CN113279007A - High temperature phase nano alpha-MoB2Electrode preparation method - Google Patents

High temperature phase nano alpha-MoB2Electrode preparation method Download PDF

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CN113279007A
CN113279007A CN202110359479.8A CN202110359479A CN113279007A CN 113279007 A CN113279007 A CN 113279007A CN 202110359479 A CN202110359479 A CN 202110359479A CN 113279007 A CN113279007 A CN 113279007A
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CN113279007B (en
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张继业
张存哲
王亮
骆军
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University of Shanghai for Science and Technology
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Abstract

The invention discloses a high-temperature phase nano alpha-MoB2The preparation method of the electrode comprises the high-temperature phase alpha-MoB2High-energy mechanical alloying synthesis of nano particles and subsequent electrode plate sintering and assembling method. Taking M in an argon protective glove boxAnd (3) o powder and B powder are mixed according to the atomic ratio of 1: 2, sealing the mixture and a certain amount of ball-milling balls into a stainless steel ball-milling tank; then placing the ball milling tank in a high-energy ball mill for ball milling; then the high-temperature phase alpha-MoB obtained by ball milling is treated2Placing the nano-particle powder in a graphite die, and sintering into a sheet by using a discharge plasma sintering method; and adhering the sheet sample obtained by sintering on a copper sheet by using conductive silver paste, and drying to prepare the electrode for the electrocatalytic reaction. The preparation material of the invention has simple process, does not relate to high temperature and high pressure, and is suitable for large-scale industrial production. The hydrogen evolution reaction electro-catalytic electrode prepared by the method has higher catalytic performance which is 10mA/cm2The overpotential is not higher than 105mV (vs. RHE), and the catalyst has high electrocatalytic activity.

Description

High temperature phase nano alpha-MoB2Electrode preparation method
Technical Field
The invention belongs to the technical field of energy materials, and relates to a high-temperature phase nano alpha-MoB with high electrocatalytic activity2The electrode preparation method is applied to the cathode HER hydrogen evolution reaction of water electrolysis reaction under acidic condition.
Background
With the development of human society, non-renewable fossil fuels are gradually exhausted, which causes many problems such as energy crisis and environmental deterioration, and it is necessary to find a new clean energy as a substitute thereof. Hydrogen (H)2) The energy storage medium is an excellent energy storage medium as an ideal clean energy carrier. At present stage H2The preparation of (a) still requires a fossil fuel steam reforming process to achieve, and therefore there is an urgent need to find a pollution-free, low-cost production method. Therefore, people utilize the electrolyzed water to generate hydrogen, but because the catalyst used by the electrolyzed water is a noble metal which is expensive and has less crustal content, the development of the electrolyzed water technology is not facilitated, so that a novel, efficient and relatively rich crustal content element is urgently needed to be found to replace the noble metal catalyst so as to reduce the hydrogen evolution potential in the reaction process.
In the past decades, researchers have made tremendous efforts to develop transition metal-based electrocatalysts as an alternative to noble metal electrocatalysts. Research on the catalytic properties of transition metal sulfides, transition metal carbides, transition metal phosphides and transition metal nitrides HER has also been actively conducted. The transition metal boride is a gap compound, and because the radius of B atoms is small, the B atoms are easily filled into gaps of metal lattices to form the compound, so that the metal atoms can keep the original metal bond connection mode to a great extent. Meanwhile, the number of electrons, electronegativity, ionization energy, unique outer-layer electron arrangement and the diversity of electron transfer number between transition metal and B atoms of B all determine the bonding mode and bonding strength of chemical bonds in the transition metal boride, and finally, the abundant crystal structure and potential catalytic multifunctional property of the transition metal boride are caused.
Among these borides, materials containing graphene-like flat boron layers, e.g. alpha-MoB2、FeB2And VB2HER activity was highest. Subsequently, researchers studied the effect of the graphene-like flat B layer on catalytic activity, and in transition metal molybdenum boride, calculation based on DFT free energy and experimental results showed that the graphene-like boron layer has higher HER activity, while the phosphoene-like boron layer has much lower activity. Thus, in recent years, α -MoB in molybdenum borides with graphene-like flat boron layers2Has received much attention due to its potentially high catalytic performance. However, alpha-MoB2The existing synthesis is mainly a high-temperature high-pressure or arc melting method, the temperature needs 1500K-2100K, the pressure is 1 GPa-6 GPa, the reaction conditions are severe, the control of the stoichiometric ratio of a sample is difficult, and alpha-MoB2The yield is low. Therefore, there is a need to develop a low cost synthetic method suitable for industrial scale applications.
Disclosure of Invention
Aiming at solving the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a high-temperature phase nano alpha-MoB2The electrode preparation method, the preparation material of the invention, has simple process, does not involve high temperature and high pressure, and is suitable for large-scale industrialized production. The hydrogen evolution reaction electro-catalytic electrode prepared by the method has higher catalytic performance which is 10mA/cm2The overpotential at time is not higher than 105mV (vs. RHE).
In order to achieve the purpose, the invention adopts the following technical scheme:
high-temperature phase nano alpha-MoB2The electrode preparation method comprises the following steps:
(1) in an argon glove box, according to the atomic ratio of Mo to B of 1: 2, weighing Mo simple substance and B simple substance powder raw materials, and sealing the raw materials and the ball-milling balls into a ball-milling tank; the purities of the Mo simple substance and the B simple substance are not lower than 99.9%;
(2) putting the ball milling tank obtained in the step (1) into a high-energy ball mill for ball milling, and performing mechanical alloying reaction to obtain high-temperature phase alpha-MoB2The nano-powder of (1);
(3) after the mechanical alloying reaction in the step (2) is finished, taking out the nano powder in an argon glove box, putting the nano powder into a graphite mold, and sintering the nano powder into a sheet material by using a discharge plasma sintering method;
(4) adopting a binder to adhere the flaky material obtained by sintering in the step (3) on a copper sheet with the thickness of 0.3-0.5 mm, packaging the rest of the copper sheet except for the exposed surface of the flaky material by using epoxy resin, and drying to obtain the combined high-temperature phase nano alpha-MoB2The electrocatalytic working electrode of the sheet is sintered.
Preferably, in the step (1), the ball-to-material ratio in the ball milling tank is 4: 1-3: 1.
preferably, in the step (1), the step (2) and the step (3), the weighing, canning and sampling are all completed in an argon glove box, and the powder is kept in a water-and oxygen-insulated environment.
Preferably, in the step (2), the mechanical alloying reaction time is 80-130 hours, and the obtained powder is high-temperature phase alpha-MoB with the particle size of 100-300 nanometers2. Further preferably, the mechanical alloying reaction time is 100 hours.
Preferably, in the step (3), the spark plasma sintering temperature is 650-800 ℃, the sintering pressure is not higher than 50MPa, the heating rate is not lower than 50 ℃/min, and the heat preservation time is not less than 30 minutes. Further preferably, the sintering temperature is 750-800 ℃.
Preferably, in the step (2), the ball mill used is a three-dimensional vibration high-energy ball mill.
Preferably, in the step (4), the adhesive for bonding the sheet material and the copper sheet is conductive silver paste.
Preferably, in the step (3), the grain size of the prepared sheet material is 100 to 300 nanometers. Preferably the maximum grain size of the flake material is maintained as compared to the maximum grain size of the powder particles obtained in said step (2).
Preferably, the combined high temperature phase nano alpha-MoB is prepared2The electrocatalytic working electrode of the sintered sheet is in an electrocatalytic hydrogen evolution reaction in a 0.5M sulfuric acid environment, and the current density is 10mA/cm2The overpotential at time is not higher than 105mV (vs. RHE). Has high electrocatalytic activity of a nano-phase structure.
Preferably, the resulting bonded high temperature phase nano-alpha-MoB2The Tafel slope of the sintered electrocatalytic working electrode was 61 mV/dec. Indicating that the hydrogen evolution reaction follows the Volmer-Heyrovsky reaction mechanism.
The high-temperature phase nano alpha-MoB with high electrocatalytic activity prepared by the invention2The method comprises the following steps: alpha-MoB synthesized by the invention2Is a high temperature phase MoB2The crystal structure of the material belongs to a hexagonal system, the space group of the crystal is P6/mmm, the grain size of the material after the electrode is manufactured is 100-300 nanometers, and the current density is 10mA/cm in the electrocatalytic hydrogen evolution reaction in a 0.5M sulfuric acid environment at room temperature2The overpotential at this time was not higher than 105mV, and the Tafel slope was 61mV/dec, indicating that the hydrogen evolution reaction followed the Volmer-Heyrovsky reaction mechanism.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the invention has high electrocatalytic activity and high temperature phase nano alpha-MoB2The electrode preparation method has mild reaction conditions, does not need extreme conditions such as high temperature and high pressure, and the like, namely, the required high-temperature hexagonal phase alpha-MoB can be synthesized in one step in a macroscopic manner by three-dimensional high-energy ball milling mechanical alloying2The sample is beneficial to the subsequent industrialized application of the material;
2. the particle size of the powder sample synthesized by mechanical alloying by the method is between 100 and 300 nm. On the basis, the sheet electrode is manufactured at a lower temperature of less than 800 ℃ and under a pressure of not higher than 50MPa by combining a discharge plasma sintering technology, so that the nano-sized microstructure and the larger specific surface area of the sheet electrode can be kept to the maximum extent, and the surface activation of material particles is promoted, thereby realizing excellent electro-catalytic performance;
3. the electrode prepared by the method has the current density of 10mA/cm in the electrocatalytic hydrogen evolution reaction in the 0.5M sulfuric acid environment2The overpotential is less than or equal to 105mV (vs. RHE), the Tafel slope is 61mV/dec, which is greatly superior to the existing alpha-MoB2The catalytic activity of (3) and the stability are good.
Drawings
FIG. 1 shows a high temperature phase nano-alpha-MoB with high electrocatalytic activity prepared according to the first embodiment of the present invention2XRD patterns of the powder and a flaky sample obtained by sintering the discharge plasma;
FIG. 2 shows a high temperature phase nano α -MoB with high electrocatalytic activity prepared according to the first embodiment of the present invention2SEM images of the powder and the flaky sample obtained by spark plasma sintering;
fig. 3 is a graph showing the test results of an electrode prepared according to the first embodiment of the present invention. 3a is the high temperature phase nano alpha-MoB with high electrocatalytic activity prepared in the first embodiment of the invention2HER polarization curve of the electrode under acidic conditions; FIG. 3b shows the high temperature phase nano-alpha-MoB with high electrocatalytic activity prepared in the first embodiment of the present invention2The tafel slope of the electrode under acidic conditions; FIG. 3c shows the high temperature phase nano α -MoB with high electrocatalytic activity prepared in the first embodiment of the present invention2An electrochemical specific surface area (ECSA) map of the electrode under acidic conditions; FIG. 3d shows the high temperature phase nano α -MoB with high electrocatalytic activity prepared according to the first embodiment of the present invention2HER stability test of the electrode under acidic conditions.
FIG. 4 high temperature phase nano α -MoB with high electrocatalytic activity prepared by the first embodiment of the present invention2Field scenario of electrode in acidic HER reaction.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this example, a high temperature phase nano-alpha-MoB2The preparation method of the electrode comprises the following steps:
(1) commercial amorphous B powder and Mo powder were selected as starting elements for the synthesis. Wherein, the purity of the powder B is 99 percent, and the particle size is less than 20 microns; the purity of Mo powder is 99.9%, and the particle size is less than 150 microns;
in order to prevent oxidation in the mechanical alloying reaction of the sample, the sample was weighed in a glove box protected with high purity argon of 99.999% in such a manner that the atomic ratio of Mo to B is 1: 2, weighing 4.0804g of amorphous molybdenum powder and 0.9196g of boron powder, putting the amorphous molybdenum powder and the boron powder into a ball milling tank in an argon protective atmosphere of a glove box, and adding stainless steel balls with the diameters of 12mm and 6mm to ensure that the ball-material ratio is 4: 1, screwing down a cover of the ball milling tank to ensure that the inside of the ball milling tank is always kept in an argon atmosphere in the synthesis process;
(2) then, a three-dimensional vibration high-energy ball mill is used for mechanical alloying reaction, in order to reduce the cold welding phenomenon of powder in the ball milling process and prevent the powder from being bonded on the wall of the tank, the ball mill is suspended after operating for 20 hours, the tank wall is simply cleaned in an argon glove box, then the ball milling is continued under the argon atmosphere, and the total set time is 100 hours in total; the material preparation, ball milling and material taking operations are all completed in an argon glove box with the water oxygen content always kept lower than 0.0001%; subsequently performing a characterization analysis of the powder sample;
(3) weighing 0.5g of a sample prepared by mechanical alloying in an argon atmosphere, immediately putting the sample into a graphite grinding tool with the diameter of 10mm for compaction, transferring the sample into discharge plasma sintering equipment for sintering under the pressure of 50MPa, wherein the heating rate is about 50 ℃/min, preserving the heat for 30min at the temperature of 750 ℃, and then immediately removing the pressure and the temperature to obtain a sheet sample with higher hardness;
(4) adhering a flaky sample after Spark Plasma Sintering (SPS) on a copper sheet by using conductive silver adhesive, keeping the top of the sample exposed, wrapping the periphery and the surface of the copper sheet by using epoxy resin adhesive, and drying for 24 hours under the condition of drying at room temperature to obtain the working electrode.
For the high temperature phase nano alpha-MoB prepared in the example and having high electrocatalytic activity2Electrode structure and performance were characterized, see fig. 1-3, with the following results:
FIG. 1 shows the high temperature phase nano α -MoB with high electrocatalytic activity prepared in this example2XRD patterns of the powder and the flaky sample obtained by spark plasma sintering. The X-ray diffraction peak position of the powder after the mechanical alloying reaction and the high-temperature hexagonal phase alpha-MoB are shown in the figure2The typical characteristic peaks (PDF #89-3785) are consistent, which indicates that the synthesized sample after mechanical alloying is single-phase alpha-MoB2And the diffraction peak has larger broadening, which indicates that the grain diameter of the sample is smaller. The peak position and half-height width of the XRD pattern of the sample after SPS are not changed greatly, which indicates that the sintering process does not change the powder alpha-MoB2Crystal structure and particle size. FIG. 2 shows the high temperature phase nano α -MoB with high electrocatalytic activity prepared in this example2SEM images of the powder and the sheet sample obtained by spark plasma sintering show that the grain size ranges of the powder sample synthesized by mechanical alloying and the sample after SPS sintering are both between 100nm and 300 nm. The grain size is not changed by spark plasma sintering, and a large amount of nano particles are tightly packed to form rich grain boundaries and a large specific surface area, so that a large electrochemical active area is provided for electrocatalysis. FIG. 3 is an electrochemical characterization chart of the sample prepared in this example, and it can be seen that the catalytic electrode prepared by the method is at 10mA/cm2The overpotential is 105mV (vs. RHE), the Tafel slope is 61mV/dec, and the electrochemical active specific surface area is 173mF/cm2Is greatly superior to the prior alpha-MoB2The catalyst has good stability, and the current density does not change obviously within 48 h.
The method for preparing the electrode for the electrocatalysis reaction has simple material process, does not relate to high temperature and high pressure, and is suitable for large-scale industrial production. The hydrogen evolution reaction electro-catalytic electrode prepared by the method has high catalytic performance.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
the ball milling time of the sample in this example was 80 h. The XRD pattern obtained in this example shows that the sample has alpha-MoB in addition to the same2The typical characteristic peaks (PDF #89-3785) corresponding to different crystal planes also have very low peaks of raw material molybdenum, but the peaks are lower than those of the sample obtained in the first example, which indicates that the phase formation is not complete and that a part of the sample which is not completely reacted exists. Electrochemical characterization showed it to be at 10mA/cm2The overpotential at time was 144mV (vs. RHE).
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, the temperature of spark plasma sintering in this example was 850 ℃ and the holding time was 20 minutes. Compared with the first example, the XRD pattern of the sample after spark plasma sintering has a mixed peak, which indicates that the sample is partially decomposed at the temperature, and then the electrochemical analysis and characterization of the sample also shows that the catalytic performance of the sample is obviously reduced, and the ratio is 10mA/cm2Overpotential of time 299mV (vs. RHE)
The above examples show high electrocatalytic activity of high temperature phase nano alpha-MoB2A method for preparing an electrode, the method comprising a high temperature phase of alpha-MoB2High-energy mechanical alloying synthesis of nano particles and subsequent electrode plate sintering and assembling method. Taking Mo powder and B powder in an argon protective glove box according to an atomic ratio of 1: 2, sealing the mixture and a certain amount of ball-milling balls into a stainless steel ball-milling tank; then placing the ball milling tank in a high-energy ball mill for ball milling; then the high-temperature phase alpha-MoB obtained by ball milling is treated2Placing the nano-particle powder in a graphite die, and sintering into a sheet by using a discharge plasma sintering method; and then, adhering the sheet sample obtained by sintering on a copper sheet by using conductive silver paste, and drying to prepare the electrode for the electrocatalytic reaction. The temperature of the discharge plasma sintering in the embodiment is 750-850 ℃, and the heat preservation time is 20-30 minutes. The precipitate prepared in the above-mentioned example of the inventionThe hydrogen reaction electro-catalytic electrode has higher catalytic performance, and the catalytic performance is 10mA/cm2The overpotential at time is not higher than 105mV (vs. RHE).
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention should be replaced with equivalents as long as the object of the present invention is met, and the technical principle and the inventive concept of the present invention are not departed from the scope of the present invention.

Claims (10)

1. High-temperature phase nano alpha-MoB2The electrode preparation method is characterized by comprising the following steps:
(1) in an argon glove box, according to the atomic ratio of Mo to B of 1: 2, weighing Mo simple substance and B simple substance powder raw materials, and sealing the raw materials and the ball-milling balls into a ball-milling tank; the purities of the Mo simple substance and the B simple substance are not lower than 99.9%;
(2) putting the ball milling tank obtained in the step (1) into a high-energy ball mill for ball milling, and performing mechanical alloying reaction to obtain high-temperature phase alpha-MoB2The nano-powder of (1);
(3) after the mechanical alloying reaction in the step (2) is finished, taking out the nano powder in an argon glove box, putting the nano powder into a graphite mold, and sintering the nano powder into a sheet material by using a discharge plasma sintering method;
(4) adopting a binder to adhere the flaky material obtained by sintering in the step (3) on a copper sheet with the thickness of 0.3-0.5 mm, packaging the rest of the copper sheet except for the exposed surface of the flaky material by using epoxy resin, and drying to obtain the combined high-temperature phase nano alpha-MoB2The electrocatalytic working electrode of the sheet is sintered.
2. The high temperature phase nano-alpha-MoB of claim 12The electrode preparation method is characterized in that: in the step (1), the ball-to-material ratio in the ball milling tank is 4: 1-3: 1.
3. the high temperature phase nano-alpha-MoB of claim 12The electrode preparation method is characterized in that: in the step (1), the step (2) and the step (3), the weighing, the canning and the sampling are all completed in an argon glove box, and the powder is kept in a water-proof and oxygen-proof environment.
4. The high temperature phase nano-alpha-MoB of claim 12The electrode preparation method is characterized in that: in the step (2), the mechanical alloying reaction time is 80-130 hours, and the obtained powder is high-temperature phase alpha-MoB with the particle size of 100-300 nanometers2。
5. The high temperature phase nano-alpha-MoB of claim 12The electrode preparation method is characterized in that: in the step (3), the sintering temperature of the discharge plasma is 650-800 ℃, the sintering pressure is not higher than 50MPa, the heating rate is not lower than 50 ℃/min, and the heat preservation time is not longer than 30 minutes.
6. The high temperature phase nano-alpha-MoB of claim 12The electrode preparation method is characterized in that: in the step (2), the ball mill is a three-dimensional vibration high-energy ball mill.
7. The high temperature phase nano-alpha-MoB of claim 12The electrode preparation method is characterized in that: in the step (4), the adhesive for bonding the sheet material and the copper sheet is conductive silver paste.
8. The high temperature phase nano-alpha-MoB of claim 12The electrode preparation method is characterized in that: in the step (3), the grain size of the prepared sheet material is 100-300 nanometers.
9. The high temperature phase nano-alpha-MoB of claim 12The electrode preparation method is characterized in that: the prepared combined high-temperature phase nano alpha-MoB2Of sintered sheetsThe electrocatalytic working electrode has a current density of 10mA/cm in the electrocatalytic hydrogen evolution reaction in a 0.5M sulfuric acid environment2The overpotential at time is not higher than 105mV (vs. RHE).
10. The high temperature phase nano-alpha-MoB of claim 12The electrode preparation method is characterized in that: the prepared combined high-temperature phase nano alpha-MoB2The Tafel slope of the sintered electrocatalytic working electrode was 61 mV/dec.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101381104A (en) * 2008-10-24 2009-03-11 北京科技大学 Method for preparing NbAl3 intermetallic compound
CN107663607A (en) * 2017-09-12 2018-02-06 中南大学 A kind of high-entropy alloy holds composite of abrasive grain and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101381104A (en) * 2008-10-24 2009-03-11 北京科技大学 Method for preparing NbAl3 intermetallic compound
CN107663607A (en) * 2017-09-12 2018-02-06 中南大学 A kind of high-entropy alloy holds composite of abrasive grain and its preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JINTAO CHE ET AL.: "Mechanical alloying assisted spark plasma sintering of Tungsten diboride ceramics", 《MATERIALS CHEMISTRY AND PHYSICS》 *
YANLI CHEN ET AL.: "ighly Active, Nonprecious Electrocatalyst Comprising Borophene Subunits for the Hydrogen Evolution Reaction", 《J. AM. CHEM. SOC.》 *
石建磊: "机械合金化结合放电等离子烧结技术制备热电材料的研究进展", 《粉末冶金技术》 *

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