CN104310381B - A kind of scale produces method and the application of three-dimensional grapheme film continuously - Google Patents
A kind of scale produces method and the application of three-dimensional grapheme film continuously Download PDFInfo
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Abstract
The invention discloses a kind of scale and produce method and the application of three-dimensional grapheme film continuously, belong to field of functional materials. Described method is: the first step: preparation graphene oxide solution; Second step: stirring concentration; 3rd step: politef groove is immersed in methanol; 4th step: the graphene oxide solution concentrated is injected politef groove, obtains graphene oxide band; 5th step: graphene oxide band outle from methanol solution is dried, then carry out reduction swellability, described three-dimensional grapheme film can be obtained; 6th step: collect three-dimensional grapheme film, rolling. Graphene oxide solution is mixed with functional nanoparticle, the three-dimensional grapheme film of functionalization can be obtained according to identical preparation process. Described method preparation process is simple, environmental friendliness, cost are low, be suitable for large-scale production, adopts the three-dimensional grapheme film that described method prepares in three-dimensional, cellular, has light weight, specific surface area is big, pliability is a good feature.
Description
Technical field
The present invention relates to a kind of scale and produce method and the application of three-dimensional grapheme film continuously, belong to field of functional materials.
Background technology
Graphene be a kind of by carbon atom with sp2Hybrid orbital composition hexangle type is the plane stratiform knot of honeycomb lattice. Three-dimensional grapheme, owing to having high specific surface area, excellent electric conductivity and loose structure, becomes one of current Graphene associated materials material the most popular; At energy storage and transition material (lithium ion battery, fuel cell, ultracapacitor etc.), catalysis material, the application of the aspects such as electromagnetic wave absorbing material has attracted the extensive concern of domestic and international researcher.
At present, the method preparing three-dimensional grapheme is mainly chemical vapour deposition technique and the method for electronation graphene oxide lyophilizing again. But generally involve some exacting terms, such as: vapour deposition process needs at argon/hydrogen (Ar/H2) and 1000 DEG C of high growth temperature Graphenes when methane gas. Chemical reduction procedure includes hydrazine hydrate (N2H4) heat reduction, sodium-ammonia (Na-NH3) solution reduces when the dry ice bath, sodium borohydride (NaBH4) reduction under alkali condition, 80 120 DEG C of reduction etc. of acetic acid-hydroiodic acid (HAC-HI) solution, these processes need to use poisonous chemical reagent, loaded down with trivial details experimental procedure in general, consume considerable time; Freeze-drying process needs to carry out when airtight vacuum again, limits the scale of three-dimensional graphene foam, produces continuously, has had a strong impact on the Graphene application as device.
Summary of the invention
Harsh for existing three-dimensional grapheme preparation condition: process is loaded down with trivial details, relate to toxic reagent, length consuming time, that scale, continuous prodution are limited shortcoming so that the problem of the application that three-dimensional grapheme is difficulty with in actual production. It is an object of the invention to provide a kind of method producing three-dimensional grapheme continuously in scale; described method preparation process is simple, environmental friendliness, cost are low, be suitable for large-scale production; adopt the three-dimensional grapheme film that described method prepares in three-dimensional, cellular, there is light weight, specific surface area is big, pliability is good feature.
The purpose of the present invention is realized by techniques below scheme:
A kind of scale produces the method for three-dimensional grapheme film continuously, and described method step is as follows:
The first step: utilize oxidation to peel off graphite method (Hummers method) and prepare 4��10mg/mL graphene oxide solution;
Second step: the graphene oxide solution of 4��10mg/mL being stirred and being concentrated into graphene oxide solution concentration is 15��25mg/mL;
3rd step: by top end opening, side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol;
4th step: the graphene oxide solution concentrated by second step is injected from the top of politef groove, and release from bottom notch with the speed of 0.8m/min, methanol solution forms continuous band-shaped structure, i.e. graphene oxide band;
5th step: the graphene oxide band that the 4th step obtains is guided to from methanol solution and carries out after drying on the first rolling warm table, lower thickness, it is re-introduced on the second rolling warm table to carry out reduction swellability, or is placed under infrared lamp to carry out reduction swellability, obtain described three-dimensional grapheme film; Graphene oxide band moment under above-mentioned heating condition becomes the graphene band of black three dimensional structure, and namely graphene oxide is reduced to Graphene; The width of graphene band and thickness depend on height and the width of notch, and inject the concentration of graphene oxide;
Wherein, the speed that graphene oxide band rolls warm table through the first rolling warm table and second is consistent with the speed to introduce of graphene oxide band;
6th step: collect three-dimensional grapheme film, three-dimensional grapheme film is entangled in rotating shaft, standby.
The stirring of preferred second step is concentrated at 45��60 DEG C to carry out.
Preferably the first rolling warm table length is 0.8��1.2m, and temperature is 45��60 DEG C.
Preferably the second rolling warm table length is 10��15cm, and temperature is 300��500 DEG C.
The power of preferred infrared lamp is 375W, and the recovery time is 15s.
The present invention also provides for a kind of method that scale produces the three-dimensional grapheme film of functionalization continuously, and step is as follows:
The first step: utilize oxidation to peel off graphite method (Hummers method) and prepare 4��10mg/mL graphene oxide solution;
Second step: the graphene oxide solution of 4��10mg/mL is mixed with functional nanoparticle, obtains mixture, then stirring is concentrated in mixture graphene oxide and the total concentration of functional nanoparticle is 15��25mg/mL;
3rd step: by top end opening, side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol;
4th step: the mixture of the graphene oxide solution concentrated with functional nanoparticle is injected in politef groove, inject from the top of politef groove, and release from bottom notch with the speed of 0.8m/min, methanol solution forms continuous band-shaped structure, i.e. the graphene oxide band of functionalization;
5th step: the graphene oxide band of the functionalization the 4th step obtained is guided to from methanol solution and carried out after drying on the first rolling warm table, lower thickness, it is re-introduced on the second rolling warm table and carries out reduction swellability, or it is placed under infrared lamp and carries out reduction swellability, obtain the three-dimensional grapheme film of described functionalization;
Wherein, the speed that the graphene oxide band of functionalization rolls warm table through the first rolling warm table and second is consistent with the speed to introduce of the graphene oxide band of functionalization;
6th step: the three-dimensional grapheme film of collecting function, is entangled in rotating shaft by the three-dimensional grapheme film of functionalization, standby.
The stirring of preferred second step is concentrated at 45��60 DEG C to carry out.
Preferably the first rolling warm table length is 0.8��1.2m, and temperature is 45��60 DEG C.
Preferably the second rolling warm table length is 10��15cm, and temperature is 300��500 DEG C.
The power of preferred infrared lamp is 375W, and the recovery time is 15s.
In preferred mixture, the quality of functional nanoparticle is less than the 1/10 of graphene oxide quality.
Described functional nanoparticle is more than one in nano-particle set forth below:
The first is Fe, Ni, Cu, Si, Co, Ag, Pd, Pt or Au nano-particle;
The second is FeNi, FeCu, NiCu, FeCo, FePt, FePd, FeAu, PdPt, PdAu, NiCo, AgNi, PtNi, AuNi, AgCo, PdCo, AuCo, PdAg, PtPd or PtAu alloy nanoparticle;
The third is SiO2��Fe3O4��Mn3O4��Co3O4��NiO��PbO��TiO2, ZnO, CuO or Cu2O oxide nano particles;
4th kind is Fe-Fe3O4��Cu-CuO��Cu-Cu2O, Ni-NiO or Pb-PbO metal-oxide composite nanometer particle;
5th kind is Fe3O4-CuO��CuO-Cu2O��Fe3O4-Cu2O��Fe3O4-NiO��Fe3O4-PbO��Fe3O4-TiO2, CuO-NiO, CuO-PbO or NiO-PbO nanoparticles of complex metal oxides.
The three-dimensional grapheme film of three-dimensional grapheme film of the present invention and functionalization can as energy storage and transition material.
Beneficial effect
(1) present invention utilizes raw material graphene oxide solution and functional nanoparticle are simple and easy to get, and cost is low, and synthetic technology is ripe, are suitable for producing in enormous quantities.
(2) present invention is by building simple experimental provision, it is possible to the three-dimensional grapheme film of scale, the continuously pure three-dimensional grapheme film of production or functionalization. The method, except low toxicity methanol, does not use other noxious substances, environmental friendliness; Graphene oxide reduction rate is fast, and yield is high; The process that graphene oxide is reduced to Graphene is reproducible, and is reduced in the process of Graphene at graphene oxide, and functional nanoparticle does not change, stable in properties so that end product quality is stable; Controlled by the notch size of politef groove so that product three-dimensional grapheme film macroscopic view size, thickness are all controlled. And described method technique is simple, cheap.
(3) three-dimensional grapheme that the method for the invention obtains, structure, in three-dimensional, cellular, has light weight, and specific surface area is big, the feature that pliability is good. And maintain the structure of macroscopically film, it is simple to collect and use.
(4) whole experimentation is avoided using surfactant, potassium chloride salt solution etc. to be difficult to the chemical substance removed, and the three-dimensional grapheme obtained is clean, it is not necessary to post processing.
(5) the method for the invention is possible not only to obtain pure three-dimensional grapheme film, as super light material, oil suction dirt material etc.; The three-dimensional grapheme membrane material of functionalization can also be prepared in batches, as energy storage and transition material, as: as lithium ion battery negative material, it is possible to avoid the use of traditional nonconducting bridging agent, there is higher lithium ion capacity and good high rate performance; As photoelectric response material, there is higher photoelectricity phase induced current; As fuel-cell catalyst, the activity higher than revealing, stability and anti-Poisoning Properties; Furthermore it is also possible to batch prepare electromagnetic wave absorbing material, thermoelectric material etc. Extend the range of application of three-dimensional grapheme.
(6) temperature stirring concentration in the method for the invention selects to need to consider following factor: temperature is too high, and graphene oxide can be reduced to Graphene, and the too low meeting of temperature makes concentration time extend, and reduces the production efficiency of three-dimensional grapheme film.Therefore, second step of the present invention stirring concentration selects to carry out at 45��60 DEG C of temperature, both can guarantee that thickening efficiency, has been avoided that again graphene oxide is reduced.
Accompanying drawing explanation
Fig. 1 is the whole experiment flow figure of embodiment;
Fig. 2 is the photo obtaining dry graphene oxide and the bending of three-dimensional grapheme band in embodiment 1;
Fig. 3 is the X-ray powder diffraction test figure of the graphene oxide membrane obtained in embodiment 1 and three-dimensional grapheme;
Fig. 4 is the Raman spectrum test figure of the dry graphene oxide obtained in embodiment 1 and three-dimensional grapheme;
Fig. 5 is photo (a figure) and the scanning electron microscope diagram (b figure) of dry graphene oxide and the three-dimensional grapheme intersection obtained in embodiment 1;
Fig. 6 is the dry graphene oxide membrane cross section obtained in embodiment 1 scanning electron microscope test figure (35 times of-a figure, 100 times of-b figure) under different multiples;
Fig. 7 is the three-dimensional grapheme film cross section obtained in embodiment 1 scanning electron microscope test figure (25 times of-a figure, 100 times of-b figure) under different multiples;
Fig. 8 is differing heights in embodiment 3: the comparison diagram (0.3cm-a schemes, and 0.4cm-b schemes, and 0.5cm-c schemes) of the three-dimensional grapheme film scanning electron microscope that the notch of 0.3cm, 0.4cm, 0.5cm obtains;
Fig. 9 is the cyclic voltammetry figure that the three-dimensional grapheme of the Pt nano-particle functionalization obtained in embodiment 6 obtains as the catalyst of ethanol electrooxidation, sweeps speed 50mVS-1;
Figure 10 is the Fe obtained in embodiment 93O4The Scanning Electron microscope figure of the three-dimensional grapheme of granule functionalization;
Figure 11 be embodiment 10 obtains by TiO2The Graphene of nano-particle functionalization is cut into shape (rectangle: the 0.5 �� 1.2cm of rule2) testing photoelectronic stream response diagram;
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited to this.
Hummers method prepares the process of graphene oxide solution: take the high purity graphite powder of 12g, by the concentrated sulphuric acid of 280mL, the sodium nitrate of 6g, at ice bath, under stirring condition, add the potassium permanganate of 36g, after stirring half an hour, temperature is adjusted to 35 DEG C, after maintaining half an hour, add the distilled water of 600mL, temperature is adjusted to 90 DEG C, and maintain 15 minutes, then, add the distilled water of 2000mL again, temperature is adjusted to room temperature, after stirring 1 hour, stand, the hydrogen peroxide of 80mL is added after 1 hour, then sucking filtration obtains solid, add after 1200��3200mL water centrifuge washing again, the graphene oxide solution of 4��10mg/mL can be obtained.
The mass concentration 80% of methanol solution used in following example.
Scale of the present invention produces the method for three-dimensional grapheme film continuously and adopts equipment as shown in Figure 1, and equipment includes: politef groove, glass guide channel, the first rolling warm table, the second rolling warm table and rotating shaft; Wherein, glass guide channel, the first rolling warm table, the second rolling warm table and rotating shaft are sequentially arranged on same horizontal axis in the order listed; Politef groove top end opening, there is square notch side, bottom; When producing, politef groove is placed in glass guide channel, and the projection of bottom notch and the first rolling warm table is on the same line.
Embodiment 1
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 10mg/mL graphene oxide solution;
2., by the heated and stirred concentration at 45 DEG C of 10mg/mL graphene oxide solution, making graphene oxide solution concentration is 25mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol.The height of square notch is 0.4cm, and width is 3cm;
4. the graphene oxide solution of the 25mg/mL that second step concentrates is injected from the top of politef groove, graphene oxide solution is made to release from bottom notch with the speed of 0.8m/min, methanol solution is formed the continuous print banded structure of graphene oxide, i.e. graphene oxide band;
5. the graphene oxide band got is guided to from methanol solution 45 DEG C, on the rolling warm table of 1.2m, graphite oxide band is dried, dry graphene band is introduced 500 DEG C again, on the rolling warm table of 15cm, graphene oxide band moment becomes the graphene band of black three dimensional structure;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
3��6 step operation charts are as shown in Figure 1.
Product is detected, and Fig. 2 is dry graphene oxide and the photo of three-dimensional grapheme band bending, illustrates that the graphene strips of heat reduction is with good pliability, and after the heated reduction of graphene oxide, lamella is thickening. From X-ray powder diffraction test figure (Fig. 3) it can be seen that the characteristic peak (10 ��) of graphene oxide disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrate that graphene oxide has been reduced to Graphene after heating; Ratio (the I of the D peak intensity of dry graphene oxide membrane and three-dimensional grapheme and G peak intensity is can be seen that Raman spectrum test result (Fig. 4)D/IG); D peak represents SP3The vibration absorption peak becoming key model of hydridization carbon, as: " C-O ", " C=O ", " O-C=O ", G peak represents SP2The vibration absorption peak becoming key model of hydridization carbon, it may be assumed that " C=C ", three-dimensional grapheme I after heat reductionD/IGValue be 0.97, than the I of graphene oxide bandD/IG(1.24) little, illustrate that graphene oxide obtains reduction, the structure of Graphene obtains reparation. In conjunction with photo (Fig. 5-(a)) and the scanning electron microscope test (Fig. 5-(b)) of dry graphene oxide and three-dimensional grapheme intersection it can be seen that the heated three-layer laminated loose structure being transformed to Graphene afterwards of the planar film structure of graphene oxide. The scanning electron microscope test figure in dry graphene oxide (Fig. 6-(a), Fig. 6-(b)) and three-dimensional grapheme (Fig. 7-(a), Fig. 7-(b)) film cross section it is also seen that, graphene oxide expand into three-dimensional grapheme after heat reduction, and membrane structure obtains maintenance.
Embodiment 2
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 4mg/mL graphene oxide solution;
2., by the heated and stirred concentration at 60 DEG C of 4mg/mL graphene oxide solution, making graphene oxide solution concentration is 15mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol. The height of square notch is 0.3cm, and width is 2cm;
4. the graphene oxide solution of the 15mg/mL that second step concentrates is injected from the top of politef groove, graphene oxide solution is made to release from bottom notch with the speed of 0.8m/min, methanol solution is formed the continuous print banded structure of graphene oxide, i.e. graphene oxide band;
5. the graphene oxide band got is guided to from methanol solution 60 DEG C, on the rolling warm table of 0.8m, graphite oxide band is dried, dry graphene band is introduced 300 DEG C again, on the rolling warm table of 15cm, graphene oxide band moment becomes the graphene band of black three dimensional structure;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, from X-ray powder diffraction test figure it can be seen that the characteristic peak (10 ��) of graphene oxide disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrate that graphene oxide has been reduced to Graphene after heating; In conjunction with scanning electron microscope test it can be seen that the planar film structure of graphene oxide heated after be transformed to the three-layer laminated loose structure of Graphene. The photo of Graphene after the film dried by graphene oxide and heating, can be seen that graphene oxide is the thin film of yellow, and become thickness after heat reduction and become black film big, loose, same explanation heating process is that graphene oxide is transformed into three-dimensional grapheme.
Embodiment 3
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2., by the heated and stirred concentration at 50 DEG C of 8mg/mL graphene oxide solution, making graphene oxide solution concentration is 20mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol; The height of square notch is 0.5cm, and width is 6cm;
4. the graphene oxide solution of the 20mg/mL that second step concentrates is injected from the top of politef groove, graphene oxide solution is made to release from bottom notch with the speed of 0.8m/min, methanol solution is formed the continuous print banded structure of graphene oxide, i.e. graphene oxide band;
5. the graphene oxide band got is guided to from methanol solution 50 DEG C, on the rolling warm table of 1.0m, graphite oxide band is dried, dry graphene band is introduced 300 DEG C again, on the rolling warm table of 15cm, graphene oxide band moment becomes the graphene band of black three dimensional structure;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, from X-ray powder diffraction test figure it can be seen that the characteristic peak (10 ��) of graphene oxide disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrate that graphene oxide has been reduced to Graphene after heating; In conjunction with scanning electron microscope test it can be seen that the planar film structure of graphene oxide heated after be transformed to the three-layer laminated loose structure of Graphene. The photo of Graphene after the film dried by graphene oxide and heating, can be seen that graphene oxide is the thin film of yellow, and become thickness after heat reduction and become black film big, loose, same explanation heating process is that graphene oxide is transformed into three-dimensional grapheme. The photo of the graphene oxide membrane obtained by differing heights notch (0.3cm, 0.5cm) can be seen that the height of square notch is different, the thickness obtaining film is also different, the groove of 0.3cm height, obtain yellow film, and the film of the graphene oxide that the groove of 0.5cm height obtains is brown, illustrating that notch is more high, obtain graphene oxide lamella more thick, light transmittance is more poor. Differing heights such as the comparison of three-dimensional grapheme scanning electron microscope diagram sheet (Fig. 8-(a), (b), (c)) that the notch of 0.3cm, 0.4cm, 0.5cm obtains, equally possible explanation, the thickness of three-dimensional grapheme can be controlled by the height of notch.
Embodiment 4
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 6mg/mL graphene oxide solution;
2., by the heated and stirred concentration at 50 DEG C of 6mg/mL graphene oxide solution, making graphene oxide solution concentration is 21mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol. The height of square notch is 0.3cm, and width is 6cm;
4. the graphene oxide solution of the 21mg/mL that second step concentrates is injected from the top of politef groove, graphene oxide solution is made to release from bottom notch with the speed of 0.8m/min, methanol solution is formed the continuous print banded structure of graphene oxide, i.e. graphene oxide band;
5. the graphene oxide band got is guided to from methanol solution 55 DEG C, on the rolling warm table of 1.0m, graphite oxide band is dried, dry graphene band is guided to heating 15s again under the infrared lamp that power is 375W, and graphene oxide band moment becomes the graphene band of black three dimensional structure;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, from X-ray powder diffraction test figure it can be seen that the characteristic peak (10 ��) of graphene oxide disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrate that graphene oxide has been reduced to Graphene after heating; In conjunction with scanning electron microscope test it can be seen that the planar film structure of graphene oxide heated after be transformed to the three-layer laminated loose structure of Graphene. The photo comparison of Graphene after the film dried by graphene oxide and heating, can be seen that graphene oxide is the thin film of yellow, and become thickness after heat reduction and become black film big, loose, same explanation heating process is that graphene oxide is transformed into three-dimensional grapheme.
Embodiment 5
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 10mg/mL graphene oxide solution;
2. 10mg/mL graphene oxide solution and the Cu powder that particle diameter is 200nm are mixed, wherein the quality of Cu powder is the 1/10 of graphene oxide quality, obtain mixture, heated and stirred concentration at 50 DEG C, making the total concentration of graphene oxide and Cu nanoparticle in mixture is 15mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol. The height of square notch is 0.3cm, and width is 2cm;
4. the mixture of the graphene oxide solution that second step concentrates and Cu nanoparticle injects from the top of politef groove, mixture is made to release from bottom notch with the speed of 0.8m/min, methanol solution is formed continuous print banded structure, i.e. the graphene oxide band of Cu nano-particle functionalization;
5. the graphene oxide band of the Cu nano-particle functionalization got is guided to from methanol solution 50 DEG C, on the rolling warm table of 1.2m, graphite oxide band is dried, dry graphene band is introduced 400 DEG C again, on the rolling warm table of 15cm, graphene oxide band moment becomes the graphene band of black three dimensional structure. The width of graphene band and thickness depend on height and the width of notch, and inject the concentration of graphene oxide;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, by X-ray powder diffraction test figure it can be seen that the characteristic peak (43 ��, 50 ��, 74 �� and 90 ��) of Cu, and the characteristic peak of graphene oxide (10 ��) disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrating that graphene oxide has been reduced to Graphene, the product obtained is the complex of Cu and Graphene;Test known in conjunction with scanning electron microscope test and transmission electron microscope, the structure of Graphene is three-layer laminated loose structure, the pattern of Cu is the nano-particle of about 200nm, being evenly dispersed in the surface of graphene sheet layer, namely product is the three-dimensional grapheme of the porous of Cu nano-particle functionalization.
Embodiment 6
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. 8mg/mL graphene oxide solution and the Pt powder that particle diameter is 5nm are mixed, wherein the quality of Pt powder is the 1/10 of graphene oxide quality, obtain mixture, heated and stirred concentration at 50 DEG C, making the total concentration of graphene oxide and Pt nanoparticle in mixture is 22mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol. The height of square notch is 0.3cm, and width is 2cm;
4. the mixture of the graphene oxide solution that second step concentrates and Pt nanoparticle injects from the top of politef groove, mixture is made to release from bottom notch with the speed of 0.8m/min, methanol solution is formed continuous print banded structure, i.e. the graphene oxide band of Pt nano-particle functionalization;
5. the graphene oxide band of the Pt nano-particle functionalization got is guided to from methanol solution 55 DEG C, on the rolling warm table of 1m, graphite oxide band is dried, dry graphene band is introduced 400 DEG C again, on the rolling warm table of 15cm, graphene oxide band moment becomes the graphene band of black three dimensional structure. The width of graphene band and thickness depend on height and the width of notch, and inject the concentration of graphene oxide;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, by X-ray powder diffraction test figure it can be seen that the characteristic peak (40 ��, 46 ��, 68 ��, 82 �� and 86 ��) of Pt, and the characteristic peak of graphene oxide (10 ��) disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrating that graphene oxide has been reduced to Graphene, the product obtained is the complex of Pt and Graphene; Test known in conjunction with scanning electron microscope test and transmission electron microscope, the structure of Graphene is three-layer laminated loose structure, the pattern of Pt is the nano-particle of about 5nm, being evenly dispersed in the surface of graphene sheet layer, namely product is the three-dimensional grapheme of the porous of Pt nano-particle functionalization. Using the three-dimensional grapheme of Pt nano-particle functionalization as the catalyst of ethanol electrooxidation, show 275mAg-1Peak point current, as shown in Figure 9. Additionally, I in figurefFor just sweeping peak-to-peak value electric current, represent the current value of oxidation of ethanol, IbSweep peak-to-peak value electric current for inverse, represent the current value (current value reflects the amount causing catalyst poisoning product) of poisoning product oxidation in the middle of oxidation of ethanol; Typically by If/IbThe size of value represent the anti-poisoning capability of catalyst, figure can be seen that IfMore than Ib(If/Ib=1.2), illustrate that this catalyst has anti-poisoning capability strong preferably.
Embodiment 7
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 9mg/mL graphene oxide solution;
2. the PtPd alloy powder of 9mg/mL graphene oxide solution and particle diameter 3nm is mixed, wherein the quality of PtPd alloy powder is the 1/10 of graphene oxide quality, obtain mixture, heated and stirred concentration at 50 DEG C, making the total concentration of graphene oxide and PtPd alloy nano particle in mixture is 24mg/mL
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol.The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of politef groove, makes mixture release from bottom notch with the speed of 0.8m/min, forms continuous print banded structure, i.e. the graphene oxide band of PtPd alloy nanoparticle functionalization in methanol solution;
5. the graphene oxide band of the PtPd alloy nanoparticle functionalization got is guided to from methanol solution 50 DEG C, on the rolling warm table of 1.2m, graphite oxide band is dried, again by dry graphene band 15s under the infrared lamp that power is 375W, graphene oxide band moment becomes the graphene band of black three dimensional structure. The width of graphene band and thickness depend on height and the width of notch, and inject the concentration of graphene oxide;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, by X-ray powder diffraction test figure it can be seen that the characteristic peak (40 ��, 47 ��, 68 ��, 82 �� and 86 ��) of PtPd alloy, and the characteristic peak of graphene oxide (10 ��) disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrating that graphene oxide has been reduced to Graphene, the product obtained is the complex of PtPd alloy and Graphene; Test known in conjunction with scanning electron microscope test and transmission electron microscope, the structure of Graphene is three-layer laminated loose structure, the pattern of PtPd alloy is the nano-particle of about 3nm, being evenly dispersed in the surface of graphene sheet layer, namely product is the three-dimensional grapheme of the porous of PtPd alloy nanoparticle functionalization.
Embodiment 8
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 10mg/mL graphene oxide solution;
2. 10mg/mL graphene oxide solution and the FeNi alloy powder that particle diameter is 20nm are mixed, wherein the quality of FeNi alloy powder is the 1/10 of graphene oxide quality, obtain mixture, heated and stirred concentration at 50 DEG C, making the total concentration of graphene oxide and FeNi alloy nano particle in mixture is 22mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol. The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of politef groove, makes mixture release from bottom notch with the speed of 0.8m/min, forms continuous print banded structure, i.e. the graphene oxide band of FeNi alloy nanoparticle functionalization in methanol solution;
5. the graphene oxide band of the FeNi nano-particle functionalization got is guided to from methanol solution 50 DEG C, on the rolling warm table of 1.2m, graphite oxide band is dried, dry graphene band is introduced 350 DEG C again, on the rolling warm table of 15cm, graphene oxide band moment becomes the graphene band of black three dimensional structure. The width of graphene band and thickness depend on height and the width of notch, and inject the concentration of graphene oxide;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, by X-ray powder diffraction test figure it can be seen that the characteristic peak (44 ��, 51 �� and 75 ��) of FeNi alloy, and the characteristic peak of graphene oxide (10 ��) disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrating that graphene oxide has been reduced to Graphene, the product obtained is the complex of FeNi alloy and Graphene;Test known in conjunction with scanning electron microscope test and transmission electron microscope, the structure of Graphene is three-layer laminated loose structure, the pattern of FeNi alloy is the nano-particle of about 20nm, being evenly dispersed in the surface of graphene sheet layer, namely product is the three-dimensional grapheme of the porous of FeNi alloy nanoparticle functionalization.
Embodiment 9
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 9mg/mL graphene oxide solution;
2. it is the Fe of 50nm by 9mg/mL graphene oxide solution and particle diameter3O4Powder, wherein Fe3O4The quality of powder is the 1/10 of graphene oxide quality, obtains mixture, and at 55 DEG C, heated and stirred concentration, makes graphene oxide and Fe in mixture3O4The total concentration of nanoparticle is 22mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol. The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of politef groove, makes mixture release from bottom notch with the speed of 0.8m/min, forms continuous print banded structure, i.e. Fe in methanol solution3O4The graphene oxide band of nano-particle functionalization;
5. the Fe that will get3O4The graphene oxide band of nano-particle functionalization guides to 45 DEG C from methanol solution, on the rolling warm table of 1.2m, graphite oxide band is dried, dry graphene band is introduced 500 DEG C again, on the rolling warm table of 15cm, graphene oxide band moment becomes the graphene band of black three dimensional structure. The width of graphene band and thickness depend on height and the width of notch, and inject the concentration of graphene oxide;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, by X-ray powder diffraction test figure it can be seen that Fe3O4Characteristic peak (30 ��, 36 ��, 43 ��, 57 �� and 63 ��), and the characteristic peak of graphene oxide (10 ��) disappears, occurring in that the characteristic peak (24 ��) of Graphene, illustrate that graphene oxide has been reduced to Graphene, the product obtained is Fe3O4Complex with Graphene; Test it can be seen that the structure of Graphene is three-layer laminated loose structure in conjunction with scanning electron microscope test (Figure 10) and transmission electron microscope, Fe3O4The pattern of granule is the nano-particle of about 50nm, is evenly dispersed in the surface of graphene sheet layer, and namely product is Fe3O4The three-dimensional grapheme of the porous of nano-particle functionalization. Fe3O4The three-dimensional grapheme film of nano-particle functionalization can be inhaled on Magnet, illustrates that it is magnetic.
Embodiment 10
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 9mg/mL graphene oxide solution;
2. it is the TiO of 20nm by 9mg/mL graphene oxide solution and particle diameter2Powder, wherein TiO2The quality of powder is the 1/10 of graphene oxide quality, obtains mixture, and at 55 DEG C, heated and stirred concentration, makes graphene oxide and TiO in mixture2The total concentration of alloy nano particle is 20mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol. The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of politef groove, makes mixture release from bottom notch with the speed of 0.8m/min, forms continuous print banded structure, i.e. TiO in methanol solution2The graphene oxide band of nano-particle functionalization;
5. by TiO2The graphene oxide band of nano-particle functionalization guides to 50 DEG C from methanol solution, on the rolling warm table of 1.2m, graphite oxide band is dried, dry graphene band is introduced 500 DEG C again, on the rolling warm table of 12cm, graphene oxide band moment becomes the graphene band of black three dimensional structure. The width of graphene band and thickness depend on height and the width of notch, and inject the concentration of graphene oxide;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, by X-ray powder diffraction test figure it can be seen that TiO2Characteristic peak (25 ��, 38 ��, 48 ��, 54 ��, 48 ��, 63 �� and 75 ��), and the characteristic peak of graphene oxide (10 ��) disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrating that graphene oxide has been reduced to Graphene, the product obtained is TiO2Complex with Graphene; Test it can be seen that the structure of Graphene is three-layer laminated loose structure in conjunction with scanning electron microscope test and transmission electron microscope, TiO2The pattern of granule is the nano-particle of about 20nm, is evenly dispersed in the surface of graphene sheet layer, and namely product is TiO2The three-dimensional grapheme of the porous of nano-particle functionalization. By TiO2The Graphene of nano-particle functionalization is cut into shape (rectangle: the 0.5 �� 1.2cm of rule2) response of testing photoelectronic stream. Photoelectric current can reach 6 microamperes (Figure 11). Test instrunment is to test on CHI760D electrochemical workstation, and light source is the electric filament lamp of 100w.
Embodiment 11
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 7mg/mL graphene oxide solution;
2. by Cu granule that 7mg/mL graphene oxide solution, particle diameter are 200nm and CuO powder that particle diameter is 200nm, wherein the 1/20 of the quality respectively graphene oxide quality of Cu granule, CuO powder, obtain mixture, heated and stirred concentration at 55 DEG C, making the total concentration of graphene oxide and Cu-CuO granule nanoparticle in mixture is 22mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol. The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of politef groove, makes mixture release from bottom notch with the speed of 0.8m/min, forms continuous print banded structure, i.e. the graphene oxide band of Cu-CuO nano-particle functionalization in methanol solution;
5. the graphene oxide band of the Cu-CuO nano-particle functionalization got is guided to from methanol solution 45 DEG C, on the rolling warm table of 1.2m, graphite oxide band is dried, dry graphene band is introduced 400 DEG C again, on the rolling warm table of 15cm, graphene oxide band moment becomes the graphene band of black three dimensional structure. The width of graphene band and thickness depend on height and the width of notch, and inject the concentration of graphene oxide;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, by X-ray powder diffraction test figure it can be seen that the characteristic peak (36 ��, 39 ��, 49 ��, 54 ��, 58 ��, 62 ��, 66 ��, 68 ��, 75 �� and 82 ��) of the characteristic peak (30 ��, 36 ��, 43 ��, 57 �� and 63 ��) of Cu and CuO, and the characteristic peak of graphene oxide (10 ��) disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrating that graphene oxide has been reduced to Graphene, the product obtained is the complex of Cu-CuO nano-particle and Graphene;Test known in conjunction with scanning electron microscope test and transmission electron microscope, the structure of Graphene is three-layer laminated loose structure, the pattern of Cu, CuO granule is the nano-particle of about 200nm, 200nm, being evenly dispersed in the surface of graphene sheet layer, namely product is the three-dimensional grapheme of the porous of Cu-CuO nano-particle functionalization.
7. the three-dimensional grapheme band of the porous that the 6th step obtains Cu-CuO nano-particle functionalization is directly cut into the circle that diameter is 1.6cm, negative pole as Li battery, it is assembled into the button cell that diameter is about 2cm, and its capacity character and recursive nature are tested. Under 0.05A/g electric current, the battery charging and discharging test of 200 circles, battery capacity is stable at 834mAh/g, and when electric current is raised to 0.4A/g time, the capacity of battery is stable at 605mAh/g, test from multiplying power, battery is under high electric current (20A/g) condition, and capacity remains to reach 241mAh/g, and when electric current returns to 0.05A/g, capacitance can return to 832mAh/g, illustrates that this negative material has good high rate performance. Cell assembling processes completes in glove box, and test system is LANDCT2001A.
Embodiment 12
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 9mg/mL graphene oxide solution;
2. it is the Fe of 50nm by 9mg/mL graphene oxide solution, particle diameter3O4Granule and the CuO powder that particle diameter is 200nm, wherein Fe3O4Granule, CuO powder quality respectively graphene oxide quality 1/20, obtain mixture, at 55 DEG C heated and stirred concentration, make graphene oxide and Fe in mixture3O4The total concentration of-CuO granule nanoparticle is 25mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol. The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of politef groove, makes mixture release from bottom notch with the speed of 0.8m/min, forms continuous print banded structure, i.e. Fe in methanol solution3O4The graphene oxide band of-CuO nano-particle functionalization;
5. the Fe that will get3O4The graphene oxide band of-CuO nano-particle functionalization guides to 55 DEG C from methanol solution, on the rolling warm table of 1.2m, graphite oxide band is dried, dry graphene band is introduced 450 DEG C again, on the rolling warm table of 15cm, graphene oxide band moment becomes the graphene band of black three dimensional structure. The width of graphene band and thickness depend on height and the width of notch, and inject the concentration of graphene oxide;
6. collect graphene band, graphene band is entangled in rotating shaft, standby. The three-dimensional grapheme film that graphene band is namely described.
Product is detected, by X-ray powder diffraction test figure it can be seen that Fe3O4Characteristic peak (30 ��, 36 ��, 43 ��, 57 �� and 63 ��) and the characteristic peak (36 ��, 39 ��, 49 ��, 54 ��, 58 ��, 62 ��, 66 ��, 68 ��, 75 �� and 82 ��) of CuO, and the characteristic peak of graphene oxide (10 ��) disappears, occur in that the characteristic peak (24 ��) of Graphene, illustrating that graphene oxide has been reduced to Graphene, the product obtained is Fe3O4The complex of-CuO nano-particle and Graphene; Test it can be seen that the structure of Graphene is three-layer laminated loose structure in conjunction with scanning electron microscope test and transmission electron microscope, Fe3O4, CuO granule the nano-particle that pattern is about 50nm, 500nm, be evenly dispersed in the surface of graphene sheet layer, namely product is Fe3O4The three-dimensional grapheme of the porous of-CuO nano-particle functionalization.
The present invention includes but not limited to above example, every any equivalent replacement carried out under the principle of spirit of the present invention or local improvement, all will be regarded as within protection scope of the present invention.
Claims (10)
1. the method that a scale produces three-dimensional grapheme film continuously, it is characterised in that described method step is as follows:
The first step: utilize oxidation to peel off graphite method and prepare 4��10mg/mL graphene oxide solution;
Second step: the graphene oxide solution of 4��10mg/mL being stirred and being concentrated into graphene oxide solution concentration is 15��25mg/mL;
3rd step: by top end opening, side, bottom has the politef groove of square notch to be immersed in equipped with in the glass guide channel of methanol, and notch is completely submerged among methanol;
4th step: the graphene oxide solution concentrated by second step is injected from the top of politef groove, and release from bottom notch with the speed of 0.8m/min, methanol solution forms continuous band-shaped structure, i.e. graphene oxide band;
5th step: the graphene oxide band that the 4th step obtains is guided to from methanol solution and carries out after drying on the first rolling warm table, it is re-introduced on the second rolling warm table and carries out reduction swellability, or it is placed under infrared lamp and carries out reduction swellability, obtain described three-dimensional grapheme film;
Wherein, the speed that graphene oxide band rolls warm table through the first rolling warm table and second is consistent with the speed to introduce of graphene oxide band;
6th step: collect three-dimensional grapheme film, three-dimensional grapheme film is entangled in rotating shaft, standby.
2. the method that a kind of scale according to claim 1 produces three-dimensional grapheme film continuously, it is characterized in that, second step, after graphene oxide solution and functional nanoparticle are mixed to get mixture, then the total concentration of the graphene oxide that is stirred being concentrated in mixture and functional nanoparticle is 15��25mg/mL; Except following difference, when other step is constant, obtain the three-dimensional grapheme film of functionalization;
4th step, replaces with the mixture of graphene oxide solution and functional nanoparticle by graphene oxide solution, and graphene oxide band replaces with the graphene oxide band of functionalization;
5th step, replaces with the graphene oxide band of functionalization by graphene oxide band, and three-dimensional grapheme film replaces with the three-dimensional grapheme film of functionalization;
6th step, three-dimensional grapheme film replaces with the three-dimensional grapheme film of functionalization.
3. the method that a kind of scale according to claim 1 and 2 produces three-dimensional grapheme film continuously, it is characterised in that second step stirring is concentrated at 45��60 DEG C to carry out.
4. the method that a kind of scale according to claim 1 and 2 produces three-dimensional grapheme film continuously, it is characterised in that the first rolling warm table length is 0.8��1.2m, and temperature is 45��60 DEG C.
5. the method that a kind of scale according to claim 1 and 2 produces three-dimensional grapheme film continuously, it is characterised in that the second rolling warm table length is 10��15cm, and temperature is 300��500 DEG C.
6. the method that a kind of scale according to claim 1 and 2 produces three-dimensional grapheme film continuously, it is characterised in that the power of infrared lamp is 375W, the recovery time is 15s.
7. the method that a kind of scale according to claim 2 produces three-dimensional grapheme film continuously, it is characterised in that in mixture, the quality of functional nanoparticle is less than the 1/10 of graphene oxide quality.
8. the method that a kind of scale according to claim 2 produces three-dimensional grapheme film continuously, it is characterised in that described functional nanoparticle is more than one in nano-particle set forth below:
The first is Fe, Ni, Cu, Si, Co, Ag, Pd, Pt or Au nano-particle;
The second is FeNi, FeCu, NiCu, FeCo, FePt, FePd, FeAu, PdPt, PdAu, NiCo, AgNi, PtNi, AuNi, AgCo, PdCo, AuCo, PdAg, PtPd or PtAu alloy nanoparticle;
The third is SiO2��Fe3O4��Mn3O4��Co3O4��NiO��PbO��TiO2, ZnO, CuO or Cu2O oxide nano particles;
4th kind is Fe-Fe3O4��Cu-CuO��Cu-Cu2O, Ni-NiO or Pb-PbO metal-oxide composite nanometer particle;
5th kind is Fe3O4-CuO��CuO-Cu2O��Fe3O4-Cu2O��Fe3O4-NiO��Fe3O4-PbO��Fe3O4-TiO2, CuO-NiO, CuO-PbO or NiO-PbO nanoparticles of complex metal oxides.
9. the scale adopted described in claim 1 produces the application of the three-dimensional grapheme film that the method for three-dimensional grapheme film obtains continuously, it is characterised in that described three-dimensional grapheme film is as energy storage and transition material.
10. the scale adopted described in claim 2 produces the application of the three-dimensional grapheme film of the functionalization that the method for three-dimensional grapheme film obtains continuously, it is characterised in that the three-dimensional grapheme film of described functionalization is as energy storage and transition material.
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