CN106145101B - A kind of bigger serface nitrogen-doped graphene and preparation method thereof - Google Patents
A kind of bigger serface nitrogen-doped graphene and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of bigger serface nitrogen-doped graphene, including following two steps using microwave vacuum high-temperature heater：(1) Hummers methods prepare microwave treatment, thermal reduction and chemical vapor deposition (CVD) doping that graphene oxide (2) carries out graphene oxide in situ.Method proposed by the present invention, it is on the basis of voluntarily improved to equipment, chemical vapor deposition adulterates the manipulation in situ of three steps after microwave prestripping, thermal reduction and thermal reduction before realization graphene oxide thermal reduction, improves combined coefficient, reduces synthesis energy consumption, is suitable for the production of big batch metaplasia.Synthesis gained doped graphene can be used for the fields such as electrochemical catalysis, ultracapacitor.
Description
Technical field
The invention belongs to technical field of inorganic material, and in particular to a kind of bigger serface nitrogen-doped graphene and its preparation side
Method.
Background technology
With continuous exhausted and environmental pollution the getting worse of the non-renewable resources such as coal, oil, natural gas, grind
Renewable, green, clean energy resource novel energy storage device can be provided for the mankind and seem particularly urgently and again by studying carefully and developing
It wants.In numerous energy substitution schemes, ultracapacitor suffers from huge potentiality and market with novel battery.
However, these energy substitution schemes still have respective deficiency at this stage.Anode material for lithium-ion batteries, super capacitor
The capacity of device electrode material is not high, and fuel cell is fast to the dependence of expensive noble metal electrode catalyst, Cathodic oxygen reduction
Rate is all bottleneck problem far below anode evolving hydrogen reaction rate.The excellent property of graphene provides very to solve these problems
Big possibility.Therefore, graphene rapidly becomes one of research topic most popular in material science in recent years.
For lithium ion battery and electrode of super capacitor, shown by the bigger serface graphene of N doping
Better capacity.For fuel cell, nitrogen doped with the adsorption activation conducive to oxygen, and then promote oxygen also
Original becomes the contenders for substituting platinum catalyst.
Invention content
The purpose of the present invention is to propose to a kind of bigger serface nitrogen-doped graphenes and preparation method thereof.
Realize that the technical solution of the object of the invention is：
A kind of preparation method of bigger serface graphene, includes the following steps：
A.Hummers methods prepare graphene oxide：
(1) it aoxidizes：Graphite raw material and potassium permanganate are weighed, the concentrated sulfuric acid is then added to graphite raw material mixes with potassium permanganate
It closes and is stirred evenly in object, temperature is maintained at 0-2 DEG C when stirring, and after stirring 60-120 minutes, temperature is adjusted to 30-40 DEG C, then
Insulated and stirred 60-120 minutes；Deionized water is added for the first time, stirs evenly, raises the temperature to 90-95 DEG C, Heat preservation 5-15
Minute, hydrogen peroxide is added, deionized water dilution is added again, obtains graphite oxide dilution；
(2) ultrasonic：The graphite oxide dilution of gained is ultrasonically treated, suspension is obtained；
(3) washing and drying：The suspension is settled, removes supernatant；Use hydrochloric acid, ethyl alcohol pair successively respectively again
Suspension is washed, is settled, removing supernatant operation；Reusability deionized water carries out washing and depositing to suspension, goes again
Except supernatant operates, final until suspension is in neutrality, then to suspension progress freeze-drying process, acquisition is pale brown
Color powder, i.e. graphene oxide powder；
B. the microwave treatment of graphene oxide, thermal reduction and chemical vapor deposition doping：
(1) microwave treatment：Under vacuum, microwave treatment, the graphene oxide powder are carried out to the graphene oxide powder
2-3 times of volume expansion after last microwave treatment, 40-60% before weight is expansion；
(2) it heat-treats：In-situ annealing is carried out to the graphene oxide powder after microwave treatment：4-8 DEG C/minute of heating rate,
Temperature keeps the temperature 20-60 minutes after rising to 800 DEG C；
(3) chemical vapor deposition：After 800 DEG C keep the temperature 20-60 minutes, starts to be passed through ammonia, keep the flow of 1-30torr
Ventilation 30-180 minutes, subsequent vacuum cooled to room temperature, you can obtain bigger serface nitrogen-doped graphene, tail gas uses
Water is collected.
Using above-mentioned preparation method, the high graphene of large specific surface area, nitrogen content can be obtained.
Preferably, in the A (1) graphite raw material be natural flake graphite, graphous graphite powder, one kind in expanded graphite or
Arbitrary combination；The natural flake graphite and the graphous graphite powder it is cheap, it is at low cost；The price of the expanded graphite
It is slightly higher, but the speed settled during subsequent A (3) washing and drying is fast, saves the time to reduce time cost.When
Right above-mentioned three kinds of raw materials can meet the needs of preparation.
Preferably, the mass ratio of graphite raw material and potassium permanganate is 3 in the A (1):5.57-7, and every gram of graphite raw material
Corresponding concentrated sulfuric acid dosage is 20-30mL；The corresponding dioxygen water consumption of every gram of graphite raw material is 2-3mL.
Preferably, for the A (1) after insulated and stirred 60-120 minutes, the temperature that deionized water is added for the first time is 0-2 DEG C, first
Secondary addition deionized water is 2 with the concentrated sulfuric acid volume ratio:1.
Preferably, after deionized water dilution is added in the A (1) again, graphite oxide concentration in graphite oxide dilution
For 6-10mg/mL.
Preferably, the graphite oxide dilution is ultrasonically treated in the A (2), ultrasonic acc power is 100-
1000W, frequency 10-5000Hz, ultrasonic time are 5-120 minutes.And the time of ultrasound is longer, the bigger serface nitrogen
The character of doped graphene is better, but since it is considered that the relationship of energy consumption, lengthening time that cannot be simply, technique parameter
It is selected as taking into account for the two.
Preferably, finally washing to solution is in gel form to suspension described in the A (3).
Preferably, microwave treatment power is 600-850W in the B (1), and the microwave time is 5-60 seconds.
Preferably, B (1) microwave treatment, B (2) thermal reductions carry out in situ with B (3) chemical vapor deposition.
Above-mentioned preferred technical parameter is for ensureing more stable preparation result unless otherwise instructed.
The present invention also provides a kind of graphene, the graphene is prepared by above-mentioned preparation method.
The beneficial effects of the present invention are：
1, high using graphene specific surface area prepared by the preparation method in the present invention, it can reach 500-1000m2/ g, N contain
Amount can meet capacity requirement completely in 5-8% for electrode material.
2, the present invention in preparation method in microwave treatment, thermal reduction and and chemical vapor deposition adulterate three steps in situ
It carries out, time and energy consumption cost substantially reduce.
Description of the drawings
Fig. 1 is graphene preparation method process flow chart of the present invention；
Fig. 2 is bigger serface nitrogen-doped graphene typical scan electron microscope prepared by embodiment 3.
Specific implementation mode
Detailed description below should not be construed as limiting the invention for illustrating the present invention.
In embodiment, unless otherwise instructed, technological means used is this field conventional technology.
Graphite raw material is general commercial graphite raw material in embodiment, wherein expanded graphite is purchased from triumphant abundant industry, and particle is average
Granularity is 10-30 microns.
Embodiment 1：
A.Hummers methods prepare graphene oxide：
(1) it aoxidizes：Weigh natural flake graphite 3g, potassium permanganate 7g, wherein a diameter of 1- of natural flake graphite particle
200 microns, two kinds of raw materials are slowly added to the concentrated sulfuric acid that 60ml mass concentrations are 98% after mixing, and concentrated sulfuric acid temperature is 2 DEG C.
Mixture keeps 0-2 DEG C of stirring after sixty minutes, temperature is adjusted to 30 DEG C, then insulated and stirred 60 minutes.It is slowly added to for the first time
150ml temperature is 2 DEG C of deionized water, while improving mixing speed.Raise the temperature to 95 DEG C, Heat preservation 15 minutes, with
The hydrogen peroxide that 6ml mass fractions are 30% is added afterwards, the dilution of 250ml deionized waters is added, graphite oxide concentration is about 6mg/
Ml obtains graphite oxide dilution.
(2) ultrasonic：Gained graphite oxide solution is ultrasonically treated, ultrasonic acc power is 100W, frequency 10Hz, is surpassed
The sound time is 5 minutes, obtains suspension.
(3) washing and drying：After being settled by the suspension, remove supernatant liquor, salt acid elution is added；And it sinks again
Drop obtains lower layer's colloid.It washed once and then settle using 100ml hydrochloric acid once, washed once again, then with 100ml ethyl alcohol
Sedimentation is primary, then Reusability deionized water is washed and settled, and is operated repeatedly to the aobvious neutrality of solution, it is existing to occur hydrogel at this time
As.Hydrogel is freeze-dried, sample lasts 72 hours and is warmed to room temperature by -35 DEG C under 1Pa air pressures, and it is dry to obtain brown color
Dry object powder 3.4g, i.e. graphene oxide powder.
B. the microwave treatment of graphene oxide, thermal reduction and chemical vapor deposition doping：
(1) microwave treatment：In vacuum 1 × 10-3Under the conditions of torr, microwave treatment is carried out to 3.4g graphene oxide powders,
Power 600W, 5 seconds microwave time.Color sample switchs to black by brown color, apparent expansion occurs, before weight is expansion
60%；
(2) it heat-treats：Keep 1 × 10-3Torr vacuum degrees keep the temperature 20 minutes after rising to 800 DEG C with 4 DEG C/min.
(3) chemical vapor deposition：800 DEG C of heat preservations after twenty minutes, are passed through ammonia, flow 30sccm, and pressure is about in storehouse
1torr ventilates 30 minutes.Subsequent vacuum cooled to room temperature.Bigger serface nitrogen-doped graphene is can be obtained, tail gas makes
It is collected with water.
It is about 500m to measure the present embodiment to prepare gained graphene specific surface area through BET method2/g.N content is about 5%.
Embodiment 2：
A.Hummers methods prepare graphene oxide：
(1) it aoxidizes：Weigh graphous graphite powder 3.5g, potassium permanganate 6.5g, wherein a diameter of 1- of artificial graphite powder particles
200 microns, two kinds of raw materials are slowly added to the concentrated sulfuric acid of 105ml a concentration of 98% after mixing, and concentrated sulfuric acid temperature is 2 DEG C.It is mixed
It closes after object keeps 0-2 DEG C of stirring 120 minutes, temperature is adjusted to 40 DEG C, then insulated and stirred 120 minutes.It is slowly added to for the first time
230ml temperature is 2 DEG C of deionized water, while improving mixing speed.Raise the temperature to 90 DEG C, Heat preservation 15 minutes, with
The hydrogen peroxide that 11ml mass fractions are 30% is added afterwards, 200ml deionized waters dilution acid solution is added, graphite oxide concentration is about
For 10mg/ml, graphite oxide dilution is obtained.
(2) ultrasonic：Gained graphite oxide solution is ultrasonically treated, ultrasonic acc power is 1000W, frequency is
5000Hz, ultrasonic time are 120 minutes, obtain suspension.
(3) washing and drying：After being settled by the suspension, remove supernatant liquor, salt acid elution is added；And it sinks again
Drop obtains lower layer's colloid.It washed once and then settle using 150ml hydrochloric acid once, washed once again, then with 150ml ethyl alcohol
Sedimentation is primary, then Reusability deionized water is washed and settled, and operates repeatedly and shows neutrality to solution and hydrogel phenomenon occur.By water
Gel is freeze-dried, and sample lasts 72 hours and is warmed to room temperature by -35 DEG C under 1Pa air pressures, obtains brown color dried object powder
Last 6g, i.e. graphene oxide powder.
B. the microwave treatment of graphene oxide, thermal reduction and chemical vapor deposition doping：
(1) microwave treatment：In vacuum 9 × 10-4Under the conditions of torr, microwave treatment, work(are carried out to 6g graphene oxide powders
Rate 850W, 60 seconds microwave time.Color sample switchs to black by brown color, apparent expansion occurs, and weight is 40% before expanding.
(2) it heat-treats：Keep 9 × 10-4Torr vacuum degrees keep the temperature 60 minutes after rising to 800 DEG C with 8 DEG C/min.
(3) chemical vapor deposition：800 DEG C of heat preservations after sixty minutes, are passed through ammonia, flow 50sccm, and pressure is about in storehouse
30torr ventilates 180 minutes.Subsequent vacuum cooled to room temperature.It can be obtained bigger serface nitrogen-doped graphene, tail gas
It is collected using water.
It is about 1000m to measure the present embodiment to prepare gained graphene specific surface area through BET method2/g.N content is about 8%.
Embodiment 3：
A.Hummers methods prepare graphene oxide：
(1) it aoxidizes：Expanded graphite 10g, potassium permanganate 20g are weighed, a diameter of 1-200 of wherein expanded graphite particles is micro-
Rice, two kinds of raw materials are slowly added to the concentrated sulfuric acid of 250ml a concentration of 98% after mixing, and concentrated sulfuric acid temperature is 2 DEG C.Mixture is protected
After holding 0-2 DEG C of stirring 90 minutes, temperature is adjusted to 35 DEG C, then insulated and stirred 90 minutes.Being slowly added to 500ml temperature for the first time is
2 DEG C of deionized water, while improving mixing speed.93 DEG C are raised the temperature to, 25ml matter is then added in Heat preservation 10 minutes
The hydrogen peroxide that score is 30% is measured, 700ml deionized waters dilution acid solution is added, graphite oxide concentration is about 8mg/ml, is obtained
Graphite oxide dilution.
(2) ultrasonic：Gained graphite oxide solution is ultrasonically treated, ultrasonic acc power is 550W, frequency 2500Hz,
Ultrasonic time is 60 minutes.
(3) washing and drying：After being settled by the suspension, remove supernatant liquor, salt acid elution is added；And it sinks again
Drop obtains lower layer's colloid.It washed once and then settle using 250ml hydrochloric acid once, washed once again, so with 250ml ethyl alcohol
Sedimentation is primary afterwards, then Reusability deionized water is washed and settled, and operates repeatedly and shows neutrality to solution and hydrogel phenomenon occur.It will
Hydrogel is freeze-dried, and sample lasts 96 hours and is warmed to room temperature by -35 DEG C under 1Pa air pressures, obtains brown color dried object
Powder 12g, i.e. graphene oxide powder.
B. the microwave treatment of graphene oxide, thermal reduction and chemical vapor deposition doping：
(1) microwave treatment：In vacuum 2 × 10-3Under the conditions of torr, microwave treatment, work(are carried out to 12g graphene oxide powders
Rate 725W, 30 seconds microwave time.Color sample switchs to black by brown color, apparent expansion occurs, and weight is 50% before expanding.
(2) it heat-treats：Keep 2 × 10-3Torr vacuum degrees keep the temperature 40 minutes after rising to 800 DEG C with 6 DEG C/min.
(3) chemical vapor deposition：800 DEG C of heat preservations after forty minutes, are passed through ammonia, flow 60sccm, and pressure is about in storehouse
15torr ventilates 105 minutes.Subsequent vacuum cooled to room temperature.It can be obtained bigger serface nitrogen-doped graphene, tail gas
It is collected using water.
It is about 850m to measure the present embodiment to prepare gained graphene specific surface area through BET method2/g.N content is about 7%.
Above embodiment be only to the present invention specific implementation mode be described, not to the scope of the present invention into
Row limits, and those skilled in the art can also do numerous modifications and variations, be set not departing from the present invention on the basis of existing technology
Under the premise of meter spirit, all variations and modifications that this field ordinary engineering and technical personnel makes technical scheme of the present invention,
It should all fall into the protection domain of claims of the present invention determination.
Claims (9)
1. a kind of preparation method of bigger serface nitrogen-doped graphene, includes the following steps：
A.Hummers methods prepare graphene oxide：
(1) it aoxidizes：Graphite raw material and potassium permanganate are weighed, the concentrated sulfuric acid is then added to graphite raw material and potassium permanganate mixture
In stir evenly, temperature is maintained at 0-2 DEG C when stirring, and after stirring 60-120 minutes, temperature is adjusted to 30-40 DEG C, then is kept the temperature
Stirring 60-120 minutes；Deionized water is added for the first time, stirs evenly, raises the temperature to 90-95 DEG C, 5-15 points of Heat preservation
Hydrogen peroxide is added in clock, and deionized water dilution is added again, obtains graphite oxide dilution；
(2) ultrasonic：The graphite oxide dilution of gained is ultrasonically treated, suspension is obtained；
(3) it washes, is dry：The suspension is settled, removes supernatant；Use hydrochloric acid, ethyl alcohol to outstanding successively respectively again
Turbid is washed, is settled, removing supernatant operation；Reusability deionized water is washed and is settled again, is operated repeatedly to solution
There is hydrogel phenomenon in aobvious neutrality, and hydrogel is carried out freeze-drying process, obtains brownish-yellow powder, i.e. graphene oxide powder
End；
B. the microwave treatment of graphene oxide, thermal reduction and chemical vapor deposition doping：
(1) microwave treatment：Under vacuum, microwave treatment is carried out to the graphene oxide powder, the graphene oxide powder is micro-
2-3 times of volume expansion after wave processing, 40-60% before weight is expansion；
(2) it heat-treats：In-situ annealing is carried out to the graphene oxide powder after microwave treatment：4-8 DEG C/minute of heating rate, temperature
20-60 minutes are kept the temperature after rising to 800 DEG C；
(3) chemical vapor deposition：After 800 DEG C keep the temperature 20-60 minutes, it is passed through the ammonia of certain flow, it is 1- to keep pressure in storehouse
30torr ventilates 30-180 minutes, subsequent vacuum cooled to room temperature, you can obtain bigger serface nitrogen-doped graphene.
2. preparation method according to claim 1, which is characterized in that graphite raw material is natural scale stone in the A (1)
One kind in ink, graphous graphite powder, expanded graphite or arbitrary combination.
3. preparation method according to claim 1, which is characterized in that the matter of graphite raw material and potassium permanganate in the A (1)
Amount is than being 3:5.57-7, and the corresponding concentrated sulfuric acid dosage of every gram of graphite raw material is 20-30mL；The corresponding dioxygen of every gram of graphite raw material
Water consumption is 2-3mL.
4. preparation method according to claim 1, which is characterized in that the A (1) is first after insulated and stirred 60-120 minutes
The secondary temperature that deionized water is added is 0-2 DEG C, and it is 2 that deionized water is added for the first time with the concentrated sulfuric acid volume ratio:1.
5. preparation method according to claim 1, which is characterized in that deionized water dilution is added in the A (1) again
Afterwards, a concentration of 6-10mg/mL of graphite oxide in graphite oxide dilution.
6. preparation method according to claim 1, which is characterized in that suspension described in the A (3) is finally washed to molten
Liquid is in gel form.
7. preparation method according to claim 1, which is characterized in that microwave treatment power is 600- in the B (1)
850W, microwave time are 5-60 seconds.
8. preparation method according to claim 1, which is characterized in that B (1) microwave treatment, B (2) thermal reductions and B
(3) chemical vapor deposition carries out in situ.
9. a kind of graphene, which is characterized in that the graphene is prepared by any preparation methods of claim 1-8
It arrives.
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| WO2019224579A1 (en) | 2018-05-23 | 2019-11-28 | Arcelormittal | A method for the manufacture of reduced graphene oxide from electrode graphite scrap |
| WO2019224578A1 (en) * | 2018-05-23 | 2019-11-28 | Arcelormittal | A method for the manufacture of graphene oxide from electrode graphite scrap |
| CN109179387B (en) * | 2018-11-16 | 2020-08-18 | 重庆大学 | Method for preparing graphene and graphene prepared by method |
| CN109346338B (en) * | 2018-11-16 | 2020-11-27 | 郑州轻工业学院 | Rapid room-temperature preparation method of nitrogen-doped graphene |
| CN110217782B (en) * | 2019-07-05 | 2021-01-05 | 郑州新世纪材料基因组工程研究院有限公司 | Application of reduced graphene oxide in electromagnetic wave absorption-reflection material and adjustment method of electromagnetic wave absorption-reflection material |
| CN110327927A (en) * | 2019-07-10 | 2019-10-15 | 大英聚能科技发展有限公司 | A kind of modified graphene material of high catalytic activity and preparation method thereof |
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