CN106315567A - Preparation method of foam graphene - Google Patents
Preparation method of foam graphene Download PDFInfo
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- CN106315567A CN106315567A CN201610671809.6A CN201610671809A CN106315567A CN 106315567 A CN106315567 A CN 106315567A CN 201610671809 A CN201610671809 A CN 201610671809A CN 106315567 A CN106315567 A CN 106315567A
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- preparation
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- graphite alkene
- foamy graphite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
Abstract
The invention provides a preparation method of foam graphene. The preparation method includes the following steps that 1, graphite oxide and polyacrylonitrile are added into a ball mill to be ball-milled, then the ball-milled mixture is added into a mixed solution of ethyl alcohol and water for ultrasonic dispersion, and suspension liquid is formed; 2, foam nickel is soaked with the suspension liquid, a solvent evaporates to dryness, the material is placed in a muffle furnace protected by hydrogen and nitrogen mixed gas for reacting, and the material is naturally cooled after reacting completely; 3, the product is soaked with hydrochloric acid for reacting, and the foam graphene is obtained after reacting is complete. The method is simple in equipment requirement and easy to operate.
Description
Technical field
The invention belongs to material with carbon element technical field, relate to the preparation method of a kind of grapheme foam.
Background technology
Graphene is a kind of Novel Carbon Nanomaterials, by monolayer sp2 carbon atom tightly packed one-tenth bi-dimensional cellular shape structure.
Graphene has electricity, calorifics, optics and the mechanical property of excellence.The theoretical specific surface area that Graphene is high simultaneously and excellent electricity
Conductance determines it as electrode material in the great potential of electrochemical energy storing device.
Cheng Huiming etc. (N. Li et al., Proc. Natl. Acad. Sci. 109 (2012) 17360) utilize chemistry
Vapour deposition (CVD)-metal form method is successfully prepared high conductivity, flexible three-dimensional porous foams Graphene, and as
Collector obtains lithium titanate/foamy graphite alkene electrode.This electrode still has 135 mAh g under the multiplying power of 200C-1Specific volume
Amount.Compared with conventional two-dimensional collector, use 3-D nano, structure current collector material can provide better for active substance
Conduction environment, reduce electrode internal resistance.Ji Hengxing etc. (H.X. Ji et al., Nano Lett. 4 (2012) 2446) pass through
Research shows that the electrode using graphene-based collector shows more preferable electrification than the electrode using tradition collector (aluminium foil)
Learn performance: electrode has higher active substance load capacity and more preferable high rate performance.The most graphene-based collector is at 2-
5Vvs.Li/Li+Voltage window shows the electrochemical stability of excellence, is a kind of high voltage with good application prospect
Lithium ion battery collector.
Prior art prepares the method for grapheme foam, it is common that utilize chemical vapour deposition technique to deposit one in nickel foam
Layer graphene, removes matrix by acid treatment thus obtains three-dimensional porous grapheme foam.But this method typically uses
CVD is carried out, and needs to consume substantial amounts of energy, and is not easy to large-scale production.
Summary of the invention
For overcoming the shortcoming of prior art, use infusion process at one layer of graphene oxide of nickel foam surface adsorption, then lead to
Cross chemical reduction method it is reduced, remove nickel foam finally by acid treatment, obtain the foamy graphite alkene of three-dimension flexible.
The present invention provides the preparation method of a kind of foamy graphite alkene to be:
Step (1) joins ball milling 30-60min in ball mill, then by the mixing after ball milling by fine to graphite oxide and polypropylene
Thing joins ethanol and ultrasonic disperse in the mixed solution of water, forms the suspension of concentration 1-20g/L.
Nickel foam is soaked 10-60min, solvent evaporated in above-mentioned suspension by step (2), places into hydrogen nitrogen mixed gas and protects
800-1100 DEG C of reaction 1-10h, natural cooling after reaction completely in the Muffle furnace protected.
Above-mentioned product be impregnated in the hydrochloric acid of 1-3mol/L by step (3), and 60-80 DEG C of reaction 5-10h, after reaction completely
Obtain foamy graphite alkene.
Further, in described step (1), Ball-milling Time is 30-60min；
Further, the 0.01-5% that quality is graphite oxide quality that in described step (1), polypropylene is fine；
Further, in described step (1), in the mixed solution of ethanol and water, the volume ratio of ethanol and water is 0.25-4；
Further, described step (1) is at the suspension that concentration is 1-20g/L of graphite oxide suspension；
Further, in described step (2), nickel foam is immersed in the time in graphite oxide suspension is 10-60min；
Further, in described step (2), the atmosphere in Muffle furnace is the hydrogen nitrogen mixed gas containing volumetric concentration 5% hydrogen；
Further, the described step (2) reaction temperature in Muffle furnace is 800-1100 DEG C, and the response time is 1-10h；
Further, in described step (3), concentration of hydrochloric acid is 1-3mol/L；
Further, the described step (3) reaction temperature in hydrochloric acid is 60-80 DEG C, and the response time is 5-10h.
There is advantages that the feature of the existing flexibility of grapheme foam that (1) is prepared by this method, again
Possess electric conductivity and the chemical stability of Graphene；(2) ethanol is used to disperse graphite oxide with water mixed solution so that it is stability
More preferably；(3) interpolation polypropylene is fine can make to couple between graphene sheet layer more fully, and beneficially sheet interlayer electric conductivity improves；(4)
The method equipment requirements of the present invention is simple, processing ease.
Accompanying drawing explanation
Fig. 1 is present invention process flow chart.
Detailed description of the invention
Below the preferably embodiment of the present invention is described in further detail:
Embodiment 1
(1) ball milling 30min in ball mill is joined, then by mixing after ball milling by fine to 10g graphite oxide and 0.001g polypropylene
Compound joins ultrasonic disperse in the mixed solution that ethanol and water volume ratio are 0.25, forms the suspension of concentration 1g/L.
(2) nickel foam is soaked in above-mentioned suspension 10min, solvent evaporated, place into containing volumetric concentration 5% hydrogen
800 DEG C of reaction 10h, natural cooling after reaction completely in the Muffle furnace of hydrogen nitrogen mixed gas protection.
(3) above-mentioned product be impregnated in the hydrochloric acid of 1mol/L, 60 DEG C of reaction 10h, obtain foam stone after reaction completely
Ink alkene.
Embodiment 2
(1) ball milling 60min in ball mill is joined, then by the mixing after ball milling by fine to 10g graphite oxide and 0.5g polypropylene
Thing joins ultrasonic disperse in the mixed solution that ethanol and water volume ratio are 4, forms the suspension of concentration 20g/L.
(2) nickel foam is soaked in above-mentioned suspension 60min, solvent evaporated, place into containing volumetric concentration 5% hydrogen
1100 DEG C of reaction 1h, natural cooling after reaction completely in the Muffle furnace of hydrogen nitrogen mixed gas protection.
(3) above-mentioned product be impregnated in the hydrochloric acid of 3mol/L, 80 DEG C of reaction 5h, obtain foam stone after reaction completely
Ink alkene.
Embodiment 3
(1) ball milling 45min in ball mill is joined, then by the mixing after ball milling by fine to 10g graphite oxide and 0.1g polypropylene
Thing joins ultrasonic disperse in the mixed solution that ethanol and water volume ratio are 0.5, forms the suspension of concentration 3g/L.
(2) nickel foam is soaked in above-mentioned suspension 30min, solvent evaporated, place into containing volumetric concentration 5% hydrogen
900 DEG C of reaction 5h, natural cooling after reaction completely in the Muffle furnace of hydrogen nitrogen mixed gas protection.
(3) above-mentioned product be impregnated in the hydrochloric acid of 2mol/L, 75 DEG C of reaction 7h, obtain foamy graphite after reaction completely
Alkene.
Embodiment 4
(1) ball milling 40min in ball mill is joined, then by the mixture after ball milling by fine to 10g graphite oxide and 3g polypropylene
Join ultrasonic disperse in the mixed solution that ethanol and water volume ratio are 2, form the suspension of concentration 10g/L.
(2) nickel foam is soaked in above-mentioned suspension 50min, solvent evaporated, place into containing volumetric concentration 5% hydrogen
1000 DEG C of reaction 3h, natural cooling after reaction completely in the Muffle furnace of hydrogen nitrogen mixed gas protection.
(3) above-mentioned product be impregnated in the hydrochloric acid of 1.5mol/L, 65 DEG C of reaction 9h, obtain foam stone after reaction completely
Ink alkene.
Embodiment 5
(1) ball milling 40min in ball mill is joined, then by the mixture after ball milling by fine to 10g graphite oxide and 1g polypropylene
Join ultrasonic disperse in the mixed solution that ethanol and water volume ratio are 1, form the suspension of concentration 5g/L.
(2) nickel foam is soaked in above-mentioned suspension 20min, solvent evaporated, place into containing volumetric concentration 5% hydrogen
950 DEG C of reaction 80h, natural cooling after reaction completely in the Muffle furnace of hydrogen nitrogen mixed gas protection.
(3) above-mentioned product be impregnated in the hydrochloric acid of 2.5mol/L, 75 DEG C of reaction 4h, obtain foam stone after reaction completely
Ink alkene.
As it is shown in figure 1, the foamy graphite alkene of preparation is carried out Kun pressure obtain electrode slice, according to the system of usual ultracapacitor
Electrode slice, barrier film and electrode slice are formed battery core by the way of lamination by standby technique, are then injected into electrolyte, the electrolyte of injection
For 1mol/L Et4NBF4AN solution, sealing, obtain ultracapacitor.
Its effect is as shown in table 1, as shown in Table 1: the present invention prepares electrode slice specific discharge capacity and reached 311.6-320.8
F/g。
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Specific discharge capacity (F/g) | 315.4 | 311.6 | 319.6 | 317.4 | 320.8 |
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert this
Bright being embodied as is confined to these explanations.For general technical staff of the technical field of the invention, do not taking off
On the premise of present inventive concept, it is also possible to make some simple deduction or replace, all should be considered as belonging to the protection of the present invention
Scope.
Claims (10)
1. the preparation method of a foamy graphite alkene, it is characterised in that include following step:
Step (1) joins ball milling in ball mill by fine to graphite oxide and polypropylene, is then joined by the mixture after ball milling
Ethanol and ultrasonic disperse in the mixed solution of water, form suspension；
Nickel foam is soaked in above-mentioned suspension by step (2), solvent evaporated, places in the Muffle furnace of hydrogen nitrogen mixed gas protection
Reaction, natural cooling after reaction completely；
Above-mentioned product be impregnated in hydrochloric acid by step (3), reaction, obtains foamy graphite alkene after reaction completely.
The preparation method of a kind of foamy graphite alkene the most as claimed in claim 1, it is characterised in that ball milling in described step (1)
Time is 30-60min.
The preparation method of a kind of foamy graphite alkene the most as claimed in claim 1, it is characterised in that in described step (1) poly-third
The 0.01-5% that quality is graphite oxide quality that alkene is fine.
The preparation method of a kind of foamy graphite alkene the most as claimed in claim 1, it is characterised in that ethanol in described step (1)
It is 0.25-4 with the volume ratio of ethanol in the mixed solution of water Yu water.
The preparation method of a kind of foamy graphite alkene the most as claimed in claim 1, it is characterised in that described step (1) is in oxidation
The concentration of graphite suspension is the suspension of 1-20g/L.
The preparation method of a kind of foamy graphite alkene the most as claimed in claim 1, it is characterised in that foam in described step (2)
It is 10-60min that nickel is immersed in the time in graphite oxide suspension.
The preparation method of a kind of foamy graphite alkene the most as claimed in claim 1, it is characterised in that Muffle in described step (2)
Atmosphere in stove is the hydrogen nitrogen mixed gas containing volumetric concentration 5% hydrogen.
The preparation method of a kind of foamy graphite alkene the most as claimed in claim 1, it is characterised in that described step (2) is in Muffle
Reaction temperature in stove is 800-1100 DEG C, and the response time is 1-10h.
The preparation method of a kind of foamy graphite alkene the most as claimed in claim 1, it is characterised in that hydrochloric acid in described step (3)
Concentration is 1-3mol/L.
The preparation method of a kind of foamy graphite alkene the most as claimed in claim 1, it is characterised in that described step (3) is at hydrochloric acid
In reaction temperature be 60-80 DEG C, the response time is 5-10h.
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| CN201610671809.6A CN106315567A (en) | 2016-08-16 | 2016-08-16 | Preparation method of foam graphene |
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| CN201610671809.6A CN106315567A (en) | 2016-08-16 | 2016-08-16 | Preparation method of foam graphene |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107248568A (en) * | 2017-07-12 | 2017-10-13 | 湖南艾威尔新能源科技有限公司 | Positive electrode adds the processing method of graphene |
| WO2018032316A1 (en) * | 2016-08-16 | 2018-02-22 | 肖丽芳 | Method for manufacturing graphene foam |
| CN107744826A (en) * | 2017-10-11 | 2018-03-02 | 肇庆市华师大光电产业研究院 | A kind of efficiently hollow tubular C3N4Photochemical catalyst and its preparation method and application |
| CN107887606A (en) * | 2017-10-29 | 2018-04-06 | 成都格莱飞科技股份有限公司 | The quick method for preparing graphene |
| CN108899215A (en) * | 2018-06-29 | 2018-11-27 | 成都三乙医疗科技有限公司 | A kind of foam nickel electrode piece preparation method |
| CN109336092A (en) * | 2018-10-17 | 2019-02-15 | 湖南大学 | A kind of three-dimensional grapheme and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018032316A1 (en) * | 2016-08-16 | 2018-02-22 | 肖丽芳 | Method for manufacturing graphene foam |
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| CN107744826A (en) * | 2017-10-11 | 2018-03-02 | 肇庆市华师大光电产业研究院 | A kind of efficiently hollow tubular C3N4Photochemical catalyst and its preparation method and application |
| CN107744826B (en) * | 2017-10-11 | 2019-03-19 | 肇庆市华师大光电产业研究院 | A kind of efficient hollow tubular C3N4Photochemical catalyst and its preparation method and application |
| CN107887606A (en) * | 2017-10-29 | 2018-04-06 | 成都格莱飞科技股份有限公司 | The quick method for preparing graphene |
| CN108899215A (en) * | 2018-06-29 | 2018-11-27 | 成都三乙医疗科技有限公司 | A kind of foam nickel electrode piece preparation method |
| CN109336092A (en) * | 2018-10-17 | 2019-02-15 | 湖南大学 | A kind of three-dimensional grapheme and preparation method |
| CN109336092B (en) * | 2018-10-17 | 2021-05-14 | 湖南大学 | Three-dimensional graphene and preparation method thereof |
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Application publication date: 20170111 |