CN105936504A - Production method of graphene - Google Patents
Production method of graphene Download PDFInfo
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- CN105936504A CN105936504A CN201610418050.0A CN201610418050A CN105936504A CN 105936504 A CN105936504 A CN 105936504A CN 201610418050 A CN201610418050 A CN 201610418050A CN 105936504 A CN105936504 A CN 105936504A
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Abstract
Belonging to the technical field of new materials, the invention provides a production method of graphene. The method solves the problems of complex production process, high production cost, severe environmental pollution and the like in existing graphene production. The production method of grapheme includes oxidation natural flake graphite and recovery of an acidic substance after oxidation. The method is characterized in that: the recovered acidic substance is further used in a next oxidation process, the recovered acidic substance and a freshly added acidic substance together compose a next oxidation solution, the acidic substance is sulfuric acid, the acidic substance separated after the oxidation process and the fresh sulfuric acid are preparation into a new round of natural flake graphite's oxidation solution according to a ratio of 1:1. The method has the advantages of simple process, low production cost and small environmental pollution.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of Graphene, particularly to the production method of a kind of Graphene.
Background technology
Graphene is a kind of special two-dimensional material arranged according to hexagon by carbon atom and be connected with each other, and have the features such as high conductivity, high mechanical properties, extra specific surface area to can be used to prepare high speed processor, high sensor, touch display screen, superbattery and high performance solar batteries etc. multiple because of itNovelDevice, has significant application value in various fields such as electronics, space flight military project, new forms of energy.
The most many reports about graphene preparation method, but from the point of view of high-quality, low cost volume production etc. are actually needed, the graphene preparation method that great majority have been reported all has various defect.Wherein oxidizing process is the most the most frequently used method preparing Graphene, and its production process is: 1, low temperature concentrated sulphuric acid+crystalline flake graphite+sodium nitrate；2, cryosphere is anti-inserted should；3, oxidant is added；4, middle temperature oxidation reaction；5, high-temperature hydrolysis；6, separating reaction liquid；7, graphite oxide pickling-deionized water cleans；8, graphite oxide ultrasound wave is peeled off；9, the electronation of graphene oxide；10, cold drying obtains Graphene.
In above-mentioned technological process, produce substantial amounts of Waste Sulfuric Acid after 6th step operation solid-liquid separation environment is polluted or produces high processing cost, the later operation of 8th step brings a lot of uncertain factor for large-scale production Graphene, the Graphene especially produced in reduction process and dry run easily forms reunion and makes Graphene come back to non-graphitic state, thus is difficult to large-scale production and obtains Graphene.
In its method, general Graphene per ton needs to consume 40 tons of concentrated sulphuric acids, the Waste Sulfuric Acid of 80 tons is produced after hydrolysis, owing to sulphuric acid market price ratio is relatively low, dilute sulfuric acid after hydrolysis does not more have recovery value, so the process of spent acid has just become the big defect using oxidation-reduction method to produce Graphene, along with the expansion of production capacity, there is threat greatly in the pollution to environment.Also result in employing oxidation-reduction method production its spent acid processing cost of Graphene to remain high, have impact on the reduction of production cost, thus have impact on standding high above the masses of Graphene market price, downstream application cost is in, and industrial chain is difficult to the situation formed.
Summary of the invention
It is an object of the invention to for the above-mentioned problems in the prior art, it is provided that a kind of technique is simple, production cost is low, the production method of the Graphene that environmental pollution is little.
The purpose of the present invention can be realized by following technical proposal: the production method of a kind of Graphene, it is characterised in that comprise the following steps that:
1) low temperature acid solution+crystalline flake graphite+sodium nitrate
2) layer is anti-inserted answers 60-240 minute
3) oxidizer low-temp reaction 30-120 minute
4) middle temperature is reacted 60-180 minute
5) solid-liquid separation
6) 60-120 minute-pickling of high-temperature hydrolysis-deionized water cleans-dries
7) high temperature reduction stripping-graphene powder.
In the production method of above-mentioned a kind of Graphene, the temperature of the low temperature acid solution in described step 1) is 4 DEG C
In the production method of above-mentioned a kind of Graphene, described step 5) have employed first solid-liquid separation, then the method for pyrohydrolysis.The liquid separated recycling is made to become possibility.
In the production method of above-mentioned a kind of Graphene, in described step 1), low temperature acid solution is to produce solid-liquid separation solution out and the mixed liquor of fresh concentrated sulphuric acid 1:1 during Graphene for previous time.
Compared with prior art, the production method of this Graphene has the advantage that
1, solid-liquid separation liquid recycling out, decreases the pollution to environment.
2, changing the processing scheme of graphite oxide, directly peeled off by conventional ultrasound wave, electronation and cold drying operation use high temperature to peel off, reduction treatment scheme, have directly obtained Graphene, enormously simplify production process, have reduced production cost.
Detailed description of the invention
Hereinafter technical scheme is further described, but the present invention is not limited to these embodiments.
The production method of this Graphene is:
1, reclaiming acid solution 100-200ml, add concentrated sulphuric acid 100-200ml, stirring is cooled to less than 4 DEG C (1:1 volume ratios).
2, layer is anti-inserted answers: adds natural flake graphite 10-15 gram, sodium nitrate 5-10 gram, stirs 60 minutes-240 minutes.
3, oxidation reaction: add 30-45 gram of potassium permanganate, stir 60 minutes
4, it is warmed to 35 degree of-50 degree stir 60 minutes-180 minutes.
5, solid, liquid separates, and liquids recovery treats that next time is again with (repeating above-mentioned 1 step sequence).
6, hydrolysis: isolated precipitate adds deionized water 200 400ml, puts into hydrolysis 60-120 minute in the water-bath being warmed to more than 95 degree.
7, separating reaction thing.
8, cleaning more than 4 times with 1:10 deionized water hydrochloric acid solution, use deionized water instead and clean more than 4 times after cleanout fluid not containing sulfate radicals, not chloride ion-containing in cleanout fluid, cleaning terminates.
9, solid-liquid separation post-drying (after can also disperseing with deionized water, ultrasound wave peels off to obtain graphene oxide), obtains graphite oxide.
10, graphite oxide heat treatment between 250 degree-500 is spent obtained Graphene after 30 minutes.
Specific embodiment described herein is only to present invention spirit explanation for example.Described specific embodiment can be made various amendment or supplements or use similar mode to substitute by those skilled in the art, but without departing from the spirit of the present invention or surmount appendedClaimScope defined in book.
Although the term such as the most more employing, but it is not precluded from using the probability of other term.Use these terms to be only used to more easily to describe and explain the essence of the present invention；It is all contrary with spirit of the present invention for being construed as any additional restriction.
Claims (4)
1. the production method of a Graphene, oxidation and the recovery of oxidized rear acidic materials including natural flake graphite, it is characterized in that: restored acid material is continuing with in upper once oxidizing process, the above-mentioned reuse reclaiming acidic materials constitutes oxidation solution next time together with the acidic materials of fresh interpolation, foregoing acidic materials are sulphuric acid, isolate the oxidation solution that acidic materials and fresh sulphuric acid become the natural flake graphite of a new round with the proportions of 1:1 after oxidized operation.
The production method of a kind of Graphene the most according to claim 1, it is characterized in that, described mixed oxidization solution adds crystalline flake graphite and a certain amount of sodium nitrate, carry out under conditions of low temperature layer anti-inserted should, layer anti-inserted answer 60 minutes after add oxidant potassium permanganate carry out oxidation reaction, oxidation reaction experience low-temperature oxidation reaction and middle temperature oxidation reaction, low-temperature oxidation reaction condition is 4 ± 0.5 degrees centigrade, 60 240 minutes time, middle temperature oxidation reaction condition is 40 ± 0.5 degrees centigrade, 60-180 minute time.
The production method of a kind of Graphene the most according to claim 2, it is characterised in that described middle temperature redox reaction continues, after completing, the reaction that is hydrolyzed, hydrolysis is at 95 degree, completes after lasting 120 minutes；The addition of the water of hydrolysis is 1:1 with the amount ratio of oxidation solution, and after clean through hydrochloric acid solution, deionized water cleans, centrifugal dry after obtain graphene oxide.
The production method of a kind of Graphene the most according to claim 3, it is characterised in that described Graphene is the form the few-layer graphene alkene of 5-8 layer.
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| CN201610418050.0A CN105936504A (en) | 2016-06-15 | 2016-06-15 | Production method of graphene |
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| CN201610418050.0A CN105936504A (en) | 2016-06-15 | 2016-06-15 | Production method of graphene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108046248A (en) * | 2017-11-24 | 2018-05-18 | 广东聚石化学股份有限公司 | A kind of method for preparing graphene with graphene production waste water |
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| CN108046248A (en) * | 2017-11-24 | 2018-05-18 | 广东聚石化学股份有限公司 | A kind of method for preparing graphene with graphene production waste water |
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