CN110484934A - Nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method - Google Patents
Nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/02—Hydrogen or oxygen
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- C25B11/042—Electrodes formed of a single material
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- C25B11/044—Impregnation of carbon
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention relates to nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation methods, belong to the technical field of hydrogen electrode material preparation, its elder generation hydro-thermal reaction on the carbon cloth of acid dip modification grows nickel hydroxide, phosphorating treatment is carried out to nickel hydroxide later and obtains nickel phosphide-carbon cloth three-dimensional self-supporting material, then the electro-deposition nickel-phosphorus alloy on nickel phosphide-carbon cloth is then prepared for the nickel phosphorus/nickel phosphide for being not required to additional adhesion, electrocatalytic hydrogen evolution is had excellent performance-carbon cloth three-dimensional self-cradling type electrode material.The present invention is simple, low in cost with technical matters, is easy to industrial applications, the made electrode material internal gutter of this patent enriches and intercommunication, its electric conductivity is excellent, large specific surface area, electro catalytic activity point are more, and made nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material has good application prospect in hydrogen energy source development and application field.
Description
Technical field
The present invention relates to nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation methods, belong to hydrogen electrode
The technical field of material preparation.
Background technique
The problems such as environmental pollution is serious, the energy consumes rapidly caused by the fast development of social economy, scarcity of resources, urgently
The development and application for needing clean reproducible energy, in numerous clean energy resourcies, Hydrogen Energy is as a kind of economical, efficient, sustainable
Green energy resource, be ideal one of energy carrier, receive more and more extensive concern.In a variety of hydrogen producing technologies
In, water power dissociation hydrogen manufacturing is considered as one of the most effective approach towards " hydrogen economy ".However in practical applications, water power dissociates
Hydrogen manufacturing generally requires to overcome higher overpotential of hydrogen evolution, so that higher energy loss is caused, effectively to solve water electrolysis isolation
The excessively high technical bottleneck of hydrogen overpotential, the application of efficient catalytic material are the key problem in technology for breaking through this bottleneck.Pt same clan material electricity
Catalytic hydrogen evolution activity highest but its reserves is limited, at high price, it is difficult to large-scale promotion application.Therefore, developing low-cost, height
Active, environmental-friendly Electrocatalytic Activity for Hydrogen Evolution Reaction material is the key that realize hydrogen energy source exploitation and engineer application.
In numerous base metal electrocatalysis materials, transition metal phosphide is due to its unique electronic structure and eka-gold
Belong to characteristic, is one of catalytic reaction activity height, the Electrocatalytic Activity for Hydrogen Evolution Reaction material that stability is good and cost effectiveness is good, has and replace Pt
The potential quality of base electrocatalysis material.In numerous metal phosphides, nickel phosphide has the water decomposition liberation of hydrogen of similar [NiFe] hydrogenase
Activity is a kind of very promising liberation of hydrogen catalysis material.Nickel-phosphorus alloy is used as protective coating previously, it was in water in recent years
The application of electrolysis isolation hydrogen is just paid close attention to.Nickel-phosphorus alloy coating for water electrolysis isolation hydrogen is generally amorphous and mixed crystal shape
State, with surface-brightening, uniformly, hardness is high, wearability is good, the characteristics such as non magnetic.In terms of nickel-phosphorus alloy coating preparation, electricity
Using more, plating solution is mostly nickel sulfate-phosphite system for plating and Electroless Plating Procedure, its main feature is that plating solution prepare it is simple, stablize
Property it is good, gained plated layer compact, binding force are good, but be electroplated and Electroless Plating Procedure preparation nickel-phosphorus alloy coating activity point it is few, analysis
Hydrogen performance distance engineer application requires still have gap.Currently, phosphide catalysis material used in water electrolysis isolation hydrogen mostly uses greatly molten
Liquid hydrothermal synthesis process and high temperature solid-state reduction process preparation, form is mostly powder, needs fully dispersed in a solvent, Zhi Houzai
It is fixed on conductive carrier using the binders such as Nafion solution and Kynoar organic solution, such catalysis electrode
Catalyst loadings are limited, and binder can reduce the electrical conduction performance of electrode material, at the same can coat there is also binder and
The amount of activated point for covering catalyst, reduces its catalytic performance；In addition, active catalytic material is easy in long-time electrolytic process
It falls off from electrode surface, causes water electrolysis isolation hydrogen catalysis electrode stability poor.Therefore, using porous conductive material as carrier, increasing
Large electrode active area, while application in-situ growth technology loads with active catalytic components in electrode material surface, avoids and reduces
Binder and conductive agent use, and preparing the excellent three-dimensional self-supporting electrode of Hydrogen Evolution Performance is water electrolysis isolation hydrogen field important development
Trend, domestic and foreign scholars have carried out many research work thus.The patent of Publication No. CN108380227 discloses a kind of liberation of hydrogen
Electrocatalysis material and preparation method thereof, the graphene for being 3% with red phosphorus and homemade sphere metal nickel powder and mass fraction
For primary raw material, preforming processing is carried out to raw material using tablet press machine, then reaction in-situ occurs at high temperature, is prepared for one kind three
Tie up porous self-cradling type nickel phosphide Electrocatalytic Activity for Hydrogen Evolution Reaction material, although the technology can guarantee to have between catalytic component and substrate it is higher
Bond strength, but its catalytic hydrogen evolution activity is not good enough, still has larger gap with precious metals pt base catalysis material.Publication No.
The patent of CN106498434 discloses the preparation method of the Ni-based porous phosphatization nickel electrode of integration, using nickel foam as substrate, first
Chemical etching is carried out to foam nickel base, Ni-based porous nickel presoma is made, then In situ phosphatization, institute are carried out using solid phase reduction method
Although prepared material shows excellent Hydrogen Evolution Performance, but the stability of hydrogen-precipitating electrode active material is poor, is easy to be lost.Based on current
In liberation of hydrogen catalysis electrode preparation process, catalyst need to use binder be adhesively fixed, nickel phosphide component poorly conductive, electrode liberation of hydrogen
The few technological deficiency of active site, probe into conduct electricity very well, active area is big, activity component load quantity is high, mass transfer in liquid phase rate
Fastly, the important development for designing and preparation method, being water power dissociates hydrogen manufacturing of the three-dimensional self-supporting hydrogen evolution electrode material of simple process
Content.
Summary of the invention
The object of the present invention is to provide nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method, tools
The effect for thering is preparation process simplicity, inexpensive, electrocatalytic hydrogen evolution to have excellent performance.It carries out acid dip parent to carbon cloth substrate first
Water is modified, nickel hydroxide is grown on carbon cloth through hydro-thermal process after, later using sodium hypophosphite as phosphorus source, low temperature phosphor is in carbon
Nickel hydroxide is converted nickel phosphide by cloth surface, then deposits nickel-phosphorus alloy on its surface again, preparation is not necessarily to binder, electro-catalysis
The excellent nickel phosphorus/nickel phosphide of Hydrogen Evolution Performance-carbon cloth three-dimensional self-cradling type electrode material.
To achieve the goals above, the technical solution adopted by the present invention is that:
Nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method, comprising the following steps:
Step 1: being successively added in the beaker for filling deionized water by nickel nitrate, hexamethylenetetramine, and placing the beaker magnetic force
On blender, being stirred at room temperature dissolves the two；
Step 2: the solution that step 1 is stirred is transferred in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, simultaneously will
Treated that carbon cloth is put into stainless steel cauldron for acid dip, tightens the sealing cover of stainless steel cauldron and is transferred in electric furnace,
Reaction a period of time；Furnace power is closed after reaction, after fire box temperature is cooled to room temperature, by stainless steel cauldron from electricity
Carbon cloth is taken out from reaction kettle, is first washed with the deionized water additionally pipetted by the sealing cover that reaction kettle is taken out and opened in furnace
Carbon cloth, then carbon cloth is washed with dehydrated alcohol；
Step 3: the carbon cloth of step 2 washes clean is placed in a vacuum drying oven drying process a period of time, hydroxide is obtained
Nickel-carbon cloth persursor material；
Step 4: nickel hydroxide-carbon cloth the persursor material and sodium hypophosphite powder that step 3 prepares are respectively put into two
In a porcelain boat, then two porcelain boats equipped with sample are placed on to the center of tube furnace, tube furnace sample is placed arrival end and is connected with
Nitrogen access tube；
Step 5: connecting working gas gas circuit, tube furnace gas outlet end is connected into mechanical pump, carries out vacuumize process to negative
Pressure, evacuates the alundum tube and gas piping of tube furnace, opens nitrogen cylinder switching knob later, opens tube furnace intake valve, makes nitrogen
Gas slowly enters in tube furnace, when tube furnace air gauge stablize in 0MPa, open tube furnace air outlet valve；Tube furnace is opened simultaneously
Heater switch makes fire box temperature with constant heating rate by room temperature to certain temperature under nitrogen protection, and warm herein
Degree lower heat preservation a period of time, the nickel hydroxide for loading with carbon cloth surfaces generate nickel phosphide by phosphatization；
Step 6: closing tube furnace power supply after the phosphating reaction of step 5 but still nitrogen being kept to be passed through, protected in nitrogen
Make the temperature cooled to room temperature in tube furnace under shield, later by the sized nickel hydroxide/carbon cloth after phosphorating treatment from tube furnace
It takes out, as nickel phosphide-carbon cloth self-supporting material；
50mL deionized water is filled Step 7: being successively added to nickel chloride, trisodium citrate, ammonium sulfate, sodium hypophosphite
It in beaker, and places the beaker on magnetic stirring apparatus, opens mixing control rotary switch, agitating solution keeps each reagent being added complete
Fully dissolved, candidate agent dissolves and solution obtains nickel-phosphorus alloy electroplating solution after mixing evenly；
Step 8: using nickel phosphide made from step 6-carbon cloth self-supporting material as working electrode, clean graphite rod as auxiliary
Electrode, Ag/AgCl electrode are as nickel-phosphorus alloy electroplating solution made from reference electrode and step 7 as three electricity of electrolyte building
Electrode systems；
Step 9: opening constant potential after working electrode, auxiliary electrode and the reference electrode in step 8 are connect with potentiostat
Instrument power switch, using constant current controlling mode in nickel phosphide-carbon cloth die surfaces electro-deposition nickel-phosphorus alloy；
Step 10: taking out the nickel phosphide-for loading with nickel phosphorus in surface from nickel-phosphorus alloy electroplating solution after electro-deposition to step 9
Carbon cloth is cleaned with deionized water and dehydrated alcohol respectively, then by the sample cleaned up be placed in a vacuum drying oven into
Row is dried, and obtains nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material.
Technical solution of the present invention further improvement lies in that: carbon cloth in step 2 is made by following steps；
Step I, by volume be 100mL, the concentrated nitric acid that mass concentration is 65~68% is added in the beaker of 250mL, then eight
The carbon cloth that piece is cut into 2cm × 2cm is added in the beaker for filling concentrated nitric acid, and is sealed beaker mouth with preservative film, and room temperature is quiet
It sets 45~48h and acid dip hydrophilic modifying is carried out to carbon cloth；
Step II is placed the beaker in ultrasonic cleaner after standing and is ultrasonically treated to it, is contained in ultrasonic cleaner
Having temperature is 20~30 DEG C of deionized water, and the power of washer is 450W, sonication treatment time is 1~2h；
Step III takes out the carbon cloth after ultrasonic treatment from beaker, first rinses the pH until washing water to it with deionized water
For neutrality；Then carbon cloth dipping is washed twice with dehydrated alcohol again at room temperature, each dip time is 10~15min, it is ensured that
Carbon cloth surfaces are clean, flushed three times again with deionized water after dehydrated alcohol washing；
After step IV, carbon cloth washes clean, places it in and carry out drying and processing in vacuum oven at a temperature of 60~80 DEG C, very
Reciprocal of duty cycle is -0.1MPa, drying time is 10~12h, obtains acid dip treated carbon cloth.
Technical solution of the present invention further improvement lies in that: carbon cloth in step 1~step 6: nickel nitrate: six methines four
Amine: sodium hypophosphite: mass ratio relationship=0.055~0.06:0.7~0.75:0.7~0.75:0.25 of deionized water~
0.3:15~20.
Technical solution of the present invention further improvement lies in that: in step 2 electric stove hearth temperature be 100~110 DEG C, and
10~12h of hydro-thermal reaction at a temperature of this
Technical solution of the present invention further improvement lies in that: in step 3 and step 10 the drying temperature of vacuum oven be 60~
80 DEG C, drying time is 10~12h, and vacuum degree is -0.1MPa.
Technical solution of the present invention further improvement lies in that: in step 4 by equipped with sodium hypophosphite porcelain boat be placed on it is close
Tube furnace nitrogen inlet side, the porcelain boat equipped with sized nickel hydroxide/carbon cloth presoma are placed on gas outlet side.
Technical solution of the present invention further improvement lies in that: vacuumize process makes vacuum meter to -0.1MPa in step 5；Furnace
Bore temperature with the heating rate of 2~3 DEG C/min by room temperature to 280~300 DEG C, and at this temperature keep the temperature 2~3h.
Technical solution of the present invention further improvement lies in that: the mass ratio relationship of raw material is nickel chloride in step 7: lemon
Lemon acid trisodium: ammonium sulfate: sodium hypophosphite: deionized water=1.0~1.25:2.75~3.0:3.0~3.25:2.75~3.0:
45~55, wherein deionized water is 50mL.
Technical solution of the present invention further improvement lies in that: in step 8 nickel-phosphorus alloy electroplating solution need to sufficiently impregnate work electricity
Pole, auxiliary electrode and reference electrode.
Technical solution of the present invention further improvement lies in that: in step 9 potentiostat current density be 1~5mAcm-2, electricity
Depositing temperature is room temperature, and electrodeposition time is 60~180s.
By adopting the above-described technical solution, the technical effect that the present invention obtains has:
1, the art of this patent simple process, low in cost, application easy to industrialized production；
2, nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode is prepared by substrate of carbon cloth, makes full use of and played the big of carbon cloth
Area and excellent characteristics of electrical conductivity are loaded with, the bond strength of nickel phosphide active component and carbon cloth is improved, electrode preparation is not necessarily to volume
Outer bonding；
3, the art of this patent is by two kinds of liberation of hydrogen material advantage effective integrations of nickel-phosphorus alloy and nickel phosphide, while nickel-phosphorus alloy deposition is also
Realize the effective use that nickel phosphide loads with remaining site, obtained nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material
There is the cellular structure of abundant intercommunication, large specific surface area, catalytic activity point is more, Hydrogen Evolution Performance is excellent, future in engineering applications
It is expected；
4, the porcelain boat equipped with sodium hypophosphite is placed on close to tube furnace nitrogen inlet side by this patent, equipped with nickel hydroxide/
The porcelain boat of carbon cloth presoma is placed on gas outlet side, the phosphine gas that sodium hypophosphite pyrolysis generates under nitrogen protection in this way
With stream of nitrogen gas can sufficiently with the nickel hydroxide asperity contact on nickel hydroxide-carbon cloth presoma, and then fully to hydrogen-oxygen
Change nickel particle and carries out phosphatization.
Detailed description of the invention
Fig. 1 is the XRD diffracting spectrum of the made three-dimensional self-supporting electrode material of embodiment 1；
Fig. 2 is nickel phosphide-carbon cloth scanning electron microscope shape appearance figure of the made homoepitaxial on carbon cloth of embodiment 1；
Fig. 3 is nickel phosphide-carbon cloth scanning electron microscope shape appearance figure of the made inhomogeneous growth on carbon cloth of embodiment 1；
Fig. 4 is the made nickel phosphorus/nickel phosphide-carbon cloth scanning electron microscope shape appearance figure of embodiment 1；
Fig. 5 is that nickel phosphide-carbon cloth made from embodiment 1 and embodiment 1,2 and 3 distinguish made nickel phosphorus/nickel phosphide-carbon cloth liberation of hydrogen electricity
The cathode linear scan polarization curve of pole；
Fig. 6 is that nickel phosphide-carbon cloth made from embodiment 1 and embodiment 1,2 and 3 distinguish made nickel phosphorus/nickel phosphide-carbon hydrogen-precipitating electrode
Tafel slope curve graph.
Specific embodiment
With reference to the accompanying drawing and specific embodiment is described in further details the present invention:
The invention discloses nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation methods, including need acidleach
The acid dip processing step of the carbon cloth of stain, carbon cloth material is as follows:
Step I, by volume be 100mL, the concentrated nitric acid that mass concentration is 65~68% is added in the beaker of 250mL, then eight
The carbon cloth with a thickness of 0.33mm that piece is cut into 2cm × 2cm, which is added to, to be filled concentrated nitric acid and is added in the beaker of 250mL, is used in combination
Preservative film seals beaker mouth, is stored at room temperature 45~48h and carries out acid dip hydrophilic modifying to carbon cloth；
Step II is placed the beaker in ultrasonic cleaner after standing and is ultrasonically treated to it, is contained in ultrasonic cleaner
Having temperature is 20~30 DEG C of deionized water, and the power of washer is 450W, sonication treatment time is 1~2h；
Step III takes out the carbon cloth after ultrasonic treatment from beaker, is first repeatedly rinsed it until washing water with deionized water
PH be neutrality；Then carbon cloth dipping being washed twice with dehydrated alcohol again at room temperature, each dip time is 10~15min,
Ensure that carbon cloth surfaces are clean, is flushed three times again with deionized water after dehydrated alcohol washing；
After step IV, carbon cloth washes clean, places it in and carry out drying and processing in vacuum oven at a temperature of 60~80 DEG C, very
Reciprocal of duty cycle is -0.1MPa, drying time is 10~12h, obtains acid dip treated carbon cloth.
Nickel phosphorus/nickel phosphide of the invention-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method, including following step
It is rapid:
Step 1: being successively added in the beaker for filling deionized water by nickel nitrate, hexamethylenetetramine, and placing the beaker magnetic force
On blender, it is stirred at room temperature and makes it dissolve；
Step 2: the solution that step 1 is stirred is transferred in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, simultaneously will
Treated that carbon cloth is put into stainless steel cauldron for acid dip, tightens the sealing cover of stainless steel cauldron and is transferred in electric furnace,
Electric stove hearth temperature is 100~110 DEG C, and 10~12h of hydro-thermal reaction at this temperature；Furnace power is closed after reaction,
After fire box temperature is cooled to room temperature, stainless steel cauldron is taken out to from electric furnace and is opened the sealing cover of reaction kettle, by carbon cloth
It is taken out from reaction kettle, first washs carbon cloth three times with the deionized water additionally pipetted, then wash carbon cloth three times with dehydrated alcohol；
It being dried Step 3: the carbon cloth of step 2 washes clean is placed in a vacuum drying oven, drying temperature is 60~80 DEG C,
Drying time is 10~12h, and vacuum degree is -0.1MPa, obtains nickel hydroxide-carbon cloth persursor material；
Step 4: nickel hydroxide-carbon cloth the persursor material and sodium hypophosphite powder that step 3 prepares are respectively put into two
In a porcelain boat, then two porcelain boats equipped with sample are placed on to the center of tube furnace, tube furnace sample is placed arrival end and is connected with
Nitrogen access tube is equipped with hydroxide wherein being placed on the porcelain boat equipped with sodium hypophosphite close to tube furnace nitrogen inlet side
The porcelain boat of nickel carbon cloth presoma is placed on gas outlet side；
Step 5: connecting working gas gas circuit, tube furnace gas outlet end is connected into mechanical pump, carries out vacuumize process, vacuum
Table evacuates the alundum tube and gas piping of tube furnace to -0.1MPa, later open nitrogen cylinder switching knob, open tube furnace into
Air valve slowly enters nitrogen in tube furnace, when tube furnace air gauge stablize in 0MPa, open tube furnace air outlet valve；Simultaneously
Diamond heating switch is opened, under nitrogen protection, fire box temperature is with the heating rate of 2~3 DEG C/min by room temperature to 280
~300, and 2~3h is kept the temperature at this temperature, the nickel hydroxide for loading with carbon cloth surfaces generates nickel phosphide by phosphatization；
Step 6: closing tube furnace power supply after the phosphating reaction of step 5 but still nitrogen being kept to be passed through, protected in nitrogen
Make the temperature cooled to room temperature in tube furnace under shield, later by the sized nickel hydroxide/carbon cloth after phosphorating treatment from tube furnace
It takes out, as nickel phosphide-carbon cloth self-supporting material；
50mL deionized water is filled Step 7: being again successively added to nickel chloride, trisodium citrate, ammonium sulfate, sodium hypophosphite
Beaker in, the dosage of above-mentioned raw materials has following mass ratio relationship, nickel chloride: trisodium citrate: ammonium sulfate: ortho phosphorous acid
Sodium: deionized water=1.0~1.25:2.75~3.0:3.0~3.25:2.75~3.0:45~55；Then magnetic force is placed the beaker
On blender, mixing control rotary switch is opened, agitating solution is completely dissolved each reagent being added, candidate agent dissolution and solution
Nickel-phosphorus alloy electroplating solution is obtained after mixing evenly；
Step 8: using nickel phosphide made from step 6-carbon cloth self-supporting material be cut into 1cm × 1cm small pieces as working electrode,
Clean graphite rod is as auxiliary electrode, Ag/AgCl electrode as nickel-phosphorus alloy electroplating solution made from reference electrode and step 7
Three-electrode system is constructed as electrolyte, nickel-phosphorus alloy electroplating solution need to sufficiently impregnate working electrode, auxiliary electrode and reference electrode；
Step 9: opening potentiostat power supply after working electrode, auxiliary electrode and reference electrode are connect with ZF-9 potentiostat
Switch, using constant current controlling mode in nickel phosphide-carbon cloth die surfaces electro-deposition nickel-phosphorus alloy, current density 1mAcm-2, electrodeposition temperature be room temperature, electrodeposition time be 60~180s；
Step 10: taking out the nickel phosphide-for loading with nickel phosphorus in surface from nickel-phosphorus alloy electroplating solution after electro-deposition to step 9
Carbon cloth small pieces, are cleaned with deionized water and dehydrated alcohol respectively, and the sample cleaned up is then placed in vacuum oven
In be dried, drying temperature be 60~80 DEG C, drying time be 10~12h, vacuum degree be -0.1MPa, obtain nickel phosphorus/
Nickel phosphide-carbon cloth three-dimensional self-supporting electrode material.
The reaction mechanism of step 3 is that hexamethylenetetramine decomposes generation ammonium hydroxide, ammonium hydroxide and the nickel gold of generation in aqueous solution
Belong to ion to generate nickel hydroxide and deposit on carbon cloth；
Here is specific embodiment:
Treated that carbon cloth is made by the above method for acid dip used in each embodiment.
Embodiment 1
Step 1: 0.7270g nickel nitrate and 0.7010g hexamethylenetetramine to be successively added to the beaker for filling 18mL deionized water
In, it places the beaker on magnetic stirring apparatus later, is stirred at room temperature and makes it dissolve；
Step 2: the solution that step 1 is stirred is transferred to the stainless steel reaction that the polytetrafluoroethylene (PTFE) that volume is 25mL is liner
In kettle, while the square carbon cloth of acid dip treated length and width is all 2cm being put into stainless steel cauldron, is tightened
The sealing cover of stainless steel cauldron is simultaneously transferred in electric furnace, and electric stove hearth temperature is 100 DEG C, and hydro-thermal reaction at this temperature
10h；Furnace power is closed after reaction, and after fire box temperature is cooled to room temperature, stainless steel cauldron is taken out from electric furnace
And the sealing cover of reaction kettle is opened, carbon cloth is taken out from reaction kettle, first washs carbon cloth three times with the deionized water additionally pipetted,
Carbon cloth is washed three times with dehydrated alcohol again；
It is dried Step 3: the carbon cloth of step 2 washes clean is placed in a vacuum drying oven, drying temperature is 60 DEG C, dry
Time is 12h, and vacuum degree is -0.1MPa, obtains nickel hydroxide-carbon cloth persursor material；
Step 4: nickel hydroxide-carbon cloth the persursor material and 0.25g sodium hypophosphite powder that step 3 prepares are put respectively
Enter in two porcelain boats, then two porcelain boats equipped with sample are placed on to the center of tube furnace, tube furnace sample is placed arrival end and connected
It is connected to nitrogen access tube, wherein being placed on the porcelain boat equipped with sodium hypophosphite close to tube furnace nitrogen inlet side, hydrogen is housed
Nickel oxide/carbon cloth presoma porcelain boat is placed on gas outlet side；
Step 5: connecting working gas gas circuit, tube furnace gas outlet end is connected into mechanical pump, carries out vacuumize process, vacuum
Table evacuates the alundum tube and gas piping of tube furnace to -0.1MPa, later open nitrogen cylinder switching knob, open tube furnace into
Air valve enters nitrogen in tube furnace with 300mL/min, when tube furnace air gauge stablize in 0MPa, open tube furnace outlet
Valve；Diamond heating switch is opened simultaneously, and under nitrogen protection, fire box temperature is with the heating rate of 2 DEG C/min by room temperature
To 300 DEG C, and 2h is kept the temperature at this temperature, the nickel hydroxide for loading with carbon cloth surfaces generates nickel phosphide by phosphatization；
Step 6: closing tube furnace power supply after the phosphating reaction of step 5 but still nitrogen being kept to be passed through, protected in nitrogen
Make the temperature cooled to room temperature in tube furnace under shield, later by the sized nickel hydroxide/carbon cloth after phosphorating treatment from tube furnace
It takes out, as nickel phosphide-carbon cloth self-supporting material；
Step 7: again successively by 1.1885g nickel chloride, 2.9410g trisodium citrate, 3.0392g ammonium sulfate, 2.9677g Asia
Sodium phosphate is added in the beaker for filling 50mL deionized water；Then it places the beaker on magnetic stirring apparatus, opens mixing control
Rotary switch, agitating solution are completely dissolved each reagent being added, and candidate agent dissolves and solution obtains the conjunction of nickel phosphorus after mixing evenly
Gold plating bath；
Step 8: using the nickel phosphide of 2cm × 2cm made from step 6-carbon cloth self-supporting material be cut into 1cm × 1cm small pieces as
Working electrode, clean graphite rod are closed as auxiliary electrode, Ag/AgCl electrode as nickel phosphorus made from reference electrode and step 7
Gold plating bath as electrolyte construct three-electrode system, nickel-phosphorus alloy electroplating solution need to sufficiently impregnate working electrode, auxiliary electrode and
Reference electrode；
Step 9: opening potentiostat power supply after working electrode, auxiliary electrode and reference electrode are connect with ZF-9 potentiostat
Switch, using constant current controlling mode in nickel phosphide-carbon cloth die surfaces electro-deposition nickel-phosphorus alloy, current density 1mAcm-2, electrodeposition temperature be room temperature, electrodeposition time 60s；
Step 10: taking out the nickel phosphide-for loading with nickel phosphorus in surface from nickel-phosphorus alloy electroplating solution after electro-deposition to step 9
Carbon cloth small pieces, are cleaned with deionized water and dehydrated alcohol respectively, and the sample cleaned up is then placed in vacuum oven
In be dried, drying temperature be 60 DEG C, drying time 12h, vacuum degree be -0.1MPa, obtain nickel phosphorus/nickel phosphide -
Carbon cloth three-dimensional self-supporting electrode material.
Using the nickel of above-mentioned preparation phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode as working electrode, graphite rod is auxiliary electricity
Pole, Ag/AgCl electrode be reference electrode, test equipment be Shanghai Chen Hua CHI650C type electrochemical workstation, under room temperature into
The linear voltammetric scan test of row cathode, to detect nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode electrochemistry Hydrogen Evolution Performance；
Before electro-chemical test, nitrogen 30min, in all tests, the Ag/AgCl potential value school that measures are led into electrolyte
Standard is the potential relative to reversible hydrogen electrode；The potential window of linear voltammetric scan is -0.3~0V, sweep speed 2mVs-1；
Tafel curve figure is to be obtained by drawing overpotential with current density logarithmic relationship curve, and the linear segment of Tafel curve is full
Sufficient Tafel equation:η=blog(j)+a, whereinηIndicate overpotential,jIndicate current density,bIndicate Tafel slope,aIt indicates
Intercept, the overpotential window of Tafel curve figure are 0~0.4V, sweep speed 2mVs-1。
It, can from XRD test curve such as the XRD diffracting spectrum that Fig. 1 is the made three-dimensional self-supporting electrode material of the present embodiment
It is relatively good with the crystallinity of nickel phosphide-carbon cloth visible in detail, 2 θ=40.7 ° of the angle of diffraction, 44.6 °, 47.4 °, 54.2 ° and 55 °
Respectively correspond (111), (201), (210), (300) and (211) diffraction crystal face of nickel phosphide, the XRD standard card with nickel phosphide
JCPDSNO.74-1385 matches, and the angle of diffraction is the position of 2 θ=26.2 ° in the spectrogram, and (002) diffraction of corresponding carbon cloth is brilliant
Face is consistent with carbon cloth XRD card for JCPDSNO.75-1621；Since the electric deposition nickel phosphorus time is short, its amount of loading with is few, and
And there are the interference of nickel phosphide and bridging effects to be not easy to be identified so the XRD characteristic diffraction peak of electric deposition nickel phosphorus is not significant
Out.
Fig. 2, Fig. 3, Fig. 4 are the scanning electron microscope shape appearance figures of the made three-dimensional self-supporting electrode material of the present embodiment, should shown in Fig. 2
Nickel phosphide-carbon cloth sample is in flower-like structure, and nickel phosphide homoepitaxial is in carbon cloth conductive substrates；It can be observed by illustration in Fig. 2
It arrives, nickel phosphide flower-like structure is stacked by nanometer sheet.Fig. 3 is the scanning figure of same material different parts shown in Fig. 2, from figure
It can be seen that it is very uniformly, i.e., not have nickel phosphide in certain points that nickel phosphide is distributed not on carbon cloth in 3.From fig. 4, it can be seen that
Nickel phosphorus/nickel phosphide-carbon cloth sample is similarly flower-like structure, by the interior illustration that amplifies it is found that compared with Fig. 2, nickel phosphide nanometer
Piece surface is more coarse, this is because nickel-phosphorus alloy coating is loaded with caused by the vacant position of alramenting nickel.
Embodiment 2
Step 1: successively 0.70g nickel nitrate and 0.70g hexamethylenetetramine are added in the beaker for filling 15mL deionized water,
It places the beaker on magnetic stirring apparatus later, is stirred at room temperature and makes it dissolve；
Step 2: the solution that step 1 is stirred is transferred to the stainless steel reaction that the polytetrafluoroethylene (PTFE) that volume is 25mL is liner
In kettle, while the square carbon cloth of acid dip treated length and width is all 2cm being put into stainless steel cauldron, is tightened
The sealing cover of stainless steel cauldron is simultaneously transferred in electric furnace, and electric stove hearth temperature is 100 DEG C, and hydro-thermal reaction at this temperature
10h；Furnace power is closed after reaction, and after fire box temperature is cooled to room temperature, stainless steel cauldron is taken out from electric furnace
And the sealing cover of reaction kettle is opened, carbon cloth is taken out from reaction kettle, first washs carbon cloth three times with the deionized water additionally pipetted,
Carbon cloth is washed three times with dehydrated alcohol again；
It is dried Step 3: the carbon cloth of step 2 washes clean is placed in a vacuum drying oven, drying temperature is 60 DEG C, dry
Time is 12h, and vacuum degree is -0.1MPa, obtains nickel hydroxide-carbon cloth persursor material；
Step 4: nickel hydroxide-carbon cloth the persursor material and 0.25g sodium hypophosphite powder that step 3 prepares are put respectively
Enter in two porcelain boats, then two porcelain boats equipped with sample are placed on to the center of tube furnace, tube furnace sample is placed arrival end and connected
It is connected to nitrogen access tube, wherein being placed on the porcelain boat equipped with sodium hypophosphite close to tube furnace nitrogen inlet side, hydrogen is housed
Nickel oxide/carbon cloth presoma porcelain boat is placed on gas outlet side；
Step 5: connecting working gas gas circuit, tube furnace gas outlet end is connected into mechanical pump, carries out vacuumize process, vacuum
Table evacuates the alundum tube and gas piping of tube furnace to -0.1MPa, later open nitrogen cylinder switching knob, open tube furnace into
Air valve enters nitrogen in tube furnace with 300mL/min, when tube furnace air gauge stablize in 0MPa, open tube furnace outlet
Valve；Diamond heating switch is opened simultaneously, and under nitrogen protection, fire box temperature is with the heating rate of 2 DEG C/min by room temperature
To 300 DEG C, and 2h is kept the temperature at this temperature, the nickel hydroxide for loading with carbon cloth surfaces generates nickel phosphide by phosphatization；
Step 6: closing tube furnace power supply after the phosphating reaction of step 5 but still nitrogen being kept to be passed through, protected in nitrogen
Make the temperature cooled to room temperature in tube furnace under shield, later by the sized nickel hydroxide/carbon cloth after phosphorating treatment from tube furnace
It takes out, as nickel phosphide-carbon cloth self-supporting material；
Step 7: successively 1.0g nickel chloride, 2.75g trisodium citrate, 3.0g ammonium sulfate, 2.75g sodium hypophosphite are added again
Into the beaker for filling 45mL deionized water；Then it places the beaker on magnetic stirring apparatus, opens mixing control rotary switch, stir
Mixing solution is completely dissolved each reagent being added, and candidate agent dissolves and solution obtains nickel-phosphorus alloy electroplating solution after mixing evenly；
Step 8: using the nickel phosphide of 2cm × 2cm made from step 6-carbon cloth self-supporting material be cut into 1cm × 1cm small pieces as
Working electrode, clean graphite rod are closed as auxiliary electrode, Ag/AgCl electrode as nickel phosphorus made from reference electrode and step 7
Gold plating bath as electrolyte construct three-electrode system, nickel-phosphorus alloy electroplating solution need to sufficiently impregnate working electrode, auxiliary electrode and
Reference electrode；
Step 9: opening potentiostat power supply after working electrode, auxiliary electrode and reference electrode are connect with ZF-9 potentiostat
Switch, using constant current controlling mode in nickel phosphide-carbon cloth die surfaces electro-deposition nickel-phosphorus alloy, current density 2mAcm-2, electrodeposition temperature be room temperature, electrodeposition time 120s；
Step 10: taking out the nickel phosphide-for loading with nickel phosphorus in surface from nickel-phosphorus alloy electroplating solution after electro-deposition to step 9
Carbon cloth small pieces, are cleaned with deionized water and dehydrated alcohol respectively, and the sample cleaned up is then placed in vacuum oven
In be dried, drying temperature be 60 DEG C, drying time 12h, vacuum degree be -0.1MPa, obtain nickel phosphorus/nickel phosphide -
Carbon cloth three-dimensional self-supporting electrode material.
Using the nickel of above-mentioned preparation phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode as working electrode, graphite rod is auxiliary electricity
Pole, Ag/AgCl electrode be reference electrode, test equipment be Shanghai Chen Hua CHI650C type electrochemical workstation, under room temperature into
The linear voltammetric scan test of row cathode, to detect nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode electrochemistry Hydrogen Evolution Performance；
Before electro-chemical test, nitrogen 30min, in all tests, the Ag/AgCl potential value school that measures are led into electrolyte
Standard is the potential relative to reversible hydrogen electrode；The potential window of linear voltammetric scan is -0.3~0V, sweep speed 2mVs-1；
Tafel curve figure is to be obtained by drawing overpotential with current density logarithmic relationship curve, and the linear segment of Tafel curve is full
Sufficient Tafel equation:η=blog(j)+a, whereinηIndicate overpotential,jIndicate current density,bIndicate Tafel slope,aIt indicates
Intercept, the overpotential window of Tafel curve figure are 0~0.4V, sweep speed 2mVs-1。
The made nickel phosphorus/nickel phosphide-carbon cloth electrode material crystal plane structure of the present embodiment and pattern and embodiment 1 are made
Sample is without marked difference, so be not described.
Embodiment 3
Step 1: successively 0.75g nickel nitrate and 0.75g hexamethylenetetramine are added in the beaker for filling 20mL deionized water,
It places the beaker on magnetic stirring apparatus later, is stirred at room temperature and makes it dissolve；
Step 2: the solution that step 1 is stirred is transferred to the stainless steel reaction that the polytetrafluoroethylene (PTFE) that volume is 25mL is liner
In kettle, while the square carbon cloth of acid dip treated length and width is all 2cm being put into stainless steel cauldron, is tightened
The sealing cover of stainless steel cauldron is simultaneously transferred in electric furnace, and electric stove hearth temperature is 100 DEG C, and hydro-thermal reaction at this temperature
10h；Furnace power is closed after reaction, and after fire box temperature is cooled to room temperature, stainless steel cauldron is taken out from electric furnace
And the sealing cover of reaction kettle is opened, carbon cloth is taken out from reaction kettle, first washs carbon cloth three times with the deionized water additionally pipetted,
Carbon cloth is washed three times with dehydrated alcohol again；
It is dried Step 3: the carbon cloth of step 2 washes clean is placed in a vacuum drying oven, drying temperature is 60 DEG C, dry
Time is 12h, and vacuum degree is -0.1MPa, obtains nickel hydroxide-carbon cloth persursor material；
Step 4: nickel hydroxide-carbon cloth the persursor material and 0.25g sodium hypophosphite powder that step 3 prepares are put respectively
Enter in two porcelain boats, then two porcelain boats equipped with sample are placed on to the center of tube furnace, tube furnace sample is placed arrival end and connected
It is connected to nitrogen access tube, wherein being placed on the porcelain boat equipped with sodium hypophosphite close to tube furnace nitrogen inlet side, hydrogen is housed
Nickel oxide/carbon cloth presoma porcelain boat is placed on gas outlet side；
Step 5: connecting working gas gas circuit, tube furnace gas outlet end is connected into mechanical pump, carries out vacuumize process, vacuum
Table evacuates the alundum tube and gas piping of tube furnace to -0.1MPa, later open nitrogen cylinder switching knob, open tube furnace into
Air valve enters nitrogen in tube furnace with 300mL/min, when tube furnace air gauge stablize in 0MPa, open tube furnace outlet
Valve；Diamond heating switch is opened simultaneously, and under nitrogen protection, fire box temperature is with the heating rate of 2 DEG C/min by room temperature
To 300 DEG C, and 2h is kept the temperature at this temperature, the nickel hydroxide for loading with carbon cloth surfaces generates nickel phosphide by phosphatization；
Step 6: closing tube furnace power supply after the phosphating reaction of step 5 but still nitrogen being kept to be passed through, protected in nitrogen
Make the temperature cooled to room temperature in tube furnace under shield, later by the sized nickel hydroxide/carbon cloth after phosphorating treatment from tube furnace
It takes out, as nickel phosphide-carbon cloth self-supporting material；
Step 7: successively 1.25g nickel chloride, 3.0g trisodium citrate, 3.25g ammonium sulfate, 3g sodium hypophosphite are added to again
In the beaker for filling 55mL deionized water；Then it places the beaker on magnetic stirring apparatus, opens mixing control rotary switch, stirring
Solution is completely dissolved each reagent being added, and candidate agent dissolves and solution obtains nickel-phosphorus alloy electroplating solution after mixing evenly；
Step 8: using the nickel phosphide of 2cm × 2cm made from step 6-carbon cloth self-supporting material be cut into 1cm × 1cm small pieces as
Working electrode, clean graphite rod are closed as auxiliary electrode, Ag/AgCl electrode as nickel phosphorus made from reference electrode and step 7
Gold plating bath as electrolyte construct three-electrode system, nickel-phosphorus alloy electroplating solution need to sufficiently impregnate working electrode, auxiliary electrode and
Reference electrode；
Step 9: opening potentiostat power supply after working electrode, auxiliary electrode and reference electrode are connect with ZF-9 potentiostat
Switch, using constant current controlling mode in nickel phosphide-carbon cloth die surfaces electro-deposition nickel-phosphorus alloy, current density 5mAcm-2, electrodeposition temperature be room temperature, electrodeposition time 180s；
Step 10: taking out the nickel phosphide-for loading with nickel phosphorus in surface from nickel-phosphorus alloy electroplating solution after electro-deposition to step 9
Carbon cloth small pieces, are cleaned with deionized water and dehydrated alcohol respectively, and the sample cleaned up is then placed in vacuum oven
In be dried, drying temperature be 60 DEG C, drying time 12h, vacuum degree be -0.1MPa, obtain nickel phosphorus/nickel phosphide -
Carbon cloth three-dimensional self-supporting electrode material.
Using the nickel of above-mentioned preparation phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode as working electrode, graphite rod is auxiliary electricity
Pole, Ag/AgCl electrode be reference electrode, test equipment be Shanghai Chen Hua CHI650C type electrochemical workstation, under room temperature into
The linear voltammetric scan test of row cathode, to detect nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode electrochemistry Hydrogen Evolution Performance；
Before electro-chemical test, nitrogen 30min, in all tests, the Ag/AgCl potential value school that measures are led into electrolyte
Standard is the potential relative to reversible hydrogen electrode；The potential window of linear voltammetric scan is -0.3~0V, sweep speed 2mVs-1；
Tafel curve figure is to be obtained by drawing overpotential with current density logarithmic relationship curve, and the linear segment of Tafel curve is full
Sufficient Tafel equation:η=blog(j)+a, whereinηIndicate overpotential,jIndicate current density,bIndicate Tafel slope,aIt indicates
Intercept, the overpotential window of Tafel curve figure are 0~0.4V, sweep speed 2mVs-1。
The made nickel phosphorus/nickel phosphide-carbon cloth electrode material crystal plane structure of the present embodiment and pattern and embodiment 1 are made
Sample is without marked difference, so be not described.
Fig. 5 is that nickel phosphide-carbon cloth obtained and embodiment 1,2 and 3 distinguish made nickel phosphorus/nickel phosphide-carbon cloth hydrogen-precipitating electrode
Cathode linear scan polarization curve, from Fig. 5 it can be observed that curve 1, curve 2, curve 3 and curve 4 are embodiment 1 respectively
Made nickel phosphide-carbon cloth, the made nickel phosphorus/nickel phosphide-carbon cloth of embodiment 1, the made nickel phosphorus/nickel phosphide-carbon cloth of embodiment 2 and implementation
The made nickel phosphorus of example 3/nickel phosphide-carbon cloth hydrogen-precipitating electrode cathode linear scan polarization curve, from test result it is found that made nickel
Phosphorus/nickel phosphide-carbon cloth electrochemistry hydrogen evolution activity is better than made nickel phosphide-carbon cloth.When current density is 10mAcm-2When, implement
The made nickel phosphide of example 1-carbon cloth sample, the made nickel phosphorus/nickel phosphide-carbon cloth sample of embodiment 1, the made nickel phosphorus/phosphatization of embodiment 2
Nickel-carbon cloth sample and the made nickel phosphorus of embodiment 3/nickel phosphide-carbon cloth sample hydrogen-precipitating electrode overpotential be respectively 120mV,
95mV, 112mV and 114mV；The made nickel phosphorus/nickel phosphide-carbon cloth sample of embodiment 1 is compared with other made samples, liberation of hydrogen mistake
Current potential is minimum, this shows in made nickel phosphorus/- nickel phosphide-carbon cloth and nickel phosphide-carbon cloth sample, and three-dimensional made from embodiment 1 is certainly
The Hydrogen Evolution Performance of support electrode material is best, and preparation condition is more excellent.
Fig. 6 is the Tafel slope curve of the embodiment of the present invention 1,2 and 3 made three-dimensional self-supporting electrodes, can be seen from Fig. 6
Observing curve a, curve b, curve c and curve d is the made nickel phosphide-carbon cloth of embodiment 1, the made nickel phosphorus/phosphatization of embodiment 1 respectively
Nickel-carbon cloth, the made nickel phosphorus/nickel phosphide-carbon cloth of embodiment 2 and the made nickel phosphorus of embodiment 3/nickel phosphide-carbon cloth hydrogen-precipitating electrode tower
Fei Er slope curve, from test result it is found that the made nickel phosphide of embodiment 1-carbon cloth sample, the made nickel phosphorus/phosphatization of embodiment 1
Nickel-carbon cloth sample, the made nickel phosphorus/nickel phosphide-carbon cloth sample of embodiment 2 and the made nickel phosphorus/nickel phosphide-carbon cloth sample of embodiment 3
Tafel slope be respectively 91.9mVdec-1、80.4mVdec-1、87.2mVdec-1And 88.5mVdec-1, it was demonstrated that nickel phosphorus/phosphatization
Nickel-carbon cloth electrode has faster evolving hydrogen reaction dynamics than nickel phosphide-carbon cloth electrode.This Tafel slope 40 ~
120mVdec-1Section show that the mechanism of the evolving hydrogen reaction is Volmer-Heyrovsky, that is to say, that Heyrovsky process is
The ratedeterming step of this process.The made nickel phosphorus of embodiment 1/nickel phosphide-carbon cloth sample Tafel slope is minimum, to further demonstrate,prove
It is best that Hydrogen Evolution Performance of the three-dimensional self-supporting electrode material in three kinds of electrode materials made from embodiment 1 is illustrated.XRD diffracting spectrum
The presence of nickel-phosphorus alloy coating cannot be sufficiently proved with scanning electron microscope shape appearance figure, but electrochemical from made nickel phosphorus/nickel phosphide-carbon cloth
It learns hydrogen evolution activity and is substantially better than made nickel phosphide-carbon cloth, further illustrate nickel-phosphorus alloy coating and load in alramenting nickel
Vacant position.
The embodiment of present embodiment is presently preferred embodiments of the present invention, not limits protection of the invention according to this
Range, therefore: the equivalence changes that all structures under this invention, shape, principle etc. are done should all be covered by protection scope of the present invention
Within.
List the optional material of various components in specification of the invention, but those skilled in the art should understand that:
Said components material enumerate and unrestricted, also nonexhaustive, various components can use other description of the invention
In the equivalent material substitution do not mentioned, and the purpose of the present invention still may be implemented.Specific embodiment noted in the disclosure
Be function only as purpose of explanation, rather than for limit the scope of the invention.
In addition, the amount ranges of each component of the invention include any lower limit noted in the disclosure and any upper limit
Any combination, also include each specific embodiment in the component concrete content constituted as the upper limit or lower values it is any
Range: all these ranges all cover within the scope of the invention, are intended merely to save space, and the range that these are composed is not
It enumerates in the description.Cited each feature of the invention in specification, can with it is of the invention any other
Feature combination, this combination also all within the scope of disclosure of the invention, are intended merely to save space, these ranges being composed
It does not enumerate in the description.
Claims (10)
1. nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method, which is characterized in that including following step
It is rapid:
Step 1: being successively added in the beaker for filling deionized water by nickel nitrate, hexamethylenetetramine, and placing the beaker magnetic force
On blender, being stirred at room temperature dissolves the two；
Step 2: the solution that step 1 is stirred is transferred in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is liner, simultaneously will
Treated that carbon cloth is also placed in stainless steel cauldron for acid dip, tightens the sealing cover of stainless steel cauldron and is transferred to electric furnace
In, reaction a period of time；Furnace power is closed after reaction, after fire box temperature is cooled to room temperature, by stainless steel cauldron
The sealing cover that reaction kettle is taken out and opened from electric furnace takes out carbon cloth from reaction kettle, first with the deionized water additionally pipetted
Carbon cloth is washed, then washs carbon cloth with dehydrated alcohol；
Step 3: the carbon cloth of step 2 washes clean is placed in a vacuum drying oven drying process a period of time, hydroxide is obtained
Nickel-carbon cloth persursor material；
Step 4: nickel hydroxide-carbon cloth the persursor material and sodium hypophosphite powder that step 3 prepares are respectively put into two
In a porcelain boat, then two porcelain boats equipped with sample are placed on to the center of tube furnace, tube furnace sample is placed arrival end and is connected with
Nitrogen access tube；
Step 5: connecting working gas gas circuit, tube furnace gas outlet end is connected into mechanical pump, carries out vacuumize process to negative
Pressure, evacuates the alundum tube and gas piping of tube furnace, opens nitrogen cylinder switching knob later, opens tube furnace intake valve, makes nitrogen
Gas slowly enters in tube furnace, when tube furnace air gauge stablize in 0MPa, open tube furnace air outlet valve；Tube furnace is opened simultaneously
Heater switch makes fire box temperature with constant heating rate by room temperature to certain temperature under nitrogen protection, and warm herein
Degree lower heat preservation a period of time, the nickel hydroxide for loading with carbon cloth surfaces generate nickel phosphide by phosphatization；
Step 6: closing tube furnace power supply after the phosphating reaction of step 5 but still nitrogen being kept to be passed through, protected in nitrogen
Make the temperature cooled to room temperature in tube furnace under shield, later by the sized nickel hydroxide/carbon cloth after phosphorating treatment from tube furnace
It takes out, as nickel phosphide-carbon cloth self-supporting material；
Step 7: nickel chloride, trisodium citrate, ammonium sulfate, sodium hypophosphite to be successively added to the beaker for filling deionized water
In, and place the beaker on magnetic stirring apparatus, mixing control rotary switch is opened, agitating solution keeps each reagent being added completely molten
Solution, candidate agent dissolves and solution obtains nickel-phosphorus alloy electroplating solution after mixing evenly；
Step 8: using nickel phosphide made from step 6-carbon cloth self-supporting material as working electrode, clean graphite rod as auxiliary
Electrode, Ag/AgCl electrode are as nickel-phosphorus alloy electroplating solution made from reference electrode and step 7 as three electricity of electrolyte building
Electrode systems；
Step 9: opening constant potential after working electrode, auxiliary electrode and the reference electrode in step 8 are connect with potentiostat
Instrument power switch, using constant current controlling mode in nickel phosphide-carbon cloth die surfaces electro-deposition nickel-phosphorus alloy；
Step 10: taking out the nickel phosphide-for loading with nickel phosphorus in surface from nickel-phosphorus alloy electroplating solution after electro-deposition to step 9
Carbon cloth is cleaned with deionized water and dehydrated alcohol respectively, then by the sample cleaned up be placed in a vacuum drying oven into
Row is dried, and obtains nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material.
2. nickel phosphorus/nickel phosphide according to claim 1-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method,
Be characterized in that: the carbon cloth in step 2 is made by following steps；
Step I, by volume be 100mL, the concentrated nitric acid that mass concentration is 65~68% is added in the beaker of 250mL, then eight
The carbon cloth that piece is cut into 2cm × 2cm is added in the beaker for filling concentrated nitric acid, and is sealed beaker mouth with preservative film, and room temperature is quiet
It sets 45~48h and acid dip hydrophilic modifying is carried out to carbon cloth；
Step II is placed the beaker in ultrasonic cleaner after standing and is ultrasonically treated to it, is contained in ultrasonic cleaner
Having temperature is 20~30 DEG C of deionized water, and the power of washer is 450W, sonication treatment time is 1~2h；
Step III takes out the carbon cloth after ultrasonic treatment from beaker, first rinses the pH until washing water to it with deionized water
For neutrality；Then carbon cloth dipping is washed twice with dehydrated alcohol again at room temperature, each dip time is 10~15min, it is ensured that
Carbon cloth surfaces are clean, flushed three times again with deionized water after dehydrated alcohol washing；
After step IV, carbon cloth washes clean, places it in and carry out drying and processing in vacuum oven at a temperature of 60~80 DEG C, very
Reciprocal of duty cycle is -0.1MPa, drying time is 10~12h, obtains acid dip treated carbon cloth.
3. nickel phosphorus/nickel phosphide according to claim 1-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method,
It is characterized in that: carbon cloth in step 1~step 6: nickel nitrate: hexamethylenetetramine: sodium hypophosphite: the mass ratio of deionized water
Example relationship=0.055~0.06:0.7~0.75:0.7~0.75:0.25~0.3:15~20.
4. nickel phosphorus/nickel phosphide according to claim 1-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method,
Be characterized in that: electric stove hearth temperature is 100~110 DEG C in step 2, and 10~12h of hydro-thermal reaction at this temperature.
5. nickel phosphorus/nickel phosphide according to claim 1-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method,
Be characterized in that: the drying temperature of vacuum oven is 60~80 DEG C in step 3 and step 10, and drying time is 10~12h, very
Reciprocal of duty cycle is -0.1MPa.
6. nickel phosphorus/nickel phosphide according to claim 1-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method,
It is characterized in that: the porcelain boat equipped with sodium hypophosphite being placed on close to tube furnace nitrogen inlet side in step 4, hydrogen-oxygen is housed
The porcelain boat for changing nickel carbon cloth presoma is placed on gas outlet side.
7. nickel phosphorus/nickel phosphide according to claim 1-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method,
Be characterized in that: vacuumize process makes vacuum meter to -0.1MPa in step 5；Fire box temperature with the heating rate of 2~3 DEG C/min by
Room temperature keeps the temperature 2~3h to 280~300 DEG C at this temperature.
8. nickel phosphorus/nickel phosphide according to claim 1-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method,
Be characterized in that: the mass ratio relationship of raw material is nickel chloride in step 7: trisodium citrate: ammonium sulfate: sodium hypophosphite: being gone
Ionized water=1.0~1.25:2.75~3.0:3.0~3.25:2.75~3.0:45~55, wherein deionized water is 50mL.
9. nickel phosphorus/nickel phosphide according to claim 1-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method,
Be characterized in that: nickel-phosphorus alloy electroplating solution need to sufficiently impregnate working electrode, auxiliary electrode and reference electrode in step 8.
10. nickel phosphorus/nickel phosphide according to claim 1-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material preparation method,
Be characterized in that: potentiostat current density is 1~5mAcm in step 9-2, electrodeposition temperature be room temperature, electrodeposition time 60
~180s.
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| CN111575729A (en) * | 2020-04-22 | 2020-08-25 | 广东工业大学 | Nickel phosphide compound with multi-level hole structure and preparation method and application thereof |
| CN111957329A (en) * | 2020-07-20 | 2020-11-20 | 广西师范大学 | Preparation method of self-supporting Ni2P-WOx hydrogen evolution electrocatalyst |
| CN113130905A (en) * | 2021-04-16 | 2021-07-16 | 陕西科技大学 | Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof |
| CN113725426A (en) * | 2021-08-27 | 2021-11-30 | 北京理工大学 | A kind of Ni (OH)2-Ni2P @ carbon cloth composite material, and preparation and application thereof |
| CN114134529A (en) * | 2021-11-30 | 2022-03-04 | 燕山大学 | Hydrogen evolution electrode and preparation method and application thereof |
| CN114497574A (en) * | 2021-12-02 | 2022-05-13 | 太原理工大学 | Self-supporting transition metal phosphide-doped porous carbon membrane hydrogen evolution electro-catalytic material |
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| CN111957329B (en) * | 2020-07-20 | 2023-09-19 | 中科润谷智慧能源科技(佛山)有限公司 | Preparation method of self-supporting Ni2P-WOx hydrogen evolution electrocatalyst |
| CN113130905A (en) * | 2021-04-16 | 2021-07-16 | 陕西科技大学 | Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof |
| CN113725426A (en) * | 2021-08-27 | 2021-11-30 | 北京理工大学 | A kind of Ni (OH)2-Ni2P @ carbon cloth composite material, and preparation and application thereof |
| CN114134529A (en) * | 2021-11-30 | 2022-03-04 | 燕山大学 | Hydrogen evolution electrode and preparation method and application thereof |
| CN114497574A (en) * | 2021-12-02 | 2022-05-13 | 太原理工大学 | Self-supporting transition metal phosphide-doped porous carbon membrane hydrogen evolution electro-catalytic material |
| CN114497574B (en) * | 2021-12-02 | 2024-02-13 | 太原理工大学 | Self-supporting transition metal phosphide doped porous carbon film hydrogen evolution electrocatalytic material |
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