CN105000553A - Method for preparing nanometer hole graphene in heat contact mode - Google Patents
Method for preparing nanometer hole graphene in heat contact mode Download PDFInfo
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- CN105000553A CN105000553A CN201510465231.4A CN201510465231A CN105000553A CN 105000553 A CN105000553 A CN 105000553A CN 201510465231 A CN201510465231 A CN 201510465231A CN 105000553 A CN105000553 A CN 105000553A
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Abstract
The invention discloses a method for preparing nanometer hole graphene in a heat contact mode. The method is characterized in that the nanometer hole graphene is obtained in the manner that graphene oxide aerogel or graphene oxide paper or other dry graphene oxide products make direct contact with a heating source at the relatively low temperature to be spontaneously burnt, expanded and reduced. The graphene oxide aerogel and other dry graphene oxide products serve as materials for preparing the graphene and make direct contact with the heating source under the air atmosphere, spontaneous burning and expanding are generated in the short several seconds, most part of oxygen-containing functional groups are removed rapidly in the form of gas, holes are formed in the defected positions, and therefore the graphene with the large specific surface area and the nanometer holes can be rapidly and efficiently prepared on a large scale.
Description
Technical field
The present invention relates to the preparation method of nano aperture Graphene.
Technical background
Graphene, the Two-dimensional Carbon material of an atomic thickness, due to the specific surface area (~ 2630m of its superelevation
2/ g), considerable thermal conductivity, excellent specific conductivity and mechanical property, continually in the past few years to attract much attention.The structure of its uniqueness and excellent performance make Graphene have in the field of electron device, sensor and stored energy/conversion etc. to apply comparatively widely.But Graphene usually can occur irreversible stacking in the process prepared and use, the interaction of the pi-pi bond stronger due to its interlayer and van der waals forces forms graphite linings, causes specific surface area sharply to reduce.When it utilizes in electrode of super capacitor, lithium cell etc. time, be unfavorable for that electrolytic solution better transmits, have impact on the expression of chemical property.
In order to make full use of Graphene high-specific surface area inherently, people to start diversion, in the research of hole Graphene, wherein to comprise nanometer grid Graphene, fold Graphene, foamy graphite alkene; Due to the vesicular structure that it is special, high specific surface area and high pore volume, and in conjunction with Graphene character inherently, hole Graphene becomes the focus of people's research for the moment.It should be noted that hole Graphene in electronics and photovoltaic device, energy storage, gas delivery/storage, adsorbed oil and sensor field obtain applies comparatively widely.
In recent years, people attempted preparing hole Graphene by different modes, and wherein photoengraving, electronics etching and plasma etching can obtain the homogeneous Graphene of hole, but these preparation methods can not scale operation, limits its use range.Someone utilizes KOH etching oxidation Graphene to obtain the Graphene of nano aperture, but preparation process introduces KOH, and also will remove KOH, total preparation flow not only expends time in, and also can produce more mass loss.Other preparation methods, as organic molecule synthesis, template, Hydrothermal Synthesis, chemical reduction and template direction CVD etc., part way introduces number acid alkali reagent, metal oxide or utilizes the conditions such as special etching, sealing, high pressure, high temperature, template, on the one hand not environmentally, the hole Graphene cost prepared on the other hand is higher, is all not suitable for large-scale preparation.Recently, have the mode of people's thermal expansion to prepare porous graphene, but they use the graphene oxide solid of graphene oxide powder or bulk drying to prepare, the process of preparation produces stronger volumetric expansion, powder is caused to waft, not easily collecting, and safe not.
Summary of the invention
The present invention is the weak point for avoiding existing for above-mentioned preparation method, provides a kind of simple, environmental protection and is applicable to the preparation method of the nano aperture Graphene of scale operation.
The present invention is that technical solution problem adopts following technical scheme:
Thermo-contact formula of the present invention prepares the method for nano aperture Graphene, and its feature is:
Carry out as follows:
Step a, by graphene oxide dispersion in deionized water, obtain graphene oxide suspension;
Step b, lyophilize is carried out to graphene oxide suspension, obtain graphite oxide aerogel; Or freeze-day with constant temperature is carried out to graphene oxide suspension, obtain graphene oxide paper;
Step c, in air atmosphere, heat source is preheated to 200 DEG C and more than, after stabilizing the temperature, described graphite oxide aerogel is placed on heat source, make graphite oxide aerogel burning expansion, graphene oxide is reduced, and namely obtains nano aperture graphene aerogel; Or in air atmosphere, heat source is preheated to 200 DEG C and more than, after stabilizing the temperature, be placed on heat source by described graphene oxide paper, make graphene oxide paper burning expansion, graphene oxide is reduced, and namely obtains nano aperture graphene paper.
Preferably, the concentration of graphene oxide suspension described in step a is 4 ~ 10mg/mL.If concentration is too low, the tightness of the sample preparing graphite oxide aerogel and graphene oxide paper can be caused inadequate, and produce a large amount of sample losses; Excessive concentration is unfavorable for the dispersion of graphene oxide, and can cause in the result of thermo-contact process, and the sample specific surface area obtained has certain loss.
Lyophilize described in step b carries out under the condition of-40 DEG C ~-60 DEG C.
Freeze-day with constant temperature described in step b carries out under the condition of 55 DEG C ~ 65 DEG C.
Heat source described in step c can be any one in warm table, tube furnace, hot plate or electromagnetic oven, or other instruments that can heat in atmosphere arbitrarily.
Described in step c, the preheating temperature of heat source is preferably 200 ~ 300 DEG C, and namely this temperature range can meet reaction requirement, can produce identical effect under high-temperature condition, so without the need to higher temperature.200 DEG C time, graphite oxide aerogel or graphene oxide paper are placed on heat source, have the preheating of 2 ~ 5s, then burn in whole graphite oxide aerogel or graphene oxide paper rapidly from its point of contact, whole combustion processes only needs about 0.01s, namely complete burning, be swift in response.300 DEG C time, graphite oxide aerogel or graphene oxide paper are placed on heat source and substantially do not need preheating, directly just from point of contact, burning is complete rapidly, and whole combustion processes also only needs 0.01s.
By the nano aperture scope of the inventive method gained nano aperture graphene aerogel or nano aperture graphene paper between 1.5nm-100nm, both containing micropore, also containing mesoporous and macropore; Specific surface area is at 280-1000m
2between/g.
In the present invention, in the preparation process of graphene oxide, because strong oxygenizement introduces a large amount of defects and oxygen-containing functional group.Through lyophilize or freeze-day with constant temperature, after being prepared into graphite oxide aerogel or graphene oxide paper, dry graphite oxide aerogel or graphene oxide paper contact thermal source, the carbon of point of contact place defective locations reaches point of ignition generation spontaneous combustion, the nano aperture of a part is produced in point of ignition, produce a large amount of heat simultaneously, make oxygen-containing functional group with the form (CO of gas
2, O
2, CO, H
2o) slough rapidly, produce larger interlayer air pressure, be greater than interlayer van der waals forces thus make splitting and expand, escaping gas gets nano aperture in the position that Graphene crystal property is poor in addition.The heat that burning produces is supplied to adjacent graphene oxide, makes it burn and produces identical experiment effect.Whole combustion processes is no more than 0.01s.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention is by obtaining graphite oxide aerogel or the graphene oxide paper starting materials as experiment using direct for graphene oxide suspension lyophilize or freeze-day with constant temperature, avoids the powder utilizing graphene oxide powdered material to bring and to waft problem; It also avoid and utilize dry graphene oxide bulk solid add the danger of thermal dilation belt and gather inconvenience, green, environmental protection, safety.
2, the present invention utilizes warm table (>=200 DEG C) at relatively low temperature, and in air atmosphere, Direct Contact Heating thermal source redox graphene, does not need the condition of special sealing, vacuum, gas processing and High Temperature High Pressure.
3, the present invention is in operation without the interpolation of any pollutent, environmental protection, quick and convenient.
4, preparation method of the present invention can on a large scale and rapidly and efficiently bigger serface processed, nano aperture redox graphene, and its cost performance is higher, and gained graphite nanometer hole scope is interval at 1.5nm-100nm, both containing micropore, also containing mesoporous and macropore.Its specific surface area is at 280-1000m
2between/g; And can be utilized in various fields such as ultracapacitor, lithium ion battery, conductive fillers.
Accompanying drawing explanation
In Fig. 1,1-a is the filemot graphite oxide aerogel prepared by embodiment 1; 1-b is the nano aperture graphene aerogel of the black prepared by embodiment 1;
In Fig. 2,2-a, 2-b are the XPS collection of illustrative plates of graphite oxide aerogel (GO) prepared by embodiment 1 and nano aperture graphene aerogel (300-RGO) respectively.
In Fig. 3,3-a is the electrochemistry cyclic voltammetry curve of the nano aperture Graphene (300-RGO) prepared by embodiment 1; 3-b is the constant temperature current charge-discharge electricity curve of Graphene; 3-c is the ratio capacitance value stable circulation performance figure of 12000 cycle charge-discharges of Graphene.
In Fig. 4, do the material prepared in Raman analysis testing example 1, solid line is graphene oxide (i.e. GO), dotted line be 300 DEG C of thermal treatments reduce the Graphene (RGO) obtained Raman figure.
In Fig. 5, transmission electron microscope (TEM) to characterize in embodiment 1 prepared hole Graphene, Fig. 5-a, the 5-b transmission electron microscope picture that to be scale be respectively under 50nm and 20nm.
In Fig. 6,6-a and 6-b is the specific surface area test pattern of the hole Graphene obtained in embodiment 1 and corresponding pore analysis figure respectively.
In Fig. 7,7-a is the filemot ganoid graphene oxide paper (GO) in embodiment 2, and 7-b is the shaggy nano aperture graphene paper (RGO) that black expands.7-c, 7-d are the optical photograph of cross section under opticmicroscope 50 times of enlargement ratios of graphene oxide (GO) and nano aperture Graphene (RGO) respectively.
In Fig. 8,8-a and 8-b is the specific surface area test pattern of the nano aperture Graphene of preparation in embodiment 2 and corresponding pore analysis figure.
In Fig. 9,9-a and 9-b is the optical photograph of the hole Graphene of the graphite oxide aerogel of brown in embodiment 3 before thermal treatment and the black after the warm table process of 200 DEG C respectively.
In Figure 10,10-a and 10-b is the specific surface area test pattern of the hole Graphene obtained in embodiment 3 and corresponding pore analysis figure respectively.
Embodiment
Embodiment 1
The present embodiment graphite oxide aerogel prepares bigger serface, nano aperture graphene aerogel as starting material, carries out in accordance with the following steps:
Step a, use improve Hummers legal system for graphene oxide, and are separated into suspension with deionized water, and concentration is 10mg/mL.
Step b, by the graphene oxide suspension lyophilize in step a: first graphene oxide suspension is placed in refrigerator and is frozen into solid, put into the freeze drier drying that cold well temperature has reached-50 DEG C again, graphite oxide aerogel can be obtained, the brown column aerogel solid as shown in Fig. 1-a.
Under step c, air atmosphere, preheated by warm table, temperature is adjusted to 300 DEG C, after temperature-stable, the graphite oxide aerogel in step b is directly placed on warm table.Waited for for about 0.1 second, graphite oxide aerogel takes fire from the point of contact of Contact Heating platform, and burn totally to whole aerogel, burn time duration is about 0.01s.The nano aperture graphene aerogel of the black as shown in Fig. 1-b can be obtained.TEM figure in Fig. 5-a and 5-b can find out the nano aperture on graphene film clearly, about 1-5nm.
The graphite oxide aerogel obtained in step b and step c and the nano aperture graphene aerogel obtained are done XPS analysis, as shown in Figure 2,2-a, 2-b are the XPS collection of illustrative plates of graphite oxide aerogel and nano aperture graphene aerogel respectively, the oxygen-containing functional group peak value of the redox graphene as can be seen from the figure after thermal treatment reduces a lot, and namely graphene oxide major part oxygen-containing functional group is removed.
Do electro-chemical test, the nano aperture graphene aerogel obtained in step c is prepared into electrode: by Graphene, polyvinylidene difluoride (PVDF) and acetylene black in mass ratio 40:5:5 add N methyl-2-pyrrolidone (NMP) reagent after mixing, stir into mud shape, all with spread upon on nickel foam collector, 60 DEG C thermostat containers dry.By the KOH solution of 6mol/L as electrolytic solution, Pt electrode is as to electrode, and Ag/AgCl electrode is as reference electrode, and the electrode of preparation is as working electrode.Respectively 0.01,0.05,0.10, test volt-ampere curve under the sweep voltage speed of 0.20V/s, as shown in Fig. 3-a, can find out the increase along with scanning speed, the area that curve surrounds also increases gradually, the shape of curve, close to rectangle, demonstrates good electric double layer capacitance performance.Under the current density of 0.1A/g, do permanent steady current charge-discharge electrical testing, as shown in Fig. 3-b, calculating ratio capacitance by formula Cg=(I Δ t)/(m Δ V) is 244.73F/g.Wherein Cg is ratio capacitance; I is charging and discharging currents density; T is discharge time; M is active material quality on working electrode; V is electromotive force window.Ratio capacitance unit is F/g.
The test of cyclical stability, as shown in Fig. 3-c, under the steady current charge-discharge power mode of perseverance, with the charging and discharging currents density cycle charge-discharge 12000 times of 10A/g, utilize above mentioned ratio capacitance calculation formula, calculate the ratio capacitance of every 500 circulations, middle desired data of publishing picture.Through 12000 cycle charge-discharges, ratio capacitance still keeps more than 96.8% of initial value, and the nano aperture Graphene that this obtains has good cyclical stability in the utilization of ultracapacitor.
Raman is tested, the graphene oxide prepared in step b and step c and hole Graphene are done respectively Raman test, as shown in Figure 4, solid line is the Raman curve of graphene oxide, dotted line is the Raman curve of hole Graphene,, GO and RGO has characteristic peak D the peak (~ 1350cm of Graphene as we can see from the figure
-1) and G peak (~ 1580cm
-1); Weak compared with GO of the D peak intensity of RGO and the ratio of G peak intensity, after thermal treatment reduction is described, defect reduces.
The test of specific surface area and pore analysis, as shown in Figure 6,6-a utilizes Brunauer – Emmett – Teller (BET) method to test, and this time measuring the specific surface area obtained is 536.155m
2/ g; 6-b figure is corresponding pore analysis figure, and with the test of Barret – Joyner – Halenda (BJH) method, it is 1.28-44.6nm that data analysis provides hole distribution scope, and as can be seen from the figure pore size is mainly distributed in 1.28-13.5nm.
Embodiment 2
Step a, use improve Hummers legal system for graphene oxide, and are separated into suspension with deionized water, and concentration is 10mg/mL.
Step b, the graphene oxide suspension in step a is evenly coated on smooth sheet glass, being placed on temperature is in the thermostatic drying chamber of 55 DEG C, allow water evaporates, afterwards the film of drying is torn it down, namely obtain smooth surface and the graphene oxide paper of interlayer densification.
Under step c, air atmosphere, preheated by warm table, temperature is adjusted to 250 DEG C, after temperature-stable, the graphene oxide paper in step b is directly placed on warm table.Wait for about 2-3 second, the graphene oxide reduced can be obtained, i.e. nano aperture graphene paper.As shown in Figure 7,7-a is filemot ganoid graphene oxide paper (GO), and 7-b is the shaggy nano aperture graphene paper (RGO) that black expands.7-c, 7-d are the optical photograph of cross section under opticmicroscope 50 times of enlargement ratios of graphene oxide (GO) and nano aperture graphene paper (RGO) respectively.Illustrate that heat treatment process creates obvious thermal expansion phenomenon.
Be the test of specific surface area and pore analysis in Fig. 8,8-a utilizes Brunauer – Emmett – Teller (BET) method to test, and this time measuring the specific surface area obtained is 286.048m
2/ g; 8-b figure is corresponding pore analysis figure, and with the test of Barret – Joyner – Halenda (BJH) method, it is 1.75-43.1nm that data analysis provides hole distribution scope, and as can be seen from the figure pore size is mainly distributed in 1.75-13.3nm.
Embodiment 3
Step a, use improve Hummers legal system for graphene oxide, and are separated into suspension with deionized water, and concentration is 10mg/mL.
Step b, by the graphene oxide suspension lyophilize in step a: first graphene oxide suspension is placed in refrigerator and is frozen into solid, put into the freeze drier drying that cold well temperature has reached-50 DEG C again, graphite oxide aerogel can be obtained, the brown column aerogel solid as shown in Fig. 9-a.
Under step c, air atmosphere, preheated by warm table, temperature is adjusted to 200 DEG C, after temperature-stable, the graphite oxide aerogel in step b is directly placed on warm table.Wait for about 3-5 second, graphite oxide aerogel to take fire and with swelling from the point of contact of Contact Heating platform, to whole aerogel burning totally, burn time duration is about 0.01s.The nano aperture graphene aerogel of the black as shown in Fig. 9-b can be obtained.
Be the test of specific surface area and pore analysis in Figure 10,10-a utilizes Brunauer – Emmett – Teller (BET) method to test, and this time measuring the specific surface area obtained is 420.028m
2/ g; 10-b figure is corresponding pore analysis figure, and with the test of Barret – Joyner – Halenda (BJH) method, it is 1.86-41.27nm that data analysis provides hole distribution scope, and as can be seen from the figure pore size is mainly distributed in 1.86-13.1nm.
Claims (7)
1. thermo-contact formula prepares a method for nano aperture Graphene, it is characterized in that carrying out as follows:
Step a, by graphene oxide dispersion in deionized water, obtain graphene oxide suspension;
Step b, lyophilize is carried out to graphene oxide suspension, obtain graphite oxide aerogel;
Or freeze-day with constant temperature is carried out to graphene oxide suspension, obtain graphene oxide paper;
Step c, in air atmosphere, heat source is preheated to 200 DEG C and more than, after stabilizing the temperature, described graphite oxide aerogel is placed on heat source, make graphite oxide aerogel burning expansion, graphene oxide is reduced, and namely obtains nano aperture graphene aerogel;
Or in air atmosphere, heat source is preheated to 200 DEG C and more than, after stabilizing the temperature, be placed on heat source by described graphene oxide paper, make graphene oxide paper burning expansion, graphene oxide is reduced, and namely obtains nano aperture graphene paper.
2. thermo-contact formula according to claim 1 prepares the method for nano aperture Graphene, it is characterized in that: the concentration of graphene oxide suspension described in step a is 4 ~ 10mg/mL.
3. thermo-contact formula according to claim 1 prepares the method for nano aperture Graphene, it is characterized in that: lyophilize described in step b carries out under the condition of-40 DEG C ~-60 DEG C.
4. thermo-contact formula according to claim 1 prepares the method for nano aperture Graphene, it is characterized in that: freeze-day with constant temperature described in step b carries out under the condition of 50 DEG C ~ 65 DEG C.
5. thermo-contact formula according to claim 1 prepares the method for nano aperture Graphene, it is characterized in that: heat source described in step c is warm table, tube furnace, hot plate or electromagnetic oven.
6. thermo-contact formula according to claim 1 prepares the method for nano aperture Graphene, it is characterized in that: graphite oxide aerogel or graphene oxide paper are placed on 0.01 ~ 3s on heat source, namely complete burning expansion.
7. thermo-contact formula according to claim 1 prepares the method for nano aperture Graphene, it is characterized in that: the nano aperture scope of gained nano aperture graphene aerogel or nano aperture graphene paper is between 1.5nm-100nm, and specific surface area is at 280-1000m
2between/g.
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| CN106809821A (en) * | 2017-01-19 | 2017-06-09 | 广东烛光新能源科技有限公司 | The preparation method of Graphene |
| CN107311152A (en) * | 2016-04-27 | 2017-11-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene aerogel, its preparation method and application |
| CN108751181A (en) * | 2018-07-03 | 2018-11-06 | 清华大学 | Heterojunction structure porous oxidation graphene film preparation method, graphene film and generator |
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| CN112687476A (en) * | 2019-10-18 | 2021-04-20 | 昆山科技大学 | Preparation and application of graphene oxide carbon aerogel |
| CN111204740A (en) * | 2020-01-14 | 2020-05-29 | 大同煤矿集团有限责任公司 | Method for rapidly preparing graphene macroscopic body through self-propagating combustion |
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