LSV curve diagram of the oxygen evolution performance test of the NiCo 2 S 4 /CFP electrocatalyst prepared in Comparative Example;

图6为实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂的析氧性能测试的Tafel斜率图；Fig. 6 is the Tafel slope graph of the oxygen evolution performance test of CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts prepared in Example 1, and NiCo 2 S 4 /CFP electrocatalysts prepared in Comparative Example;

图7为实施例1制备的NiCo2S4/CoS2/CFP电催化剂的电解水性能的LSV曲线图。FIG. 7 is an LSV curve of the water electrolysis performance of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1. FIG.

具体实施方式Detailed ways

本发明提供了一种含钴和镍的复合电催化剂的制备方法，包括以下步骤：The invention provides a method for preparing a composite electrocatalyst containing cobalt and nickel, comprising the following steps:

(1)将碳纤维纸进行亲水性处理，得到预处理的碳纤维纸；(1) Carry out hydrophilic treatment to carbon fiber paper to obtain pretreated carbon fiber paper;

(2)将所述步骤(1)得到的预处理的碳纤维纸浸渍到含钴源和硫源的水溶液中，然后进行水热反应，得到二硫化钴/碳纤维纸；(2) impregnating the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source and a sulfur source, and then carrying out a hydrothermal reaction to obtain cobalt disulfide/carbon fiber paper;

(3)将所述步骤(2)得到的二硫化钴/碳纤维纸浸渍到含钴源、镍源和硫源的水溶液中，然后进行水热反应，得到含钴和镍的复合电催化剂。(3) Immerse the cobalt disulfide/carbon fiber paper obtained in the step (2) into an aqueous solution containing a cobalt source, a nickel source and a sulfur source, and then perform a hydrothermal reaction to obtain a composite electrocatalyst containing cobalt and nickel.

在本发明中，若无特殊说明，所采用的原料均为本领域常规市售产品。In the present invention, unless otherwise specified, the raw materials used are conventional commercially available products in this field.

本发明将碳纤维纸进行亲水性处理，得到预处理的碳纤维纸。In the invention, the carbon fiber paper is subjected to hydrophilic treatment to obtain the pretreated carbon fiber paper.

在本发明中，所述碳纤维纸在使用前优选进行去污处理。在本发明中，所述去污处理优选包括对碳纤维纸进行裁剪，然后依次在丙酮、无水乙醇和去离子水中分别进行超声处理8～12min，之后置于鼓风干燥箱中干燥。In the present invention, the carbon fiber paper is preferably decontaminated before use. In the present invention, the decontamination treatment preferably includes cutting the carbon fiber paper, and then performing ultrasonic treatment in acetone, absolute ethanol and deionized water for 8-12 minutes respectively, and then placing it in a blast drying oven for drying.

在本发明中，所述亲水性处理优选为电化学处理、热处理氧化、液相处理、等离子体处理、微波处理中的一种。在本发明中，利用亲水性处理使CFP表面具有极性，并引入丰富的含氧基团，提高其表面活性，利于后续水热反应中过渡金属硫化物在CFP表面的生长。In the present invention, the hydrophilic treatment is preferably one of electrochemical treatment, thermal oxidation, liquid phase treatment, plasma treatment, and microwave treatment. In the present invention, the hydrophilic treatment is used to make the surface of CFP polar, and introduce abundant oxygen-containing groups to improve its surface activity, which is beneficial to the growth of transition metal sulfides on the surface of CFP in the subsequent hydrothermal reaction.

在本发明中，所述电化学处理优选包括设置工作电极为碳纤维纸，参比电极为饱和甘汞电极(SCE)，对电极为铂片，形成三电极体系，采用0.5M的H2SO4溶液作为电解质，利用循环伏安法对碳纤维纸进行亲水处理。In the present invention, the electrochemical treatment preferably includes setting the working electrode as carbon fiber paper, the reference electrode as a saturated calomel electrode (SCE), and the counter electrode as a platinum sheet to form a three-electrode system, using 0.5M H 2 SO 4 The solution was used as the electrolyte, and the carbon fiber paper was treated with hydrophilicity by cyclic voltammetry.

亲水处理完成后，本发明优选将亲水处理后的碳纤维纸依次用无水乙醇和去离子水超声处理，然后进行干燥，得到预处理的碳纤维纸。After the hydrophilic treatment is completed, in the present invention, the carbon fiber paper after the hydrophilic treatment is preferably ultrasonically treated with absolute ethanol and deionized water in sequence, and then dried to obtain the pretreated carbon fiber paper.

本发明对超声处理的功率和时间没有特殊的限制，实现清洗干净碳纤维纸表面的杂质即可。The present invention has no special limitation on the power and time of the ultrasonic treatment, and it only needs to clean the impurities on the surface of the carbon fiber paper.

得到预处理的碳纤维纸后，本发明将所述预处理的碳纤维纸浸渍到含钴源和硫源的水溶液中，然后进行水热反应，得到二硫化钴/碳纤维纸。After the pretreated carbon fiber paper is obtained, the present invention immerses the pretreated carbon fiber paper into an aqueous solution containing a cobalt source and a sulfur source, and then performs a hydrothermal reaction to obtain cobalt disulfide/carbon fiber paper.

本发明对所述含钴源和硫源的水溶液的制备方法没有特殊的限制，采用本领域常规技术方案即可。In the present invention, there is no special limitation on the preparation method of the aqueous solution containing cobalt source and sulfur source, and conventional technical solutions in the field can be adopted.

在本发明中，所述浸渍的温度优选为室温；所述浸渍的时间优选为20～40min，更优选为25～35min。本发明将浸渍的温度和时间控制在上述范围内，有利于含钴源和硫源的水溶液混合均匀。In the present invention, the soaking temperature is preferably room temperature; the soaking time is preferably 20-40 minutes, more preferably 25-35 minutes. The invention controls the impregnating temperature and time within the above range, which is beneficial to uniform mixing of the aqueous solution containing cobalt source and sulfur source.

在本发明中，所述含钴源和硫源的水溶液中的钴源优选为CoCl2·6H2O和Co(NO3)2·6H2O中的一种或两种。在本发明中，所述含钴源和硫源的水溶液中钴源的浓度优选为3.75×10-2～4.60×10-2mmol/mL，更优选为4.00×10-2～4.40×10-2mmol/mL。本发明将含钴源和硫源的水溶液中钴源的浓度控制在上述范围内，有利于钴源在水溶液中充分溶解。In the present invention, the cobalt source in the aqueous solution containing the cobalt source and the sulfur source is preferably one or both of CoCl 2 ·6H 2 O and Co(NO 3 ) 2 ·6H 2 O. In the present invention, the concentration of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source is preferably 3.75×10 -2 to 4.60×10 -2 mmol/mL, more preferably 4.00×10 -2 to 4.40×10 - 2 mmol/mL. In the present invention, the concentration of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source is controlled within the above range, which is beneficial to the full dissolution of the cobalt source in the aqueous solution.

在本发明中，所述含钴源和硫源的水溶液中的硫源优选为Na2S2O3·5H2O和Na2S·9H2O中的一种或两种。在本发明中，所述含钴源和硫源的水溶液中钴源和硫源的物质的量之比优选为1:(2～4)，更优选为1:(2.5～3.5)。本发明将含钴源和硫源的水溶液中钴源和硫源的物质的量之比控制在上述范围内，有利于制备得到纯相的二硫化钴CoS2。In the present invention, the sulfur source in the aqueous solution containing cobalt source and sulfur source is preferably one or both of Na 2 S 2 O 3 ·5H 2 O and Na 2 S·9H 2 O. In the present invention, the ratio of the amount of cobalt source and sulfur source in the aqueous solution containing cobalt source and sulfur source is preferably 1:(2-4), more preferably 1:(2.5-3.5). The present invention controls the amount ratio of the cobalt source and the sulfur source in the aqueous solution containing the cobalt source and the sulfur source within the above range, which is beneficial to the preparation of pure phase cobalt disulfide CoS 2 .

在本发明中，所述水热反应的温度优选为160～200℃，更优选为170～190℃；所述水热反应的时间优选为16～20h，更优选为17～19h。本发明将水热反应的温度和时间控制在上述范围，以促进钴源和硫源充分进行化学反应，在预处理的碳纤维纸CFP上原位沉积析出结晶性好的二硫化钴CoS2，得到二硫化钴/碳纤维纸，避免温度过低和时间过短，反应进行不充分，无法得到目标产物，同时避免温度过高和时间过长，析出的二硫化钴产物的晶粒尺寸过大，而降低电催化性能。In the present invention, the temperature of the hydrothermal reaction is preferably 160-200°C, more preferably 170-190°C; the time of the hydrothermal reaction is preferably 16-20h, more preferably 17-19h. In the present invention, the temperature and time of the hydrothermal reaction are controlled within the above range to promote the full chemical reaction of the cobalt source and the sulfur source, and in situ deposition and precipitation of cobalt disulfide CoS 2 with good crystallinity on the pretreated carbon fiber paper CFP to obtain Cobalt disulfide/carbon fiber paper, avoiding that the temperature is too low and the time is too short, the reaction is insufficient, and the target product cannot be obtained, while avoiding that the temperature is too high and the time is too long, the grain size of the precipitated cobalt disulfide product is too large, and reduce the electrocatalytic performance.

水热反应完成后，本发明优选将所述水热反应的产物依次进行冷却、洗涤和干燥，得到二硫化钴/碳纤维纸。After the hydrothermal reaction is completed, the present invention preferably cools, washes and dries the product of the hydrothermal reaction in sequence to obtain cobalt disulfide/carbon fiber paper.

在本发明中，所述冷却的方式优选为自然冷却。在本发明中，所述洗涤优选为依次用无水乙醇和去离子水冲洗。本发明对所述洗涤的次数没有特殊的限制，实现完全除去杂质目的即可。本发明对所述干燥的方式没有特殊的限制，实现除去水分目的即可。In the present invention, the cooling method is preferably natural cooling. In the present invention, the washing is preferably followed by rinsing with absolute ethanol and deionized water. In the present invention, there is no special limitation on the number of washings, as long as the purpose of completely removing impurities is achieved. The present invention has no special limitation on the drying method, as long as the purpose of removing moisture is achieved.

得到二硫化钴/碳纤维纸后，本发明将所述二硫化钴/碳纤维纸浸渍到含钴源、镍源和硫源的水溶液中，然后进行水热反应，得到含钴和镍的复合电催化剂。After the cobalt disulfide/carbon fiber paper is obtained, the present invention impregnates the cobalt disulfide/carbon fiber paper into an aqueous solution containing a cobalt source, a nickel source and a sulfur source, and then performs a hydrothermal reaction to obtain a composite electrocatalyst containing cobalt and nickel .

在本发明中，所述含钴源、镍源和硫源的水溶液中的钴源优选为CoCl2·6H2O和Co(NO3)2·6H2O中的一种或两种。在本发明中，所述含钴源、镍源和硫源的水溶液中钴源的浓度优选为1×10-2～45×10-2mmol/mL，更优选为1.67×10-2～41.67×10-2mmol/mL。本发明将含钴源、镍源和硫源的水溶液中钴源的浓度控制在上述范围内，有利于控制负载在二硫化钴/碳纤维纸上的NiCo2S4的物质的量，从而可以使制备得到的含钴和镍的复合电催化剂具有最优的电催化性能。In the present invention, the cobalt source in the aqueous solution containing cobalt source, nickel source and sulfur source is preferably one or both of CoCl 2 ·6H 2 O and Co(NO 3 ) 2 ·6H 2 O. In the present invention, the concentration of the cobalt source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is preferably 1×10 -2 to 45×10 -2 mmol/mL, more preferably 1.67×10 -2 to 41.67 ×10 -2 mmol/mL. The present invention controls the concentration of cobalt source in the aqueous solution containing cobalt source, nickel source and sulfur source in the above-mentioned range, helps to control the NiCo that is loaded on the cobalt disulfide/carbon fiber paper S The amount of the substance, thereby can make The prepared composite electrocatalyst containing cobalt and nickel has the best electrocatalytic performance.

在本发明中，所述含钴源、镍源和硫源的水溶液中镍源优选为Ni(NO3)2·6H2O和NiCl2·6H2O中的一种或两种。在本发明中，所述含钴源、镍源和硫源的水溶液中硫源优选为CH4N2S和CH3CSNH2中的一种或两种。在本发明中，所述含钴源、镍源和硫源的水溶液中镍源、钴源和硫源的物质的量之比为优选为1：(1～3)：(3～5)，更优选1：(1.5～2.5)：(3.5～4.5)，进一步优选为1：2：4。本发明将含镍源、钴源和硫源的水溶液中钴源、镍源和硫源的物质的量之比控制在上述范围内，有利于制备得到纯相的四硫化二钴合镍NiCo2S4。In the present invention, the nickel source in the aqueous solution containing cobalt source, nickel source and sulfur source is preferably one or both of Ni(NO 3 ) 2 ·6H 2 O and NiCl 2 ·6H 2 O. In the present invention, the sulfur source in the aqueous solution containing cobalt source, nickel source and sulfur source is preferably one or both of CH 4 N 2 S and CH 3 CSNH 2 . In the present invention, the ratio of the amount of nickel source, cobalt source and sulfur source in the aqueous solution containing cobalt source, nickel source and sulfur source is preferably 1: (1 ~ 3): (3 ~ 5), More preferably, it is 1:(1.5-2.5):(3.5-4.5), and it is still more preferable that it is 1:2:4. The present invention controls the amount ratio of the cobalt source, the nickel source and the sulfur source in the aqueous solution containing the nickel source, the cobalt source and the sulfur source within the above-mentioned range, which is conducive to the preparation of pure phase nickel dicobalt tetrasulfide NiCo2 S4 .

在本发明中，所述含钴源和硫源的水溶液中钴源和所述含钴源、镍源和硫源的水溶液中镍源的物质的量之比优选为1:(0.15～5.5)，更优选为1:(0.2～5)。本发明将含钴源和硫源的水溶液中钴源和含钴源、镍源和硫源的水溶液中镍源的物质的量之比控制在上述范围内，有利于控制负载在预处理的碳纤维纸上的NiCo2S4与CoS2的物质的量之比，从而可以使制备得到所述含钴和镍的复合电催化剂具有最优的电催化性能，避免NiCo2S4与CoS2的含量过低或过高无法使制备得到的含钴和镍的复合电催化剂表现出最优的电催化协同效应。In the present invention, the ratio of the amount of cobalt source in the aqueous solution containing cobalt source and sulfur source to the amount of nickel source in the aqueous solution containing cobalt source, nickel source and sulfur source is preferably 1:(0.15～5.5) , more preferably 1:(0.2-5). The present invention controls the ratio of the substance amount of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source to the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source within the above-mentioned range, which is beneficial to control the load on the pretreated carbon fiber The ratio of the amount of NiCo 2 S 4 and CoS 2 on the paper, so that the composite electrocatalyst containing cobalt and nickel can be prepared to have optimal electrocatalytic performance, avoiding the content of NiCo 2 S 4 and CoS 2 Too low or too high can not make the prepared composite electrocatalyst containing cobalt and nickel show the best electrocatalytic synergistic effect.

本发明对所述含钴源、镍源和硫源的水溶液的制备方法没有特殊的限制，采用本领域常规技术方案即可。The present invention has no special limitation on the preparation method of the aqueous solution containing cobalt source, nickel source and sulfur source, and conventional technical solutions in the field can be adopted.

在本发明中，所述浸渍的温度优选为室温；所述浸渍的时间优选为20～40min，更优选为25～35min。本发明将浸渍的温度和时间控制在上述范围内，有利于含钴源、镍源和硫源的水溶液混合均匀。In the present invention, the soaking temperature is preferably room temperature; the soaking time is preferably 20-40 minutes, more preferably 25-35 minutes. The invention controls the impregnating temperature and time within the above range, which is beneficial to uniform mixing of the aqueous solution containing cobalt source, nickel source and sulfur source.

在本发明中，所述水热反应的温度优选为170～190℃，更优选为175～185℃；所述水热反应的时间优选为8～12h，更优选为9～11h。本发明将水热反应的温度和时间控制在上述范围，以促进钴源、镍源和硫源充分进行化学反应，在二硫化钴/碳纤维纸上原位沉积析出结晶性好的NiCo2S4，得到含钴和镍的复合电催化剂，避免温度过低和时间过短，反应进行不充分，无法得到目标产物，同时避免温度过高和时间过长，析出NiCo2S4产物的晶粒尺寸过大，而降低电催化性能。In the present invention, the temperature of the hydrothermal reaction is preferably 170-190°C, more preferably 175-185°C; the time of the hydrothermal reaction is preferably 8-12 hours, more preferably 9-11 hours. In the present invention, the temperature and time of the hydrothermal reaction are controlled within the above range to promote the full chemical reaction of the cobalt source, the nickel source and the sulfur source, and NiCo 2 S 4 with good crystallinity is deposited in situ on the cobalt disulfide/carbon fiber paper , to obtain a composite electrocatalyst containing cobalt and nickel, avoid too low temperature and too short time, the reaction is insufficient, and the target product cannot be obtained, while avoiding too high temperature and too long time, the grain size of the precipitated NiCo 2 S 4 product If it is too large, the electrocatalytic performance will be reduced.

水热反应完成后，本发明优选将所述水热反应的产物依次进行自然冷却、洗涤和干燥，得到含钴和镍的复合电催化剂。After the hydrothermal reaction is completed, in the present invention, the product of the hydrothermal reaction is preferably naturally cooled, washed and dried in sequence to obtain a composite electrocatalyst containing cobalt and nickel.

在本发明中，所述洗涤优选为依次用无水乙醇和去离子水冲洗。本发明对所述冲洗的次数没有特殊的限制，实现完全除去杂质目的即可。本发明对干燥的方式没有特殊的限制，实现除去水分目的即可。In the present invention, the washing is preferably followed by rinsing with absolute ethanol and deionized water. In the present invention, there is no special limitation on the number of washings, as long as the purpose of completely removing impurities is achieved. The present invention has no special limitation on the drying method, as long as the purpose of removing moisture is achieved.

本发明提供的制备方法操作简单，原料来源广泛，成本低廉，反应条件温和，适宜规模化生产，制备的含钴和镍的复合电催化剂，在析氢反应、析氧反应和电解水方面都表现出优异的电催化性能。The preparation method provided by the invention is simple to operate, has wide sources of raw materials, low cost, mild reaction conditions, and is suitable for large-scale production. The prepared composite electrocatalyst containing cobalt and nickel has excellent performance in hydrogen evolution reaction, oxygen evolution reaction and electrolysis of water. Excellent electrocatalytic performance.

本发明还提供了上述技术方案所述制备方法制备得到的含钴和镍的复合电催化剂。在本发明中，所述含钴和镍的复合电催化剂包括碳纤维纸、原位生长在碳纤维纸表面的二硫化钴纳米颗粒、原位生长在碳纤维纸和二硫化钴纳米颗粒表面的四硫化二钴合镍微米球。The present invention also provides a composite electrocatalyst containing cobalt and nickel prepared by the preparation method described in the above technical solution. In the present invention, the composite electrocatalyst containing cobalt and nickel includes carbon fiber paper, cobalt disulfide nanoparticles grown on the surface of carbon fiber paper in situ, disulfide tetrasulfide grown on the surface of carbon fiber paper and cobalt disulfide nanoparticles in situ Cobalt nickel microspheres.

本发明提供的制备方法制备的含钴和镍的复合电催化剂，在析氢反应、析氧反应和电解水方面都表现出优异的电催化性能。The composite electrocatalyst containing cobalt and nickel prepared by the preparation method provided by the invention exhibits excellent electrocatalytic performance in hydrogen evolution reaction, oxygen evolution reaction and water electrolysis.

本发明还提供了上述技术方案所述制备方法制备得到的含钴和镍的复合电催化剂或上述技术方案所述含钴和镍的复合电催化剂在电解水中的应用。The present invention also provides the composite electrocatalyst containing cobalt and nickel prepared by the preparation method described in the above technical solution or the application of the composite electrocatalyst containing cobalt and nickel described in the above technical solution in the electrolysis of water.

下面将结合本发明中的实施例，对本发明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，都属于本发明保护的范围。The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

实施例1Example 1

含钴和镍的复合电催化剂的制备方法：The preparation method of the composite electrocatalyst containing cobalt and nickel:

(1)将碳纤维纸CFP裁切成大小为1cm×1.5cm的小块，对裁剪好的CFP进行去污处理，即分别在丙酮、无水乙醇和去离子水中超声处理10min，然后置于鼓风干燥箱中干燥，然后利用电化学工作站，设置工作电极为去污处理后的CFP，参比电极为饱和甘汞电极(SCE)，对电极为铂片，形成三电极体系，采用0.5M的H2SO4溶液作为电解质，利用循环伏安法对CFP进行亲水处理，亲水处理完成后，将亲水处理后的碳纤维纸依次利用无水乙醇和去离子水冲洗多次后干燥处理，得到预处理的碳纤维纸；(1) Cut the carbon fiber paper CFP into small pieces with a size of 1cm×1.5cm, and decontaminate the cut CFP, that is, ultrasonically treat them in acetone, absolute ethanol, and deionized water for 10 minutes, and then place them in a drum. Dry in an air drying oven, and then use an electrochemical workstation to set the working electrode as decontaminated CFP, the reference electrode as a saturated calomel electrode (SCE), and the counter electrode as a platinum sheet to form a three-electrode system. H 2 SO 4 solution was used as the electrolyte, and the CFP was subjected to hydrophilic treatment by cyclic voltammetry. After the hydrophilic treatment was completed, the carbon fiber paper after the hydrophilic treatment was washed several times with absolute ethanol and deionized water, and then dried. Obtain pretreated carbon fiber paper;

(2)在室温下，将所述步骤(1)得到的预处理的碳纤维纸浸渍到含钴源和硫源的水溶液中30min，使预处理的碳纤维纸与含钴源和硫源的水溶液充分接触，然后将碳纤维纸与含钴源和硫源的水溶液均转移到有聚四氟乙烯内衬的反应釜中，在鼓风干燥箱中180℃下进行水热反应18h，水热反应完成后，将水热反应的产物自然冷却，使用无水乙醇和去离子水冲洗多次，干燥处理后，得到二硫化钴/碳纤维纸即CoS2/CFP；(2) At room temperature, immerse the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source and a sulfur source for 30 minutes, so that the pretreated carbon fiber paper and the aqueous solution containing a cobalt source and a sulfur source are fully Contact, and then transfer the carbon fiber paper and the aqueous solution containing cobalt source and sulfur source to a reaction kettle lined with polytetrafluoroethylene, and perform a hydrothermal reaction at 180 ° C in a blast drying oven for 18 hours. After the hydrothermal reaction is completed , the product of the hydrothermal reaction is naturally cooled, washed with absolute ethanol and deionized water for several times, and dried to obtain cobalt disulfide/carbon fiber paper, namely CoS 2 /CFP;

所述含钴源和硫源的水溶液的制备方法为：量取48mL去离子水置于烧杯中，称取2mmol CoCl2·6H2O和3mmol Na2S2O3·5H2O，放入装有去离子水的烧杯中，使用磁力搅拌器搅拌30min，使其充分溶解，得到含钴源和硫源的水溶液；所述含钴源和硫源的水溶液中钴源CoCl2·6H2O的浓度为4.17×10-2mmol/mL；The preparation method of the aqueous solution containing cobalt source and sulfur source is: measure 48mL deionized water and place it in a beaker, weigh 2mmol CoCl 2 6H 2 O and 3mmol Na 2 S 2 O 3 5H 2 O, put In a beaker with deionized water, use a magnetic stirrer to stir for 30 minutes to fully dissolve it to obtain an aqueous solution containing a cobalt source and a sulfur source; the cobalt source CoCl 2 6H 2 O in the aqueous solution containing a cobalt source and a sulfur source The concentration is 4.17×10 -2 mmol/mL;

(3)将所述步骤(2)得到的二硫化钴/碳纤维纸浸渍到含钴源、镍源和硫源的水溶液中30min，使二硫化钴/碳纤维纸与含钴源、镍源和硫源的水溶液充分接触，将二硫化钴/碳纤维纸与含钴源、镍源和硫源的水溶液均转移到有聚四氟乙烯内衬的反应釜中，在鼓风干燥箱中180℃下进行水热反应10h，水热反应完成后，将水热反应的产物自然冷却，使用无水乙醇和去离子水冲洗多次，干燥处理后，得到含钴和镍的复合电催化剂即NiCo2S4/CoS2/CFP电催化剂；(3) The cobalt disulfide/carbon fiber paper that described step (2) obtains is immersed in the aqueous solution that contains cobalt source, nickel source and sulfur source 30min, makes cobalt disulfide/carbon fiber paper and cobalt source, nickel source and sulfur source The aqueous solution of the source is fully contacted, and the cobalt disulfide/carbon fiber paper and the aqueous solution containing the cobalt source, the nickel source and the sulfur source are all transferred to a reaction kettle lined with polytetrafluoroethylene, and carried out in a blast drying oven at 180 ° C. The hydrothermal reaction was carried out for 10 hours. After the hydrothermal reaction was completed, the product of the hydrothermal reaction was cooled naturally, rinsed with absolute ethanol and deionized water for several times, and dried to obtain a composite electrocatalyst containing cobalt and nickel, namely NiCo 2 S 4 /CoS 2 /CFP electrocatalyst;

所述含钴源、镍源和硫源的水溶液的制备方法为：量取48mL去离子水置于烧杯中，称取6mmol Ni(NO3)2·6H2O、12mmol Co(NO3)2·6H2O和24mmol CH4N2S，放入装有去离子水的烧杯中，使用磁力搅拌器搅拌处理30min，使其充分溶解，得到含钴源、镍源和硫源的水溶液；所述含钴源、镍源和硫源的水溶液中钴源的浓度为0.25mmol/mL；所述含钴源、镍源和硫源的水溶液中镍源、钴源和硫源的物质的量之比为1：2：4；The preparation method of the aqueous solution containing cobalt source, nickel source and sulfur source is: measure 48mL deionized water and place it in a beaker, weigh 6mmol Ni(NO 3 ) 2 6H 2 O, 12mmol Co(NO 3 ) 2 · 6H 2 O and 24mmol CH 4 N 2 S were put into a beaker equipped with deionized water, stirred and treated with a magnetic stirrer for 30 minutes, and fully dissolved to obtain an aqueous solution containing a cobalt source, a nickel source and a sulfur source; The concentration of the cobalt source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is 0.25mmol/mL; The ratio is 1:2:4;

所述步骤(2)中含钴源和硫源的水溶液中钴源和所述步骤(3)中含钴源、镍源和硫源的水溶液中镍源的物质的量之比为1:3。The ratio of the amount of substance of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) to the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source in the step (3) is 1:3 .

对比例comparative example

NiCo2S4/CFP电催化剂的制备方法：Preparation method of NiCo 2 S 4 /CFP electrocatalyst:

(1)将碳纤维纸CFP裁切成大小为1cm×1.5cm的小块，然后利用电化学工作站，设置工作电极为去污处理后的CFP，参比电极为饱和甘汞电极(SCE)，对电极为铂片，形成三电极体系，采用0.5M的H2SO4溶液作为电解质，利用循环伏安法对CFP进行亲水处理，亲水处理完成后，将亲水处理后的碳纤维纸依次利用无水乙醇和去离子水冲洗多次后干燥处理，得到预处理的碳纤维纸；(1) Cut the carbon fiber paper CFP into small pieces with a size of 1cm×1.5cm, and then use the electrochemical workstation to set the working electrode as the CFP after decontamination treatment, and the reference electrode as the saturated calomel electrode (SCE). The electrode is a platinum sheet to form a three-electrode system. Using 0.5M H 2 SO 4 solution as the electrolyte, the CFP is subjected to hydrophilic treatment by cyclic voltammetry. After the hydrophilic treatment is completed, the carbon fiber paper after the hydrophilic treatment is sequentially used Rinse with absolute ethanol and deionized water several times and then dry to obtain pretreated carbon fiber paper;

(2)将所述步骤(1)得到的预处理的碳纤维纸浸渍到含钴源、镍源和硫源的水溶液中30min，使碳纤维纸与含钴源、镍源和硫源的水溶液充分接触，将碳纤维纸与含钴源、镍源和硫源的水溶液均转移到有聚四氟乙烯内衬的反应釜中，在鼓风干燥箱中180℃下进行水热反应10h，水热反应完成后，将水热反应的产物自然冷却，使用无水乙醇和去离子水冲洗多次，干燥处理后，得到NiCo2S4/CFP电催化剂；(2) Immerse the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source, a nickel source and a sulfur source for 30 minutes, so that the carbon fiber paper is fully in contact with the aqueous solution containing a cobalt source, a nickel source and a sulfur source , transfer the carbon fiber paper and the aqueous solution containing cobalt source, nickel source and sulfur source to a reaction kettle lined with polytetrafluoroethylene, and carry out hydrothermal reaction at 180°C in a blast drying oven for 10h, and the hydrothermal reaction is completed Finally, the hydrothermal reaction product was naturally cooled, rinsed with absolute ethanol and deionized water for several times, and dried to obtain the NiCo 2 S 4 /CFP electrocatalyst;

所述含钴源、镍源和硫源的水溶液的制备方法为：量取48mL去离子水置于烧杯中，称取2mmol Ni(NO3)2·6H2O、4mmol Co(NO3)2·6H2O和8mmol CH4N2S，放入装有去离子水的烧杯中，使用磁力搅拌器搅拌处理30min，使其充分溶解，得到含钴源、镍源和硫源的水溶液。The preparation method of the aqueous solution containing cobalt source, nickel source and sulfur source is: measure 48mL deionized water and put it in a beaker, weigh 2mmol Ni(NO 3 ) 2 6H 2 O, 4mmol Co(NO 3 ) 2 Put 6H 2 O and 8 mmol CH 4 N 2 S into a beaker filled with deionized water, and stir for 30 minutes with a magnetic stirrer to fully dissolve them to obtain an aqueous solution containing cobalt sources, nickel sources and sulfur sources.

对实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂进行X射线衍射(XRD)测试，得到XRD图如图1所示；从图1可以发现，除了CFP的强衍射峰外，CoS2/CFP的衍射峰与CoS2的标准PDF卡片(JCPDS No.70-2865)匹配，NiCo2S4/CFP的衍射峰与NiCo2S4的标准PDF卡片(JCPDS No.43-1477)匹配，NiCo2S4/CoS2/CFP电催化剂同时存在CoS2和NiCo2S4的衍射峰，且无其他杂质相的衍射峰，这表明实施例1成功制备了NiCo2S4/CoS2/CFP电催化剂。The CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts prepared in Example 1, and the NiCo 2 S 4 /CFP electrocatalysts prepared in the comparative example were tested by X-ray diffraction (XRD), and the XRD patterns were obtained as shown in the figure 1; it can be found from Figure 1 that, except for the strong diffraction peak of CFP, the diffraction peaks of CoS 2 /CFP match the standard PDF card of CoS 2 (JCPDS No.70-2865), and the diffraction peaks of NiCo 2 S 4 /CFP The peaks match the standard PDF card of NiCo 2 S 4 (JCPDS No.43-1477), and the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst has the diffraction peaks of CoS 2 and NiCo 2 S 4 at the same time, and there is no other impurity phase Diffraction peaks, which indicates that NiCo 2 S 4 /CoS 2 /CFP electrocatalyst was successfully prepared in Example 1.

采用扫描电子显微镜(SEM)对实施例1制备的NiCo2S4/CoS2/CFP电催化剂进行形貌表征，得到SEM图如图2所示；由图2可知，在NiCo2S4/CoS2/CFP电催化剂中存在两种不同的形貌，一是块状的CoS2纳米颗粒紧紧地覆盖在CFP中的碳纤维棒表面，这样的分布有利于促进催化剂与基底之间的电子转移，另一种是在CoS2表面能够清晰地观察到球形的NiCo2S4颗粒，且颗粒尺寸较为均匀。 Scanning electron microscopy (SEM) was used to characterize the morphology of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1, and the obtained SEM image is shown in Figure 2; 2 / There are two different morphologies in the CFP electrocatalyst, one is that the massive CoS2 nanoparticles tightly cover the surface of the carbon fiber rods in the CFP, such a distribution is beneficial to promote the electron transfer between the catalyst and the substrate, The other is that spherical NiCo 2 S 4 particles can be clearly observed on the surface of CoS 2 , and the particle size is relatively uniform.

电化学性能测试：Electrochemical performance test:

(1)利用电化学工作站，在三电极体系中，分别采用实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂作为待测样品，进行析氢和析氧性能测试，具体步骤为：(1) Using an electrochemical workstation, in a three-electrode system, the CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts prepared in Example 1, and the NiCo 2 S 4 /CFP electrocatalysts prepared in Comparative Example were respectively used The catalyst is used as the sample to be tested for hydrogen evolution and oxygen evolution performance tests. The specific steps are:

设置工作电极为待测样品，对电极为石墨棒，在1M KOH电解液中进行电化学性能测试，利用线性伏安法(LSV)测试电催化性能，析氢反应对应的电压区间为-1.6～0V，析氧反应对应的电压区间为0～1.8V，扫描速度为5mV s-1；Set the working electrode as the sample to be tested, and the counter electrode as a graphite rod. The electrochemical performance test is carried out in 1M KOH electrolyte, and the electrocatalytic performance is tested by linear voltammetry (LSV). The voltage range corresponding to the hydrogen evolution reaction is -1.6～0V , the voltage range corresponding to the oxygen evolution reaction is 0-1.8V, and the scanning speed is 5mV s -1 ;

(2)对实施例1制备的NiCo2S4/CoS2/CFP电催化剂的电解水性能进行测试，具体步骤为：(2) Test the water electrolysis performance of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1, the specific steps are:

在两电极体系中，将实施例1制备的NiCo2S4/CoS2/CFP电催化剂分别作为阴极和阳极，电解液为1M KOH溶液，电压窗口为1.2～1.8V，扫描速度为5mV s-1。In the two-electrode system, the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1 was used as the cathode and the anode respectively, the electrolyte was 1M KOH solution, the voltage window was 1.2-1.8V, and the scan speed was 5mV s - 1 .

分别对实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂进行析氢性能测试，得到LSV曲线图如图3所示；由图3可知，在电流密度为10mA cm-2时，CoS2/CFP、NiCo2S4/CFP电催化剂和NiCo2S4/CoS2/CFP电催化剂的析氢过电位分别为310mV、324mV和244mV，可见将CoS2和NiCo2S4复合形成异质结，制备的NiCo2S4/CoS2/CFP电催化剂的析氢性能有了明显的提升，这是因为两者在复合后表现出协同增强作用；The CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts prepared in Example 1, and the NiCo 2 S 4 /CFP electrocatalyst prepared in the comparative example were tested for hydrogen evolution performance, and the LSV curves were obtained as shown in Figure 3 It can be seen from Figure 3 that when the current density is 10mA cm -2 , the hydrogen evolution overpotentials of CoS 2 /CFP, NiCo 2 S 4 /CFP electrocatalysts and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts are 310mV, 324mV and 244mV, it can be seen that the hydrogen evolution performance of the prepared NiCo 2 S 4 /CoS 2 /CFP electrocatalyst has been significantly improved by combining CoS 2 and NiCo 2 S 4 to form a heterojunction. a synergistic effect;

分别对实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂的LSV曲线进行转换，得到Tafel斜率图如图4所示；其中，Tafel斜率是判断催化反应动力学过程快慢的有效手段，由图4可知，CoS2/CFP、NiCo2S4/CFP电催化剂和NiCo2S4/CoS2/CFP电催化剂的Tafel斜率分别为266mV dec-1、171mV dec-1和151mV dec-1。与CoS2/CFP和NiCo2S4/CFP电催化剂相比，NiCo2S4/CoS2/CFP电催化剂的Tafel斜率明显变小，说明NiCo2S4/CoS2/CFP电催化剂具有更快的析氢反应动力学过程；The LSV curves of the CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts prepared in Example 1, and the NiCo 2 S 4 /CFP electrocatalyst prepared in the comparative example were respectively converted to obtain the Tafel slope diagram as shown in Figure 4 shown; among them, the Tafel slope is an effective means to judge the speed of the catalytic reaction kinetic process, as can be seen from Figure 4, CoS 2 /CFP, NiCo 2 S 4 /CFP electrocatalyst and NiCo 2 S 4 /CoS 2 /CFP electrocatalyst The Tafel slopes are 266mV dec -1 , 171mV dec -1 and 151mV dec -1 , respectively. Compared with CoS 2 /CFP and NiCo 2 S 4 /CFP electrocatalysts, the Tafel slope of NiCo 2 S 4 /CoS 2 /CFP electrocatalysts is significantly smaller, indicating that NiCo 2 S 4 /CoS 2 /CFP electrocatalysts have faster The kinetic process of the hydrogen evolution reaction;

分别对实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂进行析氧性能测试，得到LSV曲线图如图5所示；由图5可知，当电流密度为50mA cm-2时，CoS2/CFP、NiCo2S4/CFP电催化剂和NiCo2S4/CoS2/CFP电催化剂的析氧过电位分别为446mV、481mV和367mV，可见，NiCo2S4/CoS2/CFP电催化剂的析氧性能比CoS2/CFP和NiCo2S4/CFP电催化剂的析氧性能更为优异。The oxygen evolution performance test was carried out on the CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts prepared in Example 1, and the NiCo 2 S 4 /CFP electrocatalyst prepared in the comparative example, and the LSV curves were obtained as shown in Figure 5 It can be seen from Figure 5 that when the current density is 50mA cm -2 , the oxygen evolution overpotentials of CoS 2 /CFP, NiCo 2 S 4 /CFP electrocatalyst and NiCo 2 S 4 /CoS 2 /CFP electrocatalyst are respectively 446mV, 481mV and 367mV, it can be seen that the oxygen evolution performance of NiCo 2 S 4 /CoS 2 /CFP electrocatalyst is better than that of CoS 2 /CFP and NiCo 2 S 4 /CFP electrocatalyst.

分别对实施例1制备的CoS2/CFP和NiCo2S4/CoS2/CFP电催化剂，以及对比例制备的NiCo2S4/CFP电催化剂的LSV曲线进行转换，得到Tafel斜率图如图6所示；由图6可知，CoS2/CFP、NiCo2S4/CFP电催化剂和NiCo2S4/CoS2/CFP电催化剂的Tafel斜率分别为221mV dec-1、154mV dec-1和120mV dec-1，NiCo2S4/CoS2/CFP电催化剂的Tafel斜率最小，析氧动力学过程最快。The LSV curves of the CoS 2 /CFP and NiCo 2 S 4 /CoS 2 /CFP electrocatalysts prepared in Example 1, and the NiCo 2 S 4 /CFP electrocatalyst prepared in the comparative example were converted respectively, and the Tafel slope diagram was obtained as shown in Figure 6 It can be seen from Figure 6 that the Tafel slopes of CoS 2 /CFP, NiCo 2 S 4 /CFP electrocatalyst and NiCo 2 S 4 /CoS 2 /CFP electrocatalyst are 221mV dec -1 , 154mV dec -1 and 120mV dec respectively -1 , NiCo 2 S 4 /CoS 2 /CFP electrocatalyst has the smallest Tafel slope and the fastest oxygen evolution kinetics.

对实施例1制备的NiCo2S4/CoS2/CFP电催化剂的电解水性能进行测试，得到LSV曲线图如图7所示，由图7可知，在电流密度为10mA cm-2时，NiCo2S4/CoS2/CFP电催化剂电解水的电位为1.61V，这说明NiCo2S4/CoS2/CFP电催化剂具有优异的电解水催化性能。The water electrolysis performance of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1 was tested, and the LSV curve obtained is shown in Figure 7. It can be seen from Figure 7 that when the current density is 10mA cm -2 , NiCo The electrolysis potential of 2 S 4 /CoS 2 /CFP electrocatalyst was 1.61V, which indicated that NiCo 2 S 4 /CoS 2 /CFP electrocatalyst had excellent catalytic performance for electrolysis of water.

综上所述，与实施例1中的CoS2/CFP、对比例制备的NiCo2S4/CFP电催化剂相比，实施例1制备的NiCo2S4/CoS2/CFP电催化剂在析氢和析氧性能测试中都具有优异的电催化性能，且具有优异的电解水催化性能；在电流密度为10mA cm-2时，实施例1制备的NiCo2S4/CoS2/CFP电催化剂的析氢过电位为244mV，Tafel斜率为151mV dec-1；在电流密度为50mAcm-2时，实施例1制备的NiCo2S4/CoS2/CFP电催化剂的析氧过电位为367mV，Tafel斜率为120mV dec-1；在电流密度为10mA cm-2时，实施例1制备的NiCo2S4/CoS2/CFP电催化剂的电解水的电位为1.61V。In summary, compared with the CoS 2 /CFP in Example 1 and the NiCo 2 S 4 /CFP electrocatalyst prepared in the comparative example, the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1 is more effective in hydrogen evolution and In the oxygen evolution performance test, they all have excellent electrocatalytic performance, and have excellent electrolytic water catalytic performance; when the current density is 10mA cm -2 , the hydrogen evolution of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1 The overpotential is 244mV, and the Tafel slope is 151mV dec -1 ; when the current density is 50mAcm -2 , the oxygen evolution overpotential of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1 is 367mV, and the Tafel slope is 120mV dec -1 ; when the current density is 10mA cm -2 , the electrolyzed water potential of the NiCo 2 S 4 /CoS 2 /CFP electrocatalyst prepared in Example 1 is 1.61V.

以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a composite electrocatalyst containing cobalt and nickel comprises the following steps:
(1) Carrying out hydrophilic treatment on the carbon fiber paper to obtain pretreated carbon fiber paper;
(2) Immersing the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source and a sulfur source, and then carrying out hydrothermal reaction to obtain cobalt disulfide/carbon fiber paper; the sulfur source in the aqueous solution containing the cobalt source and the sulfur source is Na 2 S 2 O 3 ·5H 2 O and Na 2 S·9H 2 One or two of O, wherein the ratio of the mass of the cobalt source to the mass of the sulfur source in the aqueous solution containing the cobalt source and the sulfur source is 1 (2-4);
(3) Immersing the cobalt disulfide/carbon fiber paper obtained in the step (2) into an aqueous solution containing a cobalt source, a nickel source and a sulfur source, and then carrying out hydrothermal reaction to obtain NiCo 2 S 4 /CoS 2 CFP electrocatalyst; the sulfur source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is CH 4 N 2 S and CH 3 CSNH 2 The ratio of the amounts of the substances of the nickel source, the cobalt source and the sulfur source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is 1: (1-3): (3-5);
the ratio of the amount of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) to the amount of the substance of the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source in the step (3) is 1 (0.15-5.5).
2. The method according to claim 1, wherein the hydrophilic treatment in the step (1) is one of electrochemical treatment, thermal oxidation, liquid phase treatment, plasma treatment, and microwave treatment.
3. The method according to claim 1, wherein the cobalt source in the aqueous solution containing a cobalt source and a sulfur source in the step (2) and the cobalt source in the aqueous solution containing a cobalt source, a nickel source and a sulfur source in the step (3) are independently CoCl 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 One or two of O.
4. The method according to claim 1, wherein the concentration of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) is 3.75X10 -2 ～4.60×10 -2 mmol/mL。
5. The method according to claim 1, wherein the hydrothermal reaction in the step (2) is carried out at a temperature of 160 to 200 ℃ for 16 to 20 hours.
6. The method according to claim 1, wherein the temperature of the impregnation in the step (3) is room temperature, and the time of the impregnation is 20 to 40 minutes.
7. The method according to claim 1, wherein the hydrothermal reaction in the step (3) is carried out at a temperature of 170 to 190 ℃ for 8 to 12 hours.
8. The composite electrocatalyst comprising cobalt and nickel prepared by the method of any one of claims 1 to 7.
9. The composite electrocatalyst according to claim 8, comprising carbon fiber paper, cobalt disulfide nanoparticles grown in situ on the surface of the carbon fiber paper, and nickel cobalt tetrasulfide microspheres grown in situ on the surfaces of the carbon fiber paper and cobalt disulfide nanoparticles.
10. Use of the cobalt and nickel containing composite electrocatalyst according to claim 8 for the electrolysis of water.
CN202211039239.0A 2022-08-29 2022-08-29 Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof Active CN115261915B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211039239.0A CN115261915B (en) 2022-08-29 2022-08-29 Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211039239.0A CN115261915B (en) 2022-08-29 2022-08-29 Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115261915A CN115261915A (en) 2022-11-01
CN115261915B true CN115261915B (en) 2023-07-07

Family

ID=83755606

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211039239.0A Active CN115261915B (en) 2022-08-29 2022-08-29 Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115261915B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116272424B (en) * 2023-04-20 2024-04-26 中国长江三峡集团有限公司 CuFeS2Modified catalytic ceramic membrane and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108411324A (en) * 2018-03-29 2018-08-17 华南理工大学 The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application
CN109518219A (en) * 2018-12-24 2019-03-26 江苏大学 A kind of preparation method and applications of graphene-based nickel cobalt bimetallic oxygen-separating catalyst
CN110714209A (en) * 2019-10-21 2020-01-21 太原理工大学 Cobalt-nickel hydroxide sleeve type modified carbon fiber composite material and preparation method and application thereof
CN111111699A (en) * 2019-09-30 2020-05-08 天津大学 Nickel-cobalt disulfide composite material and preparation method and application thereof
CN111180216A (en) * 2020-01-15 2020-05-19 兰州理工大学 A kind of composite material for supercapacitor and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108411324A (en) * 2018-03-29 2018-08-17 华南理工大学 The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application
CN109518219A (en) * 2018-12-24 2019-03-26 江苏大学 A kind of preparation method and applications of graphene-based nickel cobalt bimetallic oxygen-separating catalyst
CN111111699A (en) * 2019-09-30 2020-05-08 天津大学 Nickel-cobalt disulfide composite material and preparation method and application thereof
CN110714209A (en) * 2019-10-21 2020-01-21 太原理工大学 Cobalt-nickel hydroxide sleeve type modified carbon fiber composite material and preparation method and application thereof
CN111180216A (en) * 2020-01-15 2020-05-19 兰州理工大学 A kind of composite material for supercapacitor and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Fabrication of hierarchical NiCo2S4@CoS2 nanostructures on highly conductive flexible carbon cloth substrate as a hybrid electrode material for supercapacitors with enhanced electrochemical performance;Mani Govindasamy et al.;Electrochimica Acta;第328-337页 *
Superdispersed NiCo2S4 nanoparticles anchored on reduced graphene oxide for efficient hydrogen evolution reaction in acidic and alkaline media;Xiong Chen et al.;Journal of Alloys and Compounds;第1-10页 *

Also Published As

Publication number Publication date
CN115261915A (en) 2022-11-01

Similar Documents

Publication Publication Date Title
CN112023946A (en) A kind of preparation method of self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst
Senthil et al. Nickel foam-supported NiFe layered double hydroxides nanoflakes array as a greatly enhanced electrocatalyst for oxygen evolution reaction
CN108736031A (en) A kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof
CN113019398B (en) High-activity self-supporting OER electrocatalyst material and preparation method and application thereof
CN110838588B (en) A kind of rechargeable zinc-air battery bifunctional catalyst and its preparation method and application
CN107502919A (en) A kind of sulfur doping catalyst of phosphatizing nickel for Hydrogen evolving reaction and preparation method thereof
CN112951623B (en) Copper-cobalt-zinc composite self-supporting nano array electrode material and preparation method and application thereof
CN110711583A (en) A kind of high-efficiency electrocatalyst material with three-dimensional structure, preparation method and application thereof
CN113512738A (en) Ternary iron-nickel-molybdenum-based composite catalyst for water electrolysis, preparation method and application thereof
CN118186400A (en) A method for preparing a transition metal-based electrocatalytic water decomposition anode catalyst material and its application
Feng et al. Simple cathodic deposition of FeS/NiS-activated Ni/NiO heterojunctions for high-concentration overall water splitting reactions
CN115261915B (en) Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof
CN110813330A (en) Co-Fe @ FeF catalyst and two-dimensional nano-array synthesis method
CN118390103A (en) A self-supporting nickel-iron hydrotalcite/graphene oxygen evolution electrocatalyst and its preparation method and application
CN110721700B (en) Copper-cobalt-sulfur nanosheet array/molybdenum foil composite material, and preparation method and application thereof
CN110137523A (en) A kind of new hydrogen production hydrazine hydrate fuel-cell device
CN115466980B (en) Nickel foam loaded with nickel sulfide as urea oxidation catalyst electrode and preparation method thereof
CN114990568B (en) Ni is loaded on foam nickel 3 S 2 Electrocatalytic electrode of-C, preparation method and application thereof
CN117352751A (en) A self-supporting electrode for urea fuel cell and preparation method thereof
CN116855996A (en) Synthesis method of oxygen-enriched vacancy ruthenium/nickel molybdate material and application of oxygen-enriched vacancy ruthenium/nickel molybdate material in hydrogen evolution reaction in seawater
CN117089881A (en) Preparation method of Pt nanoparticle modified bimetallic LDH catalyst and industrial current density electrolyzed water application thereof
CN112007647B (en) Nano nickel-iron hydroxide film and preparation method and application thereof
CN115094436A (en) A kind of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell structure catalytic material and preparation method and application thereof
CN115295813A (en) Preparation method and application of hydrotalcite-based self-supporting electrode material
CN114438544A (en) Preparation method of nickel-cobalt alloy @ nickel-cobalt oxide solid solution core-shell structure dual-functional electrocatalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant