CN111640952B - Ferroferric sulfide electrode material and preparation method and application thereof - Google Patents

Ferroferric sulfide electrode material and preparation method and application thereof Download PDF

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CN111640952B
CN111640952B CN202010477114.0A CN202010477114A CN111640952B CN 111640952 B CN111640952 B CN 111640952B CN 202010477114 A CN202010477114 A CN 202010477114A CN 111640952 B CN111640952 B CN 111640952B
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electrode material
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sulfide electrode
ferroferric sulfide
water
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CN111640952A (en
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韩晓鹏
马志慧
费峻桢
王鹏宇
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Saidiga Shandong Technology Co ltd
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses ferroferric sulfideThe invention discloses an electrode material and a preparation method and application thereof, and relates to the field of water decomposition electrocatalysis. The material is a petal-shaped structure formed by combining nanosheet crystals, the specific surface area is large, and the particle size of the nanosheets is 50-200 nm. At 10mA cm‑2The overpotential of hydrogen evolution is 210-230 mV under the current density, the electrocatalysis performance is good, the chemical stability is strong, and the cost is low. The preparation method is simple and easy to implement, the process is controllable, and the method has wide application prospect in hydrogen production by electrocatalysis full decomposition of water.

Description

Ferroferric sulfide electrode material and preparation method and application thereof
Technical Field
The invention relates to the field of water decomposition electrocatalysis, in particular to a ferroferric sulfide electrode material and a preparation method and application thereof, and especially relates to a nano-scale ferroferric sulfide material and a preparation method and application thereof.
Background
At present, the excessive use of fossil fuel brings huge pressure on energy and environment, and the application and the development of hydrogen energy as a clean, efficient and sustainable new energy source become the focus of attention in the 21 st century. Nowadays, electrochemical full-hydrolysis hydrogen production develops rapidly, but the bottlenecks faced by the electrochemical full-hydrolysis hydrogen production are as follows: the catalyst has poor stability and rapid activity attenuation; the chlorine evolution side reaction caused by local pH value change is excessive, corrosion and insoluble substance generation, so that the hydrogen and oxygen preparation by the hydro-electro-catalysis must be carried out in a near-neutral environment. Therefore, a high-performance self-supporting electrode is constructed, and finally, stable and high-selectivity electrocatalytic full-decomposition seawater hydrogen production is urgently realized.
Metal sulfides have higher electrical conductivity and thermal stability compared to metal oxides, with transition metal sulfide materials gaining attention in the process. It has abundant reserves, low price, unique structure and physical and chemical properties. Among these, iron polysulfide is a more important material. The iron polysulfide has rich oxidation-reduction property and excellent electrochemical property. Iron is used as a transition metal element, so that more electron holes can be provided, the energy band structure can be regulated, the electron transmission efficiency can be improved, the active sites can be increased, the activation energy can be reduced, and the material can show extremely high electrolytic water catalytic activity.
Chinese patent with publication No. CN110627132A discloses a method for preparing iron disulfide nano hollow spheres, which uses sulfur powder and ferric stearate as raw materials, uses liquid paraffin as reaction solution, prepares iron sulfide nano particles with different sizes by a solvothermal method, and utilizes a surfactant to make the iron sulfide nano particles into a hollow structure, the size of the iron sulfide nano particles is 10-200 nm, and the iron sulfide nano particles have good crystallinity and dispersibility.
The Chinese patent with publication number CN106784829A discloses a preparation method of a microbial fuel cell anode loaded with a graphene and iron disulfide compound, which is characterized in that based on a hydrothermal method, aerogels with different mechanical strengths are obtained by controlling the proportion of raw materials and loaded on a current collector to prepare the microbial fuel cell anode; the microbial fuel cell can be started up quickly and obtain higher voltage and power density.
The Chinese patent with publication number CN102817081A discloses a preparation method of a sheet ferroferric sulfide nano single crystal, which adopts a high boiling point solvent, namely oleylamine, and selects different sulfur sources and iron sources to control the phase purity of the product, and the product has uniform particle size and morphology and good process repeatability.
However, the product prepared by the preparation method has larger particle size, higher raw material cost, difficult obtainment and more complicated reaction operation. When the reaction is carried out by a hydrothermal method, the problems of low product yield, more impurities, large particle size and the like are often caused by insufficient contact of raw materials.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for preparing a ferroferric sulfide electrode material with high purity, small particle size and good electrochemical performance by a convenient and controllable hydrothermal method in a mode of adding an organic additive, namely ethylenediamine, in a certain sequence and fully stirring to increase the contact between a sulfur source and an iron source, and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme: the ferroferric sulfide electrode material comprises an iron source and a sulfur source, wherein the stoichiometric molar ratio of sulfur to iron is 2: 1-1: 4, preferably 1: 1-1: 2; the iron source comprises water-soluble ferrous salt, and the sulfur source comprises carbon disulfide;
preparing an iron source and a sulfur source before synthesis, and preparing the ferroferric sulfide electrode material by a high-temperature hydrothermal method, wherein the ferroferric sulfide electrode material is a petal-shaped structure formed by nano-sheet crystals, the specific surface area is large, and the particle size of the nano-sheet is 50-200 nm, preferably 100-200 nm.
Preferably, the ferroferric sulfide electrode material is 10 mA-cm-2The overpotential for hydrogen evolution is 210-230 mV at the current density of (1).
A preparation method of a ferroferric sulfide electrode material comprises the following steps:
A. preparation before synthesis: taking an iron source and a sulfur source according to a stoichiometric ratio, dissolving the iron source in deionized water or a water and ethanol solvent with a volume ratio of 1:1, adding ethylenediamine, uniformly stirring, adding the sulfur source, and continuously stirring to obtain a suspension;
B. synthesizing: placing the suspension in a high-temperature closed environment for reaction;
C. and (3) post-reaction treatment: and after the reaction is finished, naturally cooling to room temperature to obtain black precipitate, washing for a plurality of times by sequentially adopting deionized water and an organic reagent, centrifuging to obtain black powder, and freeze-drying to obtain the ferroferric sulfide electrode material.
Preferably, the step a specifically includes the following steps: preparation before synthesis: taking an iron source and a sulfur source according to a stoichiometric ratio, dissolving the iron source in deionized water or water contained in a tetrafluoroethylene liner: adding ethylenediamine into a solvent with the ratio of ethanol to ethanol being 1:1, sealing and stirring for 10-40 min, preferably 10-30 min, then adding a sulfur source, and continuing to seal and stir for 10-40 min to obtain a suspension, preferably 10-30 min, wherein the rotation speed range of stirring is 400-800 r/min. The rotating speed is too low, so that the reactants are difficult to be uniformly and fully distributed and contacted; too high a rotational speed will increase the degree of oxidation of the ferrous iron. The optimal rotating speed is 800r/min, the stirring time is too short, and reactants are not distributed uniformly and cannot be fully contacted; too long a stirring time will increase the oxidation degree of ferrous iron. The optimal stirring time is 20 min.
Preferably, the iron source comprises a water-soluble ferrous salt, and the water-soluble ferrous salt comprises one of ferrous sulfate heptahydrate, ferrous nitrate and ferrous chloride; the sulfur source comprises carbon disulfide.
Preferably, the stoichiometric ratio of the sulfur element to the iron element is 2: 1-1: 4, preferably 1: 1-2: 1; the excessive sulfur element causes more sulfur to remain without participating in the reaction after the hydrothermal reaction, and excessive irritant gas is generated; if the amount is too small, it is difficult to synthesize a definite phase of pyrite. The optimum molar ratio of S to Fe is 5 to 4.
Preferably, the addition amount of the ethylenediamine in each mole of the iron source is 300-600 mL, preferably 400-600 mL, and the addition amount of the ethylenediamine is less than 300mL per mole of the iron source, so that an effective agglomeration effect cannot be achieved, and a sufficient amount of ferroferric sulfide cannot be synthesized easily. More than 600mL does not work well for the reaction and also causes contamination. The optimum amount of ethylenediamine added is 400mL per mole of iron.
Preferably, the temperature of the high-temperature closed environment in the step B is 120-220 ℃, and preferably 150-180 ℃; the reaction time is 6-15 hours, preferably 8-10 hours. The sulfur source and the iron source are difficult to react fully to synthesize the ferro-sulphur compound at the temperature of less than 120 ℃. The temperature is higher than 220 ℃ to obtain excessive impurities and impurities of the sample phase. The optimum temperature is 180 ℃. The reaction time is less than 6h, the reaction is insufficient, and if the reaction time is too long, the crystal grains become large, the specific surface area becomes small, and the reaction time is optimal for 9 h.
Preferably, the organic solvent in step C comprises one or more of ethanol and acetone, and the freeze drying is specifically freeze drying at-60 ℃ for 12 h.
The application of the ferroferric sulfide electrode material in preparing a self-supporting catalytic electrode in preparing hydrogen by electrocatalysis full decomposition of water.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the method adopts a one-step hydrothermal method to prepare the nano ferroferric sulfide crystal, has low cost and simple process, does not need protective gas, and has good and stable electrochemical performance of the synthesized product;
(2) in preparation before synthesis, sealing is carried out during stirring, so that water-soluble ferrous salt in the raw materials is prevented from deteriorating before high-temperature and high-pressure reaction is carried out, and smooth reaction is ensured;
(3) after the iron source is added, adding the organic additive ethylenediamine and fully stirring, then adding the sulfur source and fully stirring, so that the raw materials are more fully contacted, reaction sites are increased, and the particle size of the product is finer and more uniform;
(4) the obtained ferroferric sulfide electrode material has the particle size of 50-200 nm, is a nano-scale crystal grain with a large surface area, can greatly accelerate reaction kinetics, and has the particle size of 10 mA-cm-2The overpotential of hydrogen evolution is 210-230 mV under the current density of the power grid, so that the energy is efficiently utilized;
(5) the hydrothermal method is simple and easy to realize, and is put into the high-efficiency production of the electrode material for electrolyzing water and hydrogen, so that the pressure on energy and environment is relieved. By utilizing the characteristics of solvent boiling and slightly soluble sulfur of a hydrothermal method, nano-scale crystal grains can be easily obtained by adjusting process parameters, the crystal grains are relatively complete in development and relatively uniform in particle size distribution, and relatively ideal stoichiometric composition can be obtained;
(6) the invention prepares the nano-scale pyrite compound and explores the application of the nano-scale pyrite compound as an electro-catalytic full-decomposition seawater electrode material, improves the exposure of catalytic active sites by utilizing the unique electrode structure on the basis of low cost, promotes mass and charge transmission, enhances the mechanical and chemical stability, constructs a high-performance self-supporting electrode, and finally realizes the stable and high-selectivity electro-catalytic full-decomposition seawater hydrogen production.
Drawings
FIG. 1 is an SEM image of an iron sulfide electrode material and a preparation method thereof in example 2 of the present invention;
FIG. 2 is an XRD curve of a ferroferric sulfide electrode material and a preparation method thereof in example 2 of the present invention;
FIG. 3 is a hydrogen evolution performance curve of a ferroferric sulfide electrode material and a ferroferric sulfide electrode material prepared by the preparation method in embodiment 3 of the invention;
fig. 4 is an oxygen evolution performance curve of a ferroferric sulfide electrode material and a ferroferric sulfide electrode material prepared by the preparation method in embodiment 3 of the invention.
Detailed Description
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, which ranges of values are to be considered as specifically disclosed herein, the invention is described in detail below with reference to specific examples:
example 1
A ferroferric sulfide electrode material and a preparation method thereof comprise the following steps: firstly, weighing 0.56g of ferrous sulfate heptahydrate and pouring into a polytetrafluoroethylene lining filled with 35mL of deionized water; sucking 1200 mu L of ethylenediamine by a pipette gun, adding the ethylenediamine into the solution, sealing, and magnetically stirring at the rotating speed of 800r/min for 10 min; and (3) sucking 800 mu L of carbon disulfide by using a liquid transfer gun, adding the carbon disulfide into the solution (the molar ratio of S to Fe is 1:1, 600mL of ethylenediamine is added into each mole of iron source), continuously stirring at the rotating speed of 800r/min in a sealing manner for 10min, sealing the stirred liquid in a reaction kettle, transferring the reaction kettle into an oven, and preserving the heat at 220 ℃ for 6 h. Naturally cooling, sequentially washing with water, ethanol and water to remove impurities, centrifuging to collect a sample, and freeze-drying for 9 h.
In the scanning electron microscope images of the above examples, the particles are of a sheet structure with a particle size of 50-150 nm, and the ferroferric sulfide is obtained by X-ray powder diffraction.
Example 2
A ferroferric sulfide electrode material and a preparation method thereof comprise the following steps: firstly, weighing 0.56g of ferrous sulfate heptahydrate and pouring into a polytetrafluoroethylene lining filled with 35mL of deionized water; absorbing 800 mu L of ethylenediamine by a pipette gun, adding the ethylenediamine into the solution, sealing, and magnetically stirring at the rotating speed of 600r/min for 20 min; and (3) sucking 800 mu L of carbon disulfide by using a liquid-moving gun, adding the carbon disulfide into the solution (the molar ratio of S to Fe is 1:1, and 400mL of ethylenediamine is added into each mol of iron source), continuously stirring at the rotating speed of 600r/min in a sealing manner for 20min, sealing the stirred liquid in a reaction kettle, transferring the reaction kettle into an oven, and preserving the heat at 180 ℃ for 12 h. Naturally cooling, sequentially washing with water, ethanol and water to remove impurities, centrifuging to collect a sample, and freeze-drying for 9 h.
The scanning electron microscope image of the ferroferric sulfide prepared by the embodiment is shown in fig. 1, and the appearance of the ferroferric sulfide is a flower-shaped structure formed by flaky crystals. The XRD pattern is shown in FIG. 2, which shows that the product component is ferroferric sulfide, and corresponds to JCPDS standard card 16-0713.
Example 3
A ferroferric sulfide electrode material and a preparation method thereof comprise the following steps: firstly, weighing 0.56g of ferrous sulfate heptahydrate and pouring into a polytetrafluoroethylene lining filled with 35mL of deionized water; absorbing 800 mu L of ethylenediamine by a pipette gun, adding the ethylenediamine into the solution, sealing, and magnetically stirring at the rotating speed of 800r/min for 20 min; and (3) sucking 1000 mu L of carbon disulfide by using a liquid transfer gun, adding the carbon disulfide into the solution (the mol ratio of S to Fe is 5:4, and 400mL of ethylenediamine is added into each mol of iron source), continuously stirring at the rotating speed of 800r/min in a sealing manner for 20min, sealing the stirred liquid in a reaction kettle, transferring the reaction kettle into an oven, and preserving the heat at 180 ℃ for 9 h. Naturally cooling, sequentially washing with water, ethanol and water to remove impurities, centrifuging to collect a sample, and freeze-drying for 9 h.
In the scanning electron microscope images of the above examples, the particles are sheet structures with a particle size of 100-200 nm, and the ferroferric sulfide is obtained by X-ray powder diffraction.
The prepared ferroferric sulfide, a binder and water are prepared into electrode slurry according to a proportion, wherein the amount of the active substance, the amount of the water and the amount of the binder are respectively 10mg, 965 mu L and 35 mu L. And coating 150 mu L of prepared electrode slurry on 1 x 1cm of carbon cloth to form a three-electrode system in an alkaline system as a working electrode for testing the performance of electrochemical hydrogen precipitation/oxygen precipitation, wherein a saturated calomel electrode is used as a reference electrode, a carbon rod is used as a counter electrode, and 1.0mol/L KOH solution is used as electrolyte to form the three-electrode system.
And (3) researching the electrochemical performance of ferroferric sulfide.
FIGS. 3 and 4 are graphs showing the hydrogen evolution and oxygen evolution performances of the ferroferric sulfide material prepared in example 3 in 1.0mol/LKOH, respectively. It can be seen that: the ferroferric sulfide material related to the invention is 10mA cm-2The overpotential for hydrogen evolution is 210-230 mV under the current density of (1), and the electrochemical performance is excellent.
Example 4
A ferroferric sulfide electrode material and a preparation method thereof comprise the following steps: firstly, weighing 0.56g of ferrous sulfate heptahydrate and pouring into a polytetrafluoroethylene lining filled with 35mL of deionized water; absorbing 600 mu L of ethylenediamine by a pipette gun, adding the ethylenediamine into the solution, sealing, and magnetically stirring at the rotating speed of 400r/min for 40 min; and (3) sucking 200 mu L of carbon disulfide by using a liquid transfer gun, adding the carbon disulfide into the solution (the mol ratio of S to Fe is 1:4, and 400mL of ethylenediamine is added into each mol of iron source), continuously stirring at a rotating speed of 400r/min in a sealing manner for 40min, sealing the stirred liquid in a reaction kettle, transferring the reaction kettle into an oven, and preserving the heat at 120 ℃ for 10 h. Naturally cooling, sequentially washing with water, ethanol and water to remove impurities, centrifuging to collect a sample, and freeze-drying for 9 h.
In the scanning electron microscope images of the above examples, the particles are sheet structures with a particle size of 50-200 nm, and the ferroferric sulfide is obtained by X-ray powder diffraction.
Example 5
A ferroferric sulfide electrode material and a preparation method thereof comprise the following steps: firstly, weighing 0.56g of ferrous sulfate heptahydrate and pouring into a polytetrafluoroethylene lining filled with 35mL of solution with the ratio of deionized water to ethanol being 1: 1; absorbing 800 mu L of ethylenediamine by a pipette gun, adding the ethylenediamine into the solution, sealing, and magnetically stirring at the rotating speed of 600r/min for 20 min; and (3) sucking 1600 mu L of carbon disulfide by using a liquid-moving gun, adding the carbon disulfide into the solution (the mol ratio of S to Fe is 2:1, and 400mL of ethylenediamine is added into each mol of iron source), continuously stirring at the rotating speed of 600r/min in a sealing manner for 20min, sealing the stirred liquid in a reaction kettle, transferring the reaction kettle into an oven, and preserving the heat at 180 ℃ for 15 h. Naturally cooling, sequentially washing with water, ethanol and water to remove impurities, centrifuging to collect a sample, and freeze-drying for 9 h.
In the scanning electron microscope images of the above examples, the particles are sheet structures with a particle size of 100-200 nm, and the ferroferric sulfide is obtained by X-ray powder diffraction.
Comparative example 1
A ferroferric sulfide electrode material and a preparation method thereof comprise the following steps: the difference from example 1 is that the stoichiometric ratio of elemental sulfur to elemental iron is 1:10, and the other conditions are the same as example 1. Resulting in a high product impurity with a product pyrite ratio that is biased toward 1:1 rather than 4: 3.
Comparative example 2
A ferroferric sulfide electrode material and a preparation method thereof comprise the following steps: the difference from the embodiment 3 is that the stirring is not sealed before the synthesis in the step A, other experimental conditions are the same, the ferrous iron oxidation is serious, the phase impurity ferric oxide obtained by XRD of the obtained product is greatly increased, and the molar content of oxygen element obtained by EDS is more than 20%.
Comparative example 3
A ferroferric sulfide electrode material and a preparation method thereof comprise the following steps: the difference from the example 3 is that the sulfur source is thiourea, the other test conditions are not changed, the obtained product is seriously oxidized, and the sulfur element and the iron element can not react.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (10)

1. The ferroferric sulfide electrode material is characterized by being prepared by the following preparation method, and the preparation method comprises the following steps:
A. preparation before synthesis: taking an iron source and a sulfur source according to a stoichiometric ratio, dissolving the iron source in deionized water or a water and ethanol solvent with a volume ratio of 1:1, adding ethylenediamine, uniformly stirring, adding the sulfur source, and continuously stirring to obtain a suspension; wherein the stoichiometric molar ratio of the sulfur element to the iron element is 2: 1-1: 4; the iron source comprises water-soluble ferrous salt, and the sulfur source comprises carbon disulfide;
B. synthesizing: placing the suspension in a high-temperature closed environment at 120-220 ℃ for reaction;
C. and (3) post-reaction treatment: after the reaction is finished, naturally cooling to room temperature to obtain black precipitate, washing for a plurality of times by sequentially adopting deionized water and an organic reagent, centrifuging to obtain black powder, and freeze-drying to obtain the ferroferric sulfide electrode material; the ferroferric sulfide electrode material is in a petal-shaped structure formed by nano-sheet crystals, and the particle size of the nano-sheets is 50-200 nm.
2. The ferroferric sulfide electrode material according to claim 1, wherein the ferroferric sulfide electrode material is at 10 mA-cm-2The overpotential for hydrogen evolution is 210-230 mV at the current density of (1).
3. A method for preparing a ferroferric sulfide electrode material according to claim 1 or 2, comprising the following steps:
A. preparation before synthesis: taking an iron source and a sulfur source according to a stoichiometric ratio, dissolving the iron source in deionized water or a water and ethanol solvent with a volume ratio of 1:1, adding ethylenediamine, uniformly stirring, adding the sulfur source, and continuously stirring to obtain a suspension;
B. synthesizing: placing the suspension in a high-temperature closed environment at 120-220 ℃ for reaction;
C. and (3) post-reaction treatment: and after the reaction is finished, naturally cooling to room temperature to obtain black precipitate, washing for a plurality of times by sequentially adopting deionized water and an organic reagent, centrifuging to obtain black powder, and freeze-drying to obtain the ferroferric sulfide electrode material.
4. The preparation method of the ferroferric sulfide electrode material according to claim 3, wherein the step A specifically comprises the following steps: preparation before synthesis: taking an iron source and a sulfur source according to a stoichiometric ratio, dissolving the iron source in deionized water or water contained in a tetrafluoroethylene liner: adding ethylenediamine into a solvent with the ethanol ratio of =1:1, sealing and stirring for 10-40 min, uniformly mixing, then adding a sulfur source, and continuing to seal and stir for 10-40 min to obtain a suspension, wherein the stirring rotating speed ranges from 400r/min to 800 r/min.
5. The preparation method of the ferroferric sulfide electrode material according to claim 3, wherein the iron source comprises a water-soluble ferrous salt, and the water-soluble ferrous salt comprises one of ferrous sulfate heptahydrate, ferrous nitrate and ferrous chloride; the sulfur source comprises carbon disulfide.
6. The preparation method of the ferroferric sulfide electrode material according to claim 3, wherein the stoichiometric molar ratio of sulfur to iron is 2: 1-1: 4.
7. The preparation method of the ferroferric sulfide electrode material according to claim 3, wherein the addition amount of the ethylenediamine in each mole of iron source is 300-600 mL.
8. The preparation method of the ferroferric sulfide electrode material according to claim 3, wherein the reaction time in the high-temperature closed environment in the step B is 6-15 hours.
9. The preparation method of the ferroferric sulfide electrode material according to claim 3, wherein the organic solvent in the step C comprises one or more of ethanol and acetone, and the freeze drying is specifically freeze drying at-60 ℃ for 12 hours.
10. The application of the ferroferric sulfide electrode material as claimed in claim 1 or 2, wherein the application of the self-supporting catalytic electrode prepared from the ferroferric sulfide electrode material in electrocatalysis of hydrogen production by full decomposition of water.
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