CN109264700A - A method of graphene is prepared from graphene oxide - Google Patents
A method of graphene is prepared from graphene oxide Download PDFInfo
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- CN109264700A CN109264700A CN201811492933.1A CN201811492933A CN109264700A CN 109264700 A CN109264700 A CN 109264700A CN 201811492933 A CN201811492933 A CN 201811492933A CN 109264700 A CN109264700 A CN 109264700A
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Abstract
The present invention provides a kind of methods for preparing graphene from graphene oxide, which comprises prepares low layer number graphene oxide；Low layer number graphene oxide is restored, obtains low layer number graphene, wherein preparing low layer number graphene oxide includes: to be dispersed in water graphene oxide, and form graphene oxide hydrogel；Graphene oxide hydrogel is placed at the first temperature and the first pressure, so that the hydrone in graphene oxide hydrogel is congealed into ice and molecule and sublimates, obtain the graphene oxide of low layer number；It include: that low layer number graphene oxide is obtained into low layer number graphene by self gravity sequence experience temperature and pressure differential responses area to the reduction of low layer number graphene oxide.The present invention obtains low layer number graphene oxide by the method being freeze-dried, and will not destroy the structure of oxidized graphite flake layer, preferably preservation functional group；It can make full use of graphene and melt the high feature of boiling point, metal, the nonmetallic inclusion in graphene can be removed.
Description
Technical field
The present invention relates to technical field of new material preparation, more specifically, are related to one kind from graphene oxide and prepare graphite
The method of alkene.
Background technique
Currently, the graphene preparation method of mainstream has mechanical stripping method, oxidation-reduction method, epitaxial growth method, chemical vapor
Sedimentation etc., wherein oxidation-reduction 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 becomes industrialized production most popular method.But in the method for preparing graphene, on the one hand, use
The graphene of oxidation-reduction method preparation, since during aoxidizing intercalation, the crystal structure of its own is easily broken, and is led
It causes graphene internal flaw to increase, significantly affects the performance of graphene；On the other hand, it is produced using oxidation-reduction method
Graphene there is also a large amount of metals, nonmetallic inclusion, this also further affects large-scale development and the application 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 one kind can serialization using graphene oxide prepare stone
The method of black alkene.
To achieve the goals above, of the invention to provide a kind of method for preparing graphene from graphene oxide, it is described
Method may comprise steps of: prepare low layer number graphene oxide；Low layer number graphene oxide is restored, low layer number stone is obtained
Black alkene, wherein described the step of preparing low layer number graphene oxide includes: that containing functional group and will contain with first number of plies
The graphene oxide of metal impurities and/or nonmetallic inclusion is dispersed in water, and forms graphene oxide hydrogel；Stone will be aoxidized
Black alkene hydrogel is placed at the first temperature and the first pressure, the molecule so that hydrone in graphene oxide hydrogel congeals into ice
And sublimate, to obtain the graphene oxide with second number of plies, first number of plies is ten several layers to tens of layers, described second
The number of plies is less than first number of plies, and first temperature is not higher than -50 DEG C and temperature change is no more than ± 4 DEG C, described first
Pressure is lower than 1 atmospheric pressure and pressure change is no more than ± 100Pa；Described the step of restoring to low layer number graphene oxide, wraps
It includes: low layer number graphene oxide being undergone into vertically arranged the i-th reaction zone and the n-th reaction zone by gravity sequence, is obtained
Graphene, and the temperature of n-th reaction zone and pressure are controlled as TnAnd Pn, by the temperature of i-th reaction zone and
Pressure is 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, P0Indicate 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.
In an exemplary embodiment for preparing the method for graphene from graphene oxide in the present invention, first number of plies
It can be 20 layers~30 layers, second number of plies can be 5 layers~7 layers.
In an exemplary embodiment for preparing the method for graphene from graphene oxide in the present invention, first temperature
It can be selected within the scope of -55~-65 DEG C and temperature change is no more than ± 2 DEG C.
In an exemplary embodiment for preparing the method for graphene from graphene oxide in the present invention, first pressure
It can be selected in the range of 10~100Pa and pressure change is no more than ± 10Pa.
In an exemplary embodiment for preparing the method for graphene from graphene oxide in the present invention, the graphite oxide
The solid content of alkene hydrogel can be 0.1~50wt%.
It is described to low layer number in an exemplary embodiment for preparing the method for graphene from graphene oxide in the present invention
Graphene oxide restore the step of may include: by low layer number graphene oxide by gravity sequence undergo it is vertically arranged
The i-th reaction zone and jth reaction zone of first reaction member, and the temperature of i-th reaction zone and pressure are controlled as Ti
And Pi, the temperature of the jth reaction zone and pressure are controlled as TjAnd Pj, obtain first material；By first material by weight
Power sequence of operation undergoes the m reaction zone and the n-th reaction zone of the second vertically arranged reaction member, and the m is reacted
The temperature and pressure in area are controlled as TmAnd Pm, the temperature of n-th reaction zone and pressure are controlled as TnAnd Pn, receive
Collect graphene, wherein the Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), Tj=k1·j/n·Tn, Pj=(P0-
Pn) (1-j/n), the i gets all natural numbers less than or equal to j, and j is natural number and >=1, w1And k10.80~
The T is selected between 1.20m=w2·m/n·Tn, Pm=(P0-Pn) (1-m/n), the m gets greater than j and is less than or equal to
All natural numbers of n, n are natural number and n >=2, w2It is selected between 0.80~1.20, P0Indicate 1 standard atmospheric pressure, TnWith
PnRespectively 1250 DEG C or more and 30Pa~500Pa.
In an exemplary embodiment for preparing the method for graphene from graphene oxide in the present invention, the metal impurities
It can be one of iron, manganese, potassium and sodium or a variety of, the nonmetallic inclusion can be one or both of sulphur, silicon.
It is described to low layer number in an exemplary embodiment for preparing the method for graphene from graphene oxide in the present invention
The step of graphene oxide restores can also include that air-flow is passed through into reaction zone to control the low layer number graphene oxide and exist
Decrease speed in reaction zone.
It is described to low layer number in an exemplary embodiment for preparing the method for graphene from graphene oxide in the present invention
The step of graphene oxide restores can also include the steps that recycling the metal impurities and/or nonmetallic inclusion.
Compared with prior art, the beneficial effect comprise that
(1) present invention obtains the graphene oxide of low layer number by the method being freeze-dried, and will not destroy oxidized graphite flake
Layer structure, preferably preservation functional group, it is freeze-dried after graphite oxide be not susceptible to agglomeration；
(2) dry greater than other drying means by the lamella interlamellar spacing of freeze-dried obtained low layer number graphene oxide
Graphene oxide product after dry has superior dispersion performance, the less number of plies and bigger specific surface area；
(3) present invention using high-temperature low-pressure make under different temperature, pressure region by force the graphene oxide of low layer number according to
It reacts by self gravity experience reaction zone, graphene is prepared, take full advantage of graphene and melt the high feature of boiling point；?
In low pressure environment, metal, the nonmetallic inclusion in graphene can be removed by high temperature, and remove graphene oxide institute simultaneously
A large amount of oxygen-containing functional groups of band, repair graphene oxide during the preparation process caused by SP3Hydridization defect；
(4) 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；
(5) the low layer number graphene impurity content that the present invention is prepared is low, and fault of construction is few, and the number of plies is lower, comprehensive
It can be excellent.
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:
The process for the method that the slave graphene oxide that Fig. 1 shows an illustrative embodiment of the invention prepares graphene is shown
It is intended to.
Fig. 2 shows an illustrative embodiment of the invention to the reaction zone in low layer number graphene oxide reduction step
Arrangement schematic diagram.
Specific embodiment
Hereinafter, it will be described in detail in conjunction with attached drawing and exemplary embodiment according to the present invention a kind of from graphite oxide
The method that alkene prepares graphene.
The process for the method that the slave graphene oxide that Fig. 1 shows an illustrative embodiment of the invention prepares graphene is shown
It is intended to.Fig. 2 shows an illustrative embodiment of the invention to the reaction zone cloth in low layer number graphene oxide reduction step
Set schematic diagram.
The present invention provides a kind of methods for preparing graphene from graphene oxide, of the invention from graphene oxide system
In one exemplary embodiment of the method for standby graphene, as shown in Figure 1, the method may include:
Step S100 prepares low layer number graphene oxide using freeze-drying method.
Step S200 makes the graphene oxide of the low layer number react in different reaction zones, obtains low layer number
Graphene.
Specifically, described to use freeze-drying method for step S100, prepare low layer number graphene oxide
Step may include:
Step S110 forms graphene oxide hydrogel.
Graphene oxide with first number of plies is dispersed in water, and forms graphene oxide hydrogel.Wherein, described
First number of plies can be for ten several layers to tens of layers, for example, 20~30 layers.Contain oxygen-containing functional group in graphene oxide.For example, institute
State the graphene oxide with first number of plies can be by being prepared using Bronsted acid intercalated graphite.In dispersion process, preferably
Further strengthen dispersion effect by ultrasonic disperse, thus make hydrone well into the lamellar structure to graphene oxide or
In person's fold, or with the functional groups of surface of graphene oxide graphene oxide hydrogel is formed at hydrated ion.Oxidation
Graphene hydrogel, which has, is combined with structure of water molecules in the lamella or fold of the graphene oxide of its own.Aoxidize stone
The solid content of black alkene hydrogel can be 0.1~50wt%.Water for dispersing graphene oxide is preferably secondary deionized water.
The graphene oxide of first number of plies can contain metal and/or nonmetallic inclusion.The metal impurities can be with
It is combined including one or more of iron, manganese, potassium, sodium etc..The nonmetallic inclusion may include one of impurity such as sulphur, silicon
Or two kinds of combinations.The processing for passing through low-voltage high-temperature environment in step s 200, can will contain above-mentioned in low layer number graphite
Impurity is removed.
The graphene oxide of first number of plies can be containing including one in carboxyl, hydroxyl, carbonyl, ehter bond and epoxy group
Kind or a variety of functional groups.
Step S120 carries out cryogenic vacuum freeze-drying to graphene oxide hydrogel.
Graphene oxide hydrogel is placed at the first temperature and the first pressure, so that the water in graphene oxide hydrogel
Molecule, which congeals into ice, molecule and sublimates, to obtain the graphene oxide with second number of plies to get to low layer number graphite oxide
Alkene.Also, the first temperature is controlled as not higher than -50 DEG C and the temperature change of the first temperature is no more than ± 4 DEG C always, the first pressure
It is controlled as by force being no more than ± 100Pa always lower than the variation of 1 atmospheric pressure and the first pressure.Further, the first temperature can
With the selection within the scope of -55~-65 DEG C and temperature change is no more than ± 2 DEG C.First pressure can be in the range of 10~100Pa
It selects and pressure change is no more than ± 10Pa.
Wherein, second number of plies is less than first number of plies.Under second number of plies can have significantly compared to first number of plies
Drop.Here, second number of plies can be the 1/3~1/6 of first number of plies.For example, second number of plies can be 5~7 layers.
It is not higher than 1 standard atmospheric pressure by being not higher than -50 DEG C and by the control of the first pressure by the control of the first temperature,
Hydrone can be made to become ice molecule, by volume expansion, further widen the lamellar structure of graphite；And ice is low in low temperature
The volatilization that can sublimate is depressed, temperature is low, and " entropy " value is low, and the structure for enabling to graphene oxide to be softened is maintained, and makes to prepare
Graphene oxide composite material good dispersion, large specific surface area.Moreover, by relative constant cryogenic temperature (for example, not higher than-
50 DEG C and control the intracorporal temperature change of chamber of entire cold dry chamber and be no more than ± 4 DEG C) and relative constant vacuum degree (for example, low
In 1 atmospheric pressure and the entire intracorporal pressure change of chamber of control is no more than ± 100Pa), is conducive to the rate of set for making hydrone
It is relatively stable with degree, therefore, to " strutting " effect stability of graphene oxide layer；And be conducive to the speed of sublimating for making ice molecule
Degree and degree are relatively stable, therefore, are also beneficial to avoid office caused by the local stress because of graphene oxide layer to a certain degree
Portion's defect.It further says, by the control climate of cold dry chamber is temperature at -55~-65 DEG C by control temperature unit and pressure control unit
In range and the entire intracorporal temperature change of chamber of control is no more than ± 2 DEG C and pressure is controlled in 10~100Pa and controlled entire
The intracorporal pressure change of chamber is no more than ± 10Pa, is more conducive to stablizing the rate of set of hydrone and degree further, from
And to " strutting " effect stability of graphene oxide layer；And be conducive to make ice molecule sublimate speed and degree it is further steady
It is fixed, to be also beneficial to further avoid local defect caused by the local stress because of graphene oxide layer.
Specifically, for step S200, low layer number graphite is prepared by restoring low layer number graphene oxide
May include: in the exemplary embodiment of the step of alkene
The gravity that the graphene oxide of low layer number is utilized to itself, sequentially undergoes vertically arranged along vertical direction
I-th reaction zone and the n-th reaction zone, obtain graphene.Wherein, n is natural number and >=2, i gets all natural numbers less than n.
The reaction zone is respectively arranged with different temperature and pressure, is allowed by the temperature and pressure that control differential responses area
Graphene oxide is reacted.The temperature and pressure of n-th reaction zone are controlled as TnAnd Pn.The TnIt can be 1250
Value in DEG C range above, further, the temperature TnIt can be 1700 DEG C~2500 DEG C, further, the temperature Tn
It can be 1700 DEG C~2200 DEG C.The pressure PnIt can be 30Pa~500Pa, further, the pressure PnIt can be 60Pa
~100P, further, 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, further, w1It can be selected between 0.85~1.14, for example, w1It can be with
Take 0.98.The pressure PiIt can be Pi=(P0-Pn) (1-i/n), wherein P0Indicate 1 standard atmospheric pressure.For example, by institute
It states graphene oxide and undergoes 3 vertically arranged reaction zones respectively.The temperature and pressure of 3rd reaction zone be respectively 1500 DEG C and
100Pa.According to above-mentioned temperature and 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)=0.34 × 105Pa。
For reaction time of the graphene oxide in each reaction zone can based on experience value or actual field operate into
Row determines.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.
For step S200, by restoring the step of low layer number graphene is prepared in low layer number graphene oxide
May include: in one exemplary embodiment
Step S210, as shown in Fig. 2, the first reaction member is added in low layer number graphene oxide.First reaction is single
Member includes j vertically arranged reaction zone.Each reaction zone in the j reaction zone is adjacent in the vertical direction respectively to be set
It sets.The low layer number graphene oxide relies on self gravity, since the 1st reaction zone of the first reaction member, sequence experience the
The i-th reaction zone and jth reaction zone of one reaction member, the i get all natural numbers less than or equal to j, j be natural number and
≥1.By the temperature T for controlling the i-th reaction zoneiWith the pressure P of the i-th reaction zonei, the temperature T of jth reaction zonejWith jth reaction zone
Pressure PjLow layer number graphene oxide is handled, first material is obtained.
The Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), Tj=k1·j/n·Tn, Pj=(P0-Pn)·(1-
J/n), w1And k1Selected between 0.80~1.20.Further, the w1And k1It can be selected between 0.87~1.17,
For example, w1And k1It can be 0.96.
More than, when i is equal with j, i.e. the first reaction member only has a reaction zone.
First material is added in the second reaction member step S220, and the first material relies on the gravity of itself, sequence
Undergo the m reaction zone and the n-th reaction zone being arranged in second reaction member.By the temperature T for controlling m reaction zonem
With pressure Pm, the temperature T of the n-th reaction zonenWith pressure Pn, graphene is prepared.N-m+1 in second reaction member
Reaction zone is disposed adjacent in the vertical direction.Wherein, the Tm=w2·m/n·Tn, Pm=(P0-Pn) (1-m/n), the m
All natural numbers of n are got greater than j and are less than or equal to, n is natural number and n >=2, w2It is selected between 0.80~1.20, P0Table
Show 1 standard atmospheric pressure, TnAnd PnRespectively 1250 DEG C or more and 30Pa~500Pa.Further, the w2It can be 0.88
It is selected between~1.17, for example, w2It can be 0.99.
The temperature TnIt can be 1250 DEG C or more, such as 1250 DEG C~2500 DEG C, further, the temperature TnIt can be with
It is 1700 DEG C~2200 DEG C.The pressure PnIt can be 30Pa~500Pa, further, the pressure PnCan be 60Pa~
100Pa。
More than, undergo each reaction zone to all have the sufficient time in order to preferably control low layer number graphene oxide
It is reacted, when being declined by the low layer number graphene oxide self gravity, due to the reaction ginseng of each area setting
Number is different, will there is the different reaction time in each area.When needing longer there are some or certain several reaction zone reactions
Between when, may will result in reaction zone needs excessive height, cause the preparation cost of equipment to increase, operate have difficulties.
Therefore, n reaction zone of low layer number graphite oxide alkene reaction can be carried out segmentation and set by the excessive height of equipment in order to prevent
It sets.For example, as shown in Figure 1, n reaction zone, which is respectively set, becomes two reaction members.It include j inside first reaction member
Jth of a reaction zone, i.e. low layer number graphene oxide the sequence experience from the first reaction member the 1st reaction zone to the first reaction member
Reaction zone.Then, the obtained first material after jth reaction zone will be undergone to be added in the second reaction member, it is single from the second reaction
1st reaction zone of member starts, and sequence undergoes n-m+1 reaction zone of the second reaction member, after undergoing the n-th reaction zone, instead
It should finish to obtain graphene.
The first material can be low layer number graphene oxide, graphene or low layer number graphene oxide and graphene
Mixture.Due to that can be configured with the reaction member number in the first reaction member, if anti-in the first reaction member
Answer number setting in area's more, also, theoretically speaking, functional group can be removed at 1000 DEG C of temperature or more, but in this temperature
The impurity contained in graphene cannot be effectively removed down, and therefore, first material may be graphene.When the first reaction member
The reaction zone of setting is few, and removal oxygen-containing functional group is not achieved in the final reaction zone temperature that may will have the first reaction member
Purpose, first material at this time may be low layer number graphene oxide.Certainly, if reaching the temperature of abjection functional group,
But undergoing the time of the first reaction member shorter, first material may be the mixing of graphene Yu low layer number graphene oxide
Object.
It, can be with when the first material for obtaining the first reaction member jth reaction zone is added into second reaction zone
First material is transported in the channel that a low pressure is arranged, and second unit is added in first material by way of sucking
In, certainly, first material Adding Way of the invention is without being limited thereto, for example, also may be used using elevating mechanism addition.
More than, since the impurity such as iron, manganese, potassium, sodium, sulphur, silicon may be contained in the graphene oxide of low layer number.In the present invention
High-temperature low-pressure environment under, the metal impurities and nonmetallic inclusion contained in graphene oxide are with gas under high-temperature low-pressure environment
The form of state is volatilized away.At high temperature, such as under 2000 DEG C or so of hot conditions, it can achieve in graphene oxide and contain
The fusing point and boiling point of some metal impurities and nonmetallic inclusion, to be separated from graphene oxide.Further, certain low
Pressure, the fusing point and boiling point of metal impurities and nonmetallic inclusion can reduce further, the temperature that is arranged through the invention and
Vacuum degree is easy to the metal impurities and nonmetallic inclusion contained in removal graphene oxide.Contain in graphene oxide of the invention
The type of some metals and nonmetallic inclusion is not limited to above-described impurity, other can under high temperature and pressure of the invention energy
The impurity enough to volatilize.The reaction being arranged through the invention, ferro element and manganese element in the low layer number graphene being prepared
Content can achieve less than 20PPm.In the existing method for preparing graphene, the content of preparation-obtained graphene is generally all
In 2000PPm or more, the present invention can effectively reduce the impurity iron contained in graphene, can preferably be used in as lithium
Ion battery conductive additive.
For temperature T is arranged in any one exemplary embodiment of step S200nOr TmIt is good for 1250 DEG C or more
It is in if temperature is lower than 1250 DEG C, the volatilization for being unfavorable for impurity is gone out, and fusing point and the boiling of certain impurity may be not achieved
Point.For example, the temperature of setting can be 1250 DEG C~2500 DEG C.If the temperature of setting of the invention is higher than 2800 DEG C, temperature
Too it is high may loss to stove it is serious, energy consumption is larger, higher cost, also, higher temperature will lead to and be prepared
The specific surface area of low layer number graphene becomes smaller.Further, temperature TnOr TmIt can be 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 good for 30Pa~500Pa
It is under above-mentioned pressure vacuum degree, the fusing point and boiling point for the impurity that graphene oxide contains are lower, it is easier to which volatilization is gone
It removes.
For in any one exemplary embodiment of step S200, in the n-th reaction zone and in the reaction of m reaction zone
Time can be 60min~600min.Since the n-th reaction zone and m reaction zone are each reaction member temperature highest, pressure
The smallest reaction zone is the main reaction region of graphene oxide.If heating time is lower than 60min, possible graphene oxide adds
The hot time is inadequate, cannot adequately remove impurity；Heating time is higher than 600min, and heating time is too long, and energy consumption consumption is too big.Into
One step, heating time is 120min~300min.
For in any one exemplary embodiment of step S200, since the graphene oxide of first number of plies may
Containing including one of carboxyl, hydroxyl, carbonyl, ehter bond and epoxy group or a variety of functional groups.Above-mentioned oxygen-containing functional group is at this
It invents the high temperature being arranged and carbon dioxide and water can be decomposed under pressure conditions, can effectively remove in graphene oxide
Oxygen-containing functional group.Theoretically speaking can be removed functional group at 1000 DEG C of temperature and vacuum environment of the invention, but
Be due to impurity removal temperature it is higher, the temperature that the present invention is arranged should be higher than 1250 DEG C.Certainly, of the invention to contain
Oxygen functional group is without being limited thereto, and carbon dioxide and water can be decomposed at temperature and pressure of the invention.
For in any one exemplary embodiment of step S200, on the one hand, in order to preferably control the height of reaction zone
Degree in the reasonable scope, when needing the longer reaction time, avoids the reaction zone excessive height of setting；On the other hand, in order to more
Good control low layer number graphene oxide can be realized and add according to real reaction progress in the time of the reaction of reaction zone
Fast or reduction time of the low layer number graphene oxide by reaction zone.In order to achieve the above object, the preparation method can be with
Including being passed through air-flow into reaction zone, such as it is passed through inert gas, cooperated with the gravity of low layer number graphene oxide itself,
To control the decrease speed of low layer number graphene oxide in the reaction region.When one timing of height of reaction zone setting, if necessary
Low layer number graphene oxide reacts longer time in the reaction, then needs to slow down the decrease speed of low layer number graphene oxide,
The direction of air-flow flowing at this time can be set to decline with low layer number graphene oxide contrary.When not needing low layer number oxygen
When the reaction time of graphite alkene in the reaction region is too long, the direction of air-flow can be set to under low layer number graphene oxide
The direction of drop is consistent, can increase the decrease speed of low layer number graphene oxide.
Since the impurity in graphene oxide can be at the temperature and pressure conditions that the present invention is arranged in gaseous form
Volatilization is gone out, and therefore, can be recycled to the metal impurities and/or nonmetallic inclusion of volatilization.
In conclusion the present invention utilizes the gravity of graphene oxide itself, by the way that different humidity province and pressure is arranged
Strong area completes the preparation of graphene, avoids the even problem of uneven heating in the reaction process of graphene oxide, does not need making
Additional ancillary equipment is provided during standby to transport (oxidation) graphene, preparation efficiency height, it can be achieved that graphene company
Continuous production.The present invention contains the molten boiling point difference of impurity using graphene with it, by the way that different humidity province and pressure area is arranged,
Subregion reaction, while effectively removing impurity, can repair the SP in graphene oxide3Fault of construction and to remove its oxygen-containing
Functional group, and then the higher high-quality graphene of purity is prepared.Temperature range appropriate can make the SP in graphene oxide3
Fault of construction is repaired, then is aided with low pressure condition, can remove a large amount of oxygenated functional groups of graphene oxide institute band, and
Metal and/or nonmetallic inclusion can be removed from graphene oxide in the form of a vapor.Different temperature and pressure area are set,
A pretreatment can be carried out to graphene oxide, be can be realized energy-efficient effect, be can be realized the continuous production of graphene.
Make graphite oxide alkene reaction under the conditions of low pressure, can reduce the fusing point and boiling point of impurity in graphene oxide, and then reduce
Requirement of the preparation process to temperature can achieve the effect of energy conservation and cost squeeze.
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 (9)
1. a kind of method for preparing graphene from graphene oxide, which is characterized in that the described method comprises the following steps:
Prepare low layer number graphene oxide；
Low layer number graphene oxide is restored, low layer number graphene is obtained, wherein
Described the step of preparing low layer number graphene oxide includes:
The graphene oxide containing functional group and containing metal impurities and/or nonmetallic inclusion with first number of plies is dispersed in
In water, and form graphene oxide hydrogel；
Graphene oxide hydrogel is placed at the first temperature and the first pressure, so that the hydrone in graphene oxide hydrogel
It congeals into ice and molecule and sublimates, to obtain the graphene oxide with second number of plies, first number of plies is ten several layers to number
Ten layers, second number of plies be less than first number of plies, first temperature be not higher than -50 DEG C and temperature change be no more than ±
4 DEG C, first pressure is lower than 1 atmospheric pressure and pressure change is no more than ± 100Pa；
It is described to low layer number graphene oxide restore the step of include:
Low layer number graphene oxide is undergone into vertically arranged the i-th reaction zone and the n-th reaction zone by gravity sequence, is obtained
Graphene, and the temperature of n-th reaction zone and pressure are controlled as TnAnd Pn, by the temperature of i-th reaction zone and
Pressure is 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, P0Indicate 1
A standard atmospheric pressure, TnAnd PnRespectively 1250 DEG C or more and 30Pa~500Pa, n is natural number and >=2, i gets the institute less than n
There is natural number.
2. the method according to claim 1 for preparing graphene from graphene oxide, which is characterized in that first number of plies
It is 20 layers~30 layers, second number of plies is 5 layers~7 layers.
3. the method according to claim 1 for preparing graphene from graphene oxide, which is characterized in that first temperature
It is selected within the scope of -55~-65 DEG C and temperature change is no more than ± 2 DEG C.
4. the method according to claim 1 for preparing graphene from graphene oxide, which is characterized in that first pressure
It is selected in the range of 10~100Pa and pressure change is no more than ± 10Pa.
5. the method according to claim 1 for preparing graphene from graphene oxide, which is characterized in that the graphite oxide
The solid content of alkene hydrogel is 0.1~50wt%.
6. the method according to claim 1 for preparing graphene from graphene oxide, which is characterized in that described to low layer number
Graphene oxide restore the step of include:
By low layer number graphene oxide by gravity sequence undergo the first vertically arranged reaction member the i-th reaction zone and
Jth reaction zone, and the temperature of i-th reaction zone and pressure are controlled as TiAnd Pi, by the temperature of the jth reaction zone
T is controlled as with pressurejAnd Pj, obtain first material；
First material is undergone to m reaction zone and the n-th reaction of the second vertically arranged reaction member by gravity sequence
Area, and the temperature of the m reaction zone and pressure are controlled as TmAnd Pm, by the temperature and pressure of n-th reaction zone
It is controlled as TnAnd Pn, collect graphene, wherein
The Ti=w1·i/n·Tn, Pi=(P0-Pn) (1-i/n), Tj=k1·j/n·Tn, Pj=(P0-Pn)·(1-j/
N), the i gets all natural numbers less than or equal to j, and j is natural number and >=1, w1And k1Selected between 0.80~1.20
It selects
The Tm=w2·m/n·Tn, Pm=(P0-Pn) (1-m/n), the m gets greater than j and all less than or equal to n
Natural number, n are natural number and n >=2, w2It is selected between 0.80~1.20, P0Indicate 1 standard atmospheric pressure, TnAnd PnRespectively
1250 DEG C or more and 30Pa~500Pa.
7. the method according to claim 1 for preparing graphene from graphene oxide, which is characterized in that the metal impurities
For one of iron, manganese, potassium and sodium or a variety of, the nonmetallic inclusion is one or both of sulphur, silicon.
8. the method as claimed in any of claims 1 to 7 for preparing graphene from graphene oxide, feature exist
In described the step of restoring to low layer number graphene oxide further includes being passed through air-flow into reaction zone to control low layer number oxidation stone
The decrease speed of black alkene in the reaction region.
9. the method as claimed in any of claims 1 to 7 for preparing graphene from graphene oxide, feature exist
In described the step of restoring to low layer number graphene oxide further includes returning to the metal impurities and/or nonmetallic inclusion
The step of receipts.
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| CN103058179A (en) * | 2013-01-21 | 2013-04-24 | 张家港市东大工业技术研究院 | Method for preparing spongy graphene oxide by using freeze-drying method |
| 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 |
| CN206705681U (en) * | 2017-04-18 | 2017-12-05 | 青岛华高墨烯科技股份有限公司 | A kind of continous way graphene microwave reduction stove |
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| CN103058179A (en) * | 2013-01-21 | 2013-04-24 | 张家港市东大工业技术研究院 | Method for preparing spongy graphene oxide by using freeze-drying method |
| 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 |
| CN206705681U (en) * | 2017-04-18 | 2017-12-05 | 青岛华高墨烯科技股份有限公司 | A kind of continous way graphene microwave reduction stove |
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