CN107256972A - A kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth - Google Patents
A kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth Download PDFInfo
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- CN107256972A CN107256972A CN201710390201.0A CN201710390201A CN107256972A CN 107256972 A CN107256972 A CN 107256972A CN 201710390201 A CN201710390201 A CN 201710390201A CN 107256972 A CN107256972 A CN 107256972A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention provides a kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, comprises the following steps：The synthesis of hollow carbon sphere；Growth of the cobalt acid nickel nano film presoma on hollow carbon sphere：Using hollow carbon sphere as supporter, four water cobalt acetates are cobalt source, and four water nickel acetates are nickel source, by adjusting pH value, and cobalt nickel nano film/hollow carbon sphere presoma then is made through hydro-thermal reaction；By cobalt nickel nano film/hollow carbon sphere presoma high temperature pyrolysis in air atmosphere, the sour nickel nano film/hollow carbon sphere compound of the porous cobalt being grown on hollow carbon sphere is made；Or under air/inert high temperature pyrolysis, obtain being grown in the sour nickel nano film/hollow carbon sphere compound of porous cobalt rich in Lacking oxygen on hollow carbon sphere.Sour nickel nano film/hollow carbon sphere the compound of porous cobalt made by the present invention has the advantages that satisfactory mechanical property, preparation cost is low, electric conductivity is high, ORR excellent performances, is adapted to popularization and application.
Description
Technical field
The present invention relates to micro nano structure and the interleaving techniques field of electro-catalysis, and in particular to one kind is based on hollow carbon sphere mould
The method that plate grows the sour nickel nano film of porous cobalt.
Background technology
Electrocatalytic oxidation reduction reaction (ORR, Oxygen Reduction Reaction) is used as fuel cell and metal-air
The important anode reaction of battery, has been widely used in every field, but its slow dynamics needs high catalytic activity
Catalysis material be driven, in addition, inexpensive non-precious metal catalyst be also sustainable development important goal it
One.The sour nickel of the cobalt of spinel structure has the advantages that considerable ORR is active, pollution-free and aboundresources, therefore is got over by people
Carry out more concerns.It is combined therewith using hollow carbon sphere and can effectively improves its electrical conductivity, is increased its specific surface area and effectively carry
Its high avtive spot.The preparation method of the sour nickel nano film/hollow carbon sphere of existing cobalt is single, and a step sinters to be rich in
The preparation method of the sour nickel nano film/hollow carbon sphere of the porous cobalt of Lacking oxygen has been short of.Therefore, explore and be based on hollow carbon sphere template
The method of the sour nickel nano film of porous cobalt is grown, with important scientific meaning and practical application meaning.
The content of the invention
It is an object of the invention to provide a kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, method
Simply, technology maturation, the sour nickel nano film/hollow carbon sphere compound of made porous cobalt has satisfactory mechanical property, is prepared into
This low, electric conductivity is high, ORR excellent performances the advantages of, be adapted to popularization and application.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, comprises the following steps：
1) synthesis of hollow carbon sphere；
2) growth of the sour nickel nano film presoma of cobalt on hollow carbon sphere：Using hollow carbon sphere as supporter, four water cobalt acetates
For cobalt source, four water nickel acetates are nickel source, by adjusting pH value, are then made through hydro-thermal reaction before cobalt nickel nano film/hollow carbon sphere
Drive body；
3) by cobalt nickel nano film/hollow carbon sphere presoma high temperature pyrolysis in air atmosphere, it is made and is grown in hollow carbon sphere
On the sour nickel nano film/hollow carbon sphere compound of porous cobalt；Or under air/inert high temperature pyrolysis, be grown in
Sour nickel nano film/hollow carbon sphere the compound of the porous cobalt rich in Lacking oxygen on hollow carbon sphere.
According to above scheme, the synthesis of the hollow carbon sphere comprises the following steps：
1) deionized water, absolute ethyl alcohol and ammoniacal liquor are mixed, adds resorcinol, stirring at room temperature is persistently stirred to dissolving
Mix after 10min, tetraethyl orthosilicate is added under agitation, continue to stir after 10min, add formaldehyde, 24h is stirred at room temperature；
2) by step 1) resulting solution is transferred in autoclave, and reactor is placed in 100 DEG C of baking oven, carry out
Hydro-thermal reaction 24h, then takes out reactor and naturally cools to room temperature；
3) product of hydro-thermal reaction is centrifuged, solid matter is washed with deionized 3 times, absolute ethyl alcohol is washed 3 times
Afterwards, it is placed in 70 DEG C of baking ovens and dries 6h, obtains dried orange red powder I；
4) after powder I is ground, in the nitrogen atmosphere of vacuum tube furnace, heating carbonization obtains black powder II；
5) concentration is used to distinguish for 20wt.% excessive hf etching powder II 2 times, then with deionized water and alcohol
It is placed in after washing 2 times in baking oven, in 70 DEG C of dry 6h, that is, obtains the black powder III of hollow carbon sphere.
According to above scheme, the step 1) in deionized water, absolute ethyl alcohol and ammoniacal liquor volume ratio be 20:60:3, institute
The concentration for stating ammoniacal liquor is 28wt.%.
According to above scheme, the step 1) in resorcinol and the mass ratio of deionized water be 1/100~1/25；Positive silicon
The volume ratio of sour tetra-ethyl ester and deionized water is 7/100~21/50；The volume ratio of formaldehyde and ammoniacal liquor is 14/75, the formaldehyde
Concentration is 36wt.%.
According to above scheme, the step 4) in be carbonized when heating rate be 5 DEG C/min, carburizing temperature be 700~
1000 DEG C, carbonization time is 2~6h.
According to above scheme, the preparation of the sour nickel nano film/hollow carbon sphere presoma of the cobalt is comprised the following specific steps that：
1) hollow carbon sphere is weighed, by ultrasonic disperse in absolute ethyl alcohol；
2) deionized water continual ultrasonic is added to being uniformly dispersed；
3) four water cobalt acetates, four water nickel acetates, hexamethylenetetramine are sequentially added, is stirred at room temperature to dissolving；
4) by step 3) the finely dispersed solution of gained is transferred in reactor, in the baking oven for being placed in 140 DEG C, carries out hydro-thermal
React after 6h, take out and naturally cool to room temperature；
5) hydro-thermal reaction product is centrifuged, solid matter washs 3 times with deionized water and absolute ethyl alcohol respectively, then
It is placed in drying box, in drying 24h at 70 DEG C, obtains the sour nickel nano film/hollow carbon sphere presoma of cobalt.
According to above scheme, the step 1) in hollow carbon sphere and the mass ratio of deionized water 1/1000~5/100；It is described
Step 2) in the deionized water and the step 1 that add) in the volume ratio of absolute ethyl alcohol be 2:1；The step 3) in four water cobalt acetates,
Four water nickel acetates, the mol ratio of hexamethylenetetramine are 10:5:22；The step 5) in centrifuge rotating speed for 9000 turns/
min。
According to above scheme, high temperature pyrolysis when the sour nickel nano film/hollow carbon sphere compound of porous cobalt is produced, including
Following steps：
1) the sour nickel nano film/hollow carbon sphere presoma of cobalt is placed in porcelain boat or silica crucible, be subsequently placed in Muffle furnace or
In tube furnace；
2) 260~450 DEG C in air atmosphere, are warming up to 5 DEG C/min speed, and is incubated 2h, then furnace cooling
To room temperature, the sour nickel nano film/hollow carbon sphere compound of the cobalt can be obtained.
According to above scheme, when the sour nickel nano film/hollow carbon sphere compound of the porous cobalt rich in Lacking oxygen is produced
High temperature pyrolysis, comprises the following steps：
1) the sour nickel nano film/hollow carbon sphere presoma of cobalt is placed in porcelain boat or silica crucible, is subsequently placed in tube furnace,
And vacuum state will be extracted into pipe；
2) it is 9 in the volume ratio of inert gas and air:Under 1 atmosphere, 260~450 are warming up to 5 DEG C/min speed
DEG C, and 2h is incubated, then cool to room temperature with the furnace, the sour nickel nano film/hollow carbon sphere compound of the cobalt can be obtained.
According to above scheme, the inert gas be nitrogen, argon gas, or both mixed gas.
Cobalt source and nickel source are evenly spread in the hollow carbon sphere of water/absolute ethyl alcohol mixed solution in the present invention, utilize hydro-thermal
Simultaneously the sour nickel nano film/hollow carbon sphere compound of porous cobalt is made with reference to follow-up high-temperature heat treatment in synthetic technology, or rich in oxygen
Sour nickel nano film/hollow carbon sphere the compound of the porous cobalt in room, concrete principle is as follows：Hollow carbon sphere is easily homogeneously dispersed in nothing
In hydrous ethanol solution, and surface is negatively charged, and four water cobalt acetates and the formation soluble in water of four water nickel acetates are positively charged
Cobalt ions and nickel ion, by electrostatic adsorption, cobalt ions and nickel ion absorption are on hollow carbon sphere surface, in 140 DEG C of high temperature
Under, hexamethylenetetramine decomposes to give off ammonia, makes its solution alkaline, and the amount of hexamethylenetetramine is added by adjusting, is obtained
Optimum pH, makes the sour nickel nano film of cobalt be grown on hollow carbon sphere.By it is follow-up be thermally treated resulting in the sour nickel nano film of porous cobalt/
Hollow carbon sphere compound, or the sour nickel nano film/hollow carbon sphere compound of the porous cobalt rich in Lacking oxygen.The present invention is with hollow carbon
Ball is template, effectively prevent the reunion of nanometer sheet, the compound for making it obtain more bigger serface.Hollow carbon sphere has simultaneously
There are good mechanical performance and decay resistance, be improved the mechanical stability and cyclical stability of the composite.Remove
Outside this, obtained compound is sintered under anoxic conditions has substantial amounts of Lacking oxygen, effectively increases avtive spot and leads
Electrically.Compared with the technology of existing this class composite structure of making, the sour nickel nano film/sky of the porous cobalt of gained in the present invention
Heart carbon ball catalyst, has the advantages that to prepare that cost is low, electric conductivity is high and ORR excellent performances.
The beneficial effects of the invention are as follows：
1) the invention provides the technology that a kind of new simplicity makes the sour nickel nano film/hollow carbon sphere compound of porous cobalt
Approach, the electrostatic adsorption of ingenious utilization hollow carbon sphere and cobalt ions and nickel ion, Hydrothermal Synthesiss cobalt nickel nano film/hollow carbon
Ball presoma, is made the sour nickel nano film/hollow carbon sphere compound of the porous cobalt rich in Lacking oxygen, effectively by follow-up heat treatment
Ground improves its electric conductivity and increases its specific surface area；
2) the sour nickel of porous cobalt rich in Lacking oxygen of the present invention as obtained by the heat treatment under inert gas/air atmosphere is received
Rice piece/hollow carbon sphere compound has higher electric conductivity and more relative to the sour nickel nano film/hollow carbon sphere compound of porous cobalt
Many avtive spots, make it show more preferable ORR performances and Geng Gao cyclical stability, in electro-catalysis, lithium-air battery etc.
There is good application prospect in field；
3) preparation method of the invention is simple, raw material sources are wide, equipment requirement is low, producing efficiency is high, it is low to prepare cost, fits
Close popularization and application.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention；
Fig. 2 is the XRD of the product of the embodiment of the present invention 1 and 2；
Fig. 3 is the SEM figures of the product of the embodiment of the present invention 1；
Fig. 4 is the SEM figures of the product of the embodiment of the present invention 2；
Fig. 5 is the TEM figures of the product of the embodiment of the present invention 2；
Fig. 6 is the X-ray photoelectron spectroscopy figure of the product of the embodiment of the present invention 1 and 2；
Fig. 7 is nitrogen adsorption-desorption isothermal curve figure of the product of the embodiment of the present invention 1 and 2；
Fig. 8 is the pore size distribution curve figure of the product of the embodiment of the present invention 1 and 2.
Embodiment
Technical scheme is illustrated with embodiment below in conjunction with the accompanying drawings.
Embodiment 1, is shown in Fig. 1,2,3,6,7,8：
The present invention provides a kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, comprises the following steps
(see Fig. 1)：
1. the synthesis of hollow carbon sphere：
1) 20mL deionized waters, 60mL absolute ethyl alcohols and 3mL ammoniacal liquor (28wt.%) are mixed, add 0.4g resorcinols,
Stirring is extremely dissolved；Persistently after stirring 10min, 2.8mL tetraethyl orthosilicates are added, continues to stir after 10min, adds 0.56mL first
Aldehyde (36wt.%), is stirred at room temperature 24h；
2) above-mentioned solution is transferred in 100mL autoclaves, and reactor is placed in 100 DEG C of baking oven, carried out
Hydro-thermal reaction 24h, room temperature is naturally cooled to after taking out reactor；
3) hydrothermal product is centrifuged, solid matter is washed with deionized 3 times, after absolute ethyl alcohol is washed 3 times, be placed in
6h is dried in 70 DEG C of baking ovens, by dried orange red powder I；
4) after powder I is ground, in vacuum tube furnace nitrogen atmosphere, 800 are warming up to 5 DEG C/min heating rate
DEG C, insulation carbonization 5h obtains black powder II；
5) powder II is etched 2 times using excessive hydrofluoric acid (20wt.%), washed respectively after 2 times with deionized water and alcohol
It is placed in 70 DEG C of baking ovens and dries 6 hours, that is, obtains the black powder III of hollow carbon sphere；
2. the synthesis of porous cobalt nickel nano film/hollow carbon sphere presoma：
1) 10mg hollow carbon spheres are weighed, and ultrasonic disperse is in 10mL absolute ethyl alcohols；
2) 20mL deionized waters continual ultrasonic is added to being uniformly dispersed；
3) after 30min, the water cobalt acetates of 1mmol tetra-, the water nickel acetates of 0.5mmol tetra- and the methines of 2.2mmol six are sequentially added
Tetramine, is stirred at room temperature to dissolving；
4) the finely dispersed solution of gained is transferred in 100mL reactor, in the baking oven for being placed in 140 DEG C, enters water-filling
After thermal response 6h, take out and naturally cool to room temperature.
5) hydro-thermal reaction product is centrifuged into (rotating speed is 9000 turns/min), solid matter uses deionized water and nothing respectively
Water-ethanol is washed 3 times, is subsequently placed in drying box, in drying 24h at 70 DEG C, is obtained before the sour nickel nano film/hollow carbon sphere of cobalt
Drive body；
3. the heat treatment of porous cobalt nickel nano film/hollow carbon sphere compound：
1) it will be placed in porcelain boat, be subsequently placed in Muffle furnace after the sour nickel nano film of cobalt/hollow carbon sphere presoma grinding；
2) 320 DEG C in air atmosphere, are warming up to 5 DEG C/min speed, and is incubated 2h, room is then cooled to the furnace
Temperature, that is, obtain the sour nickel nano film/hollow carbon sphere compound of porous cobalt, be named as NiCo2O4/HCS-320。
A variety of characterize is carried out to the present embodiment product：The present embodiment product is observed using SEM (SEM)
Exterior appearance, it can be seen that the micro-flowers pattern of nanometer sheet assembling (see Fig. 3)；X-ray diffraction is carried out to the present embodiment product
(XRD) characterize, it is possible to find the present embodiment product matches with standard card (JCPDS card No.01-073-1702), and
Without miscellaneous cutting edge of a knife or a sword (see Fig. 2)；In X-ray photoelectron spectroscopy analytical proof the present embodiment product cobalt with+trivalent, nickel with+divalent, oxygen
Exist in -2 valence form (see Fig. 6).(Fig. 7) analysis is tested by specific surface area, it is seen that NiCo2O4/ HCS-320 has high
Specific surface area is 90.1m2g-1, can be drawn from graph of pore diameter distribution (see Fig. 8), its average pore diameter is 6.6nm.
ORR is carried out to the electrode of the present embodiment production by RRDE-E7R9rotator electrochemical catalysis work station
Can test：The load capacity of the present embodiment product composite is 0.25mg/cm2, in 0.1M KOH electrolytic solutions, with
1600rpm rotating speed and sweeping for 5mV/S test its method of polarization curve under speed, it is 0.9V that its voltage, which plays peak, and limiting current density is
5.24mA/cm2, it is 82% to test its conservation rate through the constant-voltage power supply of 10000 seconds under 0.5V voltages, higher than most of same types
The ORR electrodes of cobalt acid nickel nano material.
Embodiment 2, is shown in Fig. 1,2,4-8：
The present invention provides a kind of method based on the sour nickel nano film of porous cobalt of the hollow carbon sphere template growth rich in Lacking oxygen,
Basic be the same as Example 1, difference is：During the heat treatment of compound, in nitrogen/air, (volume ratio is 9:1) under atmosphere, with
5 DEG C/min speed is warming up to 320 DEG C, and is incubated 2h, then cools to room temperature with the furnace, produces the porous cobalt acid rich in Lacking oxygen
Nickel nano film/hollow carbon sphere compound, is named as NiCo2O4/HCS-320-P。
A variety of characterize is carried out to the present embodiment product：Observed using SEM (SEM) and transmission electron microscope (TEM)
Sour nickel nano film/hollow carbon sphere composite the pattern of porous cobalt rich in Lacking oxygen, the micro-flowers pattern for obtaining nanometer sheet assembling (divides
Fig. 4 and Fig. 5 are not seen)；A variety of characterize is carried out to the present embodiment product：Carry out X-ray diffraction (XRD) to characterize, it is possible to find to this reality
Apply a product and carry out a variety of characterize：Material matches with standard card (JCPDS card No.01-073-1702), and without miscellaneous cutting edge of a knife or a sword
(see Fig. 2).In X-ray photoelectron spectroscopy analytical proof the present embodiment product cobalt with+trivalent, nickel with+divalent, oxygen with -2 valence
Form is present, and in O1S collection of illustrative plates, NiCo2O4The intensity of/HCS-320-P O2 cutting edges of a knife or a sword is better than NiCo2O4/ HCS-320 cutting edges of a knife or a sword, card
Bright NiCo2O4/ HCS-320-P possesses more Lacking oxygens (see Fig. 6).Specific surface area test chart (see Fig. 7) can be obtained,
NiCo2O4/ HCS-320-P shows up to 98.9m2g-1Specific surface area, can be drawn from graph of pore diameter distribution (see Fig. 8), its put down
Equal pore diameter is 10.0nm.
ORR is carried out to the electrode of the present embodiment production by RRDE-E7R9rotator electrochemical catalysis work station
Can test：The load capacity of the present embodiment product composite is 0.25mg/cm2, in 0.1M KOH electrolytic solutions, with
1600rpm rotating speed and sweeping for 5m V/S test its method of polarization curve under speed, it plays peak voltage for 0.9V, and limiting current density is
5.78mA/cm2, it is 90% to test its conservation rate through the constant-voltage power supply of 10000 seconds under 0.5V voltages, higher than the sour nickel of porous cobalt
The ORR electrodes of nanometer sheet/hollow carbon sphere composite.The sour nickel nano film of porous cobalt rich in Lacking oxygen obtained by the present embodiment/
Hollow carbon sphere combination electrode has more preferable ORR performances, and can be widely popularized should be in the field such as electro-catalysis and battery system.
Embodiment 3：
The present invention provides a kind of method based on the sour nickel nano film of porous cobalt of the hollow carbon sphere template growth rich in Lacking oxygen,
Basic be the same as Example 1, difference is：During the heat treatment of compound, in air atmosphere, heated up with 5 DEG C/min speed
To 260 DEG C, and 2h is incubated, then cools to room temperature with the furnace, produce the sour nickel nano film/hollow carbon sphere compound of porous cobalt, name
For NiCo2O4/HCS-260。
Embodiment 4：
The present invention provides a kind of method based on the sour nickel nano film of porous cobalt of the hollow carbon sphere template growth rich in Lacking oxygen,
Basic be the same as Example 1, difference is：During the heat treatment of compound, in air atmosphere, heated up with 5 DEG C/min speed
To 450 DEG C, and 2h is incubated, then cools to room temperature with the furnace, produce the sour nickel nano film/hollow carbon sphere compound of porous cobalt, name
For NiCo2O4/HCS-450。
Above example is only used to illustrative and not limiting technical scheme, although above-described embodiment enters to the present invention
Detailed description is gone, the person skilled of this area should be understood：The present invention can be modified or replaced on an equal basis, but
Not departing from any modification and local replacement of spirit and scope of the invention all should cover in scope of the presently claimed invention.
Claims (10)
1. a kind of method based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, it is characterised in that comprise the following steps：
1) synthesis of hollow carbon sphere；
2) growth of the sour nickel nano film presoma of cobalt on hollow carbon sphere：Using hollow carbon sphere as supporter, four water cobalt acetates are cobalt
Source, four water nickel acetates are nickel source, by adjusting pH value, and cobalt nickel nano film/hollow carbon sphere presoma then is made through hydro-thermal reaction；
3) by cobalt nickel nano film/hollow carbon sphere presoma high temperature pyrolysis in air atmosphere, it is made and is grown on hollow carbon sphere
Sour nickel nano film/hollow carbon sphere the compound of porous cobalt；Or under air/inert high temperature pyrolysis, obtain being grown in hollow
Sour nickel nano film/hollow carbon sphere the compound of the porous cobalt rich in Lacking oxygen in carbon ball.
2. the method according to claim 1 based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, its feature exists
In the synthesis of the hollow carbon sphere comprises the following steps：
1) deionized water, absolute ethyl alcohol and ammoniacal liquor are mixed, adds resorcinol, stirring is to dissolving at room temperature, lasting stirring
After 10min, tetraethyl orthosilicate is added under agitation, is continued to stir after 10min, is added formaldehyde, 24h is stirred at room temperature；
2) by step 1) resulting solution is transferred in autoclave, and reactor is placed in 100 DEG C of baking oven, carry out hydro-thermal
24h is reacted, reactor is then taken out and naturally cools to room temperature；
3) product of hydro-thermal reaction is centrifuged, solid matter is washed with deionized 3 times, after absolute ethyl alcohol is washed 3 times, put
In drying 6h in 70 DEG C of baking ovens, dried orange red powder I is obtained；
4) after powder I is ground, in the nitrogen atmosphere of vacuum tube furnace, heating carbonization obtains black powder II；
5) concentration is used to wash 2 respectively for 20wt.% excessive hf etching powder II 2 times, then with deionized water and alcohol
It is placed in after secondary in baking oven, in 70 DEG C of dry 6h, that is, obtains the black powder III of hollow carbon sphere.
3. the method according to claim 2 based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, its feature exists
In the step 1) in deionized water, absolute ethyl alcohol and ammoniacal liquor volume ratio be 20:60:3, the concentration of the ammoniacal liquor is
28wt.%.
4. the method according to claim 2 based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, its feature exists
In the step 1) in resorcinol and the mass ratio of deionized water be 1/100~1/25；Tetraethyl orthosilicate and deionized water
Volume ratio be 7/100~21/50；The volume ratio of formaldehyde and ammoniacal liquor is 14/75, and the concentration of the formaldehyde is 36wt.%.
5. the method according to claim 2 based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, its feature exists
In the step 4) in be carbonized when heating rate be 5 DEG C/min, carburizing temperature be 700~1000 DEG C, carbonization time be 2~
6h。
6. the method according to claim 1 based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, its feature exists
In the preparation of the sour nickel nano film/hollow carbon sphere presoma of the cobalt is comprised the following specific steps that：
1) hollow carbon sphere is weighed, by ultrasonic disperse in absolute ethyl alcohol；
2) deionized water continual ultrasonic is added to being uniformly dispersed；
3) four water cobalt acetates, four water nickel acetates, hexamethylenetetramine are sequentially added, is stirred at room temperature to dissolving；
4) by step 3) the finely dispersed solution of gained is transferred in reactor, in the baking oven for being placed in 140 DEG C, carries out hydro-thermal reaction
After 6h, take out and naturally cool to room temperature；
5) hydro-thermal reaction product is centrifuged, solid matter is washed 3 times with deionized water and absolute ethyl alcohol respectively, is subsequently placed in
In drying box, in drying 24h at 70 DEG C, the sour nickel nano film/hollow carbon sphere presoma of cobalt is obtained.
7. the method according to claim 6 based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, its feature exists
In the step 1) in hollow carbon sphere and the mass ratio of deionized water 1/1000~5/100；The step 2) in add go from
Sub- water and step 1) in the volume ratio of absolute ethyl alcohol be 2:1；The step 3) in four water cobalt acetates, four water nickel acetates, six first
The mol ratio of urotropine is 10:5:22；The step 5) in centrifuge rotating speed be 9000 turns/min.
8. the method according to claim 1 based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, its feature exists
In high temperature pyrolysis when the sour nickel nano film/hollow carbon sphere compound of porous cobalt is produced comprises the following steps：
1) the sour nickel nano film/hollow carbon sphere presoma of cobalt is placed in porcelain boat or silica crucible, is subsequently placed in Muffle furnace or tubular type
In stove；
2) 260~450 DEG C in air atmosphere, are warming up to 5 DEG C/min speed, and is incubated 2h, room is then cooled to the furnace
Temperature, can obtain the sour nickel nano film/hollow carbon sphere compound of the cobalt.
9. the method according to claim 1 based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, its feature exists
In, high temperature pyrolysis when the sour nickel nano film/hollow carbon sphere compound of the porous cobalt rich in Lacking oxygen is produced, including following step
Suddenly：
1) the sour nickel nano film/hollow carbon sphere presoma of cobalt is placed in porcelain boat or silica crucible, be subsequently placed in tube furnace, and will
Vacuum state is extracted into pipe；
2) it is 9 in the volume ratio of inert gas and air:Under 1 atmosphere, 260~450 DEG C are warming up to 5 DEG C/min speed,
And 2h is incubated, then cool to room temperature with the furnace, the sour nickel nano film/hollow carbon sphere compound of the cobalt can be obtained.
10. the method according to claim 9 based on the sour nickel nano film of the porous cobalt of hollow carbon sphere template growth, its feature exists
In, the inert gas be nitrogen, argon gas, or both mixed gas.
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| CN109824030A (en) * | 2019-03-25 | 2019-05-31 | 中国科学院福建物质结构研究所 | A kind of hollow carbon sphere and its preparation method and application |
| CN110182858A (en) * | 2019-07-09 | 2019-08-30 | 南京林业大学 | The hollow NiCo of high-sequential2O4The preparation method of electrode material |
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| CN110335758A (en) * | 2019-06-12 | 2019-10-15 | 武汉理工大学 | A kind of the mangaic acid cobalt-nitrating hollow carbon sphere composite material and preparation method and application of core-shell structure |
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| CN111768979A (en) * | 2020-05-19 | 2020-10-13 | 东南大学 | Preparation method and application of sulfur-doped intrinsic porous nickel cobalt phosphide nanosheet |
| CN111863456A (en) * | 2020-07-21 | 2020-10-30 | 多助科技(武汉)有限公司 | Preparation method and application of nickel-cobalt oxide electrode material with shell shape controllable and hollow structure |
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| WO2021093155A1 (en) * | 2019-11-15 | 2021-05-20 | 广东轻工职业技术学院 | Flexible device made by integration of microbial fuel cell and hybrid supercapacitor, preparation method therefor, and application thereof |
| CN110993359B (en) * | 2019-11-15 | 2021-08-06 | 广东轻工职业技术学院 | Flexible solid-state asymmetric supercapacitor device and preparation method and application thereof |
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| CN111768979A (en) * | 2020-05-19 | 2020-10-13 | 东南大学 | Preparation method and application of sulfur-doped intrinsic porous nickel cobalt phosphide nanosheet |
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| CN111863456A (en) * | 2020-07-21 | 2020-10-30 | 多助科技(武汉)有限公司 | Preparation method and application of nickel-cobalt oxide electrode material with shell shape controllable and hollow structure |
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| CN112939097A (en) * | 2021-02-09 | 2021-06-11 | 中国科学院山西煤炭化学研究所 | Nickel cobaltate nano material and preparation method and application thereof |
| CN112939097B (en) * | 2021-02-09 | 2023-03-28 | 中国科学院山西煤炭化学研究所 | Nickel cobaltate nano material and preparation method and application thereof |
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| CN114050281A (en) * | 2021-11-02 | 2022-02-15 | 湖北大学 | Hollow carbon nanosphere composite catalyst and preparation method and application thereof |
| CN114050281B (en) * | 2021-11-02 | 2023-12-15 | 湖北大学 | Hollow carbon nano sphere composite catalyst and preparation method and application thereof |
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