CN103553034A - Preparation method and application of three-dimensional porous graphene skeleton - Google Patents
Preparation method and application of three-dimensional porous graphene skeleton Download PDFInfo
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- CN103553034A CN103553034A CN201310558449.5A CN201310558449A CN103553034A CN 103553034 A CN103553034 A CN 103553034A CN 201310558449 A CN201310558449 A CN 201310558449A CN 103553034 A CN103553034 A CN 103553034A
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Abstract
The invention provides a preparation method and an application of a three-dimensional porous graphene skeleton, and relates to a preparation method and an application of a graphene skeleton. The preparation method is used for solving the technical problem of difficulty in the preparation of three-dimensional porous structure graphene with high property and high stability. The preparation method comprises the following steps: sealing graphite oxide in a quartz tube under the condition of vacuum or charging gas, transferring the quartz tube to a muffle furnace, heating, carrying out heat preservation, taking out the quartz tube, rapidly immersing the quartz tube in ice water, repeating the heating-quenching process time after time, and collecting a product in the quartz tube, wherein the product is the three-dimensional porous graphene skeleton. The preparation method is simple and environmentally-friendly. The three-dimensional porous graphene skeleton with the special structure can be used for effectively enlarging the available loading area of graphene and can be widely applied to the fields of lithium ion batteries, fuel batteries, solar cells, photocatalysis, catalytic oxidation, gas sensors, medicine conveying and the like.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of Graphene skeleton.
Background technology
Grapheme material is a kind of monoatomic layer material with bi-dimensional cellular shape structure, and it is the basic structural unit that forms soccerballene, carbon nanotube and graphite.Since Univ Manchester UK in 2004 the peace strong K sea nurse of moral (Andre K.Geim) is prepared single-layer graphene, be subject to the extensive concern of scientific circles and industry member.Graphene has excellent electricity, calorifics and mechanical property.For example the carrier mobility of Graphene is 10 times of commercial silicon chip carrier mobility, reaches 15000cm
2v
-1s
-1(Zhang, et al.Nature., 2005,438,201-204.); The intensity of Graphene can reach 130GPa, be more than 100 times of equivalent weight steel (A.K.Gein, Science., 2009,324,1530-4.); The thermal conductivity of Graphene reaches 5000W/mK, is adamantine 3 times (A.A.Balandin, Nano lett, 2008,8,902.) under room temperature.Along with the further of Graphene research goed deep into, there is the Graphene of special construction, as there are concern (Cao, et al.small., 2011,7,3163 that three-dimensional poroid structure graphite alkene is more and more subject to people; Hu, et al.Adv.Mater., 2013,25,2219).
Three-dimensional poroid Graphene also has much other excellent character except having the physico-chemical property of Graphene itself, as 1, the three-dimensional pore space structure of its uniqueness, there is the effect of support and alleviation internal stress, can be used for the fields such as lithium ion battery, can effectively alleviate the volumetric expansion of metal oxide negative material in storage lithium process; 2, inner void height is communicated with, and is beneficial to heat conduction and conduction, can be used for the fields such as thermally conductive material and solar cell; 3, its hole has capillary absorption power, can be used for the fields such as sorbing material.
At present, the preparation method of three-dimensional poroid Graphene mainly contains following several: 1, sol-gel method (Cong, et al.ACS Nano., 2012,6,2693; Tang, et al.J.Am.Chem.Soc., 2011,133,9262), this method generally needs to add the organism such as linking agent from graphene oxide and preparation process, reduce electricity and the thermal property of Graphene, limited its further practical application; 2, chemical Vapor deposition process (CVD method) (Cheng, et al.Nat.Mater., 2011,10,424; Cao.et al.Small., 2013,9,1703.), this three-dimensional network body material has the shape characteristic of three-dimensional network uniqueness and the physicochemical property of Graphene uniqueness, higher porosity and very large specific surface area, but it is template used is the metal forms such as copper, nickel, the hole of its gained Graphene is excessive, in the process through etching liquid removal template, tends to destroy its three-dimensional cavernous structure, has limited its application.Therefore, be difficult at present the poroid structure graphite alkene of three-dimensional of preparation high-performance, high stability.
Summary of the invention
The present invention is the technical problem that will solve the poroid structure graphite alkene of three-dimensional that is difficult at present preparation high-performance, high stability, thereby preparation method and the application thereof of the poroid Graphene skeleton of a kind of three-dimensional are provided.
The preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present invention carries out according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 8 * 10
-4～9 * 10
-4pa, closure molecule pump extraction valve, in vacuum or be filled with the condition lower seal silica tube of gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 5～20 ℃/minute and be heated to temperature and at 500～1200 ℃, be incubated after 5～30 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1～3 minute;
Three, the heating-quenching process 1～9 time of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene skeleton of three-dimensional prepared by aforesaid method can with titanium dioxide (TiO
2), tindioxide (SnO
2), Z 250 (Fe
3o
4), cobalt oxide (CoO), manganese oxide (MnO
2), cupric oxide (CuO), moly-sulfide (MoS
2), golden nanometer particle (Au), nano platinum particle (Pt) or Pd nano particle (Pd) is compound obtains the graphene composite material of three-dimensional cavernous structure and be applied to lithium ion battery, fuel cell, solar cell, photochemical catalysis, catalyzed oxidation, gas sensor, drug delivery field.
The present invention includes following beneficial effect:
The lithium ion battery specific storage of the P25/ graphene composite material assembling that three-dimensional that 1, prepared by the present invention is poroid be with similarity condition under 2.3 times of lithium ion battery of the pure P25 assembling of use, illustrate that the poroid P25/ graphene composite material of three-dimensional prepared by the present invention has high-performance and high stability.
2, the present invention does not adopt any chemical reagent, without any chemical waste, produce, and be a kind of eco-friendly method of preparing three-dimensional grapheme skeleton;
3, the present invention utilizes heating-quenching process to peel off graphite oxide, and method is simple, can primary treatment graphite oxide gram more than magnitude, applicable scale operation;
4, the prepared Graphene of the present invention effectively raises the specific surface area of graphite oxide, improves its quality, has three-dimensional porous structure, is conducive to the raising of material property.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope picture of graphite oxide;
Fig. 2 is the scanning electron microscope picture of the poroid Graphene of three-dimensional of embodiment mono-preparation;
Fig. 3 is the X-ray diffractogram of the poroid Graphene of three-dimensional of embodiment mono-preparation;
Fig. 4 is the poroid P25/ graphene composite material stereoscan photograph of three-dimensional of test one preparation;
Fig. 5 tests the poroid lithium ion battery of P25/ graphene composite material assembling and the charging and discharging curve comparison diagram of the lithium ion battery that pure P25 assembles of three-dimensional of a preparation; Wherein, 1 is the charge graph of the lithium ion battery of three-dimensional poroid P25/ graphene composite material assembling; 2 is the discharge curve of the lithium ion battery of three-dimensional poroid P25/ graphene composite material assembling; 3 is the charge graph of the lithium ion battery of pure P25 assembling; 4 is the discharge curve of the lithium ion battery of pure P25 assembling.
Embodiment
Embodiment one: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of present embodiment carries out according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 8 * 10
-4～9 * 10
-4pa, closure molecule pump extraction valve, in vacuum or be filled with the condition lower seal silica tube of gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 5～20 ℃/minute and be heated to temperature and at 500～1200 ℃, be incubated after 5～30 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1～3 minute;
Three, the heating-quenching process 1～9 time of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
Present embodiment comprises following beneficial effect:
The lithium ion battery specific storage of the P25/ graphene composite material assembling that three-dimensional that 1, prepared by present embodiment is poroid be with similarity condition under 2.3 times of lithium ion battery of the pure P25 assembling of use, illustrate that the poroid P25/ graphene composite material of three-dimensional prepared by the present invention has high-performance and high stability.
2, present embodiment does not adopt any chemical reagent, without any chemical waste, produce, and be a kind of eco-friendly method of preparing three-dimensional grapheme skeleton;
3, present embodiment is to utilize heating-quenching process to peel off graphite oxide, and method is simple, can primary treatment graphite oxide gram more than magnitude, applicable scale operation;
4, the prepared Graphene of present embodiment effectively raises the specific surface area of graphite oxide, improves its quality, has three-dimensional porous structure, is conducive to the raising of material property.
Embodiment two: present embodiment is different from embodiment one: in step 1, vacuum in silica tube is evacuated to 9 * 10
-4pa.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: being filled with gas in step 1 is argon gas or nitrogen.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: the speed with 10 ℃/minute in step 2 heats.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: being heated to temperature in step 2 is to be incubated 5～20 minutes at 600～1100 ℃.Other is identical with one of embodiment one to four.
Embodiment six: the poroid Graphene skeleton of a kind of three-dimensional of present embodiment can obtain the graphene composite material of three-dimensional cavernous structure and be applied to lithium ion battery, fuel cell, solar cell, photochemical catalysis, catalyzed oxidation, gas sensor, drug delivery field with titanium dioxide, tindioxide, Z 250, cobalt oxide, manganese oxide, cupric oxide, moly-sulfide, golden nanometer particle, nano platinum particle or Pd nano particle are compound.
By following examples, verify beneficial effect of the present invention:
Embodiment mono-: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, is being filled with the condition lower seal silica tube of argon gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and be heated to temperature and at 900 ℃, be incubated after 20 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 3 times of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The scanning electron microscope picture of graphite oxide as shown in Figure 1; The scanning electron microscope picture of the poroid Graphene skeleton of three-dimensional prepared by the present embodiment as shown in Figure 2, as can be seen from Figure 2, the about 200nm in aperture of the poroid Graphene skeleton of three-dimensional prepared by the present embodiment, the about 3nm of wall thickness, Fig. 1 and Fig. 2 contrast known, graphite oxide is thicker sheet structure, through processing gained Graphene skeleton, is cavernous structure, and hole wall is thinner.。
As shown in Figure 3, as can be seen from Figure 3, the Graphene that the poroid Graphene of three-dimensional prepared by the present embodiment is pure phase, without graphite-phase or graphene oxide phase for the X-ray diffractogram of the poroid Graphene skeleton of three-dimensional prepared by the present embodiment.
Utilize the poroid Graphene skeleton of three-dimensional of test one preparation to do following test:
Test one: get the three-dimensional poroid Graphene of 100mg gained and 200mg P25 particle ultrasonic 30min in 40ml ethanol, mixing solutions is sealed in water heating kettle to 120 ℃ of reactions 10 hours, products therefrom is dry with deionized water wash, obtain three-dimensional poroid P25/ graphene composite material; By gained three-dimensional poroid P25/ graphene composite material and tetrafluoroethylene and the black (TIMREXKS-15 of conductive acetylene, TIMCAL, Switzerlan) according to mass ratio 85:5:10, mix, spread upon the two sides of nickel screen as working electrode, 60 ℃ are dried 6 hours, and compressing tablet is also dried 24 hours at 120 ℃; Take metallic lithium as to electrode, and microporous polypropylene membrane (Celgard2300) is barrier film, the LiPF of 1mol/L
6nSC 11801 and diethyl carbonate (volume ratio 1:1) solution be electrolytic solution, assembling lithium ion battery.
The poroid P25/ graphene composite material stereoscan photograph of the three-dimensional of this test preparation as shown in Figure 4.
With pure P25, substitute three-dimensional poroid P25/ graphene composite material assembling lithium ion battery after the same method.
The charging and discharging curve comparison diagram of the lithium ion battery that the poroid P25/ graphene composite material of three-dimensional of this test preparation is assembled and the lithium ion battery of pure P25 assembling as shown in Figure 5; Wherein, 1 is the charge graph of the lithium ion battery of three-dimensional poroid P25/ graphene composite material assembling; 2 is the discharge curve of the lithium ion battery of three-dimensional poroid P25/ graphene composite material assembling; 3 is the charge graph of the lithium ion battery of pure P25 assembling; 4 is the discharge curve of the lithium ion battery of pure P25 assembling.From figure, can 5 find out, the lithium ion battery of three-dimensional poroid P25/ graphene composite material assembling, during 0.1C electric discharge, specific storage is 150mAh/g, with the lithium ion battery of pure P25 assembling, during 0.1C electric discharge, specific storage is 65mAh/g.When during the lithium ion battery 0.1C electric discharge of i.e. three-dimensional poroid P25/ graphene composite material assembling, specific storage is the lithium ion battery 0.1C electric discharge with pure P25 assembling 2.3 times of specific storage.
Test two: get the three-dimensional poroid Graphene of 100mg gained and 200mg SnO
2particle is ultrasonic 30min in 40ml ethanol, and mixing solutions is sealed in water heating kettle to 120 ℃ of reactions 10 hours, and products therefrom is dry with deionized water wash, obtains three-dimensional poroid SnO
2/ graphene composite material; By the three-dimensional poroid SnO of gained
2black (the TIMREXKS-15 of/graphene composite material and tetrafluoroethylene and conductive acetylene, TIMCAL, Switzerlan) according to mass ratio 85:5:10, mix, spread upon the two sides of nickel screen as working electrode, 60 ℃ are dried 6 hours, and compressing tablet is also dried 24 hours at 120 ℃; Take metallic lithium as to electrode, and microporous polypropylene membrane (Celgard2300) is barrier film, the LiPF of 1mol/L
6nSC 11801 and diethyl carbonate (volume ratio 1:1) solution be electrolytic solution, assembling lithium ion battery.
When gained battery be take 0.1C electric discharge, specific storage is 820mAh/g.
Test three: get the three-dimensional poroid Graphene of 50mg gained and 200mg FeCl
3at 40ml deionized water for ultrasonic 30min, mixing solutions is sealed in water heating kettle to 150 ℃ of reactions 10 hours, products therefrom is dry with deionized water wash, obtain three-dimensional poroid Fe
3o
4/ graphene composite material; By the three-dimensional poroid Fe of gained
3o
4black (the TIMREXKS-15 of/graphene composite material and tetrafluoroethylene and conductive acetylene, TIMCAL, Switzerlan) according to mass ratio 85:5:10, mix, spread upon the two sides of nickel screen as working electrode, 60 ℃ are dried 6 hours, and compressing tablet is also dried 24 hours at 120 ℃; Take metallic lithium as to electrode, and microporous polypropylene membrane (Celgard2300) is barrier film, the LiPF of 1mol/L
6nSC 11801 and diethyl carbonate (volume ratio 1:1) solution be electrolytic solution, assembling lithium ion battery.
When gained battery be take 0.1C electric discharge, specific storage is 600mAh/g.
Test four: get the three-dimensional poroid Graphene skeleton of 10mg and 200mg P25 particle ultrasonic 30min in 40ml ethanol, mixing solutions is sealed in water heating kettle to 160 ℃ of reactions 10 hours, products therefrom is dry with deionized water wash, obtain three-dimensional poroid P25/ graphene composite material; The three-dimensional poroid P25/ graphene composite material of 100mg is added in agate mortar, add the anhydrous Terpineol 350 of 80ml appropriate amount of ethanol and ethyl cellulose and grind 1h, with rotatory evaporator, ethanol evaporate to dryness is obtained to slurry, on ito glass, use scraper legal system for absorption layer, 450 ℃ of annealing 1h, take out and are assembled into battery with platinum electrode after the N719 dyestuff 20h of immersion 0.5mM.
The photoelectric transformation efficiency of gained solar cell (η) is 7.5%.
Embodiment bis-: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, sealed silica envelope;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and be heated to temperature and at 900 ℃, be incubated after 20 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 3 times of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene of three-dimensional aperture prepared by the present embodiment is about 200nm, the about 3nm of wall thickness.
Embodiment tri-: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, is being filled with the condition lower seal silica tube of nitrogen;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and be heated to temperature and at 900 ℃, be incubated after 5 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 3 times of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene of three-dimensional aperture prepared by the present embodiment is about 80nm, the about 4nm of wall thickness.
Embodiment tetra-: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, is being filled with the condition lower seal silica tube of argon gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and be heated to temperature and at 900 ℃, be incubated after 10 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 3 times of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene of three-dimensional aperture prepared by the present embodiment is about 100nm, the about 4nm of wall thickness.
Embodiment five: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, is being filled with the condition lower seal silica tube of argon gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and be heated to temperature and at 900 ℃, be incubated after 20 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 1 time of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene of three-dimensional aperture prepared by the present embodiment is about 80nm, the about 4nm of wall thickness.
Embodiment six: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, is being filled with the condition lower seal silica tube of argon gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and to temperature, at 900 ℃, be incubated after 20 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 6 times of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene of three-dimensional aperture prepared by the present embodiment is about 200nm, the about 2nm of wall thickness.
Embodiment seven: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, is being filled with the condition lower seal silica tube of argon gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and be heated to temperature and at 900 ℃, be incubated after 20 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 9 times of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene of three-dimensional aperture prepared by the present embodiment is about 220nm, the about 2nm of wall thickness.
Embodiment eight: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, is being filled with the condition lower seal silica tube of argon gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and be heated to temperature and at 600 ℃, be incubated after 20 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 3 times of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene of three-dimensional aperture prepared by the present embodiment is about 50nm, the about 4nm of wall thickness.
Embodiment nine: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, is being filled with the condition lower seal silica tube of argon gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and be heated to temperature and at 1100 ℃, be incubated after 20 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 3 times of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene of three-dimensional aperture prepared by the present embodiment is about 220nm, the about 3nm of wall thickness.
Embodiment ten: the preparation method of the poroid Graphene skeleton of a kind of three-dimensional of the present embodiment realizes according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 9 * 10
-4pa, closure molecule pump extraction valve, is being filled with the condition lower seal silica tube of argon gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 10 ℃/minute and be heated to temperature and at 1100 ℃, be incubated after 20 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1 minute;
Three, the heating-quenching process 1 time of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
The poroid Graphene of three-dimensional aperture prepared by the present embodiment is about 100nm, the about 3nm of wall thickness.
Claims (6)
1. a preparation method for the poroid Graphene skeleton of three-dimensional, the preparation method who it is characterized in that three-dimensional poroid Graphene skeleton carries out according to the following steps:
One, 500mg graphite oxide is placed in to silica tube, with molecular pump, vacuum in silica tube is evacuated to 8 * 10
-4～9 * 10
-4pa, closure molecule pump extraction valve, in vacuum or be filled with the condition lower seal silica tube of gas;
Two, the silica tube of step 1 sealing is transferred in retort furnace, retort furnace is take to the speed of 5～20 ℃/minute and be heated to temperature and at 500～1200 ℃, be incubated after 5～30 minutes, silica tube is taken out and is dipped in fast in frozen water keep 1～3 minute;
Three, the heating-quenching process 1～9 time of repeating step two, finally collects product in silica tube, and products therefrom is three-dimensional poroid Graphene skeleton.
2. the preparation method of the poroid Graphene skeleton of a kind of three-dimensional according to claim 1, is characterized in that, in step 1, vacuum in silica tube is evacuated to 9 * 10
-4pa.
3. the preparation method of the poroid Graphene skeleton of a kind of three-dimensional according to claim 1, is characterized in that in step 1, being filled with gas is argon gas or nitrogen.
4. the preparation method of the poroid Graphene skeleton of a kind of three-dimensional according to claim 1, is characterized in that in step 2, the speed with 10 ℃/minute heats.
5. the preparation method of the poroid Graphene skeleton of a kind of three-dimensional according to claim 1, is characterized in that in step 2, being heated to temperature is to be incubated 5～20 minutes at 600～1100 ℃.
6. the application of the poroid Graphene skeleton of a kind of three-dimensional as claimed in claim 1, is characterized in that three-dimensional poroid Graphene skeleton can obtain the graphene composite material of three-dimensional cavernous structure and be applied to lithium ion battery, fuel cell, solar cell, photochemical catalysis, catalyzed oxidation, gas sensor, drug delivery field with titanium dioxide, tindioxide, Z 250, cobalt oxide, manganese oxide, cupric oxide, moly-sulfide, golden nanometer particle, nano platinum particle or Pd nano particle are compound.
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