CN104310381A - Method for on-scale continuous production of three-dimensional graphene membrane and application - Google Patents
Method for on-scale continuous production of three-dimensional graphene membrane and application Download PDFInfo
- Publication number
- CN104310381A CN104310381A CN201410509947.5A CN201410509947A CN104310381A CN 104310381 A CN104310381 A CN 104310381A CN 201410509947 A CN201410509947 A CN 201410509947A CN 104310381 A CN104310381 A CN 104310381A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- graphene
- dimensional grapheme
- band
- grapheme film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a method for on-scale continuous production of a three-dimensional graphene membrane and application, belonging to the field of functional materials. The method comprises the following steps: 1, preparing a graphene oxide solution; 2, stirring and concentrating; 3, soaking a polytetrafluoroethylene bath into methanol; 4, filling the concentrated graphene oxide solution into the polytetrafluoroethylene bath, thereby obtaining graphene oxide strips; 5, leading out the graphene oxide strips from the methanol solution, firstly drying, and further performing reduction expansion, thereby obtaining the three-dimensional graphene membrane; and 6, collecting the three-dimensional graphene membrane, and coiling. The graphene oxide solution and functional nanoparticles are mixed, and the functional three-dimensional graphene membrane can be prepared by performing the above preparation steps. The method is simple in preparation process, environment-friendly, low in cost and applicable to on-scale production, and the three-dimensional graphene membrane prepared by using the method is three-dimensional and porous and has the characteristics of light mass, large specific surface area and good flexibility.
Description
Technical field
The present invention relates to a kind of method and application of mass-producing continuous seepage three-dimensional grapheme film, belong to field of functional materials.
Background technology
Graphene be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the plane stratiform knot of honeycomb lattice.Three-dimensional grapheme, owing to having high specific surface area, excellent electroconductibility and vesicular 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.), photocatalyst material, the application of the aspects such as electromagnetic wave absorbing material has attracted the extensive concern of domestic and international investigator.
At present, the method for the method preparing three-dimensional grapheme mainly chemical Vapor deposition process and chemical reduction graphene oxide freeze-drying again.But generally involve some exacting terms, such as: vapour deposition process needs at argon/hydrogen (Ar/H
2) and the lower 1000 DEG C of high growth temperature Graphenes of methane gas condition.Chemical reduction procedure comprises hydrazine hydrate (N
2h
4) heat reduction, sodium-ammonia (Na-NH
3) solution reduces under the dry ice bath condition, sodium borohydride (NaBH
4) reduction under alkaline condition, the 80 – 120 DEG C reduction etc. of acetic acid-hydroiodic acid HI (HAC-HI) solution, these processes need to use poisonous chemical reagent in general, loaded down with trivial details experimental procedure, consume considerable time; Freeze-drying process needs to carry out under airtight vacuum condition again, limits the mass-producing of three-dimensional graphene foam, continuous seepage, has had a strong impact on the application of Graphene 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, the shortcoming that mass-producing, continuous prodution are limited, makes three-dimensional grapheme be difficult to the problem of the application realized in actual production.The object of the present invention is to provide a kind of method at mass-producing continuous seepage three-dimensional grapheme; described method preparation process is simple, environmental friendliness, cost are low, be applicable to scale operation; the three-dimensional grapheme film adopting described method to prepare, in three-dimensional, vesicular, has the advantages that quality is light, specific surface area is large, snappiness is good.
Object of the present invention is realized by following technical scheme:
A method for mass-producing continuous seepage three-dimensional grapheme film, described method steps 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 tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely;
4th step: the graphene oxide solution concentrated by second step is injected from the top of tetrafluoroethylene groove, and releases from bottom notch with the speed of 0.8m/min, forms continuous band-shaped structure, i.e. graphene oxide band in methanol solution;
5th step: the graphene oxide band that the 4th step obtains is guided to from methanol solution after the first rolling warm table carries out drying, lower thickness, guide to again on the second rolling warm table and carry out reduction swellability, or carry out reduction swellability under being placed in infrared lamp, obtain described three-dimensional grapheme film; Graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously under above-mentioned heating condition, 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, graphene oxide band is consistent with the speed to introduce of graphene oxide band with the speed of the second rolling warm table through the first rolling warm table;
6th step: collect three-dimensional grapheme film, three-dimensional grapheme film is entangled in rotating shaft, for subsequent use.
Preferred second step carries out at stirring and being concentrated in 45 ~ 60 DEG C.
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 a kind of method of three-dimensional grapheme film of mass-producing continuous seepage functionalization, 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 the total concn being concentrated into graphene oxide and functional nanoparticle in mixture is 15 ~ 25mg/mL;
3rd step: by top end opening, side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely;
4th step: the mixture of the graphene oxide solution concentrated and functional nanoparticle is injected tetrafluoroethylene groove, inject from the top of tetrafluoroethylene groove, and release from bottom notch with the speed of 0.8m/min, continuous band-shaped structure is formed, i.e. the graphene oxide band of functionalization in methanol solution;
5th step: the graphene oxide band of the functionalization the 4th step obtained is guided to after the first rolling warm table carries out drying from methanol solution, lower thickness, guide to again on the second rolling warm table and carry out reduction swellability, or carry out reduction swellability under being placed in infrared lamp, obtain the three-dimensional grapheme film of described functionalization;
Wherein, the graphene oxide band of functionalization is consistent with the speed to introduce of the graphene oxide band of functionalization with the speed of the second rolling warm table through the first rolling warm table;
6th step: the three-dimensional grapheme film of collecting function, is entangled in rotating shaft by the three-dimensional grapheme film of functionalization, for subsequent use.
Preferred second step carries out at stirring and being concentrated in 45 ~ 60 DEG C.
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 no more than 1/10 of graphene oxide quality.
Described functional nanoparticle is more than one in following listed nano particle:
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 SiO
2, Fe
3o
4, Mn
3o
4, Co
3o
4, NiO, PbO, TiO
2, ZnO, CuO or Cu
2o oxide nano particles;
4th kind is Fe-Fe
3o
4, Cu-CuO, Cu-Cu
2o, Ni-NiO or Pb-PbO metal-oxide composite nanometer particle;
5th kind is Fe
3o
4-CuO, CuO-Cu
2o, Fe
3o
4-Cu
2o, Fe
3o
4-NiO, Fe
3o
4-PbO, Fe
3o
4-TiO
2, 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 be used as energy storage and transition material.
Beneficial effect
(1) the starting material graphene oxide solution that utilizes of the present invention and functional nanoparticle simple and easy to get, cost is low, and synthetic technology is ripe, is applicable to producing in enormous quantities.
(2) the present invention is by building simple experimental installation, can the three-dimensional grapheme film of the pure three-dimensional grapheme film of mass-producing, continuous seepage or functionalization.The method, except low toxicity methyl alcohol, does not use other toxic substances, environmental friendliness; Graphene oxide reduction rate is fast, and output 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, and end product quality is stablized; Controlled by the notch size of tetrafluoroethylene groove, make product three-dimensional grapheme film macroscopic view size, thickness all controlled.And described method technique is simple, cheap.
(3) three-dimensional grapheme that obtains of the method for the invention, structure, in three-dimensional, vesicular, has quality light, and specific surface area is large, the feature that snappiness is good.And maintain the structure of macroscopically film, be convenient to collect and use.
(4) whole experimentation is avoided using tensio-active agent, potassium chloride salt solution etc. to be difficult to the chemical substance removed, and the three-dimensional grapheme obtained is clean, does not need aftertreatment.
(5) the method for the invention not only can obtain pure three-dimensional grapheme film, as super light material, and the dirty material of oil suction etc.; The three-dimensional grapheme mould material of functionalization can also be prepared in batches, as energy storage and transition material, as: as lithium ion battery negative material, the use of traditional nonconducting linking agent can be avoided, 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, than revealing high activity, stability and anti-Poisoning Properties; In addition, electromagnetic wave absorbing material, thermoelectric material etc. can also be prepared in batches.Extend the range of application of three-dimensional grapheme.
(6) stir concentrated thermal creep stress in the method for the invention to need to consider following factor: temperature is too high, and graphene oxide can be reduced to Graphene, 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 stirs concentrated selection to carry out at 45 ~ 60 DEG C of temperature, can ensure thickening efficiency, graphene oxide can be avoided again to be 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 pattern of graphene oxide membrane and the three-dimensional grapheme obtained in embodiment 1;
Fig. 4 is the Raman spectrum test pattern of dry graphene oxide and the three-dimensional grapheme obtained in embodiment 1;
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 scanning electron microscope test figure of dry graphene oxide membrane cross section under different multiples (35 times of-a figure, 100 times of-b figure) obtained in embodiment 1;
Fig. 7 is the scanning electron microscope test figure of three-dimensional grapheme film cross section under different multiples (25 times of-a figure, 100 times of-b figure) obtained in embodiment 1;
Fig. 8 is different 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 electronic 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 catalyzer of ethanol electrooxidation, sweeps fast 50mV S
-1;
Figure 10 is the Fe obtained in embodiment 9
3o
4the Scanning Electron microscope figure of the three-dimensional grapheme of particle functionalization;
Figure 11 be obtain in embodiment 10 by TiO
2the Graphene of nano particle functionalization is cut into the shape (rectangle: 0.5 × 1.2cm of rule
2) test light electric current response diagram;
Embodiment
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited thereto.
Hummers legal system is for the process of graphene oxide solution: the high purity graphite powder getting 12g, by the vitriol oil of 280mL, the SODIUMNITRATE of 6g, at ice bath, under agitation 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 normal temperature, stir after 1 hour, leave standstill, the hydrogen peroxide of 80mL is added after 1 hour, then suction filtration obtains solid, to 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 examples.
The method of mass-producing continuous seepage three-dimensional grapheme film of the present invention adopts equipment as shown in Figure 1, and equipment comprises: tetrafluoroethylene 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 arranged on same horizontal axis by listed order successively; Tetrafluoroethylene groove top end opening, there is square notch side, bottom; When producing, tetrafluoroethylene groove is placed in glass guide channel, and the projection of bottom notch and the first rolling warm table on the same line.
Embodiment 1
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 10mg/mL graphene oxide solution;
2. 10mg/mL graphene oxide solution heated and stirred at 45 DEG C is concentrated, make graphene oxide solution concentration be 25mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.4cm, and width is 3cm;
4. the graphene oxide solution of 25mg/mL that second step concentrates is injected from the top of tetrafluoroethylene groove, graphene oxide solution is released from bottom notch with the speed of 0.8m/min, the continuous print zonal structure of graphene oxide is formed, i.e. graphene oxide band in methanol solution;
5. the graphene oxide band got is guided to from methanol solution 45 DEG C, on the rolling warm table of 1.2m, after the drying of graphite oxide band, the graphene band of drying is introduced 500 DEG C, on the rolling warm table of 15cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again;
6. collect graphene band, graphene band is entangled in rotating shaft, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
3 ~ 6 step operation charts as shown in Figure 1.
Detect product, Fig. 2 is the photo of dry graphene oxide and the bending of three-dimensional grapheme band, and illustrate that the graphene strips of heat reduction is with good snappiness, graphene oxide is after heat reduction, and lamella is thickening.From X-ray powder diffraction test pattern (Fig. 3), the characteristic peak (10 °) of graphene oxide disappears, and has occurred the characteristic peak (24 °) of Graphene, illustrates that graphene oxide is reduced into Graphene after heating; The D peak intensity of dry graphene oxide membrane and three-dimensional grapheme and the ratio (I of G peak intensity can be found out Raman spectrum test result (Fig. 4)
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-O ", " C=O ", " O-C=O ", G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", three-dimensional grapheme I after heat reduction
d/ I
gvalue be 0.97, than the I of graphene oxide band
d/ I
g(1.24) little, illustrate that graphene oxide obtains reduction, the structure of Graphene obtains reparation.In conjunction with the photo (Fig. 5-(a)) of dry graphene oxide and three-dimensional grapheme intersection and scanning electron microscope test (Fig. 5-(b)) known, the planar film structure of graphene oxide is transformed to the three-layer laminated vesicular structure of Graphene after heating.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 also can find out, 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. 4mg/mL graphene oxide solution heated and stirred at 60 DEG C is concentrated, make graphene oxide solution concentration be 15mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 2cm;
4. the graphene oxide solution of 15mg/mL that second step concentrates is injected from the top of tetrafluoroethylene groove, graphene oxide solution is released from bottom notch with the speed of 0.8m/min, the continuous print zonal structure of graphene oxide is formed, i.e. graphene oxide band in methanol solution;
5. the graphene oxide band got is guided to from methanol solution 60 DEG C, on the rolling warm table of 0.8m, after the drying of graphite oxide band, the graphene band of drying is introduced 300 DEG C, on the rolling warm table of 15cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again;
6. collect graphene band, graphene band is entangled in rotating shaft, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, from X-ray powder diffraction test pattern, the characteristic peak (10 °) of graphene oxide disappears, and has occurred the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene after heating; Known in conjunction with scanning electron microscope test, the planar film structure of graphene oxide is transformed to the three-layer laminated vesicular structure of Graphene after heating.By the photo of Graphene after the film of graphene oxide drying and heating, can find out that graphene oxide is yellow film, and after heat reduction, becoming large, the loose black film of thickness change, same explanation heat-processed 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. 8mg/mL graphene oxide solution heated and stirred at 50 DEG C is concentrated, make graphene oxide solution concentration be 20mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely; The height of square notch is 0.5cm, and width is 6cm;
4. the graphene oxide solution of 20mg/mL that second step concentrates is injected from the top of tetrafluoroethylene groove, graphene oxide solution is released from bottom notch with the speed of 0.8m/min, the continuous print zonal structure of graphene oxide is formed, i.e. graphene oxide band in methanol solution;
5. the graphene oxide band got is guided to from methanol solution 50 DEG C, on the rolling warm table of 1.0m, after the drying of graphite oxide band, the graphene band of drying is introduced 300 DEG C, on the rolling warm table of 15cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again;
6. collect graphene band, graphene band is entangled in rotating shaft, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, from X-ray powder diffraction test pattern, the characteristic peak (10 °) of graphene oxide disappears, and has occurred the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene after heating; Known in conjunction with scanning electron microscope test, the planar film structure of graphene oxide is transformed to the three-layer laminated vesicular structure of Graphene after heating.By the photo of Graphene after the film of graphene oxide drying and heating, can find out that graphene oxide is yellow film, and after heat reduction, becoming large, the loose black film of thickness change, same explanation heat-processed is that graphene oxide is transformed into three-dimensional grapheme.The photo of the graphene oxide membrane obtained by different heights notch (0.3cm, 0.5cm) can find out 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, illustrate that notch is higher, obtain graphene oxide lamella thicker, transmittance is poorer.Different heights is as the comparison of the three-dimensional grapheme scanning electron microscope diagram sheet (Fig. 8-(a), (b), (c)) that the notch of 0.3cm, 0.4cm, 0.5cm obtains, can illustrate equally, 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. 6mg/mL graphene oxide solution heated and stirred at 50 DEG C is concentrated, make graphene oxide solution concentration be 21mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 6cm;
4. the graphene oxide solution of 21mg/mL that second step concentrates is injected from the top of tetrafluoroethylene groove, graphene oxide solution is released from bottom notch with the speed of 0.8m/min, the continuous print zonal structure of graphene oxide is formed, i.e. graphene oxide band in methanol solution;
5. the graphene oxide band got is guided to from methanol solution 55 DEG C, on the rolling warm table of 1.0m, after the drying of graphite oxide band, the graphene band of drying being guided to power is heat 15s under the infrared lamp of 375W again, and graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously;
6. collect graphene band, graphene band is entangled in rotating shaft, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, from X-ray powder diffraction test pattern, the characteristic peak (10 °) of graphene oxide disappears, and has occurred the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene after heating; Known in conjunction with scanning electron microscope test, the planar film structure of graphene oxide is transformed to the three-layer laminated vesicular structure of Graphene after heating.By the photo comparison of Graphene after the film of graphene oxide drying and heating, can find out that graphene oxide is yellow film, and after heat reduction, becoming large, the loose black film of thickness change, same explanation heat-processed 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. be the Cu powder mixing of 200nm by 10mg/mL graphene oxide solution and particle diameter, wherein the quality of Cu powder is 1/10 of graphene oxide quality, obtain mixture, at 50 DEG C, heated and stirred concentrates, and makes the total concn of graphene oxide and Cu nanoparticle in mixture be 15mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 2cm;
4. the mixture of the graphene oxide solution that concentrates of second step and Cu nanoparticle injects from the top of tetrafluoroethylene groove, mixture is released from bottom notch with the speed of 0.8m/min, continuous print zonal structure is formed, i.e. the graphene oxide band of Cu nano particle functionalization in methanol solution;
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, after the drying of graphite oxide band, the graphene band of drying is introduced 400 DEG C, on the rolling warm table of 15cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again.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, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, the characteristic peak (43 °, 50 °, 74 ° and 90 °) of Cu can be seen by X-ray powder diffraction test pattern, and the characteristic peak of graphene oxide (10 °) disappears, there is the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene, the product obtained is the mixture 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 vesicular structure, the pattern of Cu is the nano particle of about 200nm, be 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. be the Pt powder mixing of 5nm by 8mg/mL graphene oxide solution and particle diameter, wherein the quality of Pt powder is 1/10 of graphene oxide quality, obtain mixture, at 50 DEG C, heated and stirred concentrates, and makes the total concn of graphene oxide and Pt nanoparticle in mixture be 22mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 2cm;
4. the mixture of the graphene oxide solution that concentrates of second step and Pt nanoparticle injects from the top of tetrafluoroethylene groove, mixture is released from bottom notch with the speed of 0.8m/min, continuous print zonal structure is formed, i.e. the graphene oxide band of Pt nano particle functionalization in methanol solution;
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, after the drying of graphite oxide band, the graphene band of drying is introduced 400 DEG C, on the rolling warm table of 15cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again.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, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, the characteristic peak (40 °, 46 °, 68 °, 82 ° and 86 °) of Pt can be seen by X-ray powder diffraction test pattern, and the characteristic peak of graphene oxide (10 °) disappears, there is the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene, the product obtained is the mixture 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 vesicular structure, the pattern of Pt is the nano particle of about 5nm, be 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 catalyzer of the three-dimensional grapheme of Pt nano particle functionalization as ethanol electrooxidation, show 275mA g
-1peak point current, as shown in Figure 9.In addition, I in figure
ffor just sweeping peak-to-peak value electric current, represent the current value of oxidation of ethanol, I
bsweep peak-to-peak value electric current for inverse, represent the current value (current value reflection causes the amount of poisoning of catalyst product) of poisoning product oxidation in the middle of oxidation of ethanol; Usually I is used
f/ I
bthe size of value represent the anti-poisoning capability of catalyzer, can I be found out in figure
fbe greater than I
b(I
f/ I
b=1.2), illustrate that this catalyzer 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 powdered alloy of 9mg/mL graphene oxide solution and particle diameter 3nm is mixed, wherein the quality of PtPd powdered alloy is 1/10 of graphene oxide quality, obtain mixture, at 50 DEG C, heated and stirred concentrates, and makes the total concn of graphene oxide and PtPd alloy nano particle in mixture be 24mg/mL
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of tetrafluoroethylene groove, mixture is released with the speed of 0.8m/min from bottom notch, forms continuous print zonal structure in methanol solution, be i.e. the graphene oxide band of PtPd alloy nanoparticle functionalization;
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, after the drying of graphite oxide band, be 15s under the infrared lamp of 375W again at power by the graphene band of drying, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously.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, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, the characteristic peak (40 °, 47 °, 68 °, 82 ° and 86 °) of PtPd alloy can be seen by X-ray powder diffraction test pattern, and the characteristic peak of graphene oxide (10 °) disappears, there is the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene, the product obtained is the mixture 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 vesicular structure, the pattern of PtPd alloy is the nano particle of about 3nm, be 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. be the FeNi powdered alloy mixing of 20nm by 10mg/mL graphene oxide solution and particle diameter, wherein the quality of FeNi powdered alloy is 1/10 of graphene oxide quality, obtain mixture, at 50 DEG C, heated and stirred concentrates, and makes the total concn of graphene oxide and FeNi alloy nano particle in mixture be 22mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of tetrafluoroethylene groove, mixture is released with the speed of 0.8m/min from bottom notch, forms continuous print zonal structure in methanol solution, be i.e. the graphene oxide band of FeNi alloy nanoparticle functionalization;
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, after the drying of graphite oxide band, the graphene band of drying is introduced 350 DEG C, on the rolling warm table of 15cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again.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, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, the characteristic peak (44 °, 51 ° and 75 °) of FeNi alloy can be seen by X-ray powder diffraction test pattern, and the characteristic peak of graphene oxide (10 °) disappears, there is the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene, the product obtained is the mixture 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 vesicular structure, the pattern of FeNi alloy is the nano particle of about 20nm, be 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. be the Fe of 50nm by 9mg/mL graphene oxide solution and particle diameter
3o
4powder, wherein Fe
3o
4the quality of powder is 1/10 of graphene oxide quality, obtains mixture, and at 55 DEG C, heated and stirred concentrates, and makes graphene oxide and Fe in mixture
3o
4the total concn of nanoparticle is 22mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of tetrafluoroethylene groove, mixture is released with the speed of 0.8m/min from bottom notch, forms continuous print zonal structure, i.e. Fe in methanol solution
3o
4the graphene oxide band of nano particle functionalization;
5. the Fe will got
3o
4the graphene oxide band of nano particle functionalization guides to 45 DEG C, on the rolling warm table of 1.2m from methanol solution, after the drying of graphite oxide band, the graphene band of drying is introduced 500 DEG C, on the rolling warm table of 15cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again.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, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, can Fe be seen by X-ray powder diffraction test pattern
3o
4characteristic peak (30 °, 36 °, 43 °, 57 ° and 63 °), and the characteristic peak of graphene oxide (10 °) disappears, occurred the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene, the product obtained is Fe
3o
4with the mixture of Graphene; Test known in conjunction with scanning electron microscope test (Figure 10) and transmission electron microscope, the structure of Graphene is three-layer laminated vesicular structure, Fe
3o
4the pattern of particle is the nano particle of about 50nm, is evenly dispersed in the surface of graphene sheet layer, and namely product is Fe
3o
4the three-dimensional grapheme of the porous of nano particle functionalization.Fe
3o
4the 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. be the TiO of 20nm by 9mg/mL graphene oxide solution and particle diameter
2powder, wherein TiO
2the quality of powder is 1/10 of graphene oxide quality, obtains mixture, and at 55 DEG C, heated and stirred concentrates, and makes graphene oxide and TiO in mixture
2the total concn of alloy nano particle is 20mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of tetrafluoroethylene groove, mixture is released with the speed of 0.8m/min from bottom notch, forms continuous print zonal structure, i.e. TiO in methanol solution
2the graphene oxide band of nano particle functionalization;
5. by TiO
2the graphene oxide band of nano particle functionalization guides to 50 DEG C, on the rolling warm table of 1.2m from methanol solution, after the drying of graphite oxide band, the graphene band of drying is introduced 500 DEG C, on the rolling warm table of 12cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again.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, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, can TiO be seen by X-ray powder diffraction test pattern
2characteristic peak (25 °, 38 °, 48 °, 54 °, 48 °, 63 ° and 75 °), and the characteristic peak of graphene oxide (10 °) disappears, there is the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene, the product obtained is TiO
2with the mixture of Graphene; Test known in conjunction with scanning electron microscope test and transmission electron microscope, the structure of Graphene is three-layer laminated vesicular structure, TiO
2the pattern of particle is the nano particle of about 20nm, is evenly dispersed in the surface of graphene sheet layer, and namely product is TiO
2the three-dimensional grapheme of the porous of nano particle functionalization.By TiO
2the Graphene of nano particle functionalization is cut into the shape (rectangle: 0.5 × 1.2cm of rule
2) test light current-responsive.Photoelectric current can reach 6 microamperes (Figure 11).Testing tool is that CHI 760D electrochemical workstation is tested, and light source is the incandescent light of 100w.
Embodiment 11
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 7mg/mL graphene oxide solution;
2. the CuO powder of to be the Cu particle of 200nm and particle diameter by 7mg/mL graphene oxide solution, particle diameter be 200nm, wherein the quality of Cu particle, CuO powder is respectively 1/20 of graphene oxide quality, obtain mixture, at 55 DEG C, heated and stirred concentrates, and makes the total concn of graphene oxide and Cu-CuO particle nanoparticle in mixture be 22mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of tetrafluoroethylene groove, mixture is released with the speed of 0.8m/min from bottom notch, forms continuous print zonal structure in methanol solution, be i.e. the graphene oxide band of Cu-CuO nano particle functionalization;
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, after the drying of graphite oxide band, the graphene band of drying is introduced 400 DEG C, on the rolling warm table of 15cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again.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, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, the characteristic peak (30 °, 36 °, 43 °, 57 ° and 63 °) of Cu and the characteristic peak (36 °, 39 °, 49 °, 54 °, 58 °, 62 °, 66 °, 68 °, 75 ° and 82 °) of CuO can be seen by X-ray powder diffraction test pattern, and the characteristic peak of graphene oxide (10 °) disappears, there is the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene, the product obtained is the mixture 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 vesicular structure, the pattern of Cu, CuO particle is the nano particle of about 200nm, 200nm, be 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 the 6th step being obtained the porous of Cu-CuO nano particle functionalization is directly cut into the circle that diameter is 1.6cm, as the negative pole of Li battery, be 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, cell container is stabilized in 834mAh/g, and when electric current is raised to 0.4A/g time, the capacity stablizes of battery is at 605mAh/g, test from multiplying power, battery is under high electric current (20A/g) condition, and capacity still can 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 macro is LAND CT2001A.
Embodiment 12
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 9mg/mL graphene oxide solution;
2. be the Fe of 50nm by 9mg/mL graphene oxide solution, particle diameter
3o
4particle and particle diameter are the CuO powder of 200nm, wherein Fe
3o
4the quality of particle, CuO powder is respectively 1/20 of graphene oxide quality, obtains mixture, and at 55 DEG C, heated and stirred concentrates, and makes graphene oxide and Fe in mixture
3o
4the total concn of-CuO particle nanoparticle is 25mg/mL;
3., by top end opening (diameter is 3cm), side, bottom has the tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely.The height of square notch is 0.3cm, and width is 2cm;
4. the mixture that second step concentrates injects from the top of tetrafluoroethylene groove, mixture is released with the speed of 0.8m/min from bottom notch, forms continuous print zonal structure, i.e. Fe in methanol solution
3o
4the graphene oxide band of-CuO nano particle functionalization;
5. the Fe will got
3o
4the graphene oxide band of-CuO nano particle functionalization guides to 55 DEG C, on the rolling warm table of 1.2m from methanol solution, after the drying of graphite oxide band, the graphene band of drying is introduced 450 DEG C, on the rolling warm table of 15cm, graphene oxide band becomes the graphene band of black three-dimensional structure instantaneously again.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, for subsequent use.The three-dimensional grapheme film that graphene band is namely described.
Product is detected, can Fe be seen by X-ray powder diffraction test pattern
3o
4characteristic 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, there is the characteristic peak (24 °) of Graphene, illustrate that graphene oxide is reduced into Graphene, the product obtained is Fe
3o
4the mixture of-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 vesicular structure, Fe
3o
4, CuO particle pattern be the nano particle of about 50nm, 500nm, be evenly dispersed in the surface of graphene sheet layer, namely product is Fe
3o
4the three-dimensional grapheme of the porous of-CuO nano particle functionalization.
The present invention includes but be not limited to above embodiment, every any equivalent replacement of carrying out under the principle of spirit of the present invention or local improvement, all will be considered as within protection scope of the present invention.
Claims (10)
1. a method for mass-producing continuous seepage three-dimensional grapheme film, is characterized in that, described method steps 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 tetrafluoroethylene groove of square notch to be immersed in be equipped with in the glass guide channel of methyl alcohol, and notch is immersed among methyl alcohol completely;
4th step: the graphene oxide solution concentrated by second step is injected from the top of tetrafluoroethylene groove, and releases from bottom notch with the speed of 0.8m/min, forms continuous band-shaped structure, i.e. graphene oxide band in methanol solution;
5th step: the graphene oxide band that the 4th step obtains is guided to from methanol solution after the first rolling warm table carries out drying, guide to again on the second rolling warm table and carry out reduction swellability, or carry out reduction swellability under being placed in infrared lamp, obtain described three-dimensional grapheme film;
Wherein, graphene oxide band is consistent with the speed to introduce of graphene oxide band with the speed of the second rolling warm table through the first rolling warm table;
6th step: collect three-dimensional grapheme film, three-dimensional grapheme film is entangled in rotating shaft, for subsequent use.
2. the method for a kind of mass-producing continuous seepage three-dimensional grapheme film according to claim 1, it is characterized in that, second step, after graphene oxide solution and functional nanoparticle are mixed to get mixture, then to carry out stirring the total concn being concentrated into graphene oxide and functional nanoparticle in mixture be 15 ~ 25mg/mL; Except following difference, under the condition that 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, 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, 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 for a kind of mass-producing continuous seepage three-dimensional grapheme film according to claim 1 and 2, is characterized in that, second step carries out at stirring and being concentrated in 45 ~ 60 DEG C.
4. the method for a kind of mass-producing continuous seepage three-dimensional grapheme film according to claim 1 and 2, it is characterized in that, the first rolling warm table length is 0.8 ~ 1.2m, and temperature is 45 ~ 60 DEG C.
5. the method for a kind of mass-producing continuous seepage three-dimensional grapheme film according to claim 1 and 2, it is characterized in that, the second rolling warm table length is 10 ~ 15cm, and temperature is 300 ~ 500 DEG C.
6. the method for a kind of mass-producing continuous seepage three-dimensional grapheme film according to claim 1 and 2, it is characterized in that, the power of infrared lamp is 375W, and the recovery time is 15s.
7. the method for the three-dimensional grapheme film of a kind of mass-producing continuous seepage functionalization according to claim 2, it is characterized in that, in mixture, the quality of functional nanoparticle is no more than 1/10 of graphene oxide quality.
8. the method for the three-dimensional grapheme film of a kind of mass-producing continuous seepage functionalization according to claim 2, is characterized in that, described functional nanoparticle is more than one in following listed nano particle:
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 SiO
2, Fe
3o
4, Mn
3o
4, Co
3o
4, NiO, PbO, TiO
2, ZnO, CuO or Cu
2o oxide nano particles;
4th kind is Fe-Fe
3o
4, Cu-CuO, Cu-Cu
2o, Ni-NiO or Pb-PbO metal-oxide composite nanometer particle;
5th kind is Fe
3o
4-CuO, CuO-Cu
2o, Fe
3o
4-Cu
2o, Fe
3o
4-NiO, Fe
3o
4-PbO, Fe
3o
4-TiO
2, CuO-NiO, CuO-PbO or NiO-PbO nanoparticles of complex metal oxides.
9. an application for the three-dimensional grapheme film adopting the method for mass-producing continuous seepage three-dimensional grapheme film according to claim 1 to obtain, it is characterized in that, described three-dimensional grapheme film is as energy storage and transition material.
10. an application for the three-dimensional grapheme film of the functionalization adopting the method for the three-dimensional grapheme film of mass-producing continuous seepage functionalization according to claim 2 to obtain, it is characterized in that, the three-dimensional grapheme film of described functionalization is as energy storage and transition material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410509947.5A CN104310381B (en) | 2014-09-28 | 2014-09-28 | A kind of scale produces method and the application of three-dimensional grapheme film continuously |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410509947.5A CN104310381B (en) | 2014-09-28 | 2014-09-28 | A kind of scale produces method and the application of three-dimensional grapheme film continuously |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104310381A true CN104310381A (en) | 2015-01-28 |
| CN104310381B CN104310381B (en) | 2016-06-08 |
Family
ID=52365735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410509947.5A Active CN104310381B (en) | 2014-09-28 | 2014-09-28 | A kind of scale produces method and the application of three-dimensional grapheme film continuously |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104310381B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846466A (en) * | 2015-04-09 | 2015-08-19 | 浙江泰索科技有限公司 | High thermal conductivity polyacrylonitrile fiber and preparation method thereof |
| CN105600775A (en) * | 2015-11-05 | 2016-05-25 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuous production of graphene film |
| CN106179918A (en) * | 2016-07-19 | 2016-12-07 | 广州市博欣环境科技有限公司 | Graphene strengthens energy-conservation composite membrane and preparation method thereof |
| CN108307614A (en) * | 2018-02-11 | 2018-07-20 | 中国人民解放军陆军装甲兵学院 | One kind composite wave-suction material containing cobalt and preparation method thereof |
| CN108342183A (en) * | 2018-02-11 | 2018-07-31 | 中国人民解放军陆军装甲兵学院 | A kind of nickeliferous composite wave-suction material and preparation method thereof |
| CN108346520A (en) * | 2017-01-23 | 2018-07-31 | 广州墨羲科技有限公司 | Three-dimensional graphene composite material, its manufacturing method and application |
| CN109755538A (en) * | 2019-02-01 | 2019-05-14 | 哈尔滨工程大学 | A kind of Li-Ti3C2- rGO composite film material and preparation method thereof |
| CN110247027A (en) * | 2018-03-09 | 2019-09-17 | 广州墨羲科技有限公司 | A kind of porous three-dimensional composite material based on carbon nanosheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583334A (en) * | 2012-01-19 | 2012-07-18 | 北京理工大学 | Preparation method for graphene fiber |
| CN102701188A (en) * | 2012-05-07 | 2012-10-03 | 华中科技大学 | Method for preparing three-dimensional porous graphene material by solution |
| CN103265022A (en) * | 2013-06-03 | 2013-08-28 | 北京理工大学 | Method for spontaneously depositing three-dimensional graphene on conductive substrate |
-
2014
- 2014-09-28 CN CN201410509947.5A patent/CN104310381B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583334A (en) * | 2012-01-19 | 2012-07-18 | 北京理工大学 | Preparation method for graphene fiber |
| CN102701188A (en) * | 2012-05-07 | 2012-10-03 | 华中科技大学 | Method for preparing three-dimensional porous graphene material by solution |
| CN103265022A (en) * | 2013-06-03 | 2013-08-28 | 北京理工大学 | Method for spontaneously depositing three-dimensional graphene on conductive substrate |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846466A (en) * | 2015-04-09 | 2015-08-19 | 浙江泰索科技有限公司 | High thermal conductivity polyacrylonitrile fiber and preparation method thereof |
| CN105600775A (en) * | 2015-11-05 | 2016-05-25 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuous production of graphene film |
| CN106179918A (en) * | 2016-07-19 | 2016-12-07 | 广州市博欣环境科技有限公司 | Graphene strengthens energy-conservation composite membrane and preparation method thereof |
| CN106179918B (en) * | 2016-07-19 | 2021-04-09 | 广州市博欣环境科技有限公司 | Graphene reinforced energy-saving composite membrane and preparation method thereof |
| CN108346520A (en) * | 2017-01-23 | 2018-07-31 | 广州墨羲科技有限公司 | Three-dimensional graphene composite material, its manufacturing method and application |
| CN108307614A (en) * | 2018-02-11 | 2018-07-20 | 中国人民解放军陆军装甲兵学院 | One kind composite wave-suction material containing cobalt and preparation method thereof |
| CN108342183A (en) * | 2018-02-11 | 2018-07-31 | 中国人民解放军陆军装甲兵学院 | A kind of nickeliferous composite wave-suction material and preparation method thereof |
| CN108307614B (en) * | 2018-02-11 | 2019-07-16 | 中国人民解放军陆军装甲兵学院 | One kind composite wave-suction material containing cobalt and preparation method thereof |
| CN108342183B (en) * | 2018-02-11 | 2019-07-16 | 中国人民解放军陆军装甲兵学院 | A kind of nickeliferous composite wave-suction material and preparation method thereof |
| CN110247027A (en) * | 2018-03-09 | 2019-09-17 | 广州墨羲科技有限公司 | A kind of porous three-dimensional composite material based on carbon nanosheet |
| CN109755538A (en) * | 2019-02-01 | 2019-05-14 | 哈尔滨工程大学 | A kind of Li-Ti3C2- rGO composite film material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104310381B (en) | 2016-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104310381B (en) | A kind of scale produces method and the application of three-dimensional grapheme film continuously | |
| Kumar | NiCo 2 O 4 nano-/microstructures as high-performance biosensors: a review | |
| Xu et al. | Noble-metal-free electrospun nanomaterials as electrocatalysts for oxygen reduction reaction | |
| Ghosh et al. | Conducting polymer-supported palladium nanoplates for applications in direct alcohol oxidation | |
| Wu et al. | Electrocatalytic performances of g-C3N4-LaNiO3 composite as bi-functional catalysts for lithium-oxygen batteries | |
| Wu et al. | Facile Synthesis of Hierarchical Porous Three-Dimensional Free-Standing MnCo2O4 Cathodes for Long-Life Li O2 Batteries | |
| CN101797502B (en) | Preparation method of noble metal-graphene nanometer composite | |
| CN107601580A (en) | A kind of method for preparing nickel cobalt oxide as presoma by the use of metal organic framework and application thereof | |
| Thirumal et al. | Cleaner production of tamarind fruit shell into bio-mass derived porous 3D-activated carbon nanosheets by CVD technique for supercapacitor applications | |
| CN106450357B (en) | A kind of graphene-supported Co-N-C supermolecule heterozygosis aerogel composite and its preparation method and application | |
| CN104362001B (en) | Method for preparing manganese dioxide/graphene/porous carbon (MnO2/rGO/C) composite material and application of MnO2/rGO/C composite material to supercapacitor as electrode material | |
| CN104584160A (en) | Diatomaceous energy storage devices | |
| CN110492081A (en) | A kind of preparation method and applications of cobaltous selenide/porous carbon nanotube of zinc selenide N doping | |
| Wang et al. | recent advance in self-supported electrocatalysts for rechargeable Zinc-air batteries | |
| CN102409433B (en) | Core shell structure composite fiber based on carbon nano tube and preparation method and application thereof | |
| CN103265022B (en) | Method for spontaneously depositing three-dimensional graphene on conductive substrate | |
| CN104319395A (en) | Method for preparing three-dimensional nitrogen-doped graphene/CoOx composite material | |
| CN104795250B (en) | printed battery device | |
| CN104477887A (en) | Method for preparing graphene from microcrystalline graphite | |
| Daryakenari et al. | Highly efficient electrocatalysts fabricated via electrophoretic deposition for alcohol oxidation, oxygen reduction, hydrogen evolution, and oxygen evolution reactions | |
| Zhang et al. | Preparation of 3D rose-like nickel oxide nanoparticles by electrodeposition method and application in gas sensors | |
| Silambarasan et al. | A Facile Preparation of Zinc Cobaltite (ZnCo 2 O 4) Nanostructures for Promising Supercapacitor Applications | |
| CN109904007A (en) | A kind of preparation method of spongy nitrogen sulphur codope porous carbon electrode material | |
| Zaman et al. | Comparative study of Mn-ZIF-67 derived carbon (Mn-Co/C) and its rGO-based composites for the methanol oxidation | |
| Yang et al. | Electrochemical deposition of CeO2 nanocrystals on Co3O4 nanoneedle arrays for efficient oxygen evolution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |