CN104817787A - Antistatic plastic modified by functionalized graphene oxide and preparation method thereof - Google Patents
Antistatic plastic modified by functionalized graphene oxide and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention discloses antistatic plastic modified by functionalized graphene oxide, which includes 85-95 parts of a polyvinyl chloride plastic base material and 5-15 parts of the functionalized graphene oxide being modified and being excellent in electric conduction. The modified functionalized graphene oxide not only is excellent in electric conduction and can be fully merged with the plastic base material, so that the modified functionalized graphene oxide is distributed uniformly in the plastic base material, but also can form a net-like structure with the high molecular structure of the plastic, so that the plastic, on the premise that all mechanical performances are maintained, is excellent in an antistatic property, wherein the plastic is less than 10<6> [ohm]*cm in volume resistance, so that static electricity can be released through the surface of the plastic timely when the static electricity occurs, thereby avoiding accidents caused by the static electricity and further improving security of life and property.
Description
Technical field
The present invention relates to a kind of modification anti-static plastic, be specifically related to a kind of functionalization graphene modification anti-static plastic and preparation method thereof.
Background technology
Electrostatic is the one charging savings phenomenon concentrating on insulating material surface, comes from frictional electricity, the raw electricity of contact or influence electricity.Concerning isolator, its charging is local, but makes plastics bring a series of harm because of charged.Except making product itself be easy to dust suction, absorption foul, produce except the phenomenons such as electric shock to people in processing and use, even cause the major accidents such as blast because static discharge produces spark.In recent years, along with the expansion of macromolecular material Application Areas, and a large amount of development of electronic products etc. is with universal, the noise caused by electrostatic or make Integrated circuit portion damaged etc. problem is also on the rise.Therefore, the anti-electrostatic problem of plastics also causes the attention of people day by day.The loss that the U.S. causes because of static discharge every year just reaches 10,000,000,000 dollars, and the accident because electrostatic causes also occurred in China; In the occasion of many use plastics, it is all vital for studying its anti-electrostatic problem.
Anti-static plastic is category as whole conductive plastics current and studied, and conductive plastics roughly can be divided into antistatic, semi-conductor and conduction three class.Solve the antistatic problem of plastic part, mainly adopt at present and add conductive filler material to produce composite conductive plastic and to add static inhibitor to reduce insulation resistance two class methods of plastic part, but effect is not clearly, still there is electrostatic problem.
Graphene is a kind of two-dimensional material, has higher conductivity and surface-area, is the appliance material of electrochemical field middle ideal.In macromolecular material, add Graphene, because Graphene has good conductivity, make the macromolecular material through Graphene modification also have good conductivity.Conductivity through the macromolecular material of Graphene modification depends on the degree of uniformity that Graphene and macromolecular material merge.The graphene powder that existing technique prepares all is difficult to fully merge with polymer particles in tap density and functional group content, and Graphene is skewness in polymer, makes the conductivity of modified macromolecular material not be very desirable.
Summary of the invention
In order to solve the deficiencies in the prior art, the invention provides a kind of electric conductivity utilizing functionalization graphene modified plastics can heighten plastics and then the antistatic property improving material.
The technical solution adopted in the present invention is as follows: a kind of functionalization graphene modification anti-static plastic, and its component and content are: igelite base material 85 parts ~ 95 parts, has the functionalization graphene 5 parts ~ 15 parts of satisfactory electrical conductivity through modification.
A preparation method for functionalization graphene modification anti-static plastic, comprises the following steps:
(1) graphene oxide is prepared
By 98% vitriol oil and 85% strong phosphoric acid in mass ratio for 2:1 is mixed to get in mixed acid solution, in mixed acid solution, add graphite, wherein the quality of graphite and the volume ratio of mixed acid solution are 2g ~ 5g:120ml ~ 590ml; Stir in ice-water bath, slowly must add potassium permanganate in the mixing solutions of graphite and mixing acid, be heated to 85 DEG C and carry out oxide treatment 1h, remove potassium permanganate subsequently, suction filtration, washing screening, drying, obtain graphene oxide, wherein the mass ratio of graphite and potassium permanganate is 1:4 ~ 1:6;
(2) Graphene is prepared
The graphene oxide of preparation in step (1) is placed in tube furnace, and high temperature or the lower 1000 DEG C of reduction of nitrogen protection obtain Graphene;
(3) functionalization graphene is prepared
Be ultrasonic 2h in the nitric acid of 10 ~ 30% in concentration by the Graphene of preparation in step (2), obtain the Graphene after acidifying; By after this acidifying Graphene dry after join octadecylamine ethanol and the aqueous solution in, wherein the volume ratio of second alcohol and water is 1:9 ~ 1:1, the mass ratio of Graphene and octadecylamine is 1:5 ~ 1:1,120h is stirred in oil bath 80 DEG C, suction filtration, cleaning, oven drying at low temperature, must have the functionalization graphene of excellent conductive performance;
(4) igelite substrate solution is prepared
Adopt solution-casting method, by igelite base material dissolves in dioctyl phthalate (DOP), the dioctyl phthalate (DOP) solution of configuration igelite base material;
(5) anti-static plastic is prepared
Functionalization graphene prepared by step (3) is added in the dioctyl phthalate (DOP) solution of igelite base material prepared by step (4), then water in culture dish, vacuumize, the demoulding after solvent evaporates, prepare the anti-static plastic with excellent conductive performance.
As preferably, the tap density of Graphene prepared by described step (2) is 0.10 ~ 0.25g/ml.
As preferably, the particle diameter of Graphene prepared by described step (2) is 10 ~ 100 μm.
As preferably, the thickness of Graphene prepared by described step (2) is 1 ~ 20nm.
The beneficial effect that technical scheme provided by the invention is brought is: Graphene is a kind of two-dimensional material, has higher conductivity and surface-area, is the type material of electrochemical field middle ideal.In macromolecular material, add Graphene, because Graphene has good conductivity, make the macromolecular material through Graphene modification also have good conductivity.Conductivity through the macromolecular material of Graphene modification depends on the degree of uniformity that Graphene and macromolecular material merge.Through modified functionalization graphene, not only there is good conductivity but also can fuse fully with plastic basis material, functionalization graphene can be uniformly distributed in plastic basis material, and reticulated structure can be formed with plastics polymer, on the basis retaining the every mechanical property of plastics, have good antistatic property, its volume resistance is less than 10
6Ω .cm, when so just can guarantee to occur electrostatic, can be discharged by frosting in time, avoids some accidents occurring that electrostatic problem causes, and improves the security of lives and properties.
As can be seen here, compared with prior art, have outstanding substantive distinguishing features and significant progress, its beneficial effect implemented also is apparent in the present invention.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the SEM figure of functionalization graphene.
Embodiment
Make the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.Specific embodiment described herein only in order to explain the present invention, but is not intended to limit the present invention.
Reagent of the present invention is, and market is purchased, and is conventional reagent.
Embodiment 1:
A kind of functionalization graphene modification anti-static plastic, the component of each raw material and content are: igelite base material (PVC plastic base material) 85 parts, have the functionalization graphene 5 parts of satisfactory electrical conductivity through modification.
A preparation method for functionalization graphene modification anti-static plastic, comprises the following steps:
(1) graphene oxide is prepared
By 98% vitriol oil and 85% strong phosphoric acid in mass ratio for 2:1 is mixed to get in mixed acid solution, in mixed acid solution, add graphite, wherein the quality of graphite and the volume ratio of mixed acid solution are 2g:120ml; Stir in ice-water bath, slowly potassium permanganate must be added in the mixing solutions of graphite and mixing acid, be heated to 85 DEG C and carry out oxide treatment 1h, remove potassium permanganate subsequently, suction filtration, washing screening, drying, obtain graphene oxide, wherein the mass ratio of graphite and potassium permanganate is 1:4;
(2) Graphene is prepared
The graphene oxide of preparation in step (1) is placed in tube furnace, and high temperature or the lower 1000 DEG C of reduction of nitrogen protection obtain Graphene;
(3) functionalization graphene is prepared
Be ultrasonic 2h in the nitric acid of 10% in concentration by the Graphene of preparation in step (2), obtain the Graphene after acidifying; By after this acidifying Graphene dry after join octadecylamine ethanol and the aqueous solution in, wherein the volume ratio of second alcohol and water is 1:9, the mass ratio of Graphene and octadecylamine is 1:5,120h is stirred in oil bath 80 DEG C, suction filtration, cleaning, oven drying at low temperature, must have the functionalization graphene of excellent conductive performance;
(4) igelite substrate solution is prepared
Adopt solution-casting method, by igelite base material dissolves in dioctyl phthalate (DOP), the dioctyl phthalate (DOP) solution of configuration igelite base material;
(5) anti-static plastic is prepared
Functionalization graphene prepared by step (3) is added in the dioctyl phthalate (DOP) solution of igelite base material prepared by step (4), then water in culture dish, vacuumize, the demoulding after solvent evaporates, prepare the anti-static plastic with excellent conductive performance.
The tap density of Graphene is 0.10g/ml; The particle diameter of Graphene is 10 μm, and the thickness of Graphene is 1nm.
Embodiment 2:
A kind of functionalization graphene modification anti-static plastic, the component of each raw material and content are: igelite base material (PVC plastic base material) 90 parts, have the functionalization graphene 10 parts of satisfactory electrical conductivity through modification.
A preparation method for functionalization graphene modification anti-static plastic, comprises the following steps:
(1) graphene oxide is prepared
By 98% vitriol oil and 85% strong phosphoric acid in mass ratio for 2:1 is mixed to get in mixed acid solution, in mixed acid solution, add graphite, wherein the quality of graphite and the volume ratio of mixed acid solution are 3g:200ml; Stir in ice-water bath, slowly potassium permanganate must be added in the mixing solutions of graphite and mixing acid, be heated to 85 DEG C and carry out oxide treatment 1h, remove potassium permanganate subsequently, suction filtration, washing screening, drying, obtain graphene oxide, wherein the mass ratio of graphite and potassium permanganate is 1:5;
(2) Graphene is prepared
The graphene oxide of preparation in step (1) is placed in tube furnace, and high temperature or the lower 1000 DEG C of reduction of nitrogen protection obtain Graphene;
(3) functionalization graphene is prepared
Be ultrasonic 2h in the nitric acid of 15% in concentration by the Graphene of preparation in step (2), obtain the Graphene after acidifying; By after this acidifying Graphene dry after join octadecylamine ethanol and the aqueous solution in, wherein the volume ratio of second alcohol and water is 1:6, the mass ratio of Graphene and octadecylamine is 1:2,120h is stirred in oil bath 80 DEG C, suction filtration, cleaning, oven drying at low temperature, must have the functionalization graphene of excellent conductive performance;
(4) igelite substrate solution is prepared
Adopt solution-casting method, by igelite base material dissolves in dioctyl phthalate (DOP), the dioctyl phthalate (DOP) solution of configuration igelite base material;
(5) anti-static plastic is prepared
Functionalization graphene prepared by step (3) is added in the dioctyl phthalate (DOP) solution of igelite base material prepared by step (4), then water in culture dish, vacuumize, the demoulding after solvent evaporates, prepare the anti-static plastic with excellent conductive performance.
The tap density of Graphene is 0.15g/ml; The particle diameter of Graphene is 40 μm, and the thickness of Graphene is 10nm.
Embodiment 3:
A kind of functionalization graphene modification anti-static plastic, the component of each raw material and content are: igelite base material (PVC plastic base material) 95 parts, have the functionalization graphene 5 parts of satisfactory electrical conductivity through modification.
A preparation method for functionalization graphene modification anti-static plastic, comprises the following steps:
(1) graphene oxide is prepared
By 98% vitriol oil and 85% strong phosphoric acid in mass ratio for 2:1 is mixed to get in mixed acid solution, in mixed acid solution, add graphite, wherein the quality of graphite and the volume ratio of mixed acid solution are 4g:400ml; Stir in ice-water bath, slowly potassium permanganate must be added in the mixing solutions of graphite and mixing acid, be heated to 85 DEG C and carry out oxide treatment 1h, remove potassium permanganate subsequently, suction filtration, washing screening, drying, obtain graphene oxide, wherein the mass ratio of graphite and potassium permanganate is 1:4.5;
(2) Graphene is prepared
The graphene oxide of preparation in step (1) is placed in tube furnace, and high temperature or the lower 1000 DEG C of reduction of nitrogen protection obtain Graphene;
(3) functionalization graphene is prepared
Be ultrasonic 2h in the nitric acid of 20% in concentration by the Graphene of preparation in step (2), obtain the Graphene after acidifying; By after this acidifying Graphene dry after join octadecylamine ethanol and the aqueous solution in, wherein the volume ratio of second alcohol and water is 1:5, the mass ratio of Graphene and octadecylamine is 1:3,120h is stirred in oil bath 80 DEG C, suction filtration, cleaning, oven drying at low temperature, must have the functionalization graphene of excellent conductive performance;
(4) igelite substrate solution is prepared
Adopt solution-casting method, by igelite base material dissolves in dioctyl phthalate (DOP), the dioctyl phthalate (DOP) solution of configuration igelite base material;
(5) anti-static plastic is prepared
Functionalization graphene prepared by step (3) is added in the dioctyl phthalate (DOP) solution of igelite base material prepared by step (4), then water in culture dish, vacuumize, the demoulding after solvent evaporates, prepare the anti-static plastic with excellent conductive performance.
The tap density of Graphene is 0.20g/ml; The particle diameter of Graphene is 60 μm, and the thickness of Graphene is 15nm.
Embodiment 4:
A kind of functionalization graphene modification anti-static plastic, the component of each raw material and content are: igelite base material (PVC plastic base material) 85 parts, have the functionalization graphene 15 parts of satisfactory electrical conductivity through modification.
A preparation method for functionalization graphene modification anti-static plastic, comprises the following steps:
(1) graphene oxide is prepared
By 98% vitriol oil and 85% strong phosphoric acid in mass ratio for 2:1 is mixed to get in mixed acid solution, in mixed acid solution, add graphite, wherein the quality of graphite and the volume ratio of mixed acid solution are 4.5g:500ml; Stir in ice-water bath, slowly potassium permanganate must be added in the mixing solutions of graphite and mixing acid, be heated to 85 DEG C and carry out oxide treatment 1h, remove potassium permanganate subsequently, suction filtration, washing screening, drying, obtain graphene oxide, wherein the mass ratio of graphite and potassium permanganate is 1:5.5;
(2) Graphene is prepared
The graphene oxide of preparation in step (1) is placed in tube furnace, and high temperature or the lower 1000 DEG C of reduction of nitrogen protection obtain Graphene;
(3) functionalization graphene is prepared
Be ultrasonic 2h in the nitric acid of 25% in concentration by the Graphene of preparation in step (2), obtain the Graphene after acidifying; By after this acidifying Graphene dry after join octadecylamine ethanol and the aqueous solution in, wherein the volume ratio of second alcohol and water is 1:2, the mass ratio of Graphene and octadecylamine is 1:4,120h is stirred in oil bath 80 DEG C, suction filtration, cleaning, oven drying at low temperature, must have the functionalization graphene of excellent conductive performance;
(4) igelite substrate solution is prepared
Adopt solution-casting method, by igelite base material dissolves in dioctyl phthalate (DOP), the dioctyl phthalate (DOP) solution of configuration igelite base material;
(5) anti-static plastic is prepared
Functionalization graphene prepared by step (3) is added in the dioctyl phthalate (DOP) solution of igelite base material prepared by step (4), then water in culture dish, vacuumize, the demoulding after solvent evaporates, prepare the anti-static plastic with excellent conductive performance.
The tap density of Graphene is 0.22g/ml; The particle diameter of Graphene is 80 μm, and the thickness of Graphene is 18nm.
Embodiment 5:
A kind of functionalization graphene modification anti-static plastic, the component of each raw material and content are: igelite base material (PVC plastic base material) 95 parts, have the functionalization graphene 15 parts of satisfactory electrical conductivity through modification.
A preparation method for functionalization graphene modification anti-static plastic, comprises the following steps:
(1) graphene oxide is prepared
By 98% vitriol oil and 85% strong phosphoric acid in mass ratio for 2:1 is mixed to get in mixed acid solution, in mixed acid solution, add graphite, wherein the quality of graphite and the volume ratio of mixed acid solution are 5g:590ml; Stir in ice-water bath, slowly potassium permanganate must be added in the mixing solutions of graphite and mixing acid, be heated to 85 DEG C and carry out oxide treatment 1h, remove potassium permanganate subsequently, suction filtration, washing screening, drying, obtain graphene oxide, wherein the mass ratio of graphite and potassium permanganate is 1:6;
(2) Graphene is prepared
The graphene oxide of preparation in step (1) is placed in tube furnace, and high temperature or the lower 1000 DEG C of reduction of nitrogen protection obtain Graphene;
(3) functionalization graphene is prepared
Be ultrasonic 2h in the nitric acid of 30% in concentration by the Graphene of preparation in step (2), obtain the Graphene after acidifying; By after this acidifying Graphene dry after join octadecylamine ethanol and the aqueous solution in, wherein the volume ratio of second alcohol and water is 1:1, the mass ratio of Graphene and octadecylamine is 1:1,120h is stirred in oil bath 80 DEG C, suction filtration, cleaning, oven drying at low temperature, must have the functionalization graphene of excellent conductive performance;
(4) igelite substrate solution is prepared
Adopt solution-casting method, by igelite base material dissolves in dioctyl phthalate (DOP), the dioctyl phthalate (DOP) solution of configuration igelite base material;
(5) anti-static plastic is prepared
Functionalization graphene prepared by step (3) is added in the dioctyl phthalate (DOP) solution of igelite base material prepared by step (4), then water in culture dish, vacuumize, the demoulding after solvent evaporates, prepare the anti-static plastic with excellent conductive performance.
The tap density of Graphene is 0.25g/ml; The particle diameter of Graphene is 100 μm, and the thickness of Graphene is 20nm.
Comparative example 1
Do not add PVC plastic and the common PVC plastics of functionalization graphene modification.
Comparative example 2
According to embodiment 1, change 5 parts of functionalization graphenes into 5 parts of Graphenes, this Graphene is Graphene without modification and common graphite alkene, then prepares PVC plastic according to step (4) and step (5).
Embodiment 6
By constant current table, (precision is 1 grade to the plastics that the present invention is prepared embodiment 1 ~ 5 and comparative example 1 ~ 2, range 10-6 to 10-1A) and electrostatic voltmeter (precision is 1 grade, range 0 is to 100V, input resistance is greater than 1012 ohm) carry out processing parameter and products thereof Performance Detection, Data Comparison result is as shown in table 1.
Table 1 is the comparing result of the volume resistance of the embodiment of the present invention 1 ~ 5 and comparative example 1 ~ 2
The volume resistance of table 1 plastics
| Material | Volume resistance (Ω .cm) |
| Comparative example 1 | 2.8×10 9 |
| Comparative example 2 | 3.9×10 7 |
| Embodiment 1 | 9.6×10 6 |
| Embodiment 2 | 7.8×10 6 |
| Embodiment 3 | 2.1×10 6 |
| Embodiment 4 | 5.2×10 6 |
| Embodiment 5 | 1.5×10 6 |
Compare as can be seen from Table 1 and do not add the PVC plastic of Graphene and add PVC plastic prepared by Graphene, after the present invention with the addition of the functionalization graphene with excellent conductive performance, volume resistance obviously reduces; From comparative example 2 and embodiment 1, add equal number Graphene and functionalization graphene, embodiment 1 utilizes functionalization graphene modified plastics conductivity to increase effect obviously will be better than Graphene, as can be seen here, the present invention's preparation has stronger antistatic property by the plastics of functionalization graphene modification.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a functionalization graphene modification anti-static plastic, is characterized in that: its component and content are: igelite base material 85 parts ~ 95 parts, has the functionalization graphene 5 parts ~ 15 parts of satisfactory electrical conductivity through modification.
2. the preparation method of a kind of functionalization graphene modification anti-static plastic as claimed in claim 1, is characterized in that: comprise the following steps:
(1) graphene oxide is prepared
By 98% vitriol oil and 85% strong phosphoric acid in mass ratio for 2:1 is mixed to get in mixed acid solution, in mixed acid solution, add graphite, wherein the quality of graphite and the volume ratio of mixed acid solution are 2g ~ 5g:120ml ~ 590ml; Stir in ice-water bath, slowly must add potassium permanganate in the mixing solutions of graphite and mixing acid, be heated to 85 DEG C and carry out oxide treatment 1h, remove potassium permanganate subsequently, suction filtration, washing screening, drying, obtain graphene oxide, wherein the mass ratio of graphite and potassium permanganate is 1:4 ~ 1:6;
(2) Graphene is prepared
The graphene oxide of preparation in step (1) is placed in tube furnace, and high temperature or the lower 1000 DEG C of reduction of nitrogen protection obtain Graphene;
(3) functionalization graphene is prepared
Be ultrasonic 2h in the nitric acid of 10 ~ 30% in concentration by the Graphene of preparation in step (2), obtain the Graphene after acidifying; By after this acidifying Graphene dry after join octadecylamine ethanol and the aqueous solution in, wherein the volume ratio of second alcohol and water is 1:9 ~ 1:1, the mass ratio of Graphene and octadecylamine is 1:5 ~ 1:1,120h is stirred in oil bath 80 DEG C, suction filtration, cleaning, oven drying at low temperature, must have the functionalization graphene of excellent conductive performance;
(4) igelite substrate solution is prepared
Adopt solution-casting method, by igelite base material dissolves in dioctyl phthalate (DOP), the dioctyl phthalate (DOP) solution of configuration igelite base material;
(5) anti-static plastic is prepared
Functionalization graphene prepared by step (3) is added in the dioctyl phthalate (DOP) solution of igelite base material prepared by step (4), then water in culture dish, vacuumize, the demoulding after solvent evaporates, prepare the anti-static plastic with excellent conductive performance.
3. the preparation method of a kind of functionalization graphene modification anti-static plastic according to claim 2, is characterized in that: the tap density of Graphene prepared by described step (2) is 0.10 ~ 0.25g/ml.
4. the preparation method of a kind of functionalization graphene modification anti-static plastic according to claim 2, is characterized in that: the particle diameter of Graphene prepared by described step (2) is 10 ~ 100 μm.
5. the preparation method of a kind of functionalization graphene modification anti-static plastic according to claim 2, is characterized in that: the thickness of Graphene prepared by described step (2) is 1 ~ 20nm.
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| CN105131450A (en) * | 2015-08-21 | 2015-12-09 | 宁波华安建材冶炼有限公司 | Graphene modified polyvinyl chloride material and preparation method thereof |
| CN106920592A (en) * | 2017-04-10 | 2017-07-04 | 徐州乐泰机电科技有限公司 | A kind of power cable |
| CN108690262A (en) * | 2017-04-12 | 2018-10-23 | 合肥杰事杰新材料股份有限公司 | A kind of antistatic polypropylene composite material and preparation method thereof that modified graphene is modified |
| CN110203922A (en) * | 2019-06-26 | 2019-09-06 | 武汉中科先进技术研究院有限公司 | A kind of preparation method of functional carbon material |
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| CN105131450A (en) * | 2015-08-21 | 2015-12-09 | 宁波华安建材冶炼有限公司 | Graphene modified polyvinyl chloride material and preparation method thereof |
| CN106920592A (en) * | 2017-04-10 | 2017-07-04 | 徐州乐泰机电科技有限公司 | A kind of power cable |
| CN108690262A (en) * | 2017-04-12 | 2018-10-23 | 合肥杰事杰新材料股份有限公司 | A kind of antistatic polypropylene composite material and preparation method thereof that modified graphene is modified |
| CN110203922A (en) * | 2019-06-26 | 2019-09-06 | 武汉中科先进技术研究院有限公司 | A kind of preparation method of functional carbon material |
| CN110203922B (en) * | 2019-06-26 | 2020-10-20 | 武汉中科先进技术研究院有限公司 | Preparation method of functionalized carbon material |
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| CN104817787B (en) | 2018-07-03 |
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