CN105420794A - Preparation method for graphene/ferroferric oxide composite material - Google Patents
Preparation method for graphene/ferroferric oxide composite material Download PDFInfo
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- CN105420794A CN105420794A CN201510779144.6A CN201510779144A CN105420794A CN 105420794 A CN105420794 A CN 105420794A CN 201510779144 A CN201510779144 A CN 201510779144A CN 105420794 A CN105420794 A CN 105420794A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Abstract
The invention discloses a preparation method for a graphene/ferroferric oxide composite material. According to the preparation method, graphite is directly subjected to ultrasonic peeling and oxidation in organic solvent to obtain graphene oxide dispersion liquid, then iron ion salt is added into the obtained dispersion liquid, and positively-charged graphene oxide dispersion liquid is obtained due to the fact that graphene oxide is combined with positively-charged iron ions easily; and then electrophoretic deposition is conducted, a positive plate and a negative plate are arranged in an electrophoretic deposition pool, the obtained positively-charged graphene oxide dispersion liquid serves as an electrolyte of the electrophoretic deposition, the graphene oxide and the iron ions are deposited on the negative plate together under the action of impressed currents, the negative plate is placed into a dryer to be dried and subjected to high-temperature treatment under the inert gas protection, and the graphene/ferroferric oxide composite material is obtained on the surface of the negative plate after cooling. The graphene/ferroferric oxide composite material prepared through the preparation method is even in distribution and free of other impurities.
Description
Technical field
The invention belongs to technical field of electrochemistry, relate to a kind of nano material, specifically a kind of preparation method of Graphene/ferriferrous oxide composite material.
Background technology
By a kind of method that electrochemical process composite graphite alkene and metal oxide are brand-new composite graphite alkene and metal oxide.The preparation of Graphene and ferriferous oxide mixture is the focus studied in recent years.
Since finding Graphene from 2004, just cause the extensive concern of researcher.Graphene has excellent mechanics, electronics, optics and thermal property, has great potential using value in fields such as microelectronics, stored energy, catalysis, biosensors.Due to the two-dimensional nanostructure of its uniqueness, the matrix material that with the addition of Graphene is made often to have excellent performance.Such as, Huang etc. at ChemicalSocietyReviews, 2012, describe the application of a large amount of graphene composite material on 41 (2): 666-686..Z 250 because it is cheap, aboundresources, the advantage such as environmentally friendly and receive much concern.Single Z 250 electroconductibility is poor on the other hand, and particle is easily reunited, and carbon base body not only can cushion huge volumetric expansion, but also significantly enhances electroconductibility.Mixture nano ferriferrous oxide being carried on graphenic surface formation can embody a concentrated reflection of out both excellent properties.Such as Zhang Yi etc. are at ActaPhysico-ChimicaSinica, 2011, the Fe3O4 magnetic nano-particle that the particle diameter that utilized high-temperature decomposition to prepare is 18nm is reported on 27 (5): 1261-1266, and carry out carboxylated modification, then carry out crosslinking reaction with the graphene oxide of polymine (PEI) chemically modified, obtain magnetic/functionalized graphene oxide (MGO) matrix material.Yao etc., at ChemicalEngineeringJournal, 2012,184:326-332 report by PH and Fe in modulation GO solution
2+, Fe
3+amount ratio, namely co-precipitation prepare Fe3O4 nanoparticle embed graphene composite material, to the removal of Methylene blue, there is good effect.
The method preparing Graphene/ferriferrous oxide composite material is at present main mainly with solution phase chemical reduction, take graphene oxide as raw material, add certain dispersion agent and iron ion salt, make homodisperse suspension, iron ion is made to be attached on graphene oxide sheet, add chemical reducing agent again or utilize the catalytic performance of light that graphene oxide is reduced into Graphene, thus obtain composite.But this class methods complicated operation, condition is harsh, and long reaction time, not easily large-scale production, the reductive agent added, dispersion agent can remain in prepared material, are difficult to thorough removal simultaneously.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation method of Graphene/ferriferrous oxide composite material, the preparation method of described this Graphene/ferriferrous oxide composite material solves that method complicated operation, the condition preparing Graphene/ferriferrous oxide composite material of the prior art is harsh, residue is difficult to the technical problem thoroughly removed.
The invention provides a kind of preparation method of Graphene/ferriferrous oxide composite material, comprise the following steps:
1) step prepared of graphene oxide dispersion;
Get graphite oxide and the first organic solvent, the material ratio of graphite oxide and the first organic solvent is 0.1 ~ 1g:1L, is joined by graphite oxide in the first organic solvent, control temperature 20-40 DEG C, and ultrasonic power 150 ~ 300W carries out ultrasonic 1-10h and obtains dispersion liquid; The first described organic solvent is 1-Methyl-2-Pyrrolidone, tetrahydrofuran (THF), dimethyl formamide, butyrolactone, acetone or alcohol;
2) step prepared by electrically charged graphene oxide dispersion is prepared;
Get iron ion salt and the second organic solvent, the material ratio of iron ion salt and the second organic solvent is 0.5 ~ 10mol:lL, is dissolved in the second organic solvent by iron ion salt and obtains iron ion salts solution; The second described organic solvent is 1-Methyl-2-Pyrrolidone, tetrahydrofuran (THF), dimethyl formamide, butyrolactone, acetone or alcohol; Described iron ion salt is iron nitrate, iron(ic) chloride, ferric sulfate or iron acetate; The iron ion salts solution of above-mentioned gained is joined in the graphene oxide dispersion of gained in step (1), iron concentration is made to be 0.1-5mmol/L, graphene oxide solids content is 0.05-0.4g/L, graphene oxide absorption iron ion and positively charged, obtains positively charged graphene oxide dispersion;
3) electrophoretic deposition prepares the step of Graphene/ferriferrous oxide composite material;
Positive plate is provided with and negative plate carries out electrophoretic deposition, using the electrolytic solution of the positively charged graphene dispersing solution of step (2) gained as electrophoretic deposition in electrophoretic deposition pond; With copper, aluminium, nickel, stainless steel, or with coated copper, aluminium, nickel or stainless conductive substrates, or the anode pole piece using the conductive substrates of coated with conductive material as electrophoretic deposition pond; The spacing that above-mentioned electrophoretic deposition process controls between positive and negative plate is 1-50mm; impressed voltage is 10-100V; electrophoretic deposition process temperature is 10-80 DEG C; time is 1-60min; graphene oxide in positively charged graphene oxide dispersion is deposited on cathode pole piece; then cathode pole piece is placed in oven drying; by gained dry sample under protection of inert gas; at the Temperature Treatment 1-4h of 200 DEG C-400 DEG C; and room temperature is cooled in rare gas element, namely obtain Graphene/ferriferrous oxide composite material on the surface of cathode pole piece.
Further, in step (2), the solids content of described graphene oxide is 0.2g/L.
Further, the conductive substrates of the negative plate described in step (3) is copper, aluminium, nickel or stainless steel; Or be coated copper, aluminium, nickel or stainless conducting base; Or be radio frequency matrix, described radio frequency matrix is carbon fiber textile product, glassy carbon electrode or conductive polymers.
Further, described carbon fiber textile product are carbon fiber paper; Described conductive polymers is polyaniline.
Further, in step (3), the rare gas element passed into comprises argon gas, nitrogen or Krypton.
Further, the spacing that the electrophoretic deposition process described in step (3) controls between positive and negative plate is 5-15mm, and impressed voltage is 40-60V, and electrophoretic deposition process temperature is 25-60 DEG C, and the time is 5-20min.
Further, it is 5-15mm that the electrophoretic deposition process described in step (3) controls positive and negative electrode pole piece spacing, and impressed voltage is 40V, and electrophoretic deposition process temperature is 40 DEG C, and the time is 10min.
Further, pyroprocessing temperature preferably 300 DEG C, time 3h.
The direct ultrasonic stripping graphite oxide in organic solvent of the present invention obtains graphene oxide dispersion, iron ion salt is added again in the dispersion liquid of gained, graphene oxide due to containing more hydroxyl, carboxyl, epoxy group(ing) etc. containing oxygen official can and with larger electronegativity, due to electrostatic interaction, very easily with positive charge iron ion combine, make graphene oxide electrically charged; Then take the method for electrophoretic deposition on conducting base, prepare Graphene/silicon/iron oxide composite material.
The present invention can prepare Graphene/ferriferrous oxide composite material on cathode pole piece and conductive substrates, and deposition can be carried out on the cathode pole piece of 3D structure and conductive substrates, and the Graphene/ferriferrous oxide composite material therefore prepared has multilevel hierarchy.The present invention passes through the solids content of adjustment graphene oxide with the experiment condition in the concentration of interpolation iron ion salt and deposition process as spacing, deposition voltage, depositing times etc., can control the thickness of final Graphene with the content of Z 250 and microscopic appearance, coating.Prepared Graphene/ferriferrous oxide composite material is evenly distributed, not containing other impurity, have potential using value in catalysis, photoelectricity, biosensor, energy storage field.Simultaneously because ferroferric oxide nano granules is evenly dispersed in the nano graphite flakes surface of good conductivity, therefore not only effectively improve the specific surface area of Z 250, also reduce the internal resistance of Graphene/ferriferrous oxide composite material, enhance the electroconductibility of material.
The present invention adopts electricity deposition technique, the reduction of graphene oxide can be realized while realizing graphite oxide and iron ion deposition, environmental friendliness, reduces to graphene oxide unlike traditional employing chemical process, produces some toxic gases or introduces some other elements; Secondly by regulating correlation parameter, can realize the control of thickness of coating and the regulation and control to ferriferrous oxide particles size and pattern.
The present invention compares with prior art, and its technical progress is significant.The present invention adopts the mode of electrophoretic deposition that ferriferrous oxide nano-particle is evenly compounded in graphene layer, and the load of Z 250 and Graphene can avoid the reunion of oxide compound, reduces the greying phenomenon of Graphene simultaneously.The method has the advantages such as simple to operate, production cost is low, product homogeneity is good, easy to control, and the mixture obtained by the method has application prospect widely in electromagnetic material, biosensor, energy storage material, drug release etc.
Accompanying drawing explanation
Fig. 1 is the structural representation in electrophoretic deposition pond, 1 be direct supply, 2 is wherein positive pole, 3 is negative pole, 4 is tiselius apparatus, 5 for electrolytic solution.
Fig. 2 is the scanning electron microscope (SEM) photograph of Graphene/ferriferrous oxide composite material that embodiment 2 obtains.
Fig. 3 is the Raman spectrogram of graphite oxide prepared by embodiment 1.
Fig. 4 is the Raman spectrogram of Graphene/ferriferrous oxide composite material that embodiment 2 obtains.
Fig. 5 is the scanning electron microscope (SEM) photograph of Graphene/ferriferrous oxide composite material that embodiment 3 obtains.
Embodiment
Also by reference to the accompanying drawings the present invention is set forth further below by specific embodiment, but do not limit the present invention.
Raman spectrum test of the present invention uses the silent Raman spectrometer (model DXRRamanMacroscope) flying your production of generation of U.S.'s match.
The S-3400N scanning electronic microscope that the scanning electron microscope used is produced for Hitachi.
The structural representation in the electrophoretic deposition pond that the present invention is used as shown in Figure 1.
Embodiment 1
The preparation method of graphite oxide adopts improvement Hummers legal system standby, concrete steps are: added by 1g graphite in the 40ml vitriol oil of 0 DEG C 60 ~ 80%, add 1g saltpetre, add 7g potassium ferrate in batches subsequently, through supersound process until dissolve completely, the temperature of whole process system maintains less than 5 DEG C, transfer in the water-bath of 30-40 DEG C, magnetic agitation answers two hours, add 100ml deionized water, finally transfer in 98 DEG C of water-baths, stir 1.5h, close on heat-up time to terminate, slowly add H
2o
2be oxidized, solution filtered while hot, once use a large amount of hydrochloric acid/washed with de-ionized water, until PH=7, vacuum is spent the night oven dry.
Concrete, described graphite is that particle diameter is 80 order-500 object natural graphite powders, natural flake graphite, micro crystal graphite or expanded graphite;
Embodiment 2
A preparation method for Graphene/ferriferrous oxide composite material, comprises the following steps:
(1), in graphite oxide: the first organic solvent is the ratio of 1g:1L, graphite oxide is joined in the first organic solvent, control temperature 20-40 DEG C, power 200W carries out ultrasonic 4h and obtain dispersion liquid; Concrete, the first described organic solvent is 1-Methyl-2-Pyrrolidone;
(2), in iron ion salt: the second organic solvent is the ratio of 5mmol:1L, iron ion salt is dissolved in the second organic solvent and obtains 5mmol/L iron ion salts solution; Concrete, described iron ion salt is iron nitrate; Described second organic solvent is 1-Methyl-2-Pyrrolidone; The iron ion salts solution of above-mentioned gained is joined in the graphene oxide dispersion of gained in step (1), iron concentration is made to be 1.0mmol/L, graphene oxide solids content is 0.1g/L, and then ultrasonic 30min makes graphene oxide adsorb iron ion and positively chargedly namely obtain positively charged graphene oxide dispersion;
(3) electrolytic solution of the positively charged graphene oxide dispersion prepared by 45mL step (2) as electrophoretic deposition pond, is got; With 400 order 316L stainless steel meshs for cathode pole piece, stainless steel is that anode pole piece carries out electrophoretic deposition, obtains the cathode pole piece depositing Graphene; Then the cathode pole piece depositing Graphene is placed in 60 DEG C of oven drying 12h, by gained dry sample under protection of inert gas, high temperature 300 DEG C process 3h, and room temperature is cooled in rare gas element, namely obtain Graphene/ferriferrous oxide composite material on the surface of cathode pole piece and obtain Graphene/ferriferrous oxide composite material; Above-mentioned cathode pole piece stainless steel mesh used is cut to 2.5 × 1.5cm
2, immersing electrolytic solution area is 1.5 × 1cm
2; Stainless steel anode pole piece 6# abrasive paper for metallograph used is polished, and cleans with deionized water; In above-mentioned electrophoretic deposition process, positive and negative plate spacing is 10mm, and volts DS is 40V, and depositing temperature is 40 DEG C, and depositing time is 10min.
The scanning electron microscope (SEM) photograph of the Graphene/ferriferrous oxide composite material of above-mentioned gained as shown in Figure 2, from figure, 2 can see that nano ferriferrous oxide granule lamella is together with graphene sheet layer uniform loading, and with for assembled unit, prepare the lamellar graphite alkene/silicon/iron oxide composite material of three-dimensional order.
Fig. 3,4 is respectively the Raman spectrum of Graphene/ferriferrous oxide composite material of preparation in graphite oxide Raman spectrum and embodiment 2 prepared by embodiment 1, from Fig. 3 and Fig. 4, all can see that graphite oxide and Graphene/ferriferrous oxide composite material all have two characteristic peaks, be positioned at 1580cm respectively
-1g peak, be positioned at 1350cm
-1neighbouring D peak.
Further, 325cm is positioned in the Raman spectrogram of the Graphene/ferriferrous oxide composite material of gained
-1, 670cm
-1place's characteristic peak, corresponding Fe
3o
4the raman characteristic peak of Fe-O and Fe-O-Fe.
Embodiment 3
A preparation method for Graphene/ferriferrous oxide composite material, comprises the following steps:
(1), graphene oxide dispersion preparation process is with embodiment 1;
(2), in iron ion salt: the second organic solvent is the ratio of 5mmol:1L, iron ion salt is dissolved in the second organic solvent and obtains 1g/L iron ion salts solution; Described iron ion salt is iron(ic) chloride; Described second organic solvent is 1-Methyl-2-Pyrrolidone is solvent; The iron ion salts solution of above-mentioned gained is joined in the graphene oxide dispersion of gained in step (1), iron concentration is made to be 0.5mmol/L, Graphene solids content is 0.2g/L, and then magnetic agitation 30min makes graphene oxide adsorb iron ion and positively chargedly namely obtain positively charged graphene oxide dispersion;
(3), get the electrolytic solution of the positively charged graphene oxide dispersion prepared by 45mL step (2) as electrophoretic deposition pond, with 400 copper sheets for cathode pole piece, stainless steel substrates is that anode pole piece carries out electrophoretic deposition, obtains the cathode pole piece depositing Graphene; Then by depositing the cathode pole piece of Graphene as 60 DEG C of oven drying 12h, finally Graphene/ferriferrous oxide composite material is obtained on the surface of cathode pole piece copper sheet; Cathode pole piece copper sheet used in above-mentioned electrophoretic deposition process, is cut to 2.5 × 1.5cm
2size, uses acetone, ethanol, deionized water ultrasonic cleaning 10min successively, and immersing electrolytic solution area is 1.5 × 1.0cm
2; Anode pole piece stainless steel substrates 6# abrasive paper for metallograph used is polished, and cleans with deionized water; In above-mentioned electrophoretic deposition process, positive and negative plate spacing is 5mm, and adding volts DS is 60V, and depositing temperature is 25 DEG C, and depositing time is 15min, can prepare one layer graphene/ferriferrous oxide composite material on copper sheet.
As shown in Figure 5, nano ferriferrous oxide granule uniform loading is on the lamella of Graphene as can see from Figure 5 for the scanning electron microscope (SEM) photograph of a kind of Graphene/ferriferrous oxide composite material of above-mentioned gained.
In sum, the preparation method of a kind of Graphene/ferriferrous oxide composite material of the present invention, green, nuisanceless, be produced on a large scale.Microscopic appearance and the particle diameter of ferriferrous oxide particles in matrix material effectively can be controlled by the concentration of iron ion in regulation and control solution, scanning electronic microscope and Raman spectrum indicate the existence of Graphene and Z 250 all clearly, and the composite bed namely formed on cathode pole piece and conductive substrates is formed by Graphene and Z 250.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (7)
1. a preparation method for Graphene/ferriferrous oxide composite material, is characterized in that comprising the following steps:
1) preparation process of graphene oxide dispersion;
Get graphite oxide and the first organic solvent, the material ratio 0.1 ~ 1g:1L of graphite oxide and the first organic solvent, joined by graphite oxide in the first organic solvent, control temperature 20-40 DEG C, ultrasonic power 150 ~ 300W carries out ultrasonic 1-10h and obtains dispersion liquid; The first described organic solvent is 1-Methyl-2-Pyrrolidone, tetrahydrofuran (THF), dimethyl formamide, butyrolactone, acetone or alcohol;
2) preparation process of electrically charged graphene oxide dispersion;
Get iron ion salt and the second organic solvent, the material ratio of iron ion salt and the second organic solvent is 0.5 ~ 10mol:lL, is dissolved in the second organic solvent by iron ion salt and obtains iron ion salts solution; The second described organic solvent is 1-Methyl-2-Pyrrolidone, tetrahydrofuran (THF), dimethyl formamide, butyrolactone, acetone or alcohol; Described iron ion salt is iron nitrate, iron(ic) chloride, ferric sulfate or iron acetate; The iron ion salts solution of above-mentioned gained is joined in the graphene oxide dispersion of gained in step (1), iron concentration is made to be 0.1-5mmol/L, graphene oxide solids content is 0.05-0.4g/L, then the ultrasonic graphene oxide that makes adsorbs iron ion and positively charged, obtains positively charged graphene oxide dispersion;
3) electrophoretic deposition prepares the step of Graphene/ferriferrous oxide composite material;
Positive plate is set in electrophoretic deposition pond and negative plate carries out electrophoretic deposition, using the electrolytic solution of the positively charged graphene dispersing solution of step (2) gained as electrophoretic deposition; With copper, aluminium, nickel, stainless steel, or with coated copper, aluminium, nickel or stainless conductive substrates, or the anode pole piece using the conductive substrates of coated with conductive material as electrophoretic deposition pond; The spacing that above-mentioned electrophoretic deposition process controls between positive and negative plate is 1-50mm; impressed voltage is 10-100V; electrophoretic deposition process temperature is 10-80 DEG C; time is 1-60min; graphene oxide in positively charged graphene oxide dispersion is deposited on cathode pole piece; then cathode pole piece is placed in oven drying; by gained dry sample under protection of inert gas; at the Temperature Treatment 1-4h of 200 DEG C-400 DEG C; and room temperature is cooled in rare gas element, namely obtain Graphene/ferriferrous oxide composite material on the surface of cathode pole piece.
2. the preparation method of a kind of Graphene/ferriferrous oxide composite material as claimed in claim 1, is characterized in that: in step (2), the solids content of described graphene oxide is 0.2g/L.
3. the preparation method of a kind of Graphene/ferriferrous oxide composite material as claimed in claim 1, is characterized in that: the conductive substrates of the negative plate described in step (3) is copper, aluminium, nickel or stainless steel; Or be coated copper, aluminium, nickel or stainless conducting base; Or be radio frequency matrix, described radio frequency matrix is carbon fiber textile product, glassy carbon electrode or conductive polymers.
4. the preparation method of a kind of Graphene/ferriferrous oxide composite material as claimed in claim 3, is characterized in that: described carbon fiber textile product are carbon fiber paper; Described conductive polymers is polyaniline.
5. the preparation method of a kind of Graphene/ferriferrous oxide composite material as claimed in claim 1, is characterized in that: in step (3), the rare gas element passed into comprises argon gas, nitrogen or Krypton.
6. the preparation method of a kind of Graphene/ferriferrous oxide composite material as claimed in claim 1, it is characterized in that: the spacing that the electrophoretic deposition process described in step (3) controls between positive and negative plate is 5-15mm, impressed voltage is 40-60V, electrophoretic deposition process temperature is 25-60 DEG C, and the time is 5-20min.
7. the preparation method of a kind of Graphene/ferriferrous oxide composite material as claimed in claim 6, it is characterized in that: it is 5-15mm that the electrophoretic deposition process described in step (3) controls positive and negative electrode pole piece spacing, impressed voltage is 40V, and electrophoretic deposition process temperature is 40 DEG C, and the time is 10min.
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| CN110127678A (en) * | 2019-05-20 | 2019-08-16 | 天津市职业大学 | A kind of preparation method of magnetic graphene |
| KR20230115483A (en) * | 2022-01-27 | 2023-08-03 | 인하대학교 산학협력단 | Organic-inorganic complex using electrochemical dissolution reaction and manufacturing method thereof |
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