CN111875849A - Electrochemically prepared functionalized graphene flame retardant and application thereof - Google Patents

Electrochemically prepared functionalized graphene flame retardant and application thereof Download PDF

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CN111875849A
CN111875849A CN201910794069.9A CN201910794069A CN111875849A CN 111875849 A CN111875849 A CN 111875849A CN 201910794069 A CN201910794069 A CN 201910794069A CN 111875849 A CN111875849 A CN 111875849A
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CN111875849B (en
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付少海
仇明慧
王冬
李敏
张丽萍
刘明明
田安丽
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Jiangnan University
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Abstract

The invention discloses a functionalized graphene flame retardant prepared by electrochemistry and application thereof, and belongs to the technical field of flame-retardant composite materials. According to the invention, aqueous solution of diethylenetriamine penta-methylene sodium phosphate is used as electrolyte, graphite flake is used as anode, copper bar is used as cathode, low-defect and few-layer graphene modified by diethylenetriamine penta-methylene sodium phosphate is obtained through electrolysis, and the graphene is mixed with iron source to obtain the functionalized graphene flame retardant. The functional graphene flame retardant prepared by the method is blended with polyacrylonitrile to obtain the graphene/polyacrylonitrile nano composite material, so that the flame retardant property and the thermal stability of the polyacrylonitrile material are obviously improved, the mechanical property of the material is not damaged and influenced, and the graphene/polyacrylonitrile nano composite material has wide application prospects in the fields of automobile interiors, garment materials, tarpaulins, curtains, carpets and the like.

Description

Electrochemically prepared functionalized graphene flame retardant and application thereof
Technical Field
The invention belongs to the technical field of flame-retardant composite materials, and particularly relates to an electrochemically prepared functionalized graphene flame retardant and application thereof.
Background
The polyacrylonitrile material is fluffy and curled in appearance, has better elasticity and better heat retention than wool; the sun-proof performance is excellent, and the paint is acid-resistant and oxidant-resistant; the method is widely applied to the fields of automotive interiors, garment materials, tarpaulins, curtains, carpets and the like. However, the limit oxygen index of polyacrylonitrile materials is only 17%, polyacrylonitrile materials are flammable fibers, and toxic cyanide and the like are released in the combustion process, so that the application of polyacrylonitrile materials is limited to a certain extent.
In recent years, research on high-heat-resistance graphene and graphene derivative flame-retardant polymer materials improves the fireproof performance of the materials, and becomes a hot point of research. As an important two-dimensional carbon material, the graphene has the characteristics of high stability, strong barrier, large surface adsorption and the like, and can effectively reduce heat transfer and mass transfer in the material combustion process. When the graphene-based polymer flame retardant material encounters high temperature or open fire, on the one hand, since the graphene lamellar structure is compact and continuous, it can prevent oxygen from entering deep into the material. In addition, due to the excellent thermal conductivity of the graphene, local and excessively high heat of the material can be rapidly conducted to the rest part of the material, so that the heat can be well dispersed, and the fire is not easy to spread and diffuse. On the other hand, the graphene has extremely high specific surface area, so that organic volatile matters generated in the combustion process can be adsorbed, and the release and diffusion of the organic volatile matters in the combustion process are prevented. Therefore, the unique two-dimensional carbon atom lamellar structure can be used as a good flame retardant to improve the flame retardant property of the polymer material.
The preparation method of the existing functionalized graphene flame retardant mainly comprises the following steps: (1) and (3) non-covalently modifying graphene oxide by using a flame retardant. For example, patent CN201510689007.3 discloses a method for preparing a molybdenum oxide nano-loaded graphene flame retardant material, which comprises mixing graphene oxide and ammonium molybdate according to a certain mass ratio, ball-milling, heating from 100 ℃ to 150 ℃ under the protection of nitrogen, and keeping the temperature for a period of time, to obtain the molybdenum oxide nano-loaded graphene flame retardant material, wherein the graphene oxide used in the method is prepared by an improved Hummer method, the obtained graphene has many defects, and cannot be completely reduced, and many strong acids are used in the reaction process, and the strong oxidant and the reducing agent do not meet the requirement of green production. (2) And (3) covalently modifying graphene oxide by using a flame retardant. For example, patent CN201810290541.0 discloses grafting a flame retardant DOPO to graphene oxide, and then performing melt blending and compression molding on the obtained flame retardant modified graphene and polylactic acid to obtain a functionalized graphene flame retardant reinforced polylactic acid composite material. The composite material exhibits good flame retardant properties and thermal stability. On the one hand, the graphene oxide used in the functionalized graphene flame retardant prepared by the method is prepared by adopting an improved Hummer method, the obtained graphene has more defects and can not be completely reduced, and a lot of strong acid, strong oxidant and reducing agent are used in the reaction process; on the other hand, the covalent modification of graphene oxide in an organic solvent system does not meet the requirement of green production. In addition, although the flame retardant performance of the material is improved to a certain extent by introducing graphene at present, different material substrates are different, influence factors of mechanical properties are different, and how to enable the flame retardant performance and the mechanical properties to be compatible is a technical barrier needing important breakthrough. Therefore, the development of a flame retardant functionalized graphene which has the advantages of simple method, low defect, no pollution and no damage to the mechanical property of the composite material is urgently needed in the market.
Disclosure of Invention
According to the invention, the graphite paper is subjected to anodic electrolysis stripping in the flame retardant aqueous solution by an electrochemical method to prepare the flame retardant functionalized graphene with low defect and few layers, and the method is simple, environment-friendly and easy to operate; and then preparing the polyacrylonitrile/graphene nano composite material by using the functionalized graphene flame retardant and polyacrylonitrile by adopting a solution blending method, and researching the thermal stability, the heat release performance and the mechanical property of the composite material.
The invention mainly aims to provide a preparation method of a functionalized graphene flame retardant, which comprises the following steps:
(1) electrolyzing by using an aqueous solution of sodium diethylenetriamine penta-methylene phosphate as an electrolyte, a graphite sheet as an anode and a metal rod as a cathode to obtain the graphene modified by the sodium diethylenetriamine penta-methylene phosphate;
(2) and (2) mixing the graphene modified by the diethylenetriamine penta-methylene sodium phosphate obtained in the step (1) with an iron source to obtain the functionalized graphene flame retardant.
In one embodiment of the present invention, the voltage for electrolysis in the step (1) is 5 to 15V.
In one embodiment of the invention, the concentration of the aqueous solution of sodium diethylenetriamine pentamethylene phosphate in the step (1) is 0.1mol/L to 0.5 mol/L.
In one embodiment of the present invention, the time for electrolysis in the step (1) is 1 to 6 hours.
In one embodiment of the invention, the metal rod comprises a copper rod.
In one embodiment of the invention, the graphite flakes are graphite flakes having a thickness of 0.3mm to 1 mm.
In one embodiment of the invention, the graphite sheet comprises one or more of flake graphite, highly oriented graphite, expanded graphite.
In one embodiment of the invention, the anode and the cathode are placed in parallel at a distance of 1-2 cm.
In one embodiment of the present invention, the step (2) further comprises: and after the electrolysis is finished, filtering and drying to obtain the water-dispersible graphene.
In one embodiment of the invention, the graphene modified by sodium diethylenetriamine pentamethylene phosphate in the step (3) is mixed with 10-20mmol of iron source per 1g of the graphene.
In an embodiment of the invention, the functionalized graphene flame retardant is obtained by mixing, ultrasonic treatment, filtration and drying in the step (3).
In an embodiment of the present invention, the method specifically includes:
(1) preparing an aqueous solution of diethylenetriamine penta (methylene sodium phosphate) with a certain molar concentration;
(2) the graphite flake is an anode, the copper rod is a cathode, the two electrodes are arranged in parallel at a distance of 1-2cm, a certain direct current voltage is applied to electrolyze and strip the graphite flake, and after the electrolysis is finished, the graphite flake is filtered, cleaned and dried to obtain the DTPMPA modified graphene;
(3) mixing the graphene modified by the sodium diethylenetriamine pentamethylene phosphate with an iron source, carrying out ultrasonic treatment for a period of time, filtering, and drying the obtained precipitate to obtain the functionalized graphene flame retardant.
The second purpose of the invention is to provide a functionalized graphene flame retardant, which is prepared by the method.
The third purpose of the invention is to provide a polyacrylonitrile composite material, wherein the composite material comprises the functionalized graphene flame retardant.
In one embodiment of the invention, the polyacrylonitrile composite material is obtained by blending polyacrylonitrile and a functionalized graphene flame retardant through a solution and then drying.
In one embodiment of the invention, the addition amount of the functionalized graphene flame retardant accounts for 1% -5% of the total mass of polyacrylonitrile and the functionalized graphene flame retardant.
The fourth purpose of the invention is to provide a carpet, a tarpaulin or a curtain, wherein the carpet, the tarpaulin or the curtain contains the polyacrylonitrile composite material.
The fifth purpose of the invention is to apply the functionalized graphene flame retardant or the polyacrylonitrile composite material in the field of automotive interior trim or clothing fabric.
The invention has the beneficial effects that:
(1) the number of layers of the graphene prepared by the method is less than 5; while obtaining graphene ID/IGThe value is not more than 0.8, and the defects are small.
(2) According to the invention, the phosphorus element, the nitrogen element and the iron element are successfully loaded on the surface of the graphene, so that the functionalized graphene flame retardant is prepared, the synergistic flame retardant effect of the phosphorus-nitrogen flame retardant element and the ferric iron catalyzed carbon formation and the physical barrier of graphene sheets is realized, and the flame retardant efficiency in the matrix is effectively improved.
(3) The functionalized graphene flame-retardant polyacrylonitrile composite material prepared by the invention has good flame-retardant performance and thermal stability. When the addition amount of the functionalized graphene flame retardant is 5%, the maximum heat release rate peak value (PHRR) of the polyacrylonitrile composite material is reduced to 111.2W/g from 172.5W/g, and is reduced by 35.5%; meanwhile, the carbon formation amount after combustion is increased from 46.8% to 50.3%, and the carbon layer becomes compact by SEM representation; meanwhile, the mechanical property of the material is not damaged, and even the material has a lifting effect.
The functionalized graphene flame retardant prepared by the invention improves the flame retardant property of the polyacrylonitrile composite material, and simultaneously, when the addition amount of the flame retardant is 5%, the thermal stability of the composite material is not affected, and simultaneously, the mechanical property of the material is also improved. The obtained composite material has wide application prospect in the fields of automobile interior trim, garment materials, tarpaulin, curtains, carpets and the like.
Drawings
FIG. 1 is a mechanism diagram of electrochemical preparation of a functionalized graphene flame retardant according to the present invention;
figure 2 high power TEM image of functionalized graphene flame retardant;
FIG. 3 is a Raman spectrum of a functionalized graphene flame retardant;
FIG. 4 is an X-ray photoelectron spectrum of a functionalized graphene flame retardant;
FIG. 5 is a micro calorimeter heat release rate curve of polyacrylonitrile/functionalized graphene flame retardant nanocomposite;
FIG. 6 is a thermogravimetric curve of a polyacrylonitrile/functionalized graphene flame retardant nanocomposite material under a nitrogen condition;
FIG. 7 is an SEM image of carbon residue of polyacrylonitrile/functionalized graphene flame retardant nanocomposite material burning at 550 ℃.
Detailed Description
In order to further illustrate the present invention, the electrochemical preparation of the functionalized graphene flame retardant and the polyacrylonitrile nanocomposite material flame-retarded by the same according to the present invention are described in detail below with reference to the examples.
In the following examples, polyacrylonitrile was purchased from believed to be a plastic material, Inc. and had a molecular weight of 220000.
The mechanism schematic diagram of the functionalized graphene flame retardant prepared by the invention is shown in fig. 1.
Example 1: preparation of functionalized graphene flame retardant
Taking graphite paper with the thickness of 0.5mm made of expanded graphite as an anode, a copper bar as a cathode, and 150mL of 0.2mol/L sodium diethylenetriamine pentamethylene phosphonate as electrolyte, applying a direct current voltage of 5V for electrolysis for 6h, filtering, cleaning and drying to obtain graphene modified by the sodium diethylenetriamine pentamethylene phosphonate, adding 1g of graphene modified by the sodium diethylenetriamine pentamethylene phosphonate into 0.5mol/L molten iron chloride solution (30mL) while stirring and carrying out ultrasonic treatment for 3h, filtering, and drying the obtained precipitate to obtain the functionalized graphene flame retardant.
The high-power transmission electron microscope of the prepared functionalized graphene flame retardant is shown in fig. 2. As can be seen from high power transmission electron microscope analysis, the number of layers of the obtained graphene was 2.
The raman spectrum analysis of the prepared functionalized graphene flame retardant is shown in fig. 3. The functionalized graphene flame retardant is in 1330cm-1And 1574cm-1There are two significant raman peaks, which are assigned to the D and G peaks, respectively. The D peak reflects amorphous carbon and lattice defects in the graphene sheet layer, and the G peak is caused by the phonon E2G vibration mode in the hexagonal graphite structure and is sp of carbon2A characteristic peak of vibration. Intensity ratio of D peak to G peak (I)D/IG) Can be used for measuring the size and the structural defect of the graphene, and the higher the ratio is, the carbon disordered structure and the defect are shownThe more. I of graphene prepared by the methodD/IGA value of 0.41 indicates that the structural defects of graphene are relatively small.
An X-ray photoelectron spectrum of the prepared functionalized graphene flame retardant is shown in fig. 4. From an X-ray photoelectron spectrum, the peaks are C1S and O1S at 283.4eV and 530.6eV respectively, the modified functionalized graphene has a new peak of P2P binding energy at 132.1eV, a new peak of N1s binding energy at 399.7eV, and a new peak of Fe 2P binding energy at 711.6 eV. From the result of an X-ray photoelectron spectrum, the sodium diethylenetriamine pentamethylene phosphonic acid and ferric iron are successfully modified on the surface of the graphene.
Example 2: preparation of functionalized graphene flame retardant
Taking 0.3mm graphite paper made of flake graphite as an anode, a copper bar as a cathode, and 150ml of 0.5mol/L sodium diethylenetriamine pentamethylene phosphonate as electrolyte, applying 5V direct current voltage for electrolysis for 6h, filtering, cleaning and drying to obtain the graphene modified by the sodium diethylenetriamine pentamethylene phosphonate, adding 1g of the graphene modified by the sodium diethylenetriamine pentamethylene phosphonate into 0.5mol/L molten iron chloride solution, stirring and carrying out ultrasonic treatment for 3h, filtering, and drying the obtained precipitate to obtain the functionalized graphene flame retardant.
The number of layers of the obtained graphene is 3, ID/IGThe value is 0.68, the defects are small.
Example 3: preparation of functionalized graphene flame retardant
Taking 1mm of graphite paper made of highly oriented graphite as an anode, a copper bar as a cathode, and 150ml of 0.1mol/L sodium diethylenetriamine pentamethylene phosphonate as electrolyte, applying 5V direct current voltage for electrolysis for 6h, filtering, cleaning and drying to obtain the graphene modified by the sodium diethylenetriamine pentamethylene phosphonate, adding 1g of the graphene modified by the sodium diethylenetriamine pentamethylene phosphonate into 0.5mol/L molten iron chloride solution, stirring and carrying out ultrasonic treatment for 3h, filtering, and drying the obtained precipitate to obtain the functionalized graphene flame retardant.
The number of layers of the obtained graphene is 3, ID/IGThe value is 0.71, and the defects are small.
Example 4: preparation of functionalized graphene flame retardant
Referring to example 1, the functionalized graphene flame retardant was prepared by replacing the electrolytic voltage with 10V and 15V, and keeping the other conditions unchanged.
The flame retardant materials obtained at different voltages were measured by X-ray photoelectron spectroscopy, and the results are shown in table 1.
TABLE 1 Performance results for flame retardant materials obtained at different voltages
Figure BDA0002180393260000051
The strength ratio of C to O (C/O) can be used as a measure of the structural defects of graphene, with lower carbon content or higher oxygen content, and lower ratios indicating more carbon disordered structure and defects. As can be seen from Table 1, when the electrolytic voltage is 5V, the obtained flame retardant material has small structural defects and better performance.
Example 5: preparation of graphene/polyacrylonitrile nano composite material
Adding the functionalized graphene flame retardant prepared in the embodiment 1 into a DMF (dimethyl formamide) solvent with the mass volume of 20 times, ultrasonically stripping for 2 hours, adding polyacrylonitrile into the DMF solvent of the graphene according to the mass ratio of the functionalized graphene flame retardant to the polyacrylonitrile of 1:99, treating for 5 hours at 80 ℃, cooling, introducing into a mold, and volatilizing the DMF solvent to obtain the functionalized graphene/polyacrylonitrile nano composite material (PAN/FGNS-1.0).
Example 6: preparation of graphene/polyacrylonitrile nano composite material
Adding the functionalized graphene flame retardant prepared in the embodiment 1 into a DMF (dimethyl formamide) solvent with the mass volume of 20 times, ultrasonically stripping for 2 hours, adding polyacrylonitrile with a certain mass into the DMF solvent of the graphene according to the mass ratio of the functionalized graphene flame retardant to the polyacrylonitrile of 3:97, treating for 5 hours at 80 ℃, cooling, introducing into a mold, and volatilizing the DMF solvent to obtain the functionalized graphene/polyacrylonitrile nano composite material (PAN/FGNS-3.0).
Example 7: preparation of graphene/polyacrylonitrile nano composite material
Adding the functionalized graphene flame retardant prepared in the embodiment 1 into a DMF (dimethyl formamide) solvent with the mass volume of 20 times, ultrasonically stripping for 2 hours, adding polyacrylonitrile with a certain mass into the DMF solvent of the graphene according to the mass ratio of the functionalized graphene flame retardant to the polyacrylonitrile of 5:95, treating for 5 hours at 80 ℃, cooling, introducing into a mold, and volatilizing the DMF solvent to obtain the functionalized graphene/polyacrylonitrile nano composite material (PAN/FGNS-5.0).
Example 8: preparation of polyacrylonitrile material
Preparing a polyacrylonitrile blank sample: referring to example 5, polyacrylonitrile was directly added to the DMF solvent without adding functionalized graphene, and the other conditions were unchanged, so as to obtain a polyacrylonitrile material.
The mechanical properties of the fiber materials prepared in examples 5 to 8 were measured: the breaking strength and elongation at break were measured according to GB/T3923.1-1997.
The results obtained are shown in Table 2.
TABLE 2 mechanical Properties of fiber materials prepared in examples 5-8
Figure BDA0002180393260000061
As can be seen from table 2, the functionalized graphene material of the present invention has no damage to the mechanical properties of the polyacrylonitrile composite material, and when 5% of the functionalized graphene material is added, the functionalized graphene material can also improve the mechanical properties of the material, so as to avoid the phenomenon that the mechanical properties of the material are seriously damaged and inhibited by the common graphene material in a large amount.
The heat release test of polyacrylonitrile and the graphene/polyacrylonitrile nanocomposite prepared in the embodiments 5 to 8 is performed by using a micro calorimeter, and the result is shown in fig. 5, fig. 5 is a release rate curve diagram of the polyacrylonitrile and the graphene/polyacrylonitrile nanocomposite provided in the embodiments 5 to 8 of the present invention, and as can be seen from fig. 5, the peak value of the heat release rate of the graphene/polyacrylonitrile nanocomposite provided in the present invention is gradually reduced with the increase of the addition amount of the functionalized graphene, and the maximum reduction amplitude is reduced from 172.5W/g to 111.2W/g, which is reduced by 35.5%; at least the amplitude is reduced to 147.1W/g, and the reduction is 14.7%.
Thermal performance tests are performed on the polyacrylonitrile and the graphene/polyacrylonitrile nanocomposite material prepared in the embodiments 5 to 8 by using a thermogravimetric analyzer under a nitrogen condition, and the results are shown in fig. 6, fig. 6 is a thermogravimetric curve of the polyacrylonitrile and the graphene/polyacrylonitrile nanocomposite material provided in the embodiments 5 to 8 of the present invention, and it can be seen from fig. 6 that the thermal performance of the graphene/polyacrylonitrile nanocomposite material provided by the present invention is improved along with the increase of the addition amount of the functionalized graphene; meanwhile, the carbon formation amount after combustion is increased from 46.8% to 50.3%, so that the carbon formation performance of the functionalized graphene flame retardant is relatively good.
To further illustrate the performance of the functionalized graphene catalyzed carbon formation and the flame retardant performance, the samples of examples 6 and 7 were fired in a muffle furnace at 550 ℃ to form carbon slag in air, and the carbon slag was characterized by Scanning Electron Microscopy (SEM), and the results are shown in fig. 7; as can be seen from fig. 7, the carbon residue generated by the graphene/polyacrylonitrile nanocomposite material added with 5% of functionalized graphene is relatively compact, and a sheet-formed structure is generated, so that oxygen can be prevented from entering the deep part of the material better, and a flame retardant effect is achieved.
Comparative example 1:
0.5g of graphene oxide GO, prepared by using natural graphite, sodium nitrate and potassium permanganate as raw materials through a Hummers method) is dissolved in 100mL of N, N-dimethylformamide, and after complete dissolution, 100mL of thionyl chloride is added and stirred and refluxed in an oil bath at 65 ℃ for 8 hours. After the reaction is finished, cooling to room temperature, filtering, washing to be neutral by deionized water, and vacuum-drying at 70 ℃ for 12 hours to obtain an intermediate product; and adding the intermediate product and 3.053g of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) into 300mL of tetrahydrofuran solution, stirring and refluxing for 12h in an oil bath at 85 ℃, cooling the obtained precipitate to room temperature, filtering, and drying to obtain the functionalized graphene flame retardant (FGO-HQ).
Referring to example 7, the functionalized graphene material was replaced with a functionalized graphene flame retardant FGO-HQ, and the composite material was prepared under otherwise unchanged conditions.
The flame retardant property of the obtained material is good, but mechanical property tests are carried out on the obtained composite material, and the result shows that the breaking strength is about 31.2cN, which is reduced by 26.8% compared with that of a pure polyacrylonitrile material, and the fact that the pure graphene has an obvious destructive effect on the mechanical property of the polyacrylonitrile material is demonstrated.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A preparation method of a functionalized graphene flame retardant is characterized by comprising the following steps:
(1) electrolyzing by using an aqueous solution of sodium diethylenetriamine penta-methylene phosphate as an electrolyte, a graphite sheet as an anode and a metal rod as a cathode to obtain the graphene modified by the sodium diethylenetriamine penta-methylene phosphate;
(2) and (2) mixing the graphene modified by the diethylenetriamine penta-methylene sodium phosphate obtained in the step (1) with an iron source to obtain the functionalized graphene flame retardant.
2. The method according to claim 1, wherein the voltage for electrolysis in step (1) is 5-15V.
3. The method according to claim 1 or 2, wherein the concentration of the aqueous solution of sodium diethylenetriamine pentamethylene phosphate in the step (1) is 0.1mol/L to 0.5 mol/L.
4. The method according to any one of claims 1 to 3, wherein the electrolysis time in step (1) is 1 to 6 hours.
5. The functionalized graphene flame retardant prepared by the method of any one of claims 1 to 4.
6. A polyacrylonitrile composite material, characterized in that the composite material comprises the functionalized graphene flame retardant of claim 5.
7. The composite material of claim 6, wherein the polyacrylonitrile composite material is obtained by blending polyacrylonitrile and a functionalized graphene flame retardant through a solution and then drying.
8. The composite material according to claim 6 or 7, wherein the addition amount of the functionalized graphene flame retardant accounts for 1-5% of the total mass of the polyacrylonitrile and the functionalized graphene flame retardant.
9. A carpet or tarpaulin or window covering, characterized in that the polyacrylonitrile composite material of any one of claims 6 to 8 is contained in the carpet or tarpaulin or window covering.
10. Use of the functionalized graphene flame retardant of claim 5 or the polyacrylonitrile composite material of any one of claims 6 to 8 in the field of automotive interior or clothing fabric.
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CN107353437A (en) * 2017-08-08 2017-11-17 青岛长荣化工科技有限公司 A kind of expansion type flame retardant and preparation method thereof
KR20180000248A (en) * 2016-06-22 2018-01-02 (주)윈스 A method for treating surface of particles and a suspension composition comprising the particles treated thereby
CN108862254A (en) * 2018-07-12 2018-11-23 西安交通大学 A kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene

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CN103773086A (en) * 2014-01-15 2014-05-07 哈尔滨工业大学 Amino-functionalization assembling method for graphene
CN104445177A (en) * 2014-12-16 2015-03-25 中国科学院宁波材料技术与工程研究所 Preparation method of graphene, and graphene
KR20180000248A (en) * 2016-06-22 2018-01-02 (주)윈스 A method for treating surface of particles and a suspension composition comprising the particles treated thereby
CN107353437A (en) * 2017-08-08 2017-11-17 青岛长荣化工科技有限公司 A kind of expansion type flame retardant and preparation method thereof
CN108862254A (en) * 2018-07-12 2018-11-23 西安交通大学 A kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene

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