CN105420794B - A kind of preparation method of graphene/ferriferrous oxide composite material - Google Patents
A kind of preparation method of graphene/ferriferrous oxide composite material Download PDFInfo
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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
A kind of preparation method of graphene/ferriferrous oxide composite material of the present invention, i.e. directly ultrasound stripping graphite oxide obtains graphene oxide dispersion in organic solvent, iron ion salt is added into the dispersion liquid of gained again, because graphene oxide is easily combined with positive charge iron ion, positively charged graphene oxide dispersion is obtained；Secondly electrophoretic deposition is carried out; positive plate and negative plate are provided with electrophoretic deposition pond; electrolyte using the positively charged graphene dispersing solution of gained as electrophoretic deposition; graphene oxide and iron ion co-deposition are on cathode pole piece in the presence of the impressed current; then cathode pole piece is placed in oven drying; again under inert gas shielding, high-temperature process, graphene/ferriferrous oxide composite material is obtained on the surface of cathode pole piece after cooling.Graphene/ferriferrous oxide composite material prepared by the present invention is evenly distributed, without other impurities.
Description
Technical field
The invention belongs to electrochemical technology field, is related to a kind of nano material, and specifically a kind of graphene/tetra- aoxidize
The preparation method of three iron composite materials.
Background technology
It is a kind of brand-new composite graphite alkene and metal oxide with electrochemical process composite graphite alkene and metal oxide
Method.The preparation of graphene and ferriferous oxide compound is the focus studied in recent years.
Since finding graphene from 2004, the extensive concern of researcher has just been caused.Graphene has excellent
Mechanics, electronics, optics and thermal property, have in fields such as microelectronics, energy stores, catalysis, biology sensors greatly latent
In application value.Due to its unique two-dimensional nanostructure so that with the addition of the composite of graphene often with excellent
Performance.For example, Huang etc. is in Chemical Society Reviews, 2012,41 (2):Described on 666-686. a large amount of
The application of graphene composite material.Ferroso-ferric oxide because its is cheap, aboundresources, it is environmentally friendly the advantages that enjoy pass
Note.On the other hand single ferroso-ferric oxide electric conductivity is poor, and particle is easily reunited, and carbon base body can not only buffer huge volume
Expansion, but it has been significantly enhanced electric conductivity.Nano ferriferrous oxide is carried on to the compound of graphenic surface formation to be collected
In embody both excellent properties.Such as Zhang Yi etc. is in Acta Physico-Chimica Sinica, 2011,27 (5):
Reported on 1261-1266 and be prepared for Fe3O4 magnetic nano-particle of the particle diameter for 18nm using high-temperature decomposition, and carry out carboxyl
Change modification, then the graphene oxide with polyethyleneimine (PEI) chemical modification carries out cross-linking reaction, obtains magnetic/functionalized oxygen
Graphite alkene (MGO) composite.Yao etc. is in Chemical Engineering Journal, and 2012,184:On 326-332
Report by modulating PH and Fe in GO solution2+、Fe3+Amount of substance ratio, i.e., co-precipitation prepare Fe3O4 nano-particles insertion
Graphene composite material, the removal to methyl blue has good effect.
The method for preparing graphene/ferriferrous oxide composite material at present is more based on solution phase chemical reduction, with oxidation
Graphene is raw material, adds certain dispersant and iron ion salt, dispersed suspension is made, iron ion is attached to oxidation
On graphene film, then add chemical reducing agent or graphene oxide is reduced into graphene using the catalytic performance of light, so as to
Obtain composite.But this kind of method complex operation, condition is harsh, reaction time length, is not easy scale
Production, while the reducing agent, the dispersant that add can be remained in prepared material, it is difficult to thoroughly remove.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of graphene/ferroso-ferric oxide composite wood
The preparation method of material, the preparation method of described this graphene/ferriferrous oxide composite material solve of the prior art
The method complex operation, condition harshness, residue for preparing graphene/ferriferrous oxide composite material are difficult to the technology thoroughly removed
Problem.
The invention provides a kind of preparation method of graphene/ferriferrous oxide composite material, comprise the following steps：
1) the step of prepared by graphene oxide dispersion；
Take graphite oxide and the first organic solvent, the material ratio of graphite oxide and the first organic solvent is 0.1 ~ 1g:1L, will
Graphite oxide is added in the first organic solvent, controls 20-40 DEG C of temperature, and 150 ~ 300W of ultrasonic power carries out ultrasonic 1-10h and obtained
To dispersion liquid；The first described organic solvent be 1-Methyl-2-Pyrrolidone, tetrahydrofuran, dimethylformamide, butyrolactone,
Acetone or alcohol；
2) the step of prepared by electrically charged graphene oxide dispersion is prepared；
Take 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, iron ion salt is dissolved in the second organic solvent and obtains iron ion salting liquid；The second described organic solvent is 1- methyl -2-
Pyrrolidones, tetrahydrofuran, dimethylformamide, butyrolactone, acetone or alcohol；Described iron ion salt is ferric nitrate, chlorination
Iron, ferric sulfate or ferric acetate；The iron ion salting liquid of above-mentioned gained is added to step（1）The graphene oxide of middle gained disperses
In liquid, it is 0.1-5mmol/L to make iron concentration, and graphene oxide solids content is 0.05-0.4g/L, and graphene oxide adsorbs
Iron ion and it is positively charged, produce positively charged graphene oxide dispersion；
3) electrophoretic deposition prepares the step of graphene/ferriferrous oxide composite material；
Positive plate is provided with electrophoretic deposition pond and negative plate carries out electrophoretic deposition, by step（2）The positively charged of gained
Electrolyte of the graphene dispersing solution of lotus as electrophoretic deposition；With copper, aluminium, nickel, stainless steel, or with coated copper, aluminium, nickel or stainless
The conductive substrates of steel, or to coat the conductive substrates of conductive material as the anode pole piece in electrophoretic deposition pond；Above-mentioned electrophoresis sinks
Spacing between product process control positive and negative plate is 1-50mm, and applied voltage 10-100V, electrophoretic deposition process temperature is 10-
80 DEG C, time 1-60min, the graphene oxide in positively charged graphene oxide dispersion is deposited into cathode pole piece
On, cathode pole piece is then placed in oven drying, by gained drying sample under inert gas shielding, at 200 DEG C -400 DEG C
Temperature Treatment 1-4h, and room temperature is cooled in inert gas, i.e., obtain graphene/ferroso-ferric oxide on the surface of cathode pole piece
Composite.
Further, step（2）In, the solids content of described graphene oxide is 0.2 g/L.
Further, step（3）The conductive substrates of described negative plate are copper, aluminium, nickel or stainless steel；Or for coated copper,
The conducting base of aluminium, nickel or stainless steel；Or be radio frequency matrix, described radio frequency matrix is carbon fiber textile
Product, glassy carbon electrode or conducting polymer.
Further, described carbon fiber textile product are carbon fiber paper；Described conducting polymer is polyaniline.
Further, step（3) in, the inert gas being passed through includes argon gas, nitrogen or Krypton.
Further, step（3）It is 5-15mm that described electrophoretic deposition process, which controls the spacing between positive and negative plate, outside
Making alive is 40-60V, and electrophoretic deposition process temperature is 25-60 DEG C, time 5-20min.
Further, step（3）It is 5-15mm that described electrophoretic deposition process, which controls positive and negative electrode pole piece spacing, outer power-up
It is 40 DEG C to press as 40V, electrophoretic deposition process temperature, time 10min.
Further, preferably 300 DEG C of high-temperature process temperature, time 3h.
It is of the invention that directly ultrasound peels off graphite oxide and obtains graphene oxide dispersion in organic solvent, then to gained
Iron ion salt is added in dispersion liquid, graphene oxide containing the oxygen-containing function such as more hydroxyl, carboxyl, epoxy radicals due to carrying
Larger elecrtonegativity, due to electrostatic interaction, easily it is combined with positive charge iron ion, makes graphene oxide electrically charged；So
The method of electrophoretic deposition is taken to prepare graphene/silicon/iron oxide composite material on conducting base afterwards.
The present invention can be that graphene/ferriferrous oxide composite material can be prepared in conductive substrates in cathode pole piece, deposition
Can be to be carried out in conductive substrates in the cathode pole piece of 3D structures, therefore the graphene prepared/ferriferrous oxide composite material tool
There is multilevel hierarchy.The present invention is by adjusting the solids content of graphene oxide and the concentration and deposition process of addition iron ion salt
In experiment condition such as spacing, deposition voltage, sedimentation time etc., can control final graphene with ferroso-ferric oxide content with
And the thickness of microscopic appearance, coating.Prepared graphene/ferriferrous oxide composite material is evenly distributed, without other impurities,
There is potential application value in catalysis, photoelectricity, biology sensor, energy storage field.Simultaneously because ferroferric oxide nano granules
The nano graphite flakes surface of good conductivity is evenly dispersed in, therefore not only effectively increases the specific surface area of ferroso-ferric oxide,
The internal resistance of graphene/ferriferrous oxide composite material is also reduced, enhances the electric conductivity of material.
The present invention uses electricity deposition technique, and graphite oxide can be realized while realizing that graphite oxide and iron ion deposit
The reduction of alkene, it is environment-friendly, unlike traditional use chemical method reduces to graphene oxide, produce some toxic gases
Or introduce some other elements；Secondly by regulation relevant parameter, control to thickness of coating can be achieved and to ferroso-ferric oxide
The regulation and control of granular size and pattern.
The present invention compares with prior art, and its technological progress is significant.The present invention makes four by the way of electrophoretic deposition
Fe 3 O nano-particle is uniformly compounded in graphene layer, and the load of ferroso-ferric oxide and graphene can avoid oxide
Reunite, while reduce the graphitization phenomenon of graphene.This method has that simple to operate, production cost is low, product homogeneity is good, easy
The advantages that control, by the compound that this method obtains in the side such as electromagnetic material, biology sensor, energy storage material, insoluble drug release
Face has extensive application prospect.
Brief description of the drawings
Fig. 1 is the structural representation in electrophoretic deposition pond, wherein 1 being dc source, 2 being positive pole, 3 be negative pole, 4 being electrophoresis
Pond, 5 are electrolyte.
Fig. 2 is the scanning electron microscope (SEM) photograph for graphene/ferriferrous oxide composite material that embodiment 2 obtains.
Fig. 3 is the Raman spectrograms of graphite oxide prepared by embodiment 1.
Fig. 4 is the Raman spectrograms for graphene/ferriferrous oxide composite material that embodiment 2 obtains.
Fig. 5 is the scanning electron microscope (SEM) photograph for graphene/ferriferrous oxide composite material that embodiment 3 obtains.
Embodiment
The present invention is expanded on further below by specific embodiment and with reference to accompanying drawing, but is not intended to limit the present invention.
The Raman spectrum tests of the present invention use the silent Raman spectrometer for flying your production of generation of U.S.'s match（Model DXR Raman
Macroscope）.
Used ESEM is the S-3400N SEM of Hitachi's production.
The structural representation in the electrophoretic deposition pond used in the present invention is as shown in Figure 1.
Embodiment 1
The preparation method of graphite oxide is prepared using improvement Hummers methods, is concretely comprised the following steps：1g graphite is added 0 DEG C
60 ~ 80% 40ml concentrated sulfuric acids in, add 1g potassium nitrate, then add 7g potassium ferrates in batches, it is sonicated until complete
Fully dissolved, the temperature of whole process system maintain less than 5 DEG C, are transferred in 30-40 DEG C of water-bath, and magnetic agitation answers two
Hour, 100ml deionized waters are added, are finally transferred in 98 DEG C of water-baths, stir 1.5h, the heat time is closed on and terminates, slowly
Add H2O2Aoxidized, solution filters while hot, is once cleaned with substantial amounts of hydrochloric acid/deionized water, until PH=7, vacuum are overnight
Drying.
Specifically, the graphite is the natural graphite powder, natural flake graphite, micro crystal graphite that particle diameter is the mesh of 80 mesh -500
Or expanded graphite；
Embodiment 2
A kind of preparation method of graphene/ferriferrous oxide composite material, comprises the following steps：
（1）, by graphite oxide:First organic solvent is 1g:1L ratio, graphite oxide is added to the first organic solvent
In, 20-40 DEG C of temperature of control, power 200W carry out ultrasonic 4h and obtain dispersion liquid；Specifically, the first described organic solvent is 1-
N-methyl-2-2-pyrrolidone N；
（2）, by iron ion salt:Second organic solvent is 5mmol:1L ratio, it is organic molten that iron ion salt is dissolved in second
5mmol/L iron ion salting liquids are obtained in agent；Specifically, described iron ion salt is ferric nitrate；Second organic solvent is
1-Methyl-2-Pyrrolidone；The iron ion salting liquid of above-mentioned gained is added to step（1）The graphene oxide of middle gained disperses
In liquid, it is 1.0mmol/L to make iron concentration, and graphene oxide solids content is 0.1g/L, and then ultrasonic 30min makes oxidation stone
Black alkene adsorbs iron ion and positively charged produces positively charged graphene oxide dispersion；
（3）, take 45mL steps（2）Electricity of the prepared positively charged graphene oxide dispersion as electrophoretic deposition pond
Solve liquid；Using 400 mesh 316L stainless steel mesh as cathode pole piece, stainless steel is that anode pole piece carries out electrophoretic deposition, and obtaining deposition has
The cathode pole piece of graphene；Then the cathode pole piece that deposition has graphene is placed in 60 DEG C of oven drying 12h, gained is dried into sample
Product are under inert gas shielding, 300 DEG C of processing 3h of high temperature, and room temperature is cooled in inert gas, i.e. the table in cathode pole piece
Face obtains graphene/ferriferrous oxide composite material and obtains graphene/ferriferrous oxide composite material；Above-mentioned negative pole pole used
Piece stainless steel mesh is cut to 2.5 × 1.5cm2, it is 1.5 × 1cm to immerse electrolyte area2；Stainless steel anode pole piece used is used
6# abrasive paper for metallograph is polished, and is washed with deionized water net；Positive and negative plate spacing is 10mm in above-mentioned electrophoretic deposition process, directly
Stream voltage is 40V, and depositing temperature is 40 DEG C, sedimentation time 10min.
The scanning electron microscope (SEM) photograph of graphene/ferriferrous oxide composite material of above-mentioned gained is as shown in Fig. 22 can be with from figure
See together with nano ferriferrous oxide granule lamella and graphene sheet layer uniform load, and using it as module units, prepare three
Tie up orderly lamellar graphite alkene/silicon/iron oxide composite material.
Fig. 3,4 are respectively the oxygen of graphene/tetra- prepared in graphite oxide Raman spectrum and embodiment 2 prepared by embodiment 1
Change the Raman spectrum of three iron composite materials, it can be seen that graphite oxide and graphene/ferroso-ferric oxide are multiple from Fig. 3 and Fig. 4
Condensation material has characteristic peak at two, is to be located at 1580cm respectively-1G peaks, positioned at 1350cm-1Neighbouring D peaks.
Further, 325 cm are located in the Raman spectrograms of graphene/ferriferrous oxide composite material of gained-1、670
cm-1Locate characteristic peak, corresponding Fe3O4Fe-O and Fe-O-Fe raman characteristic peak.
Embodiment 3
A kind of preparation method of graphene/ferriferrous oxide composite material, comprises the following steps：
（1）, graphene oxide dispersion preparation process is the same as embodiment 1；
（2）, by iron ion salt:Second organic solvent is 5mmol:1L ratio, it is organic molten that iron ion salt is dissolved in second
1g/L iron ion salting liquids are obtained in agent；Described iron ion salt is iron chloride；Second organic solvent is 1- methyl -2-
Pyrrolidones is solvent；The iron ion salting liquid of above-mentioned gained is added to step（1）The graphene oxide dispersion of middle gained
In, it is 0.5mmol/L to make iron concentration, and graphene solids content is 0.2g/L, and then magnetic agitation 30min makes graphite oxide
Alkene adsorbs iron ion and positively charged produces positively charged graphene oxide dispersion；
（3）, take 45mL steps（2）Electricity of the prepared positively charged graphene oxide dispersion as electrophoretic deposition pond
Liquid is solved, using 400 copper sheets as cathode pole piece, stainless steel substrates are that anode pole piece carries out electrophoretic deposition, and obtaining deposition has the negative of graphene
Pole pole piece；Then the cathode pole piece for having graphene will be deposited as 60 DEG C of oven drying 12h, finally in the table of cathode pole piece copper sheet
Face obtains graphene/ferriferrous oxide composite material；Cathode pole piece copper sheet used, is cut in above-mentioned electrophoretic deposition process
2.5×1.5cm2Size, be cleaned by ultrasonic 10min with acetone, ethanol, deionized water successively, immerse electrolyte area be 1.5 ×
1.0cm2；Anode pole piece stainless steel substrates used are polished with 6# abrasive paper for metallograph, and are washed with deionized water net；Above-mentioned electrophoresis sinks
Positive and negative plate spacing is 5mm during product, and it is 60V to add DC voltage, and depositing temperature is 25 DEG C, sedimentation time 15min, i.e.,
One layer graphene/ferriferrous oxide composite material can be prepared on copper sheet.
A kind of scanning electron microscope (SEM) photograph of graphene/ferriferrous oxide composite material of above-mentioned gained is as shown in figure 5, from Fig. 5
It can be seen that nano ferriferrous oxide granule uniform load is on the lamella of graphene.
In summary, the preparation method of a kind of graphene/ferriferrous oxide composite material of the invention, green is nuisanceless,
It is produced on a large scale.Ferriferrous oxide particles in composite can effectively be controlled by the concentration for regulating and controlling iron ion in solution
Microscopic appearance and particle diameter, SEM and Raman spectrum all clearly indicate depositing for graphene and ferroso-ferric oxide
That is, it is being that the composite bed formed in conductive substrates is formed by graphene and ferroso-ferric oxide in cathode pole piece.
Described above is only the citing of embodiments of the present invention, it is noted that for the ordinary skill of the art
For personnel, without departing from the technical principles of the invention, some improvement and modification can also be made, these improve and become
Type also should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of preparation method of graphene/ferriferrous oxide composite material, it is characterised in that comprise the following steps：
1）The preparation process of graphene oxide dispersion；
Take graphite oxide and the first organic solvent, the material ratio of graphite oxide and the first organic solvent is 0.1 ~ 1g:1L, it will aoxidize
Graphite is added in the first organic solvent, controls 20-40 DEG C of temperature, and 150 ~ 300W of ultrasonic power carries out ultrasonic 1-10h and divided
Dispersion liquid；The first described organic solvent is 1-Methyl-2-Pyrrolidone, dimethylformamide or butyrolactone；
2）The preparation process of electrically charged graphene oxide dispersion；
Take 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, will
Iron ion salt, which is dissolved in the second organic solvent, obtains iron ion salting liquid；The second described organic solvent is 1- methyl -2- pyrroles
Alkanone, dimethylformamide or butyrolactone；Described iron ion salt is ferric nitrate, iron chloride, ferric sulfate or ferric acetate；Will be upper
The iron ion salting liquid for stating gained is added to step（1）In the graphene oxide dispersion of middle gained, the iron concentration is set to be
0.1-5mmol/L, graphene oxide solids content are 0.05-0.4g/L, then ultrasound make graphene oxide absorption iron ion and
It is positively charged, produce positively charged graphene oxide dispersion；
3）Electrophoretic deposition prepares the step of graphene/ferriferrous oxide composite material；
Positive plate and negative plate is set to carry out electrophoretic deposition in electrophoretic deposition pond, by step（2）The positively charged stone of gained
Electrolyte of the black alkene dispersion liquid as electrophoretic deposition；With copper, aluminium, nickel, stainless steel, or to coat the conductive substrates of conductive material work
For the anode pole piece in electrophoretic deposition pond；It is 5-15mm that above-mentioned electrophoretic deposition process, which controls the spacing between positive and negative plate, additional
Voltage is 40-60V, and electrophoretic deposition process temperature is 25-60 DEG C, time 5-20min, by positively charged graphene oxide point
Graphene oxide in dispersion liquid is deposited on cathode pole piece, and cathode pole piece then is placed in into oven drying, by gained drying sample
Under inert gas shielding, in 200 DEG C -400 DEG C of Temperature Treatment 1-4h, and room temperature is cooled in inert gas, i.e., negative
The surface of pole pole piece obtains graphene/ferriferrous oxide composite material.
A kind of 2. preparation method of graphene/ferriferrous oxide composite material as claimed in claim 1, it is characterised in that：Step
Suddenly（2）In, the solids content of described graphene oxide is 0.2g/L.
A kind of 3. preparation method of graphene/ferriferrous oxide composite material as claimed in claim 1, it is characterised in that：Step
Suddenly（3）The conductive substrates of described negative plate are copper, aluminium, nickel or stainless steel；Or the conduction for coated copper, aluminium, nickel or stainless steel
Matrix；Or be radio frequency matrix, described radio frequency matrix is carbon fiber textile product, glassy carbon electrode or conductive poly-
Compound.
A kind of 4. preparation method of graphene/ferriferrous oxide composite material as claimed in claim 3, it is characterised in that：Institute
The carbon fiber textile product stated are carbon fiber paper；Described conducting polymer is polyaniline.
A kind of 5. preparation method of graphene/ferriferrous oxide composite material as claimed in claim 1, it is characterised in that：Step
（3) in, the inert gas being passed through includes argon gas, nitrogen or Krypton.
A kind of 6. preparation method of graphene/ferriferrous oxide composite material as claimed in claim 1, it is characterised in that：Step
Suddenly（3）It is 5-15mm that described electrophoretic deposition process, which controls positive and negative electrode pole piece spacing, applied voltage 40V, electrophoretic deposition process
Temperature is 40 DEG C, time 10min.
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| CN108774879B (en) * | 2018-07-06 | 2020-05-12 | 东华大学 | Preparation method of graphene coating conductive fiber |
| CN110127678B (en) * | 2019-05-20 | 2022-04-29 | 天津市职业大学 | Preparation method of magnetic graphene |
| KR102616717B1 (en) * | 2022-01-27 | 2023-12-21 | 인하대학교 산학협력단 | Organic-inorganic complex using electrochemical dissolution reaction and manufacturing method thereof |
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| CN103614902A (en) * | 2013-11-20 | 2014-03-05 | 上海应用技术学院 | Preparation method of graphene/carbon fiber composite |
| CN104241062A (en) * | 2014-09-12 | 2014-12-24 | 中国科学院深圳先进技术研究院 | Carbon nano tube emitting cathode preparation method and carbon nano tube emitting cathode |
| CN104818511A (en) * | 2015-01-12 | 2015-08-05 | 刘艳娇 | Composite electro-thermal film |
| CN104830273A (en) * | 2015-01-12 | 2015-08-12 | 刘艳娇 | Preparation method of composite electro-thermal thin film |
| CN104830274A (en) * | 2015-01-12 | 2015-08-12 | 刘艳娇 | Preparation method of thermoelectric composite thin film |
| CN104830271A (en) * | 2015-01-12 | 2015-08-12 | 刘艳娇 | Preparation method of thermoelectric thin film |
| CN104711655A (en) * | 2015-03-26 | 2015-06-17 | 兰州明仁智能科技有限公司 | Method for preparing graphene-based anti-corrosion and wear-resistant coating on magnesium alloy surface through liquid phase electrophoretic deposition method |
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