CN109250709A - A kind of production system preparing graphene using low layer number graphene oxide - Google Patents
A kind of production system preparing graphene using low layer number graphene oxide Download PDFInfo
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- CN109250709A CN109250709A CN201811494486.3A CN201811494486A CN109250709A CN 109250709 A CN109250709 A CN 109250709A CN 201811494486 A CN201811494486 A CN 201811494486A CN 109250709 A CN109250709 A CN 109250709A
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Abstract
The present invention provides a kind of production systems that graphene is prepared using low layer number graphene oxide.The production system includes graphene oxide purification devices, low layer number graphene oxide preparation facilities and reduction apparatus, wherein, the graphene oxide purification devices include first charging aperture, tank body, first partition, second partition, supersonic generation unit and the first discharge port；The purifying graphene that the low layer number graphene oxide preparation facilities is used to obtain graphene oxide purification devices carries out freeze-drying process, including hydrogel forms unit, low temperature drying unit and transport mechanism；The reduction apparatus includes that the graphene oxide with second number of plies obtained to low layer number graphene oxide preparation facilities restores, including feed bin, walking mechanism, reaction member and atmosphere control unit.System structure of the invention is simple, high production efficiency, and graphene oxide undergoes reaction member by self gravity, can be realized the continuous production of graphene.
Description
Technical field
The present invention relates to technical field of graphene preparation, more particularly, are related to a kind of utilization low layer number graphene oxide
Prepare the production system of graphene.
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.On the one hand, the graphene prepared with oxidation-reduction method, by
During aoxidizing intercalation, the crystal structure of its own is easily broken, and causes graphene internal flaw to increase, very greatly
The performance for affecting graphene of degree；On the other hand, using the graphene of oxidation-reduction method production, there is also a large amount of metals, non-
Metal impurities, 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 by self gravity experience reaction zone and
Prepare the graphene production system of low impurity content.
To achieve the goals above, of the invention to provide a kind of life that graphene is prepared using low layer number graphene oxide
Production system, the production system may include graphene oxide purification devices, low layer number graphene oxide preparation facilities and go back
Original device, wherein
The graphene oxide purification devices include first charging aperture, tank body, first partition, second partition, ultrasound generation
Unit and the first discharge port, wherein the first partition and second partition are arranged in tank body along the cross section of tank body, by tank
Body is divided into the reaction zone, filtering area and collecting region being sequentially distributed up and down, and being provided in the first partition can be by reaction zone
The retractable component being connected to filtering area is provided with the filter element that can be realized separation of solid and liquid on the second partition；It is described
First charging aperture is arranged on tank body top and is connected to the reaction zone, so that purifying object, complexing agent and acid solution pass through
The feed inlet enters the reaction zone, and the purifying object includes being combined with foreign ion in functional group and having first number of plies
Graphene oxide；First discharge port is arranged on the side wall of tank body and is located above the second partition, heavy to be discharged
Graphene oxide of the product on the filter element after purification, the graphene oxide after purification are the oxygen with first number of plies
Graphite alkene；The supersonic generation unit is arranged in the reaction zone, to provide ultrasound environments to reaction zone, makes complex reaction
Sufficiently carry out；
The low layer number graphene oxide preparation facilities includes that hydrogel forms unit, low temperature drying unit and conveyer
Structure, wherein the hydrogel, which forms unit, has dispersion slot, and the dispersion slot can receive water and first discharge port discharge
Graphene oxide after purification, and graphene oxide after purification is dispersed in water, to form graphene oxide hydrogel；
The low temperature drying unit has control temperature unit, pressure control unit and cold dry chamber, wherein the cold dry chamber is constituted and had by shell
Second charging aperture, the second discharge port and cavity, the control temperature unit are used for the intracorporal temperature control of the chamber as not higher than -50
DEG C and the entire intracorporal temperature change of chamber of control be no more than ± 4 DEG C, the pressure control unit is used for the intracorporal pressure control of the chamber
It is made as lower than 1 atmospheric pressure and the entire intracorporal pressure change of chamber of control is no more than ± 100Pa；The transport mechanism, which has, to be run through
The transmission parts of the cold dry chamber and the speed adjusting gear that can adjust transmission parts travel speed, the transmission parts are for receiving institute
Hydrogel is stated to form graphene oxide hydrogel that unit is formed and make the graphene oxide hydrogel after entire cold dry chamber,
To obtain the graphene oxide with second number of plies from second discharge port, second number of plies is less than first number of plies；
The reduction apparatus may include reaction member and atmosphere control unit, wherein the reaction member includes vertical
The i-th reaction zone and the n-th reaction zone being linked in sequence on direction, the reaction member are configured to receive described with second
The graphene oxide of the number of plies simultaneously makes the graphene oxide with second number of plies successively undergo reaction by self gravitation effect
The i-th reaction zone and the n-th reaction zone of unit react, and n is natural number and >=2, i gets all natural numbers less than n；It is described
Control climate unit includes mutually matched temperature control mechanism and control vacuum mechanism, wherein temperature control mechanism is configured to institute
The temperature control for stating the n-th reaction zone is Tn, and the temperature of i-th reaction zone is controlled as Ti, wherein Ti=w1·i/n·Tn,
w1It is selected between 0.80~1.20, TnIt is 1250 DEG C or more；The control vacuum mechanism is configured to react described n-th
The pressure control in area is Pn, and the pressure of i-th reaction zone is controlled as Pi, wherein Pi=(P0-Pn) (1-i/n), P0Table
Show 1 standard atmospheric pressure, PnFor 30Pa~500Pa.
Compared with prior art, the beneficial effect comprise that
(1) it so that graphene oxide and foreign ion is separated using system of the invention, oxidation can be improved
The completeness of graphene purifying, purification efficiency height, at low cost, features simple structure, are easy to use and transport, occupied area are small；
(2) oxidized graphite flake layer will not be destroyed using the freezing dry process of system processing graphene oxide of the invention
Structure, preferably preservation functional group, it is freeze-dried after graphite oxide be not susceptible to agglomeration；Freeze-dried oxidation
Graphene sheet layer interlamellar spacing be greater than other drying means it is dry after graphene oxide product, have superior dispersion performance,
The less number of plies and bigger specific surface area；
(3) rely on the graphene oxide of low layer number by the different temperature of setting, pressure region using the system of invention
Self gravity experience reaction zone reacts, and can pre-process to graphene oxide, can be improved the production effect of graphene
Rate；
(4) system of the invention takes full advantage of the high feature of the molten boiling point of graphene, is removed in graphene by high temperature
Metal, nonmetallic inclusion, while removing a large amount of oxygen-containing functional groups of graphene oxide institute band, graphene oxide can be repaired and existed
SP resulted in preparation process3Hydridization defect, is able to produce to obtain that impurity content is low, and fault of construction is few, excellent combination property
Graphene；
(5) system structure of the invention is simple, high production efficiency, and the continuous production of graphene may be implemented.
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 shows in the low impurity content graphene continuous process system of an illustrative embodiment of the invention and aoxidizes stone
Black alkene purification devices schematic diagram；
Fig. 2 shows also original-pack in the low impurity content graphene continuous process system of an illustrative embodiment of the invention
Set schematic diagram.
Marginal data:
10- first charging aperture, the sub- feed inlet of 11- first, the sub- feed inlet of 12- second；20- reaction zone, 21- ultrasonic wave occur
Device, 22- first partition；30- filtering area, 31- second partition, the first discharge port of 32-, 33-ICP ion concentration detector, 34- are slow
Rush layer, 40- collecting region, 41- liquid outlet, 42- vacuum pump.
Specific embodiment
Hereinafter, utilization low layer number according to the present invention will be described in detail in conjunction with attached drawing and exemplary embodiment to aoxidize
Graphene prepares the production system of graphene.
Fig. 1 shows in the low impurity content graphene continuous process system of an illustrative embodiment of the invention and aoxidizes stone
Black alkene purification devices schematic diagram；Fig. 2 shows the low impurity content graphene continuous productions of an illustrative embodiment of the invention
Reduction apparatus schematic diagram in system.
The present invention provides a kind of production systems that graphene is prepared using low layer number graphene oxide, in benefit of the invention
It is prepared in an exemplary embodiment of the production system of graphene with low layer number graphene oxide, the production system can wrap
Include graphene oxide purification devices, low layer number graphene oxide preparation facilities and reduction apparatus.
In exemplary embodiments of the present invention, as shown in Figure 1, graphene oxide purification devices can be integrated.
Purification devices include tank body, and first charging aperture 10 is provided at the top of tank body, and first charging aperture 10 includes the first sub- feed inlet 11
With the second sub- feed inlet 12；First partition 22 that tank body is successively laterally arranged from top to bottom, second partition 31 are isolated into reaction
Area 20, filtering area 30 and collecting region 40.Supersonic generator 21 is provided in reaction zone 20.Being provided in first partition 22 can open
Component is closed, the opening of retractable component is equipped with metal coarse filtration sieve (not shown).Second partition 31 may include filtering
Component (not shown).The bottom of filtering area 30 is provided with the first discharge port 32, and it is dense that the first discharge port 32 is provided with ICP ion
Spend detector 33.It further include the buffer layer 34 being arranged on second partition in filtering area 30.The bottom of collecting region 40 is provided with
Liquid outlet 41, vacuum pump 42.Retractable component in first partition 22 connects reaction zone 20 and filtering area 30, the
Filter element on 31 on two partitions connects filtering area 30 and collecting region 40.
The graphene oxide with first number of plies containing impurity can enter from the first sub- feed inlet 11, complexing agent and dilute salt
Acid can enter from the second sub- feed inlet 12；The impurity heavy metal ion contained in complexing agent and graphene oxide network in acid condition
It closes, then complex compound and the lesser graphene oxide of size and foreign ion are entered by the retractable component in first partition 22
To filtering area 20；Buffer protection layer 34 can slow down impact of the ultrasonic wave to the membrane structure in 31 filter element of second partition,
Due to vacuum filtration system (the inverted U-shaped cavity of the annular of vacuum pump 42 and collecting region) effect, complex compound and foreign ion are in negative pressure
It is filtered under effect and arrives collecting region 30, the lesser graphene oxide of size is purified, can flow out, can lead to from the first discharge port 32
The graphene oxide residual ion concentration with first number of plies of the detection of ICP ion concentration detector 33 after purification is crossed, and contains network
The waste liquid for closing object and impurity acid ion can be flowed out from liquid outlet 41.
Obtain the graphene oxide with first number of plies after purification in the first discharge port of purification devices, by ICP from
The sub- detection of concentration detector 33 detects it, and testing result shows on the graphene oxide with first number of plies after purification
The weight percent of foreign ion is 0.005% hereinafter, foreign ion removal rate reaches 99% or more.
In exemplary embodiments of the present invention, the low layer number graphene oxide preparation facilities can receive the oxidation stone
Black alkene purification devices graphene oxide after purification simultaneously carries out freeze-drying process to it.The system of the low layer number graphene oxide
Standby device can be formed unit, low temperature drying unit and transport mechanism by hydrogel and be constituted.
The hydrogel, which forms unit, has dispersion slot.Dispersion slot can receive in the graphene oxide purification devices
The graphene oxide and water with first number of plies after purification of one discharge port discharge, and will be after purification with first number of plies
Graphene oxide be dispersed in water, to form graphene oxide hydrogel.For example, dispersion slot can have groove body, setting exists
The second feed opening above groove body and the second discharge port that groove body side or bottom are set.Wherein, the second feed opening is used for
The graphene oxide and water with first number of plies after purification as raw material is added.Here, first number of plies can be ten
Several layers to tens of layers, for example, 20~30 layers.Second discharge port is for being discharged graphene oxide hydrogel.In addition, the hydrogel
Forming unit can be further provided with ultrasonic generating mechanism.The ultrasound generating mechanism can emit ultrasonic wave to the dispersion slot,
To form ultrasonic vibration to the graphene oxide in the water in dispersion slot, to be conducive to strengthen dispersion effect.
The graphene oxide with first number of plies after purification can be dispersed in water by dispersion slot, and form oxidation
Graphene hydrogel.As containing oxygen-containing functional group in the graphene oxide of raw material.For example, the oxidation with first number of plies
Graphene can be by being prepared using Bronsted acid intercalated graphite.It is preferably further strong by ultrasonic disperse in dispersion process
Change dispersion effect, thus make hydrone well into the lamellar structure to graphene oxide perhaps in fold or with oxidation
The functional groups of graphene surface form graphene oxide hydrogel at hydrated ion.Graphene oxide hydrogel has
Structure of water molecules are combined in the lamella or fold of the graphene oxide of its own.The solid content of graphene oxide hydrogel
It can be 0.1~50wt%.
The low temperature drying unit has control temperature unit, pressure control unit and cold dry chamber.Wherein, the cold dry chamber is enclosed by shell
At and with feed inlet, discharge port and the cavity for determining length.The cavity of cold dry chamber can be U-shaped or with annular jaggy,
To save space.However, present exemplary embodiment is not limited to this, the cavity of cold dry chamber can also S-type or linear type.Feed inlet
The front-end and back-end of cavity are separately positioned on along the direction of travel of material with discharge port, and are each provided with openable and closable valve
Cavity and the external world to be separated.The control temperature unit can be the refrigeration for connecting and having constant temperature control function with cold dry chamber
The control of the chamber of cold dry chamber intracorporal temperature not higher than -50 DEG C and can be controlled the chamber of entire cold dry chamber by machine, the refrigeration machine
Intracorporal temperature change is no more than ± 4 DEG C.Also, the pressure control unit can be to connect and with constant pressure control function with cold dry chamber
The vacuum pump of energy, the vacuum pump can be by the intracorporal pressure controls of the chamber of the cold dry chamber for lower than 1 atmospheric pressure and control
The entire intracorporal pressure change of chamber is no more than ± 100Pa.
Further, the control temperature unit can be by the intracorporal temperature control of the chamber is within the scope of -55~-65 DEG C and control is whole
A intracorporal temperature change of chamber is no more than ± 2 DEG C, and the pressure control unit can by the control of the chamber intracorporal pressure 10~
The 100Pa and entire intracorporal pressure change of chamber of control is no more than ± 10Pa, has both metastable low temperature to help to obtain
And the atmosphere of metastable vacuum degree.
By the coordinative role of control temperature unit and pressure control unit, hydrone can be made to become ice molecule, by volume expansion,
Further widen the lamellar structure of graphite；And ice can sublimate volatilization under low-temp low-pressure, and temperature is low, and " entropy " value is low, can
So that the structure that graphene oxide is softened is maintained, make graphene oxide composite material good dispersion, the large specific surface area of preparation.
Moreover, by relative constant cryogenic temperature (for example, the intracorporal temperature of chamber for being not higher than -50 DEG C and the entire cold dry chamber of control becomes
Change and be no more than ± 4 DEG C) and relative constant vacuum degree (for example, lower than 1 atmospheric pressure and controlling the entire intracorporal pressure change of chamber
No more than ± 100Pa), be conducive to the rate of set for making hydrone and degree is relatively stable, therefore, to graphene oxide layer
" strutting " effect stability；And be conducive to make ice molecule sublimate speed and degree it is relatively stable, therefore, be also beneficial to certain journey
Degree avoids local defect caused by the local stress because of graphene oxide layer.It further says, passes through control temperature unit and pressure control
Unit is temperature within the scope of -55~-65 DEG C for the control climate of cold dry chamber and the entire intracorporal temperature change of chamber of control does not surpass
± 2 DEG C and pressure control are crossed in 10~100Pa and the entire intracorporal pressure change of chamber of control is no more than ± 10Pa, more added with
Further stablize conducive to the rate of set and degree for making hydrone, thus to " strutting " effect stability of graphene oxide layer；And
And be conducive to make ice molecule sublimate speed and degree is further stablized, to be also beneficial to further avoid because of graphene oxide
Local defect caused by the local stress of layer.
The tune that the transfer structure has the transmission parts for running through the cold dry chamber and can adjust transmission parts travel speed
Fast mechanism.The transmission parts can receive the hydrogel and form the graphene oxide hydrogel that unit is formed, and make the oxygen
Graphite alkene hydrogel is advanced finally to obtain from the discharge outlet of the cold dry chamber with second number of plies by entire cold dry chamber
Graphene oxide.The transmission parts can be conveyer belt.The speed adjusting gear can control conveyer belt with pre-set velocity at the uniform velocity
Pass through cold dry chamber.Second number of plies is less than first number of plies.Second number of plies can have compared to first number of plies to significantly decrease.This
In, 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.
In another exemplary embodiment of the invention, the preparation facilities of low layer number graphene oxide can be with above-mentioned
It further comprise buffer area on the basis of the structure of exemplary embodiment.Specifically, buffer area can connect with the second discharge port
It connects, suitably to be heated up to the graphene oxide entered in buffer area from the second discharge port, to make the oxygen as product
Graphite alkene can adapt to room temperature environment or subsequent treatment process.For example, the length of buffer area can be 1.5~4 meters, but originally show
Example property embodiment is without being limited thereto.
In another exemplary embodiment of the invention, the preparation facilities of low layer number graphene oxide can be with above-mentioned
On the basis of the structure of exemplary embodiment, pretreating zone is further wrapped.Specifically, pretreating zone can with described second into
Material mouth connects and itself is run through by the transmission parts.Pretreating zone has cooling component, so as to enter to by transmission parts
Graphene oxide hydrogel in it carries out cooling processing appropriate, so that the temperature of graphene oxide hydrogel reduces.For example,
Temperature in pretreating zone can be stably held in the 1/6~3/5 of the intracorporal temperature of the chamber.It, can by the setting of pretreating zone
Cooled down for the first time to graphene oxide, convenient for control temperature-fall period, and is conducive to operation.For example, the length of pretreating zone can be with
It is 1.5~4 meters, but present exemplary embodiment is not limited to this.
In an exemplary embodiment of the present invention, the preparation facilities of the low layer number graphene oxide can pass through coordinated control
The length of the cavity of cold dry chamber, the cold speed for doing intracavitary temperature and pressure and transmission parts are dry complete described to obtain
Graphene oxide with second number of plies.Specifically, it when designing preparation facilities of the invention, can first be wanted according to above-mentioned correlation
It asks determination is cold to do intracavitary temperature and pressure, the speed of service of cavity length and transmission parts is then determined according to requirements such as places,
With the graphene oxide hydrogel for ensuring to convey and run by transmission parts through cold dry chamber can sufficiently complete cryogenic freezing and
It sublimates dry process.For example, the cavity length of cold dry chamber can be 10~20 meters, but present exemplary embodiment is not limited to this.
In an exemplary embodiment of the present invention, as shown in Fig. 2, the reduction apparatus may include reaction member and
Control climate unit.
The reaction member includes n extended along the vertical direction reaction zone.With the low layer number graphene oxide
The graphene oxide with second number of plies that is prepared of preparation facilities be raw material, since the 1st reaction zone of reaction member,
Gravity and in order successively i-th reaction of experience reaction member of the graphene oxide with second number of plies by itself
Graphene is collected until the n-th reaction zone to reaction terminates in area.Wherein, the n is natural number and >=2, i gets the institute less than n
There is natural number.
The control climate unit includes mutually matched temperature control mechanism and control vacuum mechanism.The temperature control mechanism is for controlling
The temperature for making the i-th reaction zone is Ti, the temperature control of the n-th reaction zone of control is Tn.The Ti=w1·i/n·Tn, w1It can be
It is selected between 0.80~1.20.For example, w1It can be with value 0.9.The control vacuum mechanism can control the pressure of the i-th reaction zone and be
Pi, the pressure control of the n-th reaction zone of control is Pn.The Pi=(P0-Pn) (1-i/n), P0Indicate 1 standard atmospheric pressure.
The TnIt can be 1250 DEG C or more, further, the TnIt can be 1700 DEG C~2800 DEG C.The PnIt can be with
For 30Pa~500Pa.Further, the PnIt can be 60Pa~100Pa.Further, the PnCan for 85Pa~
95Pa.The w1It can be selected between 0.85~1.14, for example, w10.95 can be taken.Temperature T is setnIt is 1250 DEG C or more
It is advantageous in that, 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.Further, temperature TnIt can be 2200 DEG C.By
It is carbon material graphitization temperature in 2200 DEG C, and also helps the self-defect for repairing graphene oxide.Pressure P is setnFor
30Pa~500Pa is advantageous in that, under above-mentioned pressure vacuum degree, the fusing point and boiling point for the impurity that graphene oxide contains compared with
It is low, it is easier to volatilization removal.
In an exemplary embodiment of the present invention, the reduction apparatus can also include speed adjustment unit.Due to having second
The graphene oxide of the number of plies undergoes reaction zone by the gravity of itself.After the height of reaction zone is set as definite value, have the
Reaction time of the graphene oxide of two numbers of plies in each area cannot effectively control, and be unfavorable for the oxidation with second number of plies
The reaction of graphene in the reaction region.Therefore, in order to effectively control the graphene oxide with second number of plies in each reaction
Reaction time in area needs to control the decrease speed of the graphene oxide with second number of plies.The speed adjustment unit can be used
In being blown inert gas into reaction zone.When with second number of plies graphene oxide decrease speed it is too fast, need at some
When reacting the long period in reaction zone, the direction of speed adjustment unit blowing gas can be arranged and the oxidation stone with second number of plies
Black alkene declines contrary, is conducive to prevent hurtling down for the graphene oxide with second number of plies.Have if necessary
The graphene oxide of second number of plies accelerates to fall, and reduces the reaction for having the graphene oxide of second number of plies in some reaction zone
It is time, then the direction setting of speed adjustment unit blowing gas is identical as the direction that the graphene oxide with second number of plies declines,
Accelerate the whereabouts with the graphene oxide of second number of plies.
Purifying object institute oxygen-containing functional group may include one of carboxyl, hydroxyl, carbonyl, ehter bond and epoxy group or
A variety of functional groups.Under the high temperature and pressure conditions that the present invention is arranged, functional group can be decomposed into carbon dioxide and water, can
Effectively to remove the oxygen-containing functional group in graphene oxide.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.
More than, it may include at least one of manganese, iron, potassium, sodium, sulphur, silicon impurity in the purifying object.It was purifying
Complexing agent used in journey can be combined with the metal impurities in impurity to remove metal impurities, for example, manganese, iron, potassium,
Sodium etc..At this point, the additional amount of the complexing agent is can be with 1.0~1.2 times of the theoretical amount of impurity complex reaction.Certainly, network
Close that removable metal impurities are without being limited thereto, for example, beavy metal impurity or other can be equal with the impurity in conjunction with complexing agent
It can.After purifying removes partial impurities, in reduction step, metal and nonmetallic inclusion can be removed under high-temperature low-pressure environment,
For example, manganese, iron, potassium, sodium, sulphur, silicon etc..At high temperature, metal impurities contained in graphene oxide and nonmetallic be can achieve
The fusing point and boiling point of impurity, can separate in the form of a vapor from graphene oxide.Under certain low pressure subsidiary conditions, gold
The fusing point and boiling point for belonging to impurity and nonmetallic inclusion can be reduced further, be easy to by the temperature and vacuum degree of setting
Except the metal impurities and nonmetallic inclusion contained in graphene oxide.It is anti-by purification process and high-temperature vacuum reaction process two
It answers the stage to cooperate the impurity for removing and containing in raw material jointly, can be good at removing oxygen-containing functional group, energy under high-temperature vacuum degree
Access the graphene of low impurity content.In the existing method for preparing graphene, the content one of preparation-obtained graphene
As ferro element and manganese element contain all in the graphene of 2000PPm or more, the method for the invention low impurity content being prepared
Amount can achieve less than 20PPm, further, can achieve less than 15ppm, and can also remove well nitrate anion from
The impurity such as son, chloride ion.
In conclusion system of the invention can effectively be such that graphene oxide and foreign ion separates, oxygen can be improved
The completeness of graphite alkene purifying.The freezing dry process of system processing graphene oxide of the invention will not destroy graphite oxide
The structure of lamella, preferably preservation functional group, it is freeze-dried after graphite oxide be not susceptible to agglomeration.The system of invention
The graphene oxide of low layer number is set to undergo reaction zone to occur instead by self gravity by the different temperature of setting, pressure region
It answers, graphene oxide can be pre-processed, can be improved the production efficiency of graphene, the gold in graphene can be removed
Belong to, nonmetallic inclusion, while removing a large amount of oxygen-containing functional groups of graphene oxide institute band, graphene oxide can be repaired and prepared
SP caused by the process3Hydridization defect, is able to produce to obtain that impurity content is low, and fault of construction is few, the stone of excellent combination property
Black alkene.
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 production system for preparing graphene using low layer number graphene oxide, which is characterized in that the production system packet
Include graphene oxide purification devices, low layer number graphene oxide preparation facilities and reduction apparatus, wherein
The graphene oxide purification devices include first charging aperture, tank body, first partition, second partition, supersonic generation unit
With the first discharge port, wherein
The first partition and second partition are arranged in tank body along the cross section of tank body, and tank body is divided into and is successively divided up and down
Reaction zone, filtering area and the collecting region of cloth are provided with and can be opened what reaction zone was connected to filtering area in the first partition
Component is closed, is provided with the filter element that can be realized separation of solid and liquid on the second partition；
The first charging aperture is arranged on tank body top and is connected to the reaction zone, so that purifying object, complexing agent and acidity
Solution enters the reaction zone by the feed inlet, and the purifying object includes foreign ion being combined in functional group and with the
The graphene oxide of one number of plies；
First discharge port is arranged on the side wall of tank body and is located above the second partition, so as to be discharged be deposited on it is described
Graphene oxide on filter element after purification, the graphene oxide after purification are the graphite oxide with first number of plies
Alkene；
The supersonic generation unit is arranged in the reaction zone, to provide ultrasound environments to reaction zone, keeps complex reaction abundant
It carries out；
The low layer number graphene oxide preparation facilities includes that hydrogel forms unit, low temperature drying unit and transport mechanism,
In,
The hydrogel, which forms unit, has a dispersion slot, and the dispersion slot is used to receive the pure of water and first discharge port discharge
Graphene oxide after change, and graphene oxide after purification is dispersed in water, to form graphene oxide hydrogel；
The low temperature drying unit have control temperature unit, pressure control unit and cold dry chamber, wherein the cold dry chamber be made of shell and
With second charging aperture, the second discharge port and cavity, the control temperature unit is used to the intracorporal temperature control of the chamber be not high
In -50 DEG C and the entire intracorporal temperature change of chamber of control is no more than ± 4 DEG C, and the pressure control unit is used for the intracorporal pressure of the chamber
Strong control is lower than 1 atmospheric pressure and the entire intracorporal pressure change of chamber of control is no more than ± 100Pa；
The governor that the transport mechanism has the transmission parts for running through the cold dry chamber and can adjust transmission parts travel speed
Structure, the transmission parts are used to receive the hydrogel and form the graphene oxide hydrogel of unit formation and make the graphite oxide
Alkene hydrogel is after entire cold dry chamber, to obtain the graphene oxide with second number of plies from second discharge port, described the
Two numbers of plies are less than first number of plies；
The reduction apparatus includes reaction member and atmosphere control unit, wherein
The reaction member includes the i-th reaction zone and the n-th reaction zone being linked in sequence on vertical direction, and the reaction member is set
The graphene oxide with second number of plies can be received and rely on the graphene oxide with second number of plies by being set to
Self gravitation effect successively undergoes the i-th reaction zone of reaction member and the n-th reaction zone to react, and n is natural number and >=2, i takes
To all natural numbers for being less than n；
The control climate unit includes mutually matched temperature control mechanism and control vacuum mechanism, wherein temperature control mechanism is arranged to
The temperature of n-th reaction zone can be controlled as Tn, and the temperature of i-th reaction zone is controlled as Ti, wherein Ti=
w1·i/n·Tn, w1It is selected between 0.80~1.20, TnIt is 1250 DEG C or more；The control vacuum mechanism be configured to by
The pressure control of n-th reaction zone is Pn, and the pressure of i-th reaction zone is controlled as Pi, wherein Pi=(P0-Pn)·
(1-i/n), P0Indicate 1 standard atmospheric pressure, PnFor 30Pa~500Pa.
2. the production system according to claim 1 for preparing graphene using low layer number graphene oxide, which is characterized in that
The graphene oxide purification devices further include the ion concentration detection unit that first discharge port is arranged in, described in detection
The concentration of foreign ion in graphene oxide after purification.
3. the production system according to claim 2 for preparing graphene using low layer number graphene oxide, which is characterized in that
The graphene oxide purification devices further include the returning charge unit with controller and conveying component, the controller and it is described from
Sub- concentration detecting unit connection, and judged whether to start conveying component according to the testing result of ion concentration detection unit, it is described
The graphene oxide after purification being discharged from the first discharge port can be provided to first charging aperture by conveying component.
4. the production system according to claim 1 for preparing graphene using low layer number graphene oxide, which is characterized in that
The graphene oxide purification devices further include the buffer protection layer being arranged between first partition and filter element, the buffering
Protective layer can absorb and buffer ultrasonic wave caused by the supersonic generation unit, to protect the filter element.
5. the production system according to claim 1 for preparing graphene using low layer number graphene oxide, which is characterized in that
The low layer number graphene oxide preparation facilities further includes the buffer area connecting with second discharge port, and the buffer area can
It heats up to the graphene oxide entered in it from the second discharge port.
6. the production system according to claim 1 for preparing graphene using low layer number graphene oxide, which is characterized in that
The low layer number graphene oxide preparation facilities further includes connecting with the second charging aperture and perforative pre- by the transmission parts
Treatment region, the pretreating zone can carry out cooling processing to the graphene oxide hydrogel entered in it, so that graphite oxide
The temperature of alkene hydrogel reduces and keeps the 1/6~3/5 of temperature in the cavity.
7. the production system according to claim 1 for preparing graphene using low layer number graphene oxide, which is characterized in that
The low layer number graphene oxide preparation facilities by the length of the cavity of the cold dry chamber of coordinated control, cold do intracavitary temperature and pressure
By force and the speed of transmission parts obtains the graphene oxide with second number of plies.
8. the production system according to claim 1 for preparing graphene using low layer number graphene oxide, which is characterized in that
The control temperature unit of the low layer number graphene oxide preparation facilities is by the intracorporal temperature control of the chamber in -55~-65 DEG C of ranges
The interior and entire intracorporal temperature change of chamber of control is no more than ± 2 DEG C.
9. the production system according to claim 1 for preparing graphene using low layer number graphene oxide, which is characterized in that
The pressure control unit of the low layer number graphene oxide preparation facilities is by the intracorporal pressure control of the chamber in 10~100Pa and control
The entire intracorporal pressure change of chamber is no more than ± 10Pa.
10. according to the production system described in claim 1 for preparing graphene using low layer number graphene oxide, which is characterized in that
The reduction apparatus further includes speed adjustment unit, the speed adjustment unit be used for into first reaction member blast pass to control
The decrease speed of the graphene oxide in the reaction cell.
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