CN103265022A - Method for spontaneously depositing three-dimensional graphene on conductive substrate - Google Patents
Method for spontaneously depositing three-dimensional graphene on conductive substrate Download PDFInfo
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Abstract
The invention discloses a method for spontaneously depositing three-dimensional graphene on a conductive substrate and belongs to the field of a functional material. The method comprises the following steps of: step one, preparing an 8-20 mg/mL oxidized graphene solution by an oxidizing graphite stripping method; step two, diluting the 8-20 mg/mL oxidized graphene solution so that the concentration of the oxidized graphene solution is changed into 0.5-3 mg/mL; step three, putting the conductive substrate in the oxidized graphene solution for standing, taking out the conductive substrate after reacting for 6-12 hours, thereby obtaining the conductive substrate with three-dimensional graphene deposited on the surface of the conductive substrate; and step four, directly carrying out freeze drying on the three-dimensional graphene obtained in the step three or performing freeze drying after washing, thus obtaining dry porous functionalized three-dimensional graphene or pure dry porous three-dimensional graphene. The method is simple in preparation process and friendly to environment; and the obtained three-dimensional graphene is three-dimensional and porous in structure, and has the characteristics of large specific surface area and good toughness.
Description
Technical field
The present invention relates to a kind of on conductive substrates the method for the three-dimensional Graphene of spontaneous deposition, belong to field of functional materials.
Background technology
Graphene is a kind of laminate structure of being made up of by bonding action the six-ring of carbon.Because Graphene has high electroconductibility, big specific surface area, and good chemical stability, environmental stability and mechanical stability, so at photoelectric material, photocatalyst material, the energy stores and transition material (fuel cell, Li batteries etc.), the application of aspect such as magnetic absorbing material has attracted domestic and international investigator's attention.
At present, the method for preparing Graphene in enormous quantities is the chemical reduction graphene oxide, and simultaneously, self assembled three-dimensional Graphene porous material has good effect for it in application facet.Be usually directed to some exacting terms but prepare Graphene at present, such as hydrazine hydrate (N
2H
4) add thermal reduction, argon/hydrogen (Ar/H
2) gas is at the high temperature reduction of 1000 ℃ of 600 –, sodium borohydride (NaBH
4) reduction under the alkaline condition, 120 ℃ of reduction of 80 – of acetic acid-hydroiodic acid HI (HAC-HI) solution, sodium-ammonia (Na-NH
3) solution reduces under the dry ice bath condition.These reduction processes need to use poisonous chemical reagent in general, need a plurality of trivial step, consume considerable time, and the Graphene that obtains reduction is thorough inadequately, very difficult assurance is assembled into three-dimensional porous structure, and these have all had a strong impact on the application of Graphene as device.
Summary of the invention
At loaded down with trivial details, the consuming time length of existing Graphene preparation process, relate to toxic reagent, and the Graphene of preparing reduction is thorough, the very difficult shortcoming that guarantees to be assembled into three-dimensional porous structure inadequately, the object of the present invention is to provide a kind of on conductive substrates the method for the three-dimensional Graphene of spontaneous deposition, described method preparation process is simple, environmental friendliness, low, the suitable scale operation of cost, the three-dimensional grapheme material structure that adopts described method to prepare is three-dimensional, vesicular, has the advantages that volume is big, quality is light, specific surface area is big, snappiness is good.
Purpose of the present invention is realized by following technical scheme:
A kind of on conductive substrates the method for the three-dimensional Graphene of spontaneous deposition, described method steps is as follows:
The first step: utilize oxidation to peel off graphite method (Hummers method) and prepare 8～20mg/mL graphene oxide solution;
Second step: with 8～20mg/mL graphene oxide solution dilution, the concentration that makes graphene oxide solution is 0.5～3mg/mL;
The 3rd step: conductive substrates is put in the second graphene oxide solution for preparing of step leaves standstill, react and take out conductive substrates after 6～12 hours, graphene oxide is reduced and obtains three-dimensional Graphene, and is deposited on the surface of conductive substrates, and metal oxide is attached on the three-dimensional Graphene;
The 4th step: the three-dimensional Graphene that the 3rd step was obtained directly carries out lyophilize, obtains the three-dimensional Graphene of functionalization of dry porous; Or carry out lyophilize again after washing the metal oxide that adheres on the 3rd three-dimensional Graphene that obtain of step earlier, obtain pure dry porous three-dimensional Graphene;
Described conductive substrates is a kind of in following six kinds, wherein:
First kind is Zn, Fe, Al, Co or Cu(reactive metal);
Second kind of Ag, Pt or Au paper tinsel (inert metal) for vacuum sputtering spray Cu;
The third for by chemical reaction deposit the Cu paper tinsel of the Ag of nanostructure, Pt or Au;
The 4th kind of Si sheet for vacuum sputtering spray Cu;
The 5th kind is the conductive glass (ITO) of the demifacet vacuum sputtering spray Cu of conducting surface;
The 6th kind for having the Cu substrate of graphene film;
Dilution is adopted and is reached distilled water purity and above water in second step;
When conductive substrates was Al or Co, dwell temperature was 60 ℃ in the 3rd step; When conductive substrates was not Al or Co, dwell temperature was room temperature～60 ℃.
Beneficial effect
(1) to use a kind of method of simple possible to prepare quality light in the present invention, the three-dimensional grapheme material of the little and functionalization of density, and this method technology is simple, environmental friendliness, cheap, output height, constant product quality, macroscopic view size, controllable thickness are fit to scale operation.
(2) the starting material graphene oxide of the present invention's utilization, the synthetic technology maturation, the quality height, cost is low, can produce in enormous quantities.
(3) the method for the invention not only can be deposited on three-dimensional Graphene reactive metal surface Zn, Fe, Al, Co, Cu surface; Can also be deposited on inert metal Ag, Pt, the surface of Au; Nonmetal Si, the surface of graphene film; And conductive glass (ITO) surface, the range of application of having widened three-dimensional Graphene widely.
(4) the three-dimensional Graphene that obtains of the method for the invention, structure is three-dimensional, vesicular.It is big to have volume, and quality is light, and specific surface area is big, and the characteristics that snappiness is good can be used as super light material, the dirty material of oil suction etc.
(5) the method for the invention is according to the difference of base material, the Graphene of complex functionalityization at an easy rate, and these matrix materials have good photoelectric response as photoelectric material; As the Li cell negative electrode material, can break away from traditional non-conductive linking agent, have good recursive nature and exceed the capacity of general carbon material, in addition, can also be potential be applied to magneticsubstance, absorbing material etc.
Description of drawings
The scanning electron microscope diagram of Fig. 1 after for the direct freeze-drying of three-dimensional Graphene of the functionalization that obtains among the embodiment 1;
Fig. 2 is the scanning electron microscope diagram after the three-dimensional Graphene washing freeze-drying that obtains among the embodiment 2;
Fig. 3 is the transmission electron microscope picture after the direct freeze-drying of three-dimensional Graphene that obtains among the embodiment 3;
Fig. 4 is the scanning electron microscope diagram after the three-dimensional Graphene washing freeze-drying that obtains among the embodiment 8;
Fig. 5 is the scanning electron microscope diagram after the three-dimensional Graphene washing freeze-drying that obtains among the embodiment 9;
Fig. 6 is the scanning electron microscope diagram after the three-dimensional Graphene washing freeze-drying that obtains among the embodiment 14;
Fig. 7 is capacity and the efficiency test figure of the button cell that obtains among the embodiment 15;
Fig. 8 is the photocurrent response test pattern of the three-dimensional Graphene that obtains among the embodiment 16.
Embodiment
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited thereto.
Conductive substrates is of a size of 2cm(length among the embodiment 1～16) * 2cm(is wide) * 100 μ m(height).
The Hummers legal system is equipped with the process of graphene oxide solution: the high purity graphite powder of getting 3g, with the vitriol oil of 70mL, the SODIUMNITRATE of 1.5g is at ice bath, under the agitation condition, the potassium permanganate that adds 9g, after stirring half an hour, temperature is transferred to 35 ℃, keep half an hour after, the distilled water that adds 150mL, temperature transfers to 90 ℃, and keeps 15 minutes, then, the distilled water that adds 500mL again, temperature transfers to normal temperature, stirs after 1 hour, leaves standstill, the hydrogen peroxide that adds 20mL after 1 hour, suction filtration obtains solid then, adds behind 100～400mL water centrifuge washing again, can obtain the graphene oxide solution of 8～20mg/mL.
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 20mg/mL graphene oxide solution;
2. with 20mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 3mg/mL;
3. the Zn conductive substrates is put into that normal temperature leaves standstill in the second graphene oxide solution for preparing of step, reacts and take out conductive substrates after 6 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of conductive substrates;
4. will go up earlier to go on foot in the Graphene immersion liquid nitrogen that obtains and freeze reality, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, can see the characteristic peak (32 °, 34 °, 36 °, 48 °, 57 °, 63 °, 66 °, 68 ° and 69 °) of ZnO by the X-ray powder diffraction test pattern, and the characteristic peak of graphene oxide (10 °) disappears, the characteristic peak (23 °) of Graphene occurred, illustrated that graphene oxide has been reduced into Graphene; In conjunction with scanning electron microscope test (Fig. 1) as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the three-dimensional Graphene of the dry porous of ZnO nano particle functionalization.
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the Fe conductive substrates is put into that normal temperature leaves standstill in the second graphene oxide solution for preparing of step, reacts and take out conductive substrates after 6 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope test (Fig. 2) as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the pure three-dimensional Graphene of dry porous.
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 14mg/mL graphene oxide solution;
2. with 14mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 1.7mg/mL;
3. the Cu conductive substrates is put in the second graphene oxide solution for preparing of step 30 ℃ and leaves standstill, react and take out conductive substrates after 10 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of conductive substrates;
4. will go up earlier to go on foot in the Graphene immersion liquid nitrogen that obtains and freeze reality, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, and product is detected, and can see Cu by the X-ray powder diffraction test pattern
2The characteristic peak of O (40 °, 47 °, 68 °, 82 ° and 86 °), and the characteristic peak of graphene oxide (10 °) disappears, and the characteristic peak (23 °) of Graphene occurred, illustrates that graphene oxide has been reduced into Graphene; Test (Fig. 3) as can be known in conjunction with scanning electron microscope test and transmission electron microscope, the structure of Graphene is three-layer laminated vesicular structure, Cu
2The pattern of O is the particle of 50nm, and namely product is Cu
2The three-dimensional Graphene of the dry porous of O nano particle functionalization.
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the Al conductive substrates is put in the second graphene oxide solution for preparing of step 60 ℃ and leaves standstill, react and take out conductive substrates after 12 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the pure three-dimensional Graphene of dry porous.
Embodiment 5
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the Co conductive substrates is put in the second graphene oxide solution for preparing of step 60 ℃ and leaves standstill, react and take out conductive substrates after 12 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the pure three-dimensional Graphene of dry porous.
Embodiment 6
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the Ag conductive substrates of vacuum sputtering being sprayed Cu is put in the graphene oxide solution that second step prepared 60 ℃ and leaves standstill, and reacts and takes out conductive substrates after 12 hours, and graphene oxide is reduced and obtains Graphene, and is deposited on the surface of Ag conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the pure three-dimensional Graphene of dry porous.
Embodiment 7
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the Pt conductive substrates of vacuum sputtering being sprayed Cu is put in the graphene oxide solution that second step prepared 60 ℃ and leaves standstill, and reacts and takes out conductive substrates after 12 hours, and graphene oxide is reduced and obtains Graphene, and is deposited on the surface of Pt conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the pure three-dimensional Graphene of dry porous.
Embodiment 8
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the Au conductive substrates of vacuum sputtering being sprayed Cu is put in the graphene oxide solution that second step prepared 60 ℃ and leaves standstill, and reacts and takes out conductive substrates after 12 hours, and graphene oxide is reduced and obtains Graphene, and is deposited on the surface of Au conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram (Fig. 4) as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the pure three-dimensional Graphene of dry porous.
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. drip the AgNO of 0.01M in the Cu substrate
3After leaving standstill one minute, use the HCl solution washing, can see on the surface sweeping Electronic Speculum that dendritic Ag nanostructure deposition is on the surface of Cu conductive substrates, the Cu substrate that will have an Ag nanostructure is put into that normal temperature leaves standstill in the graphene oxide solution that second step prepared, react and take out conductive substrates after 10 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of Ag conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram (Fig. 5) as can be known, the structure of Graphene is three-layer laminated vesicular structure, namely obtains the pure three-dimensional graphene-supported surface in the Ag nanostructure of dry porous.
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. drip the HAuCl of 0.01M in the Cu substrate
4Solution, after leaving standstill one minute, use the HCl solution washing, can see on the surface sweeping Electronic Speculum that the Au nanoparticle deposition is on the surface of Cu conductive substrates, the Cu conductive substrates that will have an Au nano particle is put into that normal temperature leaves standstill in the graphene oxide solution that second step prepared, react and take out conductive substrates after 10 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of Au conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, namely obtains the pure three-dimensional graphene-supported surface at the Au nano particle of dry porous.
Embodiment 11
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. drip the H of 0.01M in the Cu substrate
2PtCl
6Solution, after leaving standstill one minute, use the HCl solution washing, can see on the surface sweeping Electronic Speculum that the Pt nanoparticle deposition is on the surface of Cu conductive substrates, the Cu conductive substrates that will have a Pt nano particle is put into that normal temperature leaves standstill in the graphene oxide solution that second step prepared, react and take out conductive substrates after 10 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of Pt conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, and what namely obtain is the pure three-dimensional graphene-supported surface at the Pt nano particle of dry porous.
Embodiment 12
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the Si conductive substrates of vacuum sputtering being sprayed Cu is put in the graphene oxide solution that second step prepared 60 ℃ and leaves standstill, and reacts and takes out conductive substrates after 12 hours, and graphene oxide is reduced and obtains Graphene, and is deposited on the surface of Si conductive substrates;
4. the Graphene 100mL that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the pure three-dimensional Graphene of dry porous.
Embodiment 13
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the ITO conductive substrates of conducting surface demifacet vacuum sputtering spray Cu being put in the graphene oxide solution that second step prepared 60 ℃ leaves standstill, react and take out conductive substrates after 12 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of ITO conductive substrates;
4. the Graphene 100mL that is deposited on the ITO surface that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, remove Graphene and Cu on the demifacet ITO that sprays Cu, the residue demifacet ITO that has deposited Graphene is tested, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the surface that the pure three-dimensional Graphene of dry porous is deposited on ITO.
Embodiment 14
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the Cu conductive substrates is put into that normal temperature leaves standstill in the second graphene oxide solution for preparing of step, react and take out conductive substrates after 10 hours, after the washing, the normal temperature seasoning, by scanning electron microscope test as can be known, graphene oxide is reduced the Graphene that obtains and is shrunk to the surface that a skim is attached to the Cu conductive substrates in the Air drying process;
4. the Cu conductive substrates that will have one deck graphene film is put into that normal temperature leaves standstill in the graphene oxide solution that second step prepared, and reacts and takes out conductive substrates after 10 hours, deposits the last layer Graphene on the film of Graphene again;
5. the Graphene 100mL that is deposited on the graphene film surface that the last step was obtained, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram (Fig. 6) as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the surface that the pure three-dimensional Graphene of dry porous is deposited on graphene film.
Embodiment 15
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. Cu paper tinsel conductive substrates is cut into the circle that diameter is 1.6cm, is put into that normal temperature leaves standstill in the second graphene oxide solution for preparing of step, react and take out conductive substrates after 10 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of conductive substrates;
To the last step obtain be deposited on Graphene 100mL on the Cu conductive substrates, after the hydrochloric acid soln washing of 2mol/L, earlier Graphene is immersed and freeze reality in the liquid nitrogen, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, the characteristic peak (10 °) that can see graphene oxide by the X-ray powder diffraction test pattern disappears, the characteristic peak (23 °) that Graphene occurred, illustrate that graphene oxide has been reduced into Graphene, and the characteristic peak that does not have metal oxide illustrates not have metal oxide; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the three-dimensional porous Graphene that loads on the circular Cu paper tinsel conductive substrates;
5. the 4th step was obtained loading on three-dimensional porous Graphene on the circular Cu paper tinsel conductive substrates directly 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.Test under the 0.1A/g electric current, cell container is stabilized in 1076mAh/g, when electric current is raised to 300mAh/g, the capacity of battery is stabilized in 725mAh/g(Fig. 7), from the multiplying power test, battery is under high electric current (20A/g) condition, and capacity still can reach 231mAh/g.The series of cells process of assembling is finished in glove box, and test macro is LAND CT2001A.
Embodiment 16
1. utilize oxidation to peel off graphite method (Hummers method) and prepare 8mg/mL graphene oxide solution;
2. with 8mg/mL graphene oxide solution distilled water diluting, the concentration that makes graphene oxide solution is 0.5mg/mL;
3. the Zn conductive substrates is put into that normal temperature leaves standstill in the second graphene oxide solution for preparing of step, reacts and take out conductive substrates after 6 hours, graphene oxide is reduced and obtains Graphene, and is deposited on the surface of conductive substrates;
4. will go up earlier to go on foot in the Graphene immersion liquid nitrogen that obtains and freeze reality, the freeze drier lyophilize of putting into-50 ℃ then namely obtains product, product is detected, can see the serial characteristic peak (32 °, 34 °, 36 °, 48 °, 57 °, 63 °, 66 °, 68 ° and 69 °) of ZnO by the X-ray powder diffraction test pattern, and the characteristic peak of graphene oxide (10 °) disappears, the characteristic peak (23 °) of Graphene occurred, illustrated that graphene oxide has been reduced into Graphene; In conjunction with scanning electron microscope diagram as can be known, the structure of Graphene is three-layer laminated vesicular structure, and namely product is the three-dimensional Graphene of the ZnO nano particle functionalization of dry porous.Graphene after the lyophilize is cut into the shape (rectangle: 0.4 * 0.8cm of rule
2) response of test light electric current.Photoelectric current can reach 3 microamperes (Fig. 8).Testing tool is to test on the CHI760D electrochemical workstation, and light source is the incandescent light of 100w.
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the principle of spirit of the present invention, replace or local improvement, all will be considered as within protection scope of the present invention.
Claims (1)
1. the method for the three-dimensional Graphene of spontaneous deposition on conductive substrates is characterized in that described method steps is as follows:
The first step: utilize oxidation to peel off the graphite method and prepare 8～20mg/mL graphene oxide solution;
Second step: with 8～20mg/mL graphene oxide solution dilution, the concentration that makes graphene oxide solution is 0.5～3mg/mL;
The 3rd step: conductive substrates is put in the second graphene oxide solution for preparing of step leaves standstill, react and take out conductive substrates after 6～12 hours, graphene oxide is reduced and obtains three-dimensional Graphene, and is deposited on the surface of conductive substrates;
The 4th step: the three-dimensional Graphene that the 3rd step was obtained directly carries out lyophilize, obtains the three-dimensional Graphene of functionalization of dry porous; Or carry out lyophilize again after washing the metal oxide that adheres on the 3rd three-dimensional Graphene that obtain of step earlier, obtain pure dry porous three-dimensional Graphene;
Described conductive substrates is a kind of in following six kinds, wherein:
First kind is Zn, Fe, Al, Co or Cu;
Second kind of Ag, Pt or Au paper tinsel for vacuum sputtering spray Cu;
The third for by chemical reaction deposit the Cu paper tinsel of the Ag of nanostructure, Pt or Au;
The 4th kind of Si sheet for vacuum sputtering spray Cu;
The 5th kind is the conductive glass of the demifacet vacuum sputtering spray Cu of conducting surface;
The 6th kind for having the Cu substrate of graphene film;
Dilution is adopted and is reached distilled water purity and above water in second step;
When conductive substrates was Al or Co, dwell temperature was 60 ℃ in the 3rd step; When conductive substrates was not Al or Co, dwell temperature was room temperature～60 ℃.
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| CN106629689A (en) * | 2016-12-16 | 2017-05-10 | 复旦大学 | High-efficiency catalysis macroscopic quantity preparation method for graphene oxide or compound thereof reduced and peeled based on microwaves |
| CN108298529A (en) * | 2018-04-11 | 2018-07-20 | 西北工业大学 | A kind of preparation method of graphene |
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