CN109231197A - A kind of low impurity and low layer number graphene oxide preparation system - Google Patents
A kind of low impurity and low layer number graphene oxide preparation system Download PDFInfo
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Abstract
The present invention provides a kind of low impurity and low layer number graphene oxide preparation systems, the system comprises graphene oxide purification devices and low layer number graphene oxide preparation facilities, 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 low layer number graphene oxide preparation facilities includes that hydrogel forms unit, low temperature drying unit and transport mechanism, and the low layer number graphene oxide preparation facilities can receive graphene oxide purification devices graphene oxide after purification and be freeze-dried to it.System of the invention can effectively be such that graphene oxide and foreign ion separates, and the completeness of graphene oxide purifying can be improved, and purification efficiency is high, at low cost；The structure of oxidized graphite flake layer will not be destroyed by freezing dry process, preferably preservation functional group, it is freeze-dried after graphite oxide be not susceptible to agglomeration.
Description
Technical field
The present invention relates to graphene oxide production technical fields, more particularly, are related to a kind of low impurity and low layer number oxygen
Graphite alkene preparation system.
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 foreign ion in the graphene oxide slurry of production.There are low efficiency, washings in washing process for existing equipment
The problems such as effect is poor, so that the graphene oxide product purity produced is not high, quality decline.Also, due to graphite oxide
Thermal stability is poor, often just will appear pyrolysis phenomenon during the drying process, and the graphite oxide after heated drying is easy to reunite
At lump, it is unfavorable for subsequent dispersion.
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 oxidations that one kind can prepare low impurity content, low layer number
The system of graphene.
It is to achieve the goals above, of the invention to provide a kind of low impurity and low layer number graphene oxide preparation system,
The preparation system may include graphene oxide purification devices and low layer number graphene oxide preparation facilities, 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 after purification of the product on the filter element；The supersonic generation unit is arranged in the reaction zone, with
Ultrasound environments are provided to reaction zone, carry out complex reaction sufficiently；
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.
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 is high, at low cost；Features simple structure, is easy to use and transport, occupied area are small；
(2) graphene oxide is handled using system of the invention, freezing dry process will not destroy oxidized graphite flake layer
Structure, preferably preservation functional group, it is freeze-dried after graphite oxide be not susceptible to agglomeration；
(3) freeze-dried graphene oxide layer interlamellar spacing is greater than the graphene oxide after the drying of other drying means
Product has superior dispersion performance, the less number of plies and bigger specific surface area.
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 oxygen in the low impurity and low layer number graphene oxide preparation system of an illustrative embodiment of the invention
Graphite alkene purification devices 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, low impurity and low layer number according to the present invention will be described in detail in conjunction with attached drawing and exemplary embodiment
Graphene oxide preparation system.
Fig. 1 shows oxygen in the low impurity and low layer number graphene oxide preparation system of an illustrative embodiment of the invention
Graphite alkene purification devices schematic diagram.
The present invention provides a kind of low impurity and low layer number graphene oxide preparation system, in low impurity of the invention and low
In one exemplary embodiment of number of plies graphene oxide preparation system, the preparation system may include graphene oxide purifying
Device and low layer number graphene oxide preparation facilities.
In an exemplary embodiment of the present invention, as shown in Figure 1, graphene oxide purification devices can be integrated makeup
It sets.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 and 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 instead
Answer 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
Component is opened and closed, the opening of retractable component is equipped with metal coarse filtration sieve (not shown).Second partition 31 may include
Filter component (not shown).The bottom of filtering area 30 is provided with the first discharge port 32, and the first discharge port 32 is provided with ICP ion
Concentration 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 arranged
There are liquid outlet 41, vacuum pump 42.Retractable component in first partition 22 connects reaction zone 20 and filtering area 30,
Filter element on 31 on second partition 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 the present example embodiment, the low layer number graphene oxide preparation facilities can receive the graphene oxide
Purification devices graphene oxide after purification simultaneously carries out freeze-drying process to it.The preparation of the low layer number graphene oxide fills
Unit, low temperature drying unit and transport mechanism can be formed by hydrogel by, which setting, is 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 conclusion so that graphene oxide and foreign ion is separated using system of the invention, Ke Yiti
The completeness of high oxidation graphene purifying；Purification efficiency height, at low cost, features simple structure are easy to use and transport, occupied area
It is small.Graphene oxide is handled using system of the invention, freezing dry process will not destroy the structure of oxidized graphite flake layer, preferably
Preservation functional group, it is freeze-dried after graphite oxide be not susceptible to agglomeration.Oxidation through freeze-drying of the invention
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.
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 and low layer number graphene oxide preparation system, which is characterized in that the preparation system includes oxidation stone
Black alkene purification devices and low layer number graphene oxide preparation facilities, 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.
2. low impurity according to claim 1 and low layer number graphene oxide preparation system, which is characterized in that the oxidation
Graphene purification devices further include the ion concentration detection unit that first discharge port is arranged in, with detect it is described after purification
The concentration of foreign ion in graphene oxide.
3. low impurity according to claim 2 and low layer number graphene oxide preparation system, which is characterized in that the oxidation
Graphene purification devices further include the returning charge unit with controller and conveying component, and the controller and the ion concentration are examined
Unit connection is surveyed, and is judged whether to start conveying component, the conveying component according to the testing result of ion concentration detection unit
The graphene oxide after purification being discharged from the first discharge port can be provided to first charging aperture.
4. low impurity according to claim 1 and low layer number graphene oxide preparation system, which is characterized in that the oxidation
Graphene purification devices further include that decompression filters unit, and the decompression filters unit and is arranged in the collecting region and makes the collection
Area forms inverted U-shaped cavity.
5. low impurity according to claim 1 and low layer number graphene oxide preparation system, which is characterized in that the oxidation
Graphene purification devices further include the buffer protection layer being arranged between first partition and filter element, the buffer protection layer energy
Ultrasonic wave caused by the supersonic generation unit is enough absorbed and buffers, to protect the filter element.
6. low impurity according to claim 1 and low layer number graphene oxide preparation system, which is characterized in that the low layer
Number graphene oxide preparation facilities further include the buffer area connecting with second discharge port, and the buffer area can be to from second
The graphene oxide that discharge port enters in it heats up.
7. low impurity according to claim 1 and low layer number graphene oxide preparation system, which is characterized in that the low layer
Number graphene oxide preparation facilities further includes connecting with the second charging aperture and by the perforative pretreating zone of the transmission parts, institute
Cooling processing can be carried out to the graphene oxide hydrogel entered in it by stating pretreating zone, so that graphene oxide hydrogel
Temperature reduces and keeps the 1/6~3/5 of temperature in the cavity.
8. low impurity according to claim 1 and low layer number graphene oxide preparation system, 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, it is cold do intracavitary temperature and pressure and
The speed of transmission parts has the graphene oxide of second number of plies to obtain described in drying completely.
9. low impurity according to claim 1 and low layer number graphene oxide preparation system, which is characterized in that the temperature control
Unit is by the intracorporal temperature control of the chamber is within the scope of -55~-65 DEG C and the entire intracorporal temperature change of chamber of control is no more than
±2℃。
10. low impurity according to claim 1 and low layer number graphene oxide preparation system, which is characterized in that the control
Press unit by the control of the chamber intracorporal pressure in 10~100Pa and the entire intracorporal pressure change of chamber of control be no more than ±
10Pa。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2014201492A (en) * | 2013-04-05 | 2014-10-27 | 国立大学法人北海道大学 | Method for manufacturing a graphene oxide-containing liquid and uses of the same |
| US20160101398A1 (en) * | 2014-09-12 | 2016-04-14 | Lawrence Livermore National Security, Llc | Nanoporous metal-carbon composite |
| CN205252914U (en) * | 2015-12-30 | 2016-05-25 | 安徽易能新材料科技有限公司 | A filter equipment for graphite alkene is hierarchical |
-
2018
- 2018-12-07 CN CN201811493703.7A patent/CN109231197B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2014201492A (en) * | 2013-04-05 | 2014-10-27 | 国立大学法人北海道大学 | Method for manufacturing a graphene oxide-containing liquid and uses of the same |
| US20160101398A1 (en) * | 2014-09-12 | 2016-04-14 | Lawrence Livermore National Security, Llc | Nanoporous metal-carbon composite |
| CN205252914U (en) * | 2015-12-30 | 2016-05-25 | 安徽易能新材料科技有限公司 | A filter equipment for graphite alkene is hierarchical |
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