CN110219017A - Molybdenum disulfide/expanded graphite hydrogen-precipitating electrode preparation method - Google Patents
Molybdenum disulfide/expanded graphite hydrogen-precipitating electrode preparation method Download PDFInfo
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- CN110219017A CN110219017A CN201910491644.8A CN201910491644A CN110219017A CN 110219017 A CN110219017 A CN 110219017A CN 201910491644 A CN201910491644 A CN 201910491644A CN 110219017 A CN110219017 A CN 110219017A
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- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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Abstract
The present invention provides a kind of preparation method of molybdenum disulfide/expanded graphite hydrogen-precipitating electrode, expansible graphite is made using oxidation graft process first, expanded graphite is obtained through high temperature puffing again, secondly compressing tablet process is carried out to it, then using hydrothermal synthesis method in its area load molybdenum disulfide, molybdenum disulfide/expanded graphite hydrogen-precipitating electrode is finally made, a series of electrochemistry liberation of hydrogen materials are made by adjusting increment of the molybdenum disulfide on expanded graphite matrix material, the additional amount range of the present invention corresponding ammonium molybdate of expanded graphite matrix tabletting every square centimeter is 0.071 mM~0.284 mM.The problem of manufacture craft of the present invention is simple, low in cost, and the catalytic hydrogen evolution efficiency of molybdenum disulfide can be improved in application composite electrode prepared by the present invention, can effectively solve the problem that molybdenum disulfide poorly conductive.
Description
Technical field
The invention belongs to electrocatalytic hydrogen evolution technical fields, are related to a kind of preparation of molybdenum disulfide/expanded graphite hydrogen-precipitating electrode
Method
Background technique
It is well known that hydrogen energy source as a kind of ideal, pollution-free, effective secondary energy sources, helps to solve due to fossil
Problem of environmental pollution brought by fuel combustion, and water electrolysis hydrogen production is the easy to operate, technology maturation of one kind and has engineering
One technology of application prospect, is widely paid close attention to by people, and anode material generallys use Pt and graphite electrode, and suitable has
The cathode material of electrochemical catalysis H2-producing capacity is the key that can the technology realize engineering application.However catalysis produces hydrogen and most has
Catalyst Pt, Pd of effect etc. can not be promoted due to expensive, so developing efficient and low-cost novel cathode electrification
It learns liberation of hydrogen material and has become current research hotspot.Molybdenum disulfide (MoS2), have the characteristics of cheap, stable chemical performance,
The active site S of edge exposure has very high catalytic activity, therefore with MoS2It has been subjected to for the electrochemistry liberation of hydrogen material of matrix
Universal attention is arrived.However, MoS21 point of catalytic activity is concentrated mainly on (002) face edge, and face central active is relatively
It is weak, and MoS2Interlayer electronic conductivity is poor, so seeking a kind of suitable basis material load molybdenum disulfide is raising two
The key of the catalytic hydrogen evolution performance of molybdenum sulfide.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of molybdenum disulfide/expanded graphite hydrogen-precipitating electrode preparation sides
Method after loading molybdenum disulfide on it, can improve leading for molybdenum disulfide using the expanded graphite of electrical conductance function admirable as carrier
Electrically, to improve its electrochemistry liberation of hydrogen efficiency.
The present invention is implemented as follows:
A kind of preparation method of molybdenum disulfide/expanded graphite hydrogen-precipitating electrode, specifically includes the following steps:
S1, expanded graphite compressing tablet process:
S11, expanded graphite and acetylene black are added in solvent absolute ethyl alcohol, stir 1~2h at room temperature, adds in whipping process
Enter polytetrafluoroethylene (PTFE), obtain dispersion liquid, the mass ratio of expanded graphite, acetylene black and polytetrafluoroethylene (PTFE) be 1:0.1~0.15:5~
7；
S12, by obtained dispersion liquid at 90 DEG C heated at constant temperature, so that the dehydrated alcohol in dispersion liquid is volatilized, then dry
Obtain expanded graphite mix powder；
S13, dry expanded graphite mix powder is put into cold forming mold processing is pressed, mold is straight
Diameter is 50mm, and setting pressing pressure is 8~10Mpa, and the pressing time is 15~20min, obtains expanded graphite casting die；
S14, expanded graphite casting die is sintered 120~130min at 375~380 DEG C, sintered part is cut into pre-
If shape, as expanded graphite matrix tabletting；
S2, molybdenum disulfide/expanded graphite hydrogen-precipitating electrode is prepared:
The dosage of raw material are as follows: the mass ratio of the tabletting of expanded graphite matrix, ammonium molybdate and thiocarbamide is 1:0.618~2.472:
1.14~4.56, and the additional amount of the corresponding ammonium molybdate of expanded graphite matrix tabletting every square centimeter be 0.071 mM~
0.284 mM；
S21, ammonium molybdate and thiocarbamide are add to deionized water, magnetic agitation keeps ammonium molybdate and thiocarbamide sufficiently molten at room temperature
Solution；
S22, expanded graphite matrix tabletting is placed in ethanol solution, 1~2h of ultrasound, it is dry；
S23, ammonium molybdate and thiocarbamide mixed solution are added into the expanded graphite matrix tabletting after drying, at 199~201 DEG C
After lower heating for 24 hours, it is cooled to room temperature, molybdenum disulfide is directly loaded in expanded graphite matrix tabletting；
S24, the expanded graphite matrix tabletting for being loaded with molybdenum disulfide respectively carries out it with deionized water and dehydrated alcohol
Cleaning, it is dry, obtain molybdenum disulfide/expanded graphite hydrogen-precipitating electrode.
Preferably, the expanded graphite the preparation method comprises the following steps:
At room temperature, natural flake graphite, potassium permanganate and ammonium nitrate are sufficiently mixed, are then slowly added into perchloric acid, with
It is stirred at 30~35 DEG C afterwards, speed of agitator 200r/min, using Potassium Permanganate as Oxidant, perchloric acid makees intercalator, nitre
Sour ammonium makees auxiliary intercalator and carries out oxidation intercalation, and the reaction time controls in 60~70min；
After the completion of intercalation to be oxidized, after mixing liquid cooled to room temperature, deionized water washs mixture extremely
Then neutrality is filtered dehydration, drying obtains expansible graphite at 70 DEG C later；By expansible graphite at 950 DEG C into
Row extruding, obtains expanded graphite.
Preferably, the drying temperature of step S12 is 65~70 DEG C, and drying time is 23~25h.
Preferably, when being sintered in step S14,375~380 DEG C of sintering temperature are warming up to from room temperature with the speed of 1 DEG C/min.
Preferably, sintered part is cut into the square part of 20mm × 20mm by step S14.
Preferably, the drying temperature of step S22 is 90~95 DEG C, and drying time is 10~15min.
Preferably, 199~201 DEG C of heating temperature are risen to from room temperature with the speed of 5 DEG C/min in step S23.
Preferably, the additional amount of the corresponding ammonium molybdate of expanded graphite matrix tabletting every square centimeter is 0.142 mM.
Compared with prior art, the invention has the following advantages:
1, expansible graphite is made using oxidation graft process first in the present invention, then obtains expanded graphite through high temperature puffing,
It is secondary that compressing tablet process is carried out to it, then using hydrothermal synthesis method in its area load molybdenum disulfide, molybdenum disulfide/swollen is finally made
A series of electrochemistry are made by adjusting increment of the molybdenum disulfide on expanded graphite matrix material in swollen graphite hydrogen-precipitating electrode
Liberation of hydrogen material, the additional amount range of the present invention corresponding ammonium molybdate of expanded graphite matrix tabletting every square centimeter are 0.071 milli
Mole~0.284 mM.Manufacture craft of the present invention is simple, low in cost, and applies composite electrode prepared by the present invention
The catalytic hydrogen evolution efficiency that molybdenum disulfide can be improved, the problem of can effectively solve the problem that molybdenum disulfide poorly conductive.
2, expanded graphite conductivity prepared by the present invention is high, and sulfur-bearing, not environmentally friendly, and by after its blending processing, presses
It is higher than common carbon material that electrode base material intensity made from piece is made, in addition, the binding force of the material and molybdenum disulfide compared with
By force, the stability of composite material is enhanced；
3, the Hydrogen Evolution Performance of composite electrode prepared by the present invention is good, is not influenced by electrolyte pH, can acid, in
With electrolysis aquatic products hydrogen in the environment of alkali.
Detailed description of the invention
Fig. 1 a is molybdenum disulfide/expanded graphite that molybdenum disulfide different loads amount is made in the embodiment of the present invention 1,2 and 3 respectively
Compound hydrogen-precipitating electrode cathodic linear polarization method curve graph；
Fig. 1 b is Tafel slope figure corresponding to Fig. 1 a；
Fig. 2 is MoS2With the XRD diffracting spectrum of MoS2/EG-2 obtained in embodiment 2；
Fig. 3 a is the scanning electron microscope shape appearance figure of expanded graphite matrix tabletting；
Fig. 3 b is the scanning electron microscope shape appearance figure of molybdenum disulfide；
Fig. 3 c is MoS made from embodiment 22The scanning electron microscope shape appearance figure of/EG-2.
Specific embodiment
Below with reference to the attached drawing exemplary embodiment that the present invention will be described in detail, feature and aspect of performance.
The present invention provides a kind of preparation method of molybdenum disulfide/expanded graphite hydrogen-precipitating electrode, specifically includes the following steps:
Firstly, expanded graphite is prepared, the preparation method comprises the following steps:
At room temperature, natural flake graphite, potassium permanganate and ammonium nitrate are sufficiently mixed, are then slowly added into perchloric acid, with
It is stirred at 30~35 DEG C afterwards, speed of agitator 200r/min, using Potassium Permanganate as Oxidant, perchloric acid makees intercalator, nitre
Sour ammonium makees auxiliary intercalator and carries out oxidation intercalation, and the reaction time controls in 60~70min；
After the completion of intercalation to be oxidized, after mixing liquid cooled to room temperature, deionized water washs mixture extremely
Then neutrality is filtered dehydration, drying obtains expansible graphite at 70 DEG C later；By expansible graphite at 950 DEG C into
Row extruding obtains expanded graphite, and expanded graphite conductivity obtained is high, and sulfur-bearing, not environmentally friendly.
S1, expanded graphite compressing tablet process:
S11, expanded graphite and acetylene black are added in solvent absolute ethyl alcohol, stir 1~2h at room temperature, adds in whipping process
Enter polytetrafluoroethylene (PTFE), obtain dispersion liquid, the mass ratio of expanded graphite, acetylene black and polytetrafluoroethylene (PTFE) be 1:0.1~0.15:5~
7；
S12, by obtained dispersion liquid at 90 DEG C heated at constant temperature, so that the dehydrated alcohol in dispersion liquid is volatilized, then dry
Processing obtains expanded graphite mix powder, and drying temperature is 65~70 DEG C, and drying time is 23~25h；
S13, dry expanded graphite mix powder is put into cold forming mold processing is pressed, mold is straight
Diameter is 50mm, and setting pressing pressure is 8~10Mpa, and the pressing time is 15~20min, obtains expanded graphite casting die；
S14, expanded graphite casting die is sintered 120~130min at 375~380 DEG C, sintered part is cut into
The square part of 20mm × 20mm, as expanded graphite matrix tabletting；
Due to acetylene black conductivity with higher, acetylene black is added in basis material to improve basis material in the present invention
Electric conductivity, dry after ptfe emulsion and active material (expanded graphite and acetylene black) mixing, PTFE can be with netted
The form " package " of structure is lived active material particle and is connected with each other to achieve the purpose that adherency.Polytetrafluoroethyl-ne is used in the present invention
Alkene lotion is bonded together expanded graphite mutually as binder, is conducive to expanded graphite compression moulding.
S2, molybdenum disulfide/expanded graphite hydrogen-precipitating electrode is prepared:
The dosage of raw material are as follows: the mass ratio of the tabletting of expanded graphite matrix, ammonium molybdate and thiocarbamide is 1:0.618~2.472:
1.14~4.56, the additional amount of the corresponding ammonium molybdate of expanded graphite matrix tabletting every square centimeter is 0.071 mM~
0.284 mM,
S21, ammonium molybdate and thiocarbamide are add to deionized water, magnetic agitation keeps ammonium molybdate and thiocarbamide sufficiently molten at room temperature
Solution, obtains precursor liquid, and the additional amount for controlling the corresponding ammonium molybdate of expanded graphite matrix tabletting every square centimeter is 0.071 mmoles
You~0.284 mM, so that the Hydrogen Evolution Performance of the electrode finally prepared is reached best；
S22, expanded graphite matrix tabletting is placed in ethanol solution, 1~2h of ultrasound, dry, drying temperature is 90~95
DEG C, drying time is 10~15min；
S23, ammonium molybdate and thiocarbamide mixed solution are added into the expanded graphite matrix tabletting after drying, at 199~201 DEG C
After lower heating for 24 hours, it is cooled to room temperature, molybdenum disulfide is directly loaded in expanded graphite matrix tabletting；
S24, the expanded graphite matrix tabletting for being loaded with molybdenum disulfide respectively carries out it with deionized water and dehydrated alcohol
Cleaning, it is dry, obtain molybdenum disulfide/expanded graphite hydrogen-precipitating electrode.
Preferably, when being sintered in step S14,375~380 DEG C of sintering temperature are warming up to from room temperature with the speed of 1 DEG C/min.
Preferably, 199~201 DEG C of heating temperature are risen to from room temperature with the speed of 5 DEG C/min in step S23.
Preferably, the additional amount of the corresponding ammonium molybdate of expanded graphite matrix tabletting every square centimeter is 0.142 mM.
Embodiment 1
Successively 1g natural flake graphite, 0.45g potassium permanganate and 0.12g ammonium nitrate are added at room temperature first dry
In the beaker that dry clean, volume is 250mL, then pipettes 8mL perchloric acid and be slowly added in beaker, be put into magnetic rotor, use is close
Sealer seals beaker, and the beaker being sealed is placed in heat collecting type constant-temperature heating magnetic stirring apparatus later, sets bath temperature
30 DEG C, adjusting revolving speed is 200r/min, mixing time 60min；After the completion of intercalation, beaker is taken out immediately, is placed in draught cupboard
It is interior, it opens beaker and seals film, after the mixture in beaker is cooled to room temperature, take out magnetic rotor using clean tweezers, it
Mixture is repeatedly rinsed with deionized water afterwards, until flushing water pH is about 7；Then vacuum pump using circulatory water is used, to washes clean
Mixture carry out suction filtration dehydration, the mixture retained on filter paper is transferred in clean culture dish later, is placed in drying box
In, dry 12h, is made expansible graphite at 70 DEG C；Muffle furnace is opened and is preheated, after it is warming up to 950 DEG C, is weighed on 1g
It states expansible graphite obtained to be placed in the quartz beaker dry, clean, volume is 250mL, quartz beaker is put into horse later
4~5s is not waited in furnace, is then taken out, and expanded graphite is finally made.
S1, expanded graphite compressing tablet process:
1g expanded graphite and 0.1g acetylene black are weighed first in drying, cleaning, the beaker that volume is 500mL, are then measured
It takes the dehydrated alcohol of 150mL to be slowly added in beaker, places the beaker first stirred at room temperature on magnetic stirring apparatus later
30min, measure 5mL mass fraction be 60% polytetrafluoroethylsolution solution be poured slowly into mixed liquor continue stir 60min make to mix
Liquid is closed to be sufficiently mixed；Thermostat water bath is preheated and is heated to 90 DEG C, the mixed liquor after stir process is then placed in thermostatted water
In bath, the dehydrated alcohol in mixed liquor is made to volatilize, expanded graphite mixture is poured into later in clean culture dish and then will
It is placed in drying box and is dried, and drying temperature and time are respectively 65 DEG C and for 24 hours；Dried expanded graphite is mixed
It closes object powder to take out, is put into cold forming mold and processing is pressed, mould diameter 50mm, pressing pressure, which is arranged, is
8Mpa, pressing time 15min；It is 50mm, with a thickness of the pressure of 2mm by diameter after expanded graphite mix powder is suppressed
Part takes out from cold forming mold, is placed in Muffle furnace and is sintered.First by the temperature of Muffle furnace from in-furnace temperature with 1 DEG C/min
Speed rise to 375 DEG C, then react 120min at this temperature, finally close Muffle furnace, after so that it is naturally cooled to room temperature
Sintered part is taken out, sintered part is finally cut into the square smallclothes of 20mm × 20mm, the tabletting of expanded graphite matrix is made.
The preparation of S2, molybdenum disulfide/expanded graphite hydrogen-precipitating electrode
0.618g ammonium molybdate is weighed first and 1.14g thiocarbamide is added in the beaker for the deionized water for filling 35mL, is being burnt
It is put into the rotor of dried and clean in cup, beaker is sealed with sealing film, beaker is placed on magnetic stirring apparatus later, revolving speed is set
For 200r/min, 60min is stirred at room temperature, is dissolved completely in ammonium molybdate and thiocarbamide in deionized water；By expanded graphite matrix
Tabletting is put into the container for filling dehydrated alcohol, is then placed it in and is carried out 1~2h of ultrasonic treatment in processor for ultrasonic wave, to super
Expanded graphite matrix tabletting taking-up is placed in clean culture dish after sonication, is then placed in drying box and is dried
Processing, drying time are 10~15min, and drying temperature is 90 DEG C；First by the expanded graphite matrix pressure after ultrasonic treatment and drying
Piece is placed in the liner of the polytetrafluoroethylene (PTFE) of 25mL, then adds ammonium molybdate and thiocarbamide mixed solution after completely dissolution
Liner is finally put into stainless steel cauldron and is tightened sealing cover, puts it into Muffle furnace later by 20mL.First by Muffle
The temperature of furnace rises to 200 DEG C from in-furnace temperature with the speed of 5 DEG C/min, then reacts for 24 hours at this temperature, finally closes Muffle
Stainless steel cauldron is taken out from Muffle furnace and is unclamped reaction kettle sealing cover, by reaction kettle by furnace after so that it is naturally cooled to room temperature
It is cleaned with deionized water and dehydrated alcohol respectively after being inside loaded with the expanded graphite matrix tabletting taking-up of molybdenum disulfide；Most
The composite material after cleaning is placed in culture dish afterwards and is placed it in drying box, is dried at 60 DEG C for 24 hours to get arriving
Molybdenum disulfide/expanded graphite hydrogen-precipitating electrode is labeled as MoS2/EG-1。
Embodiment 2
Successively 1g natural flake graphite, 0.45g potassium permanganate and 0.12g ammonium nitrate are added at room temperature first dry
In the beaker that dry clean, volume is 250mL, then pipettes 8mL perchloric acid and be slowly added in beaker, be put into magnetic rotor, use is close
Sealer seals beaker, and the beaker being sealed is placed in heat collecting type constant-temperature heating magnetic stirring apparatus later, sets bath temperature
30 DEG C, adjusting revolving speed is 200r/min, mixing time 60min；After the completion of intercalation, beaker is taken out immediately, is placed in draught cupboard
It is interior, it opens beaker and seals film, after the mixture in beaker is cooled to room temperature, take out magnetic rotor using clean tweezers, it
Mixture is repeatedly rinsed with deionized water afterwards, until flushing water pH is about 7；Then vacuum pump using circulatory water is used, to washes clean
Mixture carry out suction filtration dehydration, the mixture retained on filter paper is transferred in clean culture dish later, is placed in drying box
In, dry 12h, is made expansible graphite at 70 DEG C；Muffle furnace is opened and is preheated, after it is warming up to 950 DEG C, is weighed on 1g
It states expansible graphite obtained to be placed in the quartz beaker dry, clean, volume is 250mL, quartz beaker is put into horse later
4~5s is not waited in furnace, is then taken out, and expanded graphite is finally made.
S1, expanded graphite compressing tablet process:
1g expanded graphite and 0.1g acetylene black are weighed first in drying, cleaning, the beaker that volume is 500mL, are then measured
It takes the dehydrated alcohol of 150mL to be slowly added in beaker, places the beaker first stirred at room temperature on magnetic stirring apparatus later
30min, measure 5mL mass fraction be 60% polytetrafluoroethylsolution solution be poured slowly into mixed liquor continue stir 60min make to mix
Liquid is closed to be sufficiently mixed；Thermostat water bath is preheated and is heated to 90 DEG C, the mixed liquor after stir process is then placed in thermostatted water
In bath, the dehydrated alcohol in mixed liquor is made to volatilize, expanded graphite mixture is poured into later in clean culture dish and then will
It is placed in drying box and is dried, and drying temperature and time are respectively 65 DEG C and for 24 hours；Dried expanded graphite is mixed
It closes object powder to take out, is put into cold forming mold and processing is pressed, mould diameter 50mm, pressing pressure, which is arranged, is
8Mpa, pressing time 15min；It is 50mm, with a thickness of the pressure of 2mm by diameter after expanded graphite mix powder is suppressed
Part takes out from cold forming mold, is placed in Muffle furnace and is sintered.First by the temperature of Muffle furnace from in-furnace temperature with 1 DEG C/min
Speed rise to 375 DEG C, then react 120min at this temperature, finally close Muffle furnace, after so that it is naturally cooled to room temperature
Sintered part is taken out, sintered part is finally cut into the square smallclothes of 20mm × 20mm, the tabletting of expanded graphite matrix is made.
The preparation of S2, molybdenum disulfide/expanded graphite hydrogen-precipitating electrode
1.236g ammonium molybdate is weighed first and 2.28g thiocarbamide is added in the beaker for the deionized water for filling 35mL, is being burnt
It is put into the rotor of dried and clean in cup, beaker is sealed with sealing film, beaker is placed on magnetic stirring apparatus later, revolving speed is set
For 200r/min, 60min is stirred at room temperature, is dissolved completely in ammonium molybdate and thiocarbamide in deionized water；By expanded graphite matrix
Tabletting is put into the container for filling dehydrated alcohol, is then placed it in and is carried out 1~2h of ultrasonic treatment in processor for ultrasonic wave, to super
Expanded graphite matrix tabletting taking-up is placed in clean culture dish after sonication, is then placed in drying box and is dried
Processing, drying time are 10~15min, and drying temperature is 90 DEG C；First by the expanded graphite matrix pressure after ultrasonic treatment and drying
Piece is placed in the liner of the polytetrafluoroethylene (PTFE) of 25mL, then adds ammonium molybdate and thiocarbamide mixed solution after completely dissolution
Liner is finally put into stainless steel cauldron and is tightened sealing cover, puts it into Muffle furnace later by 20mL.First by Muffle
The temperature of furnace rises to 200 DEG C from in-furnace temperature with the speed of 5 DEG C/min, then reacts for 24 hours at this temperature, finally closes Muffle
Stainless steel cauldron is taken out from Muffle furnace and is unclamped reaction kettle sealing cover, by reaction kettle by furnace after so that it is naturally cooled to room temperature
It is cleaned with deionized water and dehydrated alcohol respectively after being inside loaded with the expanded graphite matrix tabletting taking-up of molybdenum disulfide；Most
The composite material after cleaning is placed in culture dish afterwards and is placed it in drying box, is dried at 60 DEG C for 24 hours to get arriving
Molybdenum disulfide/expanded graphite hydrogen-precipitating electrode is labeled as MoS2/EG-2。
Embodiment 3
Successively 1g natural flake graphite, 0.45g potassium permanganate and 0.12g ammonium nitrate are added at room temperature first dry
In the beaker that dry clean, volume is 250mL, then pipettes 8mL perchloric acid and be slowly added in beaker, be put into magnetic rotor, use is close
Sealer seals beaker, and the beaker being sealed is placed in heat collecting type constant-temperature heating magnetic stirring apparatus later, sets bath temperature
30 DEG C, adjusting revolving speed is 200r/min, mixing time 60min；After the completion of intercalation, beaker is taken out immediately, is placed in draught cupboard
It is interior, it opens beaker and seals film, after the mixture in beaker is cooled to room temperature, take out magnetic rotor using clean tweezers, it
Mixture is repeatedly rinsed with deionized water afterwards, until flushing water pH is about 7；Then vacuum pump using circulatory water is used, to washes clean
Mixture carry out suction filtration dehydration, the mixture retained on filter paper is transferred in clean culture dish later, is placed in drying box
In, dry 12h, is made expansible graphite at 70 DEG C；Muffle furnace is opened and is preheated, after it is warming up to 950 DEG C, is weighed on 1g
It states expansible graphite obtained to be placed in the quartz beaker dry, clean, volume is 250mL, quartz beaker is put into horse later
4~5s is not waited in furnace, is then taken out, and expanded graphite is finally made.
S1, expanded graphite compressing tablet process:
1g expanded graphite and 0.1g acetylene black are weighed first in drying, cleaning, the beaker that volume is 500mL, are then measured
It takes the dehydrated alcohol of 150mL to be slowly added in beaker, places the beaker first stirred at room temperature on magnetic stirring apparatus later
30min, measure 5mL mass fraction be 60% polytetrafluoroethylsolution solution be poured slowly into mixed liquor continue stir 60min make to mix
Liquid is closed to be sufficiently mixed；Thermostat water bath is preheated and is heated to 90 DEG C, the mixed liquor after stir process is then placed in thermostatted water
In bath, the dehydrated alcohol in mixed liquor is made to volatilize, expanded graphite mixture is poured into later in clean culture dish and then will
It is placed in drying box and is dried, and drying temperature and time are respectively 65 DEG C and for 24 hours；Dried expanded graphite is mixed
It closes object powder to take out, is put into cold forming mold and processing is pressed, mould diameter 50mm, pressing pressure, which is arranged, is
8Mpa, pressing time 15min；It is 50mm, with a thickness of the pressure of 2mm by diameter after expanded graphite mix powder is suppressed
Part takes out from cold forming mold, is placed in Muffle furnace and is sintered.First by the temperature of Muffle furnace from in-furnace temperature with 1 DEG C/min
Speed rise to 375 DEG C, then react 120min at this temperature, finally close Muffle furnace, after so that it is naturally cooled to room temperature
Sintered part is taken out, sintered part is finally cut into the square smallclothes of 20mm × 20mm, the tabletting of expanded graphite matrix is made.
The preparation of S2, molybdenum disulfide/expanded graphite hydrogen-precipitating electrode
2.472g ammonium molybdate is weighed first and 4.56g thiocarbamide is added in the beaker for the deionized water for filling 35mL, is being burnt
It is put into the rotor of dried and clean in cup, beaker is sealed with sealing film, beaker is placed on magnetic stirring apparatus later, revolving speed is set
For 200r/min, 60min is stirred at room temperature, is dissolved completely in ammonium molybdate and thiocarbamide in deionized water；By expanded graphite matrix
Tabletting is put into the container for filling dehydrated alcohol, is then placed it in and is carried out 1~2h of ultrasonic treatment in processor for ultrasonic wave, to super
Expanded graphite matrix tabletting taking-up is placed in clean culture dish after sonication, is then placed in drying box and is dried
Processing, drying time are 10~15min, and drying temperature is 90 DEG C；First by the expanded graphite matrix pressure after ultrasonic treatment and drying
Piece is placed in the liner of the polytetrafluoroethylene (PTFE) of 25mL, then adds ammonium molybdate and thiocarbamide mixed solution after completely dissolution
Liner is finally put into stainless steel cauldron and is tightened sealing cover, puts it into Muffle furnace later by 20mL.First by Muffle
The temperature of furnace rises to 200 DEG C from in-furnace temperature with the speed of 5 DEG C/min, then reacts for 24 hours at this temperature, finally closes Muffle
Stainless steel cauldron is taken out from Muffle furnace and is unclamped reaction kettle sealing cover, by reaction kettle by furnace after so that it is naturally cooled to room temperature
It is cleaned with deionized water and dehydrated alcohol respectively after being inside loaded with the expanded graphite matrix tabletting taking-up of molybdenum disulfide；Most
The composite material after cleaning is placed in culture dish afterwards and is placed it in drying box, is dried at 60 DEG C for 24 hours to get arriving
Molybdenum disulfide/expanded graphite hydrogen-precipitating electrode is labeled as MoS2/EG-3。
Molybdenum disulfide/expanded graphite hydrogen-precipitating electrode electrocatalytic hydrogen evolution performance is tested using three-electrode system, with
Platinum electrode is to electrode, and saturation silver chloride electrode is reference electrode, and molybdenum disulfide/expanded graphite hydrogen-precipitating electrode is working electrode,
Test equipment is Shanghai Chen Hua CHI650C type electrochemical workstation, the sulfuric acid solution that test solution is 0.5mol/L, test result
As illustrated in figs. 1A and ib；It can be seen that being 10mAcm in current density from Fig. 1 a-2When, MoS2/EG-1、MoS2/EG-2
And MoS2The overpotential of/EG-3 hydrogen-precipitating electrode respectively reaches 280mV, 230mV and 270mV, and comparison obtains MoS2/ EG-2 composite wood
The overpotential of hydrogen evolution of material is minimum, so cathode of composite material Hydrogen Evolution Performance made from embodiment 2 is best in three kinds of composite materials.
MoS is shown in Fig. 1 b2/EG-1、MoS2/ EG-2 and MoS2The Tafel slope of/EG-3 composite material is respectively 94mVdec-1、
77mV·dec-1And 91mVdec-1, MoS2The Tafel slope of/EG-2 composite material is minimum, to further demonstrate implementation
Hydrogen Evolution Performance of the composite material made from example 2 in three kinds of composite materials is best.
Fig. 2 is to distinguish at 2 θ=13.7 ° of the angle of diffraction, 32.3 ° and 57.2 ° in the X ray diffracting spectrum of pure molybdenum disulfide
The characteristic diffraction peak of (002), (100) and (110) crystal face of corresponding molybdenum disulfide.Molybdenum disulfide/exfoliated-graphite composite
In map, the characteristic diffraction peak of expanded graphite is 2 θ=26.86 ° and 54.84 °, is also detected other than the diffraction maximum of expanded graphite
The characteristic diffraction peak of (002), (100) and (110) crystal face of molybdenum disulfide is arrived, it was demonstrated that the present invention has successfully prepared curing
Molybdenum/exfoliated-graphite composite electrode.
It can be seen that molybdenum disulfide is in flower-like structure from Fig. 3 b, and active site is located at the side of flower-like structure
Edge.Figure c shows that there is also the flower-like structures in Fig. 3 b in composite material produced by the present invention, and is evenly distributed in expansion
In graphite matrix composite sheet, the lamella edge of molybdenum disulfide is exposed, it was demonstrated that the present invention has successfully prepared molybdenum disulfide/expansion
Graphite composite material electrode.
In the prior art, molybdenum disulfide/best Hydrogen Evolution Performance of exfoliated-graphite composite electrode obtained exists in the present invention
Current density is 10mA/cm2When, overpotential can reach 230mV, compared with the molybdenum disulfide electrode of the prior art, liberation of hydrogen
Performance improves 23%.So the Hydrogen Evolution Performance of composite electrode prepared by the present invention significantly improves, and not by electrolyte pH
Influence, can acid, in and be electrolysed aquatic products hydrogen in the environment of alkali.
Finally, it should be noted that above-described each embodiment is merely to illustrate technical solution of the present invention, rather than it is limited
System；Although the present invention is described in detail referring to the foregoing embodiments, those skilled in the art should understand that: its
It can still modify to technical solution documented by previous embodiment, or part of or all technical features are carried out
Equivalent replacement；And these modifications or substitutions, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution
Range.
Claims (8)
1. a kind of molybdenum disulfide/expanded graphite hydrogen-precipitating electrode preparation method, it is characterised in that: itself specifically includes the following steps:
S1, expanded graphite compressing tablet process:
S11, expanded graphite and acetylene black are added in solvent absolute ethyl alcohol, stir 1~2h at room temperature, is added in whipping process poly-
Tetrafluoroethene, obtains dispersion liquid, and the mass ratio of expanded graphite, acetylene black and polytetrafluoroethylene (PTFE) is 1:0.1~0.15:5~7；
S12, by obtained dispersion liquid at 90 DEG C heated at constant temperature, so that the dehydrated alcohol in dispersion liquid is volatilized, be then dried to obtain
Expanded graphite mix powder；
S13, dry expanded graphite mix powder is put into cold forming mold processing is pressed, mould diameter is
50mm, setting pressing pressure are 8~10Mpa, and the pressing time is 15~20min, obtain expanded graphite casting die；
S14, expanded graphite casting die is sintered 120~130min at 375~380 DEG C, sintered part is cut into default shape
Shape, as expanded graphite matrix tabletting；
S2, molybdenum disulfide/expanded graphite hydrogen-precipitating electrode is prepared:
The dosage of raw material are as follows: the mass ratio of the tabletting of expanded graphite matrix, ammonium molybdate and thiocarbamide be 1:0.618~2.472:1.14~
4.56, and the additional amount of the corresponding ammonium molybdate of expanded graphite matrix tabletting every square centimeter is 0.071 mM~0.284 milli
Mole；
S21, ammonium molybdate and thiocarbamide are add to deionized water, magnetic agitation dissolves ammonium molybdate and thiocarbamide sufficiently at room temperature；
S22, expanded graphite matrix tabletting is placed in ethanol solution, 1~2h of ultrasound, it is dry；
S23, ammonium molybdate and thiocarbamide mixed solution are added into the expanded graphite matrix tabletting after drying, add at 199~201 DEG C
Heat for 24 hours after, be cooled to room temperature, molybdenum disulfide be directly loaded in expanded graphite matrix tabletting；
S24, the expanded graphite matrix tabletting for being loaded with molybdenum disulfide respectively cleans it with deionized water and dehydrated alcohol,
It is dry, obtain molybdenum disulfide/expanded graphite hydrogen-precipitating electrode.
2. molybdenum disulfide according to claim 1/expanded graphite hydrogen-precipitating electrode preparation method, it is characterised in that: described
Expanded graphite the preparation method comprises the following steps:
At room temperature, natural flake graphite, potassium permanganate and ammonium nitrate are sufficiently mixed, are then slowly added into perchloric acid, then exist
It is stirred at 30~35 DEG C, speed of agitator 200r/min, using Potassium Permanganate as Oxidant, perchloric acid makees intercalator, ammonium nitrate
Make auxiliary intercalator and carry out oxidation intercalation, the reaction time controls in 60~70min；
After the completion of intercalation to be oxidized, after mixing liquid cooled to room temperature, deionized water washing mixture to neutrality,
Then dehydration is filtered, drying obtains expansible graphite at 70 DEG C later；Expansible graphite is carried out at 950 DEG C swollen
Change, obtains expanded graphite.
3. molybdenum disulfide according to claim 1 or 2/expanded graphite hydrogen-precipitating electrode preparation method, it is characterised in that: step
The drying temperature of rapid S12 is 65~70 DEG C, and drying time is 23~25h.
4. molybdenum disulfide according to claim 1 or 2/expanded graphite hydrogen-precipitating electrode preparation method, it is characterised in that: step
When being sintered in rapid S14,375~380 DEG C of sintering temperature are warming up to from room temperature with the speed of 1 DEG C/min.
5. molybdenum disulfide according to claim 1 or 2/expanded graphite hydrogen-precipitating electrode preparation method, it is characterised in that: step
Sintered part is cut into the square part of 20mm × 20mm by rapid S14.
6. molybdenum disulfide according to claim 1/expanded graphite hydrogen-precipitating electrode preparation method, it is characterised in that: step
The drying temperature of S22 is 90~95 DEG C, and drying time is 10~15min.
7. molybdenum disulfide according to claim 1/expanded graphite hydrogen-precipitating electrode preparation method, it is characterised in that: step
199~201 DEG C of heating temperature are risen to from room temperature with the speed of 5 DEG C/min in S23.
8. molybdenum disulfide according to claim 1/expanded graphite hydrogen-precipitating electrode preparation method, it is characterised in that: often put down
The additional amount of square centimetre of the corresponding ammonium molybdate of expanded graphite matrix tabletting is 0.142 mM.
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| CN114790000A (en) * | 2022-04-19 | 2022-07-26 | 宁波信远炭材料有限公司 | High-temperature-resistant sealing material based on expanded graphite and preparation method thereof |
| CN117466644A (en) * | 2023-10-20 | 2024-01-30 | 青岛磁龙石墨有限公司 | High-heat-conductivity flexible graphite plate and preparation method thereof |
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| CN117466644A (en) * | 2023-10-20 | 2024-01-30 | 青岛磁龙石墨有限公司 | High-heat-conductivity flexible graphite plate and preparation method thereof |
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