CN109292764A - A kind of low impurity content graphene preparation method - Google Patents
A kind of low impurity content graphene preparation method Download PDFInfo
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- CN109292764A CN109292764A CN201811492622.5A CN201811492622A CN109292764A CN 109292764 A CN109292764 A CN 109292764A CN 201811492622 A CN201811492622 A CN 201811492622A CN 109292764 A CN109292764 A CN 109292764A
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Abstract
The present invention provides a kind of low impurity content graphene preparation methods, which comprises purifies to the graphene oxide containing functional group and containing impurity；Graphene oxide after purification is restored, wherein the purifying includes: to mix the graphene oxide containing functional group and containing impurity, complexing agent with acid solution, forms mixed liquor；Ultrasonic vibration is carried out to the mixed liquor, filtering obtains graphene oxide after purification；Described the step of restoring to graphene oxide after purification includes: that graphene oxide sequence after purification is undergone temperature and pressure differential responses area, obtains graphene.Purifying of the invention can effectively be such that graphene oxide and foreign ion separates, and the completeness of graphene oxide purifying can be improved；Prepare graphene under region using in different temperature, pressure, can remove metal, nonmetallic inclusion in graphene, repair graphene oxide during the preparation process caused by SP3Hydridization defect.
Description
Technical field
The present invention relates to technical field of new material preparation, more specifically, it relates to a kind of graphene preparation method.
Background technique
At the beginning of 21 century, there is this material of nano graphite flakes in scientific circles.2006, Britain The University of
The method that two scientists of Manchester are by mechanically pulling off dexterously is prepared for mono-layer graphite, to formally open stone
Therefore the veil of black this material of alkene, two people also obtain Nobel Prize in physics in 2010.Ideal grapheme material has
Mono-layer graphite is constituted, and passes through sp between carbon atom and carbon atom2Hybridized orbit is connected, and forms stable hexatomic ring knot
Structure.The study found that grapheme material has good various physicochemical properties.Such as: than metallic gold, better electronics is led
The general character, mechanical strength more better than steel, the specific surface area of super large, good optical property, superconduction etc..In view of these special property
Matter, grapheme material military affairs, traffic, in terms of have huge application potential.
In the industrial production, graphene oxide powder can be produced on a large scale using oxidation graft process.It is raw to aoxidize graft process
Contain a large amount of impurity in the graphene oxide of production.There are efficiency in washing process for the method for existing purification of graphite oxide alkene
Low, the problems such as washing effect is poor, keeps the graphene oxide product purity of production not high, quality decline.
The method for preparing grapheme material now has mechanical stripping method, epitaxial growth method, CVD method etc., wherein redox
Method due to its is low in cost, production equipment is simple, single yield is maximum, in gas producing formation manifold, the advantages that lateral dimension is uniform at
For industrialized production most popular method.On the one hand, the graphene prepared with oxidation-reduction method, due to the process in oxidation intercalation
In, the crystal structure of its own is easily broken, and is caused graphene internal flaw to increase, is significantly affected graphene
Performance；On the other hand, using the graphene of oxidation-reduction method production, there is also a large amount of metals, nonmetallic inclusion, this is also into one
The large-scale development for affecting graphene of step and application；In another aspect, there is production using oxidation-reduction method production graphene
The problems such as under scale, energy consumption consumption is big, is unable to continuous production, equally will affect the large-scale production of graphene.
Summary of the invention
It is above-mentioned existing in the prior art it is an object of the present invention to solving for the deficiencies in the prior art
One or more problems.For example, one of the objects of the present invention is to provide the systems that one kind can prepare low impurity content graphene
Preparation Method.
To achieve the goals above, the present invention provides a kind of low impurity content graphene preparation method, the preparation sides
Method may include: to purify to the graphene oxide containing functional group and containing impurity；To graphene oxide after purification into
Row reduction, obtains low impurity content graphene, wherein
The step of described pair of graphene oxide containing functional group and containing impurity purifies includes: that will contain functional group
And graphene oxide, the complexing agent containing impurity are mixed with acid solution, form mixed liquor；Ultrasonic shake is carried out to the mixed liquor
It swings, filters, obtain graphene oxide after purification；
Described the step of restoring to graphene oxide after purification includes: to pass through graphene oxide sequence after purification
The i-th reaction zone and the n-th reaction zone are gone through, obtains graphene, and the temperature of n-th reaction zone and pressure are controlled as Tn
And Pn, the temperature of i-th reaction zone and pressure are controlled as TiAnd Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-
Pn) (1-i/n), wherein w1It is selected between 0.80~1.20, P0For 1 standard atmospheric pressure, TnAnd PnRespectively 1250 DEG C with
Upper and 30Pa~500Pa, n are natural number and >=2, i gets all natural numbers less than n.
It is described to contain functional group in an exemplary embodiment of low impurity content graphene preparation method of the invention
And the preparation method of the graphene oxide containing impurity may include: to weigh weight ratio as 0.8~1.2:0.4~0.6:2~4
Graphite, potassium nitrate and potassium permanganate uniformly mix, and the concentrated sulfuric acid is added, obtains the first mixture；By the first mixture respectively at 0 DEG C
Oxidation processes are carried out under~4 DEG C, 35 DEG C~45 DEG C and 80 DEG C~100 DEG C three temperature sections, obtain the second mixture；It is mixed second
It closes addition oxidant in object to be aoxidized, pickling is obtained after washing containing functional group and containing the graphene oxide of impurity.Into one
Step, the graphite can be one of expanded graphite or crystalline flake graphite, can be with described 0 DEG C~4 DEG C of reaction time
For 3h~40h, it can be 2h~6h 35 DEG C~45 DEG C of reaction time, can be 80 DEG C~100 DEG C of reaction time
5min~15min.The oxidant can be hydrogen peroxide.
It is described to after purification in the exemplary embodiment of low impurity content graphene preparation method of the invention
The step of graphene oxide is restored may include: to pass through the feed bin sequence for being contained with first graphene oxide after purification
The i-th reaction zone and the n-th reaction zone for going through the first reaction member, collect the graphene in the feed bin；Is held to the feed bin
Two batches of graphene oxides after purification, and its sequence is made to undergo the jth reaction zone and m reaction zone of the second reaction member, it collects
Graphene in the feed bin；The graphene oxide of third batch after purification is held to the feed bin, and its sequence experience first is anti-
The i-th reaction zone and the n-th reaction zone for answering unit, collect the graphene in the feed bin, wherein the temperature of n-th reaction zone
T is controlled as with pressurenAnd Pn, the temperature and pressure of i-th reaction zone be controlled as TiAnd Pi, wherein Ti=w1·
i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w1It is selected between 0.80~1.20, P0For 1 standard atmospheric pressure, TnAnd Pn
Respectively 1250 DEG C or more and 30Pa~500Pa, n is natural number and >=2, i gets all natural numbers less than n；The m is anti-
The temperature and pressure for answering area are controlled as tmAnd Pm, the temperature and pressure of the jth reaction zone be controlled as tjAnd Pj,
In, tj=k1·j/m·tm, Pj=(P0-Pm) (1-j/m), wherein k1It is selected between 0.80~1.20, P0It is big for 1 standard
Air pressure, tmAnd PmRespectively 1250 DEG C or more and 30Pa~500Pa, m is natural number and >=2, j gets all natures less than m
Number.Further, graphite coating can be set inside the feed bin.
It is described to after purification in the exemplary embodiment of low impurity content graphene preparation method of the invention
The step of graphene oxide is restored may include: to pass through the feed bin sequence for being contained with first graphene oxide after purification
Go through the i-th reaction zone and the n-th reaction zone of the first reaction member；The feed bin enters the 1st reaction zone of the second reaction member, collects
Graphene in the feed bin simultaneously holds the graphene oxide of second batch after purification to the feed bin, and its sequence is made to undergo second
The jth reaction zone and m reaction zone of reaction member；The feed bin enters the 1st reaction zone of the first reaction member, collects the material
Graphene in storehouse simultaneously holds the graphene oxide of third batch after purification to the feed bin, and its sequence undergoes the first reaction member
The i-th reaction zone and the n-th reaction zone, collect the graphene in the feed bin, wherein the temperature and pressure of n-th reaction zone
It is controlled as TnAnd Pn, the temperature and pressure of i-th reaction zone be controlled as TiAnd Pi, wherein Ti=w1·i/n·
Tn, Pi=(P0-Pn) (1-i/n), wherein w1It is selected between 0.80~1.20, P0For 1 standard atmospheric pressure, TnAnd PnRespectively
For 1250 DEG C or more and 30Pa~500Pa, n is natural number and >=2, i gets all natural numbers less than n；The m reaction zone
Temperature and pressure be controlled as tmAnd Pm, the temperature and pressure of the jth reaction zone be controlled as tjAnd Pj, wherein tj
=k1·j/m·tm, Pj=(P0-Pm) (1-j/m), wherein k1It is selected between 0.80~1.20, P0For 1 normal atmosphere
Pressure, tmAnd PmRespectively 1250 DEG C or more and 30Pa~500Pa, m is natural number and >=2, j gets all natural numbers less than m.
Further, graphite coating can be set inside the feed bin.
It is described to after purification in the exemplary embodiment of low impurity content graphene preparation method of the invention
The step of graphene oxide is restored may include: to pass through the feed bin sequence for being contained with first graphene oxide after purification
The i-th reaction zone and the n-th reaction zone are gone through, the graphene in the feed bin is collected；The oxygen of second batch after purification is held to the feed bin
Graphite alkene enters the 1st reaction zone from the n-th reaction zone and its sequence undergoes the i-th reaction zone and the n-th reaction zone, collects the material
Graphene in storehouse, wherein the temperature and pressure of n-th reaction zone are controlled as TnAnd Pn, the temperature of i-th reaction zone
Degree and pressure are controlled as TiAnd Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w10.80
It is selected between~1.20, P0For 1 standard atmospheric pressure, TnAnd PnRespectively 1250 DEG C or more and 30Pa~500Pa, n is natural number
And >=2, i gets all natural numbers less than n.Further, graphite coating can be set inside the feed bin.
It is described to after purification in the exemplary embodiment of low impurity content graphene preparation method of the invention
The step of graphene oxide is restored may include: to pass through the feed bin sequence for being contained with first graphene oxide after purification
Go through the i-th reaction zone and the n-th reaction zone；The feed bin enters the 1st reaction zone, collects the graphene in the feed bin and to the material
Storehouse holds the graphene oxide of second batch after purification, and the feed bin sequence for holding the graphene oxide of second batch after purification passes through
Go through the i-th reaction zone and the n-th reaction zone, into the 1st reaction zone after collect graphene in the feed bin, wherein n-th reaction
The temperature and pressure in area are controlled as TnAnd Pn, the temperature and pressure of i-th reaction zone be controlled as TiAnd Pi, wherein
Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w1It is selected between 0.80~1.20, P0For 1 normal atmosphere
Pressure, TnAnd PnRespectively 1250 DEG C or more and 30Pa~500Pa, n is natural number and >=2, i gets all natural numbers less than n.
Further, graphite coating can be set inside the feed bin.
In an exemplary embodiment of low impurity content graphene preparation method of the invention, the complexing agent can be with
Including citric acid, sodium citrate, sodium thiosulfate, sodium sulfite, sodium ethylene diamine tetracetate, polyacrylic acid, sodium gluconate or
Sodium alginate.
In an exemplary embodiment of low impurity content graphene preparation method of the invention, the impurity be can wrap
Include at least one of manganese, iron, potassium, sodium, sulphur, silicon.Wherein, the complexing agent can be combined with the metal impurities in impurity
To remove part metals impurity, for example, manganese, iron, potassium, sodium etc..At this point, the additional amount of the complexing agent can be can be with impurity
1.0~1.2 times of the theoretical amount of complex reaction.In the step of reduction, high temperature can remove metal and nonmetallic inclusion, example
Such as, manganese, iron, potassium, sodium, sulphur, silicon etc..
In an exemplary embodiment of low impurity content graphene preparation method of the invention, the acid solution can
To include the hydrochloric acid solution that concentration is 0.005~0.02mol/L or the sulfuric acid solution that concentration is 0.01~0.04mol/L.
In an exemplary embodiment of low impurity content graphene preparation method of the invention, the acid solution
PH can be 0.1~6.
In an exemplary embodiment of low impurity content graphene preparation method of the invention, the filtration step packet
It includes and is filtered by filter membrane.
In an exemplary embodiment of low impurity content graphene preparation method of the invention, in the mistake of the filtering
Decompression suction filtration is carried out in journey.
In an exemplary embodiment of low impurity content graphene preparation method of the invention, the ultrasonic shake of the progress
When swinging, the frequency of ultrasonic wave is 50~750Hz.
In an exemplary embodiment of low impurity content graphene preparation method of the invention, the oxygen after purification
The carbon-to-oxygen ratio of graphite alkene can be between 0.5~2.0.
In an exemplary embodiment of low impurity content graphene preparation method of the invention, the functional group can be with
For one of carboxyl, hydroxyl, carbonyl, ehter bond and epoxy group or a variety of.
Compared with prior art, the beneficial effect comprise that
(1) purifying of the invention can effectively be such that graphene oxide and foreign ion separates, and graphite oxide can be improved
The completeness of alkene purifying, purification efficiency are high, at low cost；
(2) present invention prepares graphene under region in different temperature, pressure by force using high-temperature low-pressure, takes full advantage of stone
Black alkene melts the high feature of boiling point.In low pressure environment, metal, the nonmetallic inclusion in graphene can be removed by high temperature, and
Remove a large amount of oxygen-containing functional groups of graphene oxide institute band simultaneously, repair graphene oxide during the preparation process caused by SP3
Hydridization defect.
(3) present invention can pre-process to reduce energy consumption graphene oxide in lower temperature region, can effectively close
Reason utilizes waste heat, can significantly improve reduction efficiency, can be realized the continuous production of graphene.
(4) the graphene impurity content that the present invention is prepared is low, and fault of construction is few, excellent combination property.
Detailed description of the invention
By the description carried out with reference to the accompanying drawing, above and other purpose of the invention and feature will become more clear
Chu, in which:
Fig. 1 show an illustrative embodiment of the invention to the graphene oxide containing functional group and containing impurity into
The flow diagram of row purifying；
Fig. 2 shows carrying out in reduction step to graphene oxide after purification for an illustrative embodiment of the invention
Reaction zone arrangement schematic diagram；
Fig. 3 show another exemplary embodiment of the invention to after purification graphene oxide carry out reduction step
In reaction zone arrangement schematic diagram；
Fig. 4 show further exemplary embodiment of the invention to after purification graphene oxide carry out reduction step
In reaction zone arrangement schematic diagram.
Fig. 5 show further exemplary embodiment of the invention to after purification graphene oxide carry out reduction step
In reaction zone arrangement schematic diagram.
Specific embodiment
Hereinafter, a kind of low impurity content according to the present invention will be described in detail in conjunction with attached drawing and exemplary embodiment
Graphene preparation method.
Specifically, on the one hand, during producing graphene oxide, especially oxidation graft process produces graphene oxide
In the process, foreign ion can be combined together with graphene oxide, this results in the purity of graphene oxide not high.Existing oxygen
Graphite alkene purification process there are inefficiency, it is not thorough enough the problems such as.And the present invention is in the purification process of graphene oxide
The method for applying complexing agent and dilute hydrochloric acid washing simultaneously, and cooperate ultrasonication, more can effectively make graphite oxide with this
Alkene and foreign ion separation, while isolate foreign ion under the action of complexing agent will not again with graphene oxide combine, from
And the completeness of purifying is improved, it avoids it and combines repeatedly.On the other hand, in the existing preparation process for preparing graphene oxide
In, such as using Hummers prepare graphene oxide, comparable metal and/or nonmetallic miscellaneous is contained in the product of preparation
Matter causes the graphene of preparation impure.Also, in existing graphene preparation process, in particular with oxide-reduction method
The graphene of preparation will lead to containing a large amount of metal and/or nonmetallic inclusion in graphene, and in oxidation intercalation process
In, the crystal structure of graphene itself is easily broken, and the internal flaw that will lead to graphene increases, and understands significantly shadow
Ring the performance of graphene.The present invention contains the molten boiling point difference of impurity using graphene with it, by the way that different humidity provinces is arranged
With pressure area, subregion reaction while effectively removing impurity, can repair the SP in graphene oxide3Fault of construction is simultaneously
Its oxygen-containing functional group is removed, and then the higher high-quality graphene of purity is prepared.Temperature range appropriate can make to aoxidize stone
SP in black alkene3Fault of construction is repaired, then is aided with low pressure condition, can remove a large amount of oxidations of graphene oxide institute band
Functional group, and metal and/or nonmetallic inclusion can be removed from graphene oxide in the form of a vapor.Different temperature is set
It spends with pressure area, a pretreatment can be carried out to graphene oxide, and can be rationally using generated in preprocessing process
Waste heat can be realized energy-efficient effect, can be realized the continuous production of graphene.Make graphene oxide under the conditions of low pressure
Reaction can reduce the fusing point and boiling point of impurity in graphene oxide, and then reduce requirement of the preparation process to temperature, Ke Yida
To the effect of energy conservation and cost squeeze.
Fig. 1 show an illustrative embodiment of the invention to the graphene oxide containing functional group and containing impurity into
The flow diagram of row purifying.Fig. 2 shows an illustrative embodiment of the invention to graphene oxide progress after purification
Reaction zone arrangement schematic diagram in reduction step.Fig. 3 show another exemplary embodiment of the invention to after purification
Graphene oxide carries out the reaction zone arrangement schematic diagram in reduction step.Fig. 4 shows the exemplary implementation of another of the invention
The reaction zone arrangement schematic diagram of example graphene oxide after purification carried out in reduction step.Fig. 5 show it is of the invention again
The reaction zone arrangement schematic diagram of one exemplary embodiment graphene oxide after purification carried out in reduction step.
The present invention provides a kind of low impurity content graphene preparation methods, in low impurity content graphene system of the invention
In one exemplary embodiment of Preparation Method, the preparation method may include:
S100 purifies the graphene oxide containing functional group and containing impurity.
S200 restores graphene oxide after purification under high-temperature low-pressure, obtains low impurity content graphene.
More than, the impurity may include at least one of manganese, iron, potassium, sodium, sulphur, silicon.Above-mentioned impurity is usually with ion
Form be present in graphene oxide.In the step s 100, complexing agent used in purification process can in impurity
Metal impurities are combined to remove metal impurities, for example, manganese, iron, potassium, sodium etc..At this point, the additional amount of the complexing agent is energy
1.0~1.2 times of enough and impurity complex reaction theoretical amount.Certainly, it is without being limited thereto that removable metal impurities are complexed, example
Such as, beavy metal impurity or other can be with the impurity in conjunction with complexing agent.After purifying removes partial impurities, in reduction step
In, metal and nonmetallic inclusion can be removed under high-temperature low-pressure environment, for example, manganese, iron, potassium, sodium, sulphur, silicon etc..In high temperature
Under, it can achieve the fusing point and boiling point of the metal impurities and nonmetallic inclusion that contain in graphene oxide, it can be from graphite oxide
It is separated in the form of a vapor in alkene.Under certain low pressure subsidiary conditions, the fusing point and boiling point of metal impurities and nonmetallic inclusion
Can further reduce, by the temperature and vacuum degree of setting be easy in removal graphene oxide the metal impurities that contain and
Nonmetallic inclusion.Cooperate to remove jointly by two stages of reaction of purification process and high-temperature vacuum reaction process and contain in raw material
Impurity can be good at removing oxygen-containing functional group under high-temperature vacuum degree, can obtain the graphene of low impurity content.Existing
It prepares in the method for graphene, the iron content of preparation-obtained graphene is generally all in 2000PPm or more, method of the invention
Ferro element and manganese element content can achieve less than 20PPm in the graphene for the low impurity content being prepared, further, can
To be less than 15ppm, and the impurity such as nitrate ion, chloride ion can also be removed well, can be very good to be used in
As lithium ion battery conductive additive.
After step S100 purifies graphene oxide, graphene oxide after purification can be dried,
Then S200 step is carried out again.But since S200 step is the oxygen reacted under different temperature, pressure, after purification
When graphite alkene starts to carry out S200 step reaction, what is initially entered is that temperature is lower, the biggish reaction zone of pressure, in this way can be right
Graphene oxide after purification is dried, therefore, it may not be necessary to carry out one individually to graphene oxide after purification
Drying process is conducive to shorten reaction process.
The functional group that the graphene oxide after purification contains is oxygen-containing functional group, and the oxygen-containing functional group may include
One of carboxyl, hydroxyl, carbonyl, ehter bond and epoxy group are a variety of.Oxygen-containing function contained by graphene oxide before purification
The type of group is identical as the type of oxygenated functional group contained by graphene oxide after purification.
In the present embodiment, as shown in Figure 1, in the step s 100, to containing functional group and containing the graphite oxide of impurity
Alkene carries out purifying
S110 mixes the graphene oxide containing functional group and containing impurity, complexing agent with acid solution, is formed
Mixed liquor.
The complexing agent may include citric acid, sodium citrate, sodium thiosulfate, sodium sulfite, sodium ethylene diamine tetracetate, gather
The combination of one or more of acrylic acid, sodium gluconate and sodium alginate.
Liquid reactions environment needed for the acid solution is capable of providing reaction.Acid solution may include that concentration is 0.005
The hydrochloric acid solution or concentration of~0.02mol/L is the dilution heat of sulfuric acid of 0.01~0.04mol/L, further, dilute hydrochloric acid concentration
It can be 0.01mol/L, dilute sulfuric acid concentration can be 0.02mol/L.Further, acid solution may include dilute hydrochloric acid solution, this is
It, can be faster using dilute hydrochloric acid because a certain amount of sulfuric acid can be contained in the graphene oxide ontology of intercalation oxidizing process preparation
Clean graphene oxide.
S120 carries out ultrasonic vibration to the mixed liquor.
The purpose of the concussion is to enable in the graphene oxide containing can be with the impurity and network in conjunction with complexing agent
Mixture stable bond.
When carrying out ultrasound, the frequency of ultrasonic wave can be 50~750Hz, and the supersonic frequency of the range can make graphite oxide
Foreign ion in alkene functional group preferably removes.
The weight percent of the foreign ion on graphene oxide after purification can be not higher than 0.01%；The removal rate of impurity
Up to 99% or more.
S130, filtering, obtains graphene oxide after purification.
The filtering can be filtered by filter membrane, so that graphene oxide after purification and the solution comprising impurity
To separation.Wherein, graphene oxide stays on filter layer, and the solution containing impurity can penetrate filter membrane.The filter membrane can
Including polycarbonate membrane (i.e. PC film).Further, also pressure-reduction filter device can be set in the lower section of filter layer, so that containing miscellaneous
The solution of matter preferably penetrates filter layer.Wherein, it can realize that decompression filters by the way that vacuum pump is arranged under filter membrane.
When being filtered using filter membrane, the method may further comprise the step of: is arranged buffer protection on filter membrane
Layer, influence of the ultrasonic wave to filter membrane when absorbing and buffer ultrasonic vibration.Buffer protection layer may include sponge.
More than, the purification process, which may further comprise the step of:, carries out detection ion concentration to the obtained graphene oxide
Detection, to determine whether graphene oxide also needs to continue to purify.Wherein, ICP (Inductively can be passed through
Coupled Plasma, inductively coupled plasma) ion concentration detector detected.
In the present embodiment, for step S200, graphene oxide after purification is carried out restoring under high-temperature low-pressure
It may comprise steps of to graphene:
Successively experience temperature i-th reaction zone different with pressure and the n-th reaction in order by graphene oxide after purification
Area is reacted, and graphene oxide is obtained, wherein n is natural number and >=2, i gets all natural numbers less than n.
The temperature T of n-th reaction zonenIt indicates, pressure PnIt indicates.Here temperature TnIt can be 1250 DEG C or more.
Further, the temperature TnIt can be 1700 DEG C~2800 DEG C, further, 1700 DEG C~2800 DEG C, further,
Temperature TnIt can be 2200 DEG C.Since 2200 DEG C be carbon material graphitization temperature, and also help and repair graphene oxide
Self-defect.The pressure PnIt can be 30Pa~500Pa, further, the pressure PnIt can be 60Pa~100Pa.More into
One step, the pressure PnIt can be 85Pa~95Pa.
The temperature T of i-th reaction zoneiIt indicates, pressure PiIt indicates.The temperature TiIt can be Ti=w1·i/n·
Tn, wherein w1It is selected between 0.80~1.20.The pressure PiIt can be Pi=(P0-Pn) (1-i/n), wherein P0It is 1
A standard atmospheric pressure.Different temperature and pressure is arranged in different reaction zones, can preferably pre-process to graphene oxide,
Graphene oxide impurity elimination can be more advantageous to and go functional group's process, can be improved the production efficiency of graphene oxide.Further
, w1It can be selected between 0.85~1.14, for example, w10.98 can be taken.For example, graphene oxide undergoes to the 1st respectively,
2nd and the 3rd totally 3 reaction zones.The temperature and pressure of 3rd reaction zone are respectively set to 1500 DEG C and 100Pa.According to above-mentioned temperature
With pressure formula, w is taken1The temperature for being the 0.9, the 1st reaction zone is T1=0.9 × 1/3 × 1500=450 DEG C, pressure P1=
(1.01×105- 100) (1-1/3)=0.67 × 105Pa, the temperature of the 2nd reaction zone are T2=0.9 × 2/3 × 1500=900
DEG C, pressure P1=(1.01 × 105- 100) × (1-2/3)=0.64 × 105Pa。
More than, for reaction time of the graphene oxide in each reaction zone can based on experience value or actual field grasp
It is determined.For example, it is assumed that the reaction time in the n-th reaction zone is tn, then the reaction time of the i-th reaction zone can be ti=
r1·i/n·tn, the r1It can be selected between 0.9~1.1.
In the present embodiment, for step S200, the schematic layout pattern of reaction zone and reaction member as shown in Figure 2.Knot
Close attached drawing 2, graphene oxide after purification is restored to obtain graphene under high-temperature low-pressure may include:
Step S210 will be contained with feed bin sequence first reaction member of experience of first graphene oxide after purification
I-th reaction zone and the n-th reaction zone, collect the graphene in the feed bin.Wherein, the temperature of n-th reaction zone and pressure point
T is not may be controlled tonAnd Pn, the temperature and pressure of i-th reaction zone may be controlled to T respectivelyiAnd Pi, wherein Ti=w1·
i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w1It is selected between 0.80~1.20, P0For 1 standard atmospheric pressure, n is certainly
It so counts and >=2, i gets all natural numbers less than n.
The temperature TnIt can be 1250 DEG C or more, further, the temperature TnIt can be 1700 DEG C~2200 DEG C.More
Further, temperature TnIt can be 2200 DEG C.Since 2200 DEG C be carbon material graphitization temperature, and also help reparation oxidation
The self-defect of graphene.The pressure PnIt can be 30Pa~500Pa.Further, the pressure PnCan be 60Pa~
100Pa。
More than, the feed bin for being loaded with first graphene oxide after purification passes through different temperatures and pressure respectively
Region carries out heating reaction, then takes out the graphene that reaction is prepared in final reaction zone.Feed bin is due to having centainly
Waste heat, it is not necessary to be taken out in final reaction zone, and be directly entered the 1st reaction zone of the second reaction member, material can be efficiently used
Storehouse waste heat improves reaction efficiency, energy saving.
Further, w1It can be selected between 0.85~1.14, for example, w10.95 can be taken.
Step S220, after the n-th reaction zone of the first reaction member takes out the graphene being prepared, to the feed bin
It is middle that the graphene oxide of second batch after purification is added.Since feed bin has had certain temperature in the n-th reaction zone, will hold
There is the feed bin of the graphene oxide of second batch to be after purification directly entered the first reaction zone of the second reaction member, and passes through its sequence
The jth reaction zone and m reaction zone for going through the second reaction member, collect the graphene in the feed bin, obtain second batch graphene.
Wherein, the temperature of the m reaction zone and pressure are controlled as tmAnd Pm, the temperature and pressure of the jth reaction zone control respectively
It is made as tjAnd Pj.Wherein, tj=k1·j/m·tm, Pj=(P0-Pm) (1-j/m), wherein k1It is selected between 0.80~1.20,
P0For 1 standard atmospheric pressure, m is natural number and >=2, j gets all natural numbers less than m.The temperature TmIt can be 1250 DEG C
More than, further, the temperature TmIt can be 1700 DEG C~2200 DEG C.The pressure PmIt can be 30Pa~500Pa, into one
Step, the pressure PmIt can be 85Pa~95Pa.Further, k1It can be selected between 0.83~1.16, for example, w1It can
To take 0.92.
More than, the discharge port of the n-th reaction zone of the first anti-unit and the 1st reaction zone of the second reaction member into
Material mouth is disposed adjacent.After first graphite oxide alkene reaction after purification is completed to take out product graphene, it is pure that second batch is added
Graphene oxide after change, the feed bin for filling the graphene oxide of second batch after purification enter the 1st reaction of the second reaction member
Area is reacted in the reaction zone of the second reaction member.Feed bin for just going out first the n-th reaction zone of reaction member has one
Fixed waste heat, when entering the second reaction member, can use the waste heat of feed bin to second batch graphene oxide after purification into
Row heating, may be implemented the effective use to high temperature material waste heat, energy saving.
Step S230, when the graphene oxide of second batch after purification the second reaction member after the reaction was completed, it is anti-second
It answers the n-th reaction zone of unit to take out second batch graphene, and the graphene oxide of third batch after purification is added simultaneously, and its sequence
The i-th reaction zone and the n-th reaction zone for undergoing the first reaction member, are collected the graphene in the feed bin, are recycled with this, realize stone
The continuous production of black alkene.
More than, the discharge port of the m reaction zone of second reaction member and the 1st reaction zone of the first reaction member
Feed inlet is disposed adjacent, the 1st reaction zone of the discharge port and the second reaction member of the n-th reaction zone of first reaction member
Feed inlet is disposed adjacent, and can be formed a continuous circular response region in this way, be can be realized the continuous production of graphene.
Likewise, third is added and criticizes after purification after the graphite oxide alkene reaction of second batch after purification is completed to take out product graphene
Graphene oxide.The feed bin for filling the graphene oxide of third batch after purification enters the 1st reaction zone progress of the first reaction member
Reaction.The second reaction member after the reaction was completed, fill the graphene oxide of third batch after purification feed bin have it is certain remaining
Heat can use graphite oxide of the waste heat of feed bin to third batch after purification when entering 1 reaction zone of the first reaction member
Alkene is heated, and realizes the effective use to feed bin waste heat.
Likewise, in reaction time and previous embodiment in each reaction zone of graphene oxide in the present embodiment
Graphene oxide can be identical in the time that each reaction zone reacts.
In the present embodiment, for step S200, as shown in figure 3, to graphene oxide after purification under high-temperature low-pressure
Restored to obtain graphene may include:
Step S210 will be contained with feed bin sequence first reaction member of experience of first graphene oxide after purification
I-th reaction zone and the n-th reaction zone.Wherein, the temperature of n-th reaction zone and pressure are controlled as TnAnd Pn, described i-th is anti-
The temperature and pressure for answering area are controlled as TiAnd Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein
w1It is selected between 0.80~1.20, P0For 1 standard atmospheric pressure, n is natural number and >=2, i gets all natures less than n
Number.
The temperature TnIt can be 1250 DEG C~2500 DEG C, further, the temperature TnIt can be 1700 DEG C~2200
℃.The pressure PnIt can be 30Pa~500Pa, further, the pressure PnIt can be 60Pa~100Pa.
Step S220, the feed bin enter the 1st reaction zone of the second reaction member, collect graphene in the feed bin simultaneously
The graphene oxide of second batch after purification is held to the feed bin, and makes the jth reaction zone of its sequence the second reaction member of experience
With m reaction zone, wherein the temperature and pressure of the m reaction zone are controlled as tmAnd Pm, the jth reaction zone
Temperature and pressure be controlled as tjAnd Pj, wherein tj=k1·j/m·tm, Pj=(P0-Pm) (1-j/m), wherein k1?
It is selected between 0.80~1.20, P0For 1 standard atmospheric pressure, m is natural number and >=2, j gets all natural numbers less than m.Institute
State temperature TmIt can be 1250 DEG C or more, further, the temperature TmIt can be 1700 DEG C~2200 DEG C.The pressure PmIt can
To be 30Pa~500Pa, further, the pressure PmIt can be 60Pa~100Pa.For example, second reaction member has 3
A reaction zone needs the oxidation stone of second batch after purification after the graphene oxide of second batch after purification is added in the 1st reaction zone
The 1st reaction zone of black alkene sequence experience, the 2nd reaction zone and the 3rd reaction zone.
More than, the discharge port of the m reaction zone of second reaction member and the 1st reaction zone of the first reaction member
Feed inlet is disposed adjacent, the 1st reaction zone of the discharge port and the second reaction member of the n-th reaction zone of first reaction member
Feed inlet is disposed adjacent, and can be formed a continuous circular response region in this way, be can be realized the continuous production of graphene.
When the graphene that first graphene oxide after purification is prepared after the reaction was completed is n-th anti-not in the first reaction member
It answers in area and takes out, but further taken out after the 1st reaction zone for entering the second reaction member, it is such to be advantageous in that, on the one hand, by
It has surplus heat, waste heat can be utilized again in feed bin, the graphene oxide of second batch after purification can be carried out to add in advance
Heat, energy saving；On the other hand, the temperature and pressure in holding the n-th reaction zone of the first reaction member of limits can be done；Again
On the one hand, since the pressure of the 1st reaction zone of the second reaction member is less than the pressure of first the n-th reaction zone of reaction member, such as
Fruit takes out graphene in the n-th reaction zone, will certainly reveal more air pressures, causes to waste.Therefore, lower in temperature, pressure
The graphene that first is prepared in 1st reaction zone of strong the second relatively low reaction member takes out, and then adds the
The reaction was continued for two batches of graphene oxides after purification, can be significant energy saving.
Step S230, when the graphene oxide of second batch after purification the second reaction member after the reaction was completed, the feed bin
Into the 1st reaction zone of the first reaction member, collects the graphene in the feed bin and hold third batch purifying to the feed bin
Graphene oxide afterwards, and its sequence undergoes the i-th reaction zone and the n-th reaction zone of the first reaction member, is recycled with this, completes stone
The continuous production of black alkene.
More than, it is taken out in the 1st reaction zone of the first reaction member likewise, second batch is prepared in graphene, and
The effect that the graphene oxide of third batch after purification obtains is added simultaneously to be prepared with above-described first in graphene
It is taken out in the 1st reaction zone of the second reaction member, and the effect that the graphene oxide of second batch after purification obtains is added simultaneously
It is identical.
In the present embodiment, for step S200, as shown in figure 4, to graphene oxide after purification under high-temperature low-pressure
Restored to obtain graphene may include:
Step S210 will be contained with feed bin sequence experience i-th reaction zone and n-th of first graphene oxide after purification
Reaction zone collects the graphene in the feed bin.Wherein, the temperature of n-th reaction zone and pressure are controlled as TnAnd Pn,
The temperature and pressure of i-th reaction zone are controlled as TiAnd Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-Pn)·(1-
I/n), wherein w1It is selected between 0.80~1.20, P0For 1 standard atmospheric pressure, n is natural number and >=2, i is got less than n's
All natural numbers.
The temperature TnIt can be 1250 DEG C or more, further, the temperature TnIt can be 1700 DEG C~2200 DEG C.Institute
State pressure PnIt can be 30Pa~500Pa, further, the pressure PnIt can be 85Pa~95Pa.
More than, the feed bin for being loaded with first graphene oxide after purification passes through different temperatures and pressure respectively
Region carries out heating reaction, then takes out the graphite that is prepared in final reaction zone, and feed bin is due to certain waste heat, directly
It taps into next reaction zone, feed bin waste heat can be efficiently used, improve reaction efficiency, energy saving.
The graphene oxide of second batch after purification is added in step S220 in the feed bin for taking out graphene, and its sequence passes through
The i-th reaction zone and the n-th reaction zone are gone through, the graphene in the feed bin is collected, wherein the discharge port and the 1st of n-th reaction zone
The feed inlet of reaction zone is connected.
More than, the n reaction zone is in end to end annular setting, the i.e. feed inlet and the n-th reaction zone of the 1st reaction zone
Discharge port connection.When first graphene oxide after purification the n-th reaction zone after the reaction was completed, take out the stone being prepared
Black alkene, while the graphene oxide of second batch after purification is added, feed bin is directly entered the 1st reaction zone, in the n-th reaction zone, collects
The graphene being prepared, and the graphene oxide of third batch after purification is added simultaneously, it circuits sequentially, realizes the continuous of graphene
Production.
Likewise, for the parameter phase being arranged in the parameter and exemplary embodiment above that are arranged in the present exemplary embodiment
Together.
In the present embodiment, for step S200, as shown in figure 5, to graphene oxide after purification under high-temperature low-pressure
Restored to obtain graphene may include:
Step S210 will be contained with feed bin sequence experience i-th reaction zone and n-th of first graphene oxide after purification
Reaction zone.Wherein, the temperature of n-th reaction zone and pressure are controlled as TnAnd Pn, the temperature and pressure of i-th reaction zone
It is controlled as T by forceiAnd Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w10.80~1.20
Between select, P0For 1 standard atmospheric pressure, n is natural number and >=2, i gets all natural numbers less than n.The temperature TnIt can
Think 1250 DEG C or more, further, the temperature TnIt can be 1700 DEG C~2200 DEG C.The pressure PnCan be 30Pa~
500Pa, further, the pressure PnIt can be 60Pa~100Pa.
Step S220, when first described graphene oxide after purification after the reaction was completed, obtained graphene is with material
Storehouse enters the 1st reaction zone, i.e. the feed inlet of the discharge port of the n-th reaction zone and the 1st reaction zone is connected to.It is obtained at first
It after graphene enters the 1st reaction zone, takes out graphene and the graphene oxide of second batch after purification is added, then from the 1st reaction
Area starts, and sequence undergoes the i-th reaction zone and the n-th reaction zone, until the graphite oxide alkene reaction of second batch after purification is completed, with this
The graphene oxide of subsequent batches is added, to realize the continuous production of graphene.
More than, likewise, taking out the graphene being prepared in the 1st reaction member and graphene oxide to be reacted being added
It is advantageous in that, on the one hand, since feed bin has surplus heat, waste heat can be utilized again, it can be to second batch after purification
Graphene oxide is heated in advance, energy saving；On the other hand, the temperature in the n-th reaction zone of holding of limits can be done
And pressure；In another aspect, since the pressure of the 1st reaction zone is less than the pressure of the n-th reaction zone, if will in the n-th reaction zone
Graphene takes out, and will certainly reveal more air pressures, cause to waste.Therefore, lower in temperature, the 1st relatively low reaction of pressure
The graphene that first is prepared in area takes out, and then adding the graphene oxide of second batch after purification, the reaction was continued,
It can significant energy saving.
In the embodiment of above-mentioned any one step S200, temperature T is setnOr TmBenefit for 1250 DEG C or more exists
In if temperature is lower than 1250 DEG C, the volatilization for being unfavorable for impurity is gone out, and the fusing point and boiling point of certain impurity may be not achieved.Example
Such as, the temperature of setting can be 1250 DEG C~2800 DEG C, for example, the temperature of setting can be 1250 DEG C~2500 DEG C.The present invention
If the temperature of setting be higher than 2800 DEG C, temperature too it is high may loss to stove it is serious, energy consumption is larger, higher cost,
Also, the specific surface area that higher temperature will lead to the graphene being prepared becomes smaller.Further, temperature TnOr TmIt can
Think 2200 DEG C.Since 2200 DEG C be carbon material graphitization temperature, and also help the self-defect for repairing graphene oxide.
Pressure P is setnIt is advantageous in that for 30Pa~500Pa, under above-mentioned pressure vacuum degree, the fusing point for the impurity that graphene oxide contains
It is lower with boiling point, it is easier to volatilization removal.
In the embodiment of above-mentioned any one step S200, in the n-th reaction zone and in the time of m reaction zone reaction
It can be 60min~600min.Since the n-th reaction zone and m reaction zone are each reaction member temperature highest, pressure is minimum
Reaction zone, be graphene oxide main reaction region.If heating time is lower than 60min, when the heating of possible graphene oxide
Between not enough, cannot adequately remove impurity；Heating time is higher than 600min, and heating time is too long, and energy consumption consumption is too big.Further
, heating time is 120min~300min.
In the embodiment of above-mentioned any one step S200, graphene oxide after purification may contain metal impurities
Iron, manganese, potassium or sodium etc., nonmetallic inclusion sulphur or silicon etc..The metal impurities and nonmetallic inclusion contained are under high-temperature low-pressure environment
It is to volatilize away in the form of a vapor.At high temperature, such as under 2000 DEG C or so of hot conditions, it can achieve oxygen after purification
The fusing point and boiling point of the metal impurities and nonmetallic inclusion that contain in graphite alkene, to divide from graphene oxide after purification
From.Further, under certain low pressure, the fusing point and boiling point of metal impurities and nonmetallic inclusion can be reduced further, be led to
It crosses the temperature that is arranged of the present invention and vacuum degree is easy to remove metal impurities contained in graphene oxide after purification and non-
Metal impurities.The type of the metal and nonmetallic inclusion that contain in graphene oxide after purification of the invention is not limited to the above institute
The impurity stated, other impurity that can be volatilized under high temperature and pressure of the invention.
In the embodiment of above-mentioned any one step S200, oxygen-containing functional group packet in the graphene oxide after purification
Include one of carboxyl, hydroxyl, carbonyl, ehter bond and epoxy group or a variety of.I.e. purifying object is containing functional group and to contain impurity
Graphene oxide in the functional group contained may include one of carboxyl, hydroxyl, carbonyl, ehter bond and epoxy group or a variety of.
Above-mentioned oxygen-containing functional group can be decomposed into carbon dioxide and water under the high temperature and pressure conditions that the present invention is arranged, can be effective
The removal oxygen-containing functional group in graphene oxide after purification.Theoretically speaking in 1000 DEG C of temperature and vacuum of the invention
Functional group can be removed under environment, but since the temperature of impurity removal is higher, the temperature that the present invention is arranged should be high
In 1250 DEG C.Certainly, oxygen-containing functional group of the invention is without being limited thereto, can be decomposed into titanium dioxide at temperature and pressure of the invention
Carbon and water.
In the embodiment of above-mentioned any one step S200, in order to avoid feed bin impacts graphene purity, and
And since the fusing point of graphite is up to 3652 DEG C, much higher than the molten boiling point of common metal impurity and nonmetallic inclusion, and treatment process
In, it should it avoids introducing other elements impurity because of feed bin material in graphene.Therefore, it is possible to use graphite feed bin or
It is coated with the feed bin of graphite linings on surface, for example, graphite alms bowl.But the present invention is not limited to this, and the feed bin material also can be selected
Other the molten higher materials of boiling point, such as tungsten foil, tantalum carbide feed bin or hafnium carbide feed bin etc..In order to make the heated of graphene oxide
Area is bigger, is conducive to sufficiently removal impurity, while in a certain amount of situation of graphene oxide, generating the bigger graphite of area
Alkene, it is preferable that pave the graphene oxide after purification in the feed bin.
In the embodiment of above-mentioned any one step S200, the carbon-to-oxygen ratio that contains in the graphene oxide after purification
It can be between 0.5~2.0.Carbon-to-oxygen ratio highest can achieve 2 (C:O=2:1).After method reaction of the invention, graphite
Carbon-to-oxygen ratio in alkene can be improved to 18 or more, for example, can achieve 20.Oxygen mainly from the oxygen-containing official in graphene oxide
It can roll into a ball, oxygen content is lower, shows that the performance for the graphene that the quantity of oxygen-containing functional group is fewer, is prepared is better.
In an embodiment of the present invention, the preparation method of the graphene oxide containing functional group and containing impurity can be with
Include:
Weighing weight ratio is that 0.8~1.2:0.4~0.6:2~4 graphite, potassium nitrate and potassium permanganate uniformly mix, and is added
Enter the concentrated sulfuric acid, obtains the first mixture.The mass ratio of the graphite, potassium nitrate and potassium permanganate can be 0.85~1.1:0.4
~0.6:2~3, for example, the mass ratio of graphite, potassium nitrate and potassium permanganate can be 1:0.5:3.The additional amount of the concentrated sulfuric acid
It can be empirical value, such as the corresponding concentrated sulfuric acid that 115mL~3450mL 98% is added of graphite of 5g~150g.The graphite can
Think one of expanded graphite or crystalline flake graphite.
First mixture is subjected to oxygen under 0 DEG C~4 DEG C, 35 DEG C~45 DEG C and 80 DEG C~100 DEG C three temperature sections respectively
Change processing, obtains the second mixture.First mixture needs to undergo three constant temperature oxidation times of low, medium and high temperature
Section.It can be 3h~40h described 0 DEG C~4 DEG C of reaction time, can be 2h~6h 35 DEG C~45 DEG C of reaction time,
It can be 5min~15min 80 DEG C~100 DEG C of reaction time.The oxidant can be hydrogen peroxide.Certainly, the present invention exists
The time reacted under above-mentioned each temperature section is without being limited thereto, can be adjusted according to real reaction situation.
Oxidant is added in the second mixture to be aoxidized, pickling, washing is obtained containing functional group and containing impurity
Graphene oxide.The oxidant can be hydrogen peroxide.
Certainly, the graphene oxide of the invention containing functional group and containing impurity is not limited in above-mentioned preparation method
It is prepared.Graphene oxide containing functional group and containing impurity of the invention can include carboxyl, hydroxyl, carbonyl for functional group
One of base, ehter bond and epoxy group are a variety of, and impurity is the metal impurities such as manganese, iron, potassium, sodium, sulphur, silicon or nonmetallic inclusion
Graphene oxide.
In conclusion method of the invention can effectively be such that graphene oxide and foreign ion separates, oxygen can be improved
The completeness of graphite alkene purifying, purification efficiency are high, at low cost；It can be using high-temperature low-pressure by force in different temperature, pressure area
Graphene is prepared under domain, graphene is taken full advantage of and melts the high feature of boiling point；Can be in low pressure environment, it can by high temperature
Metal, the nonmetallic inclusion in graphene are removed, and removes a large amount of oxygen-containing functional groups of graphene oxide institute band simultaneously, repairs oxygen
Graphite alkene during the preparation process caused by SP3Hydridization defect；Can be effective and reasonable utilize waste heat, can significantly improve also
Former efficiency can be realized the continuous production of graphene；The graphene impurity content being prepared is low, and fault of construction is few, comprehensive
It has excellent performance.
Although those skilled in the art should be clear above by combining exemplary embodiment to describe the present invention
Chu can carry out exemplary embodiment of the present invention each without departing from the spirit and scope defined by the claims
Kind modifications and changes.
Claims (10)
1. a kind of low impurity content graphene preparation method, which is characterized in that the preparation method comprises the following steps:
Graphene oxide containing functional group and containing impurity is purified；
Graphene oxide after purification is restored, low impurity content graphene is obtained, wherein
The step of described pair of graphene oxide containing functional group and containing impurity purifies include:
Graphene oxide containing functional group and containing impurity, complexing agent are mixed with acid solution, form mixed liquor；To described
Mixed liquor carries out ultrasonic vibration, and filtering obtains graphene oxide after purification；
Described the step of restoring to graphene oxide after purification includes:
By graphene oxide sequence experience the i-th reaction zone and the n-th reaction zone after purification, graphene is obtained, and by described n-th
The temperature and pressure of reaction zone are controlled as TnAnd Pn, the temperature of i-th reaction zone and pressure are controlled as TiWith
Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w1It is selected between 0.80~1.20, P0It is 1
Standard atmospheric pressure, TnAnd PnRespectively 1250 DEG C or more and 30Pa~500Pa, n is natural number and >=2, i gets owning less than n
Natural number.
2. low impurity content graphene preparation method according to claim 1, which is characterized in that it is described containing functional group simultaneously
The preparation method of graphene oxide containing impurity includes:
Weighing weight ratio is that 0.8~1.2:0.4~0.6:2~4 graphite, potassium nitrate and potassium permanganate uniformly mix, and is added dense
Sulfuric acid obtains the first mixture；
First mixture is carried out at oxidation under 0 DEG C~4 DEG C, 35 DEG C~45 DEG C and 80 DEG C~100 DEG C three temperature sections respectively
Reason, obtains the second mixture；
Oxidant is added in the second mixture to be aoxidized, pickling is obtained after washing containing functional group and containing the oxygen of impurity
Graphite alkene.
3. low impurity content graphene preparation method according to claim 1, which is characterized in that described to oxygen after purification
The step of graphite alkene is restored include:
The i-th reaction zone and the of feed bin sequence first reaction member of experience of first graphene oxide after purification will be contained with
N reaction zone collects the graphene in the feed bin；
The graphene oxide of second batch after purification is held to the feed bin, and the jth for making its sequence undergo the second reaction member is anti-
Area and m reaction zone are answered, the graphene in the feed bin is collected；
The graphene oxide of third batch after purification is held to the feed bin, and its sequence undergoes the i-th reaction of the first reaction member
Area and the n-th reaction zone, collect the graphene in the feed bin, wherein
The temperature and pressure of n-th reaction zone are controlled as TnAnd Pn, the temperature and pressure of i-th reaction zone control respectively
It is made as TiAnd Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w1It is selected between 0.80~1.20,
P0For 1 standard atmospheric pressure, TnAnd PnRespectively 1250 DEG C or more and 30Pa~500Pa, n is natural number and >=2, i gets and is less than
All natural numbers of n；
The temperature and pressure of the m reaction zone are controlled as tmAnd Pm, the temperature and pressure of the jth reaction zone control respectively
It is made as tjAnd Pj, wherein tj=k1·j/m·tm, Pj=(P0-Pm) (1-j/m), wherein k1It is selected between 0.80~1.20,
P0For 1 standard atmospheric pressure, tmAnd PmRespectively 1250 DEG C or more and 30Pa~500Pa, m is natural number and >=2, j gets and is less than
All natural numbers of m.
4. low impurity content graphene preparation method according to claim 1, which is characterized in that described to oxygen after purification
The step of graphite alkene is restored include:
The i-th reaction zone and the of feed bin sequence first reaction member of experience of first graphene oxide after purification will be contained with
N reaction zone；
The feed bin enters the 1st reaction zone of the second reaction member, collects the graphene in the feed bin and contains to the feed bin
The graphene oxide of second batch after purification is put, and makes the jth reaction zone and m reaction zone of its sequence the second reaction member of experience；
The feed bin enters the 1st reaction zone of the first reaction member, collects the graphene in the feed bin and contains to the feed bin
The graphene oxide of third batch after purification is put, and its sequence undergoes the i-th reaction zone and the n-th reaction zone of the first reaction member, received
Collect the graphene in the feed bin, wherein
The temperature and pressure of n-th reaction zone are controlled as TnAnd Pn, the temperature and pressure of i-th reaction zone control respectively
It is made as TiAnd Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w1It is selected between 0.80~1.20,
P0For 1 standard atmospheric pressure, TnAnd PnRespectively 1250 DEG C or more and 30Pa~500Pa, n is natural number and >=2, i gets and is less than
All natural numbers of n；
The temperature and pressure of the m reaction zone are controlled as tmAnd Pm, the temperature and pressure of the jth reaction zone control respectively
It is made as tjAnd Pj, wherein tj=k1·j/m·tm, Pj=(P0-Pm) (1-j/m), wherein k1It is selected between 0.80~1.20,
P0For 1 standard atmospheric pressure, tmAnd PmRespectively 1250 DEG C or more and 30Pa~500Pa, m is natural number and >=2, j gets and is less than
All natural numbers of m.
5. low impurity content graphene preparation method according to claim 1, which is characterized in that described to oxygen after purification
The step of graphite alkene is restored include:
It will be contained with feed bin sequence i-th reaction zone of experience and the n-th reaction zone of first graphene oxide after purification, collects institute
State the graphene in feed bin；
The graphene oxide of second batch after purification is held to the feed bin, enters the 1st reaction zone and its sequence warp from the n-th reaction zone
The i-th reaction zone and the n-th reaction zone are gone through, the graphene in the feed bin is collected, wherein
The temperature and pressure of n-th reaction zone are controlled as TnAnd Pn, the temperature and pressure of i-th reaction zone control respectively
It is made as TiAnd Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w1It is selected between 0.80~1.20,
P0For 1 standard atmospheric pressure, TnAnd PnRespectively 1250 DEG C or more and 30Pa~500Pa, n is natural number and >=2, i gets and is less than
All natural numbers of n.
6. low impurity content graphene preparation method according to claim 1, which is characterized in that described to oxygen after purification
The step of graphite alkene is restored include:
Feed bin sequence i-th reaction zone of experience and the n-th reaction zone of first graphene oxide after purification will be contained with；
The feed bin enters the 1st reaction zone, collects the graphene in the feed bin and holds second batch after purification to the feed bin
Graphene oxide, and feed bin sequence i-th reaction zone of experience for holding the graphene oxide of second batch after purification and n-th anti-
Answer area, into the 1st reaction zone after collect graphene in the feed bin, wherein
The temperature and pressure of n-th reaction zone are controlled as TnAnd Pn, the temperature and pressure of i-th reaction zone control respectively
It is made as TiAnd Pi, wherein Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), wherein w1It is selected between 0.80~1.20,
P0For 1 standard atmospheric pressure, TnAnd PnRespectively 1250 DEG C or more and 30Pa~500Pa, n is natural number and >=2, i gets and is less than
All natural numbers of n.
7. the low impurity content graphene preparation method according to any one of claim 3 to 6, which is characterized in that institute
It states feed bin and is internally provided with graphite coating.
8. low impurity content graphene preparation method according to claim 1, which is characterized in that the acid solution includes
The sulfuric acid solution that the hydrochloric acid solution or concentration that concentration is 0.005~0.02mol/L are 0.01~0.04mol/L.
9. low impurity content graphene preparation method according to claim 1, which is characterized in that the pH of the acid solution
It is 0.1~6.
10. low impurity content graphene preparation method according to claim 1, which is characterized in that the ultrasonic shake of the progress
When swinging, the frequency of ultrasonic wave is 50Hz~750Hz.
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| CN103250739A (en) * | 2012-08-20 | 2013-08-21 | 苏州大学 | Preparation method and application of graphene oxide/silver particle nano composite |
| CN103395780A (en) * | 2013-08-19 | 2013-11-20 | 济宁利特纳米技术有限责任公司 | Method for reducing manganese content in graphene oxide |
| CN106809821A (en) * | 2017-01-19 | 2017-06-09 | 广东烛光新能源科技有限公司 | The preparation method of Graphene |
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