CN105817648A - Iron-nickel alloy nanocluster-graphene composite material and preparation method and application thereof - Google Patents
Iron-nickel alloy nanocluster-graphene composite material and preparation method and application thereof Download PDFInfo
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Abstract
The embodiment of the invention discloses a method for preparing an iron-nickel alloy nanocluster-graphene composite material. The method includes the following steps that (1), graphite oxide is added into a first organic solvent to be dispersed; (2), ferric acetylacetonate, nickel acetylacetonate and octadecylamine are added, the mixture is heated to 100 DEG C to 150 DEG C in inertia protective gas, the temperature is kept for 20 min to 50 min, and then the temperature rises till a solution is boiled and flows back, and is kept for 1 h to 5 h; and (3), a second organic solvent is added to suddenly stop the reaction, and reaction products are separated out, washed and dried. The invention further discloses the iron-nickel alloy nanocluster-graphene composite material prepared through the method, and application of the composite material to electromagnetic wave absorption. According to the method, the iron-nickel alloy nanocluster-graphene composite material and the application, graphene is used as a substrate, the iron-nickel alloy nanocluster-graphene composite material is obtained through one-step reduction of a thermal decomposition method, and therefore iron-nickel alloy nanoparticles are protected and dispersed, and the nanometer composite material good in wave absorbing property is obtained.
Description
Technical field
The present invention relates to electromagnetic wave absorbent material field, particularly to iron-nickel alloy nano-cluster-graphene composite material, its
Preparation method and use.
Background technology
Along with the development of electronic communication, the harm that electromagnetic wave causes in people's daily life highlights the most day by day, because of
This needs the electromagnetic wave absorbent material that absorbing property is excellent.
Iron-nickel alloy, as typical alloy soft magnetic material, has the excellent magnetic energy of metallic monomer concurrently, has higher
Saturated magnetization rate and relatively low coercivity, and show big magnetic anisotropy, the most undersized iron-nickel alloy nanocluster can
Hope and obtain stronger electromagnetic performance.But undersized iron-nickel alloy nanocluster is easy to reunite and oxidation in atmosphere, raw
Become the oxide of anti-ferromagnetic ferrum and nickel, reduce its electromagnetic performance.
Summary of the invention
Graphene has fabulous pliability, corrosion resistance, electric conductivity, lighter quality and bigger specific surface area, because of
This carries other active materials frequently as substrate.Graphene nanometer sheet has good dispersibility, it is possible to is effectively prevented and receives
Rice corpuscles is reunited, and is provided that efficient unidirectional electric conductivity.Based on this, the invention discloses a kind of iron-nickel alloy nanometer
Bunch-graphene composite material, Preparation Method And The Use, it is used for solving undersized iron-nickel alloy nanocluster and holds in atmosphere
Easily reunite and the problem of oxidation.Technical scheme is as follows:
A kind of method preparing iron-nickel alloy nano-cluster-graphene composite material, comprises the following steps:
1), graphite oxide joined in the first organic solvent and disperse；
2), add ferric acetyl acetonade, nickel acetylacetonate and 18-amine., heat the mixture in inertia protective gas
100 DEG C～150 DEG C, maintain 20～50min, then heat to solution boiling reflux, maintain 1～5h；
Described graphite oxide is 0.2～0.3 with the mass ratio of described ferric acetyl acetonade；Described graphite oxide and described acetyl
The mass ratio of acetone nickel is 0.1～0.2；Described graphite oxide is 1:80～1:40 with the mass ratio of described 18-amine.；
3) add the second organic solvent to stop sudden for reaction, isolate product, wash and be dried described product.
In the preferred embodiment of the present invention, step 1) in the first organic solvent be 2-Pyrrolidone, N-first
At least one in base ketopyrrolidine and oleyl amine.
One in the present invention is more highly preferred in embodiment, step 1) described in graphite oxide first organic molten with described
The mass volume ratio of agent is 0.8mg/mL～1.2mg/mL.
One in the present invention is more highly preferred in embodiment, step 1) in be separated into ultrasonic disperse.
One in the present invention is more highly preferred in embodiment, step 2) in inertia protective gas be argon or nitrogen
Gas.
One in the present invention is more highly preferred in embodiment, step 2) in be heated to 110～130 DEG C.
One in the present invention is more highly preferred in embodiment, step 3) in the second organic solvent be ethanol.
One in the present invention is more highly preferred in embodiment, step 3) middle normal hexane, acetone alternately washing, and in 40
DEG C be vacuum dried described product.
The invention also discloses a kind of iron-nickel alloy prepared by said method nano-cluster-graphene composite material.
The invention also discloses a kind of iron-nickel alloy nano-cluster-graphene composite material purposes for electromagnetic wave absorption.
The invention provides a kind of iron-nickel alloy nano-cluster-graphene composite material, Preparation Method And The Use.The present invention
With Graphene as substrate, obtain iron-nickel alloy nano-cluster-graphene composite material by the reduction of thermal decomposition method one step, thus protect
With dispersion iron-nickel alloy nano particle, thus obtain the nano composite material that absorbing property is good.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to
Other accompanying drawing is obtained according to these accompanying drawings.
Fig. 1 is graphite (a), graphite oxide (b), Graphene (c) and the embodiment 1 of preparation used in the embodiment of the present invention
XRD (the X-Ray of iron-nickel alloy nano-cluster-graphene composite material prepared by (d), embodiment 2 (e), embodiment 3 (f)
Diffraction, X-ray diffraction) figure；
Fig. 2 is graphite (a), graphite oxide (b), Graphene (c) and the embodiment 1 of preparation used in the embodiment of the present invention
The Raman spectrogram of iron-nickel alloy nano-cluster-graphene composite material prepared by (d), embodiment 2 (e), embodiment 3 (f)；
Fig. 3 (a) is the TEM of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 1 preparation
(Transmission Electron Microscope, transmission electron microscope) figure；
Fig. 3 (b) is the HRTEM (High of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 1 preparation
Resolution Transmission Electron Microscopy, high resolution transmission electron microscopy) figure；
Fig. 3 (c) is the SEM of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 1 preparation
(Scanning Eelectron Microscope, scanning electron microscope) figure；
Fig. 3 (d) is the carbon analysis chart of scanning electron microscope corresponding for Fig. 3 (c)；
Fig. 3 (e) is the ferrum element analysis chart of scanning electron microscope corresponding for Fig. 3 (c)；
Fig. 3 (f) is the nickel element analysis chart of scanning electron microscope corresponding for Fig. 3 (c)；
Fig. 4 (a) and Fig. 4 (d) is the SEM of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 2 preparation
Figure；
Fig. 4 (b) is the TEM figure of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 2 preparation；
Fig. 4 (c) is the HRTEM figure of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 2 preparation；
Fig. 4 (e) is the carbon analysis chart of scanning electron microscope corresponding for Fig. 4 (d)；
Fig. 4 (f) is the ferrum element analysis chart of scanning electron microscope corresponding for Fig. 4 (d)；
Fig. 4 (g) is the nickel element analysis chart of scanning electron microscope corresponding for Fig. 4 (d)；
Fig. 5 (a) and Fig. 5 (d) is the SEM of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 3 preparation
Figure；
Fig. 5 (b) is the TEM figure of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 3 preparation；
Fig. 5 (c) is the HRTEM figure of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 3 preparation；
Fig. 5 (e) is the carbon analysis chart of scanning electron microscope corresponding for Fig. 5 (d)；
Fig. 5 (f) is the ferrum element analysis chart of scanning electron microscope corresponding for Fig. 5 (d)；
Fig. 5 (g) is the nickel element analysis chart of scanning electron microscope corresponding for Fig. 5 (d)；
Fig. 5 (h) is the EDS (Energy of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 3 preparation
Dispersive Spectrometer, energy disperse spectroscopy) figure；
Fig. 6 is iron-nickel alloy nano-cluster-graphite prepared by the embodiment of the present invention 1 (a), embodiment 2 (b) and embodiment 3 (c)
The microwave reflection rate loss value of alkene composite and the graph of a relation of thickness of sample.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Describe, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments wholely.Based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under not making creative work premise
Embodiment, broadly falls into the scope of protection of the invention.
The invention provides a kind of method preparing iron-nickel alloy nano-cluster-graphene composite material, comprise the following steps:
1), graphite oxide joined in the first organic solvent and disperse；
2), add ferric acetyl acetonade, nickel acetylacetonate and 18-amine., heat the mixture in inertia protective gas
100 DEG C～150 DEG C, maintain 20～50min (minute), then heat to solution boiling reflux, maintain 1～5h (hour)；
Described graphite oxide is 0.2～0.3 with the mass ratio of described ferric acetyl acetonade；Described graphite oxide and described acetyl
The mass ratio of acetone nickel is 0.1～0.2；Described graphite oxide is 1:80～1:40 with the mass ratio of described 18-amine.；
3) add the second organic solvent to stop sudden for reaction, isolate product, wash and be dried described product.
Wherein, described graphite oxide refers to the chemical combination that a kind of carbon indefinite by the ratio of the amount of material, hydrogen, oxygen element are constituted
Thing.Described graphite oxide can be concrete by preparing with strong oxidizer graphite oxide, can use improvement
Hummers method prepares that (the method is recorded in the reference book of the work such as Zhu Hongwei, Xu Zhiping, Xie Dan, and " Graphene is tied
Structure, preparation method and performance characterization " page 32 the 2nd section of (publishing house of Tsing-Hua University, the 1st printing November in 2011)).Described
Graphite oxide is 0.8mg/mL～1.2mg/mL with the mass volume ratio of described first organic solvent, it is preferred that described oxidation stone
Black is 1mg/mL with described first organic solvent mass volume ratio.Described first organic solvent can be 2-Pyrrolidone, N-
At least one in methyl pyrrolidone and oleyl amine.Described dispersion can be ultrasonic disperse, mechanical agitation dispersion etc., it is preferred that
Described it is separated into ultrasonic disperse.
Step 2) in add ferric acetyl acetonade, nickel acetylacetonate and 18-amine., by mixture in inertia protective gas
Being heated to 100 DEG C～150 DEG C, it is preferred that be heated to 110～130 DEG C, maintain 20～50min, now, reaction generates middle producing
Thing；Then heating to solution boiling reflux, maintain 1～5h, now, intermediate product decomposes and generates iron-nickel alloy nano-cluster, wherein,
Ferrum in iron-nickel alloy nano-cluster is from ferric acetyl acetonade, and nickel is from nickel acetylacetonate.Noble gas is to prevent ferrum nickel from closing
Gold nanoclusters is oxidized, the preferred nitrogen of inertia protective gas or argon.It will be appreciated by persons skilled in the art that described
One organic solvent is different, and the temperature needed for solution boiling reflux is the most different；In whole course of reaction, it is also possible to reaction solution
It is stirred so that react more uniform.
In experimentation, inventor finds that adding the second organic solvent will react the sudden ferrum stopping to obtain size uniform
Nickel alloy nano-cluster, it is preferred that ethanol can be added and make the temperature of reaction system be rapidly decreased to room temperature, stop sudden for reaction.Permissible
Being understood by, described separation refers to solid-liquid separation, in actual application, can use centrifugation, it would however also be possible to employ filter and separate
Deng.After product being separated, wash and be dried this product, it is preferred that normal hexane, acetone can be used alternately to wash
Wash, make iron-nickel alloy nano-cluster more be uniformly dispersed on Graphene, and be vacuum dried this product in 40 DEG C.
Present invention also offers the iron-nickel alloy nano-cluster-graphene composite material prepared by said method and this is combined
Material is for the purposes of electromagnetic wave absorption.
Below will be by specific embodiment, the present invention is described in detail.Reagent used in embodiment is the most commercially available can
?.
Graphite oxide in embodiment is adopted and is prepared with the following method:
The Hummers method improved is used to prepare graphite oxide, as preparing iron-nickel alloy nano-cluster-Graphene composite wood
The raw material of material.
Weigh 5g graphite powder, 5g NaNO3, and the dense H of 230mL2SO4, it is placed in ice-water bath, is slowly added to 30g while stirring
KMnO4, this process about 15min.Removing ice-water bath, put in 35 DEG C of water-baths, be slowly added to 460mL distilled water, this process is about
30min, product is graduated into brown by black.Be placed in 98 DEG C of oil baths insulation 15min.After withdrawing from oil bath, add
1400mL warm water, stirring, add 100mL H2O2, now product becomes golden yellow.Being soaked in mass fraction after filtration is 5%
Dilute HCl solution in wash, refilter afterwards, repeat above-mentioned washing step in filtrate without SO4 2-Till.Products therefrom
In 70 DEG C of air dryings.
Prepare iron-nickel alloy nano-cluster-graphene composite material:
Embodiment 1
Weigh 40mg graphite oxide and 40mL N-Methyl pyrrolidone in 50mL beaker, ultrasonic disperse about 2h, obtain palm fibre
The mixed solution of color；It follows that by 176.5mg (0.5mmol) ferric acetyl acetonade, 385.5mg (1.5mmol) nickel acetylacetonate and
2g 18-amine. adds in above-mentioned brown solution, first heats the mixture to 120 DEG C and maintains 30min in this temperature, then raising
Temperature to 202 DEG C, maintains 2h in this temperature, and whole course of reaction carries out under argon shield, and is always maintained at magnetic agitation.So
After, add 20mL ethanol and stop sudden for reaction, make the temperature of reaction system be rapidly decreased to room temperature.Finally, separated by centrifugation
Going out product, and alternately wash with normal hexane, acetone, product is in 40 DEG C of vacuum drying.
Embodiment 2
Weighing 40mg graphite oxide and 50mL oleyl amine in 100mL beaker, ultrasonic disperse about 2h, the mixing obtaining brown is molten
Liquid；It follows that 159mg (0.45mmol) ferric acetyl acetonade, 257mg (1mmol) nickel acetylacetonate and 1.6g 18-amine. are added
In above-mentioned brown solution, first heat the mixture to 100 DEG C and maintain 50min in this temperature, then increasing the temperature to 290 DEG C,
Maintaining 5h in this temperature, whole course of reaction carries out under nitrogen protection, and is always maintained at magnetic agitation.Then, 20mL is added
Ethanol stops sudden for reaction, makes the temperature of reaction system be rapidly decreased to room temperature.Finally, isolate product by filter type,
And alternately wash with normal hexane, acetone, product is in 40 DEG C of vacuum drying.
Embodiment 3
Weigh 40mg graphite oxide and 34mL 2-Pyrrolidone in 50mL beaker, ultrasonic disperse about 2h, obtain brown
Mixed solution；It follows that by 134mg (0.38mmol) ferric acetyl acetonade, 200mg (0.78mmol) nickel acetylacetonate and 3.2g ten
Eight amine add in above-mentioned brown solution, first heat the mixture to 150 DEG C and maintain 20min in this temperature, then rising high-temperature
To 245 DEG C, maintaining 1h in this temperature, whole course of reaction carries out under argon shield, and is always maintained at magnetic agitation.Then,
Add 20mL ethanol to stop sudden for reaction, make the temperature of reaction system be rapidly decreased to room temperature.Finally, isolated instead by centrifugation
Answering product, and alternately wash with normal hexane, acetone, product is in 40 DEG C of vacuum drying.
In order to preferably the iron-nickel alloy nano-cluster-graphene composite material of preparation in embodiment is analyzed, this
Bright embodiment is also prepared for Graphene, and preparation method is as follows:
Weigh 100mg graphite oxide in 250mL there-necked flask, add the distilled water of 100mL, 45 DEG C of 3h the most ultrasonic,
Obtain the brown solution of stable dispersion.25mL hydrazine hydrate, 70 DEG C of water-bath backflows it are slowly added in above-mentioned scattered solution
24h.Then cooling down, centrifugation goes out product, and with absolute ethanol washing, is placed in 45 DEG C of vacuum drying ovens and is dried,
To Graphene.
Iron-nickel alloy nano-cluster-the graphene composite material prepared the embodiment of the present invention below is analyzed,
The analysis result arrived is as follows:
XRD analysis
Fig. 1 is graphite (a), graphite oxide (b), Graphene (c) and the embodiment 1 of preparation used in the embodiment of the present invention
The XRD figure of iron-nickel alloy nano-cluster-graphene composite material prepared by (d), embodiment 2 (e), embodiment 3 (f).By Fig. 1 (a)
It can be seen that the crystallinity of raw graphite used is good, the diffraction maximum of (002) crystal face occurs at 2 θ=26.5 °, correspondence
Interlamellar spacing is 0.34nm.As shown in Fig. 1 (b), diffraction maximum moves to low angle, about diffraction maximum occurs at 2 θ=10.9 °, and
And the interlamellar spacing of correspondence also becomes greatly 0.76nm, two peaks more weak at 23 ° and 42 ° disappear, it was demonstrated that graphite is substantially oxidized.
Can be seen that from Fig. 1 (c), occurring in that two weak and diffraction maximums of widthization at 23.5 DEG C and 41.9 °, corresponding is Graphene
(002), the diffraction maximum of (100) crystal face, this result demonstrates the existence of amorphous graphite alkene, shows that graphite oxide is reduced,
It is unordered that the Graphene that stratiform is piled up gradually becomes.In Fig. 1 (d) and 1 (e), 2 θ go out 44.38 °, 51.73 ° and 76.04 ° respectively
Existing three peaks, the most identical with JCPDS card number 38-0419, it is the FeNi of face-centered cubic phase3, lattice parameter isIn Fig. 1 (f), 2 θ are at 39.30 °, 41.70 °, 44.71 °, 58.42 °, 70.98 ° and the peak of 78.05 °, with
JCPDS card number 45-1027 is the most identical, and corresponding is the peak of hexagonal closs packing Ni；And 2 θ are at 43.86 °, 50.71 °, 74.91 °
Peak, relative to the peak (JCPDS card number 65-4150) of face-centered cubic phase Fe, move about 1 ° to high angle direction, this with reason
Opinion is analyzed consistent.Because the radius of iron-nickel alloy is less than Fe, so theory analysis obtains the diffraction maximum of iron-nickel alloy relative to Fe's
Diffraction maximum moves to high angle direction.Therefore, it will be seen from figure 1 that the method provided by the present invention has successfully obtained ferrum nickel
Alloy nanocluster, and the first organic solvent is different, reaction temperature is different, can obtain the iron-nickel alloy nano-cluster of not jljl phase.
Raman analysis
Fig. 2 is graphite (a), graphite oxide (b), Graphene (c) and the embodiment 1 of preparation used in the embodiment of the present invention
The Raman spectrogram of iron-nickel alloy nano-cluster-graphene composite material prepared by (d), embodiment 2 (e), embodiment 3 (f).At Raman
In spectrogram, having two basic changes, one of them change is G band and the change of D band peak position.G band is corresponding to the six of two dimension
Prismatic crystal lattice sp2The plane vibration of the carbon atom of hydridization, D band is corresponding to unordered sp3The vibration of the carbon atom of hydridization.In Fig. 2 (a)
The G band of graphite and D band peak respectively appear in 1578cm-1And 1332cm-1, in Fig. 2 (b), the G band of graphite oxide is with D band peak respectively
Occur in 1603cm-1And 1343cm-1, in Fig. 2 (c), G band and the D band peak of Graphene respectively appear in 1579cm-1And 1327cm-1,
In Fig. 2 (d), 2 (e) and 2 (f), G band and the D band peak of three kinds of composites respectively appear in 1595cm-1And 1330cm-1, with Fig. 2
B () is compared, in Fig. 2 (d), 2 (e) and 2 (f), the position at G band peak is moved to lower wave number, by 1603cm-1Move to 1595cm-1, this
Show that the graphite oxide in composite is reduced.Another change is D band and the strength ratio (I of G bandD/IG).Fig. 2 (a) graphite
Raman spectrogram in and Fig. 2 (b) graphite oxide Raman spectrogram in ID/IGIt is respectively 0.30:1 and 0.96:1, Fig. 2 (c) graphite
I in the Raman spectrogram of alkeneD/IGFor 1.41:1, after this is reduced with graphite oxide, along with removing and sp of oxygen-containing functional group2Hydridization
Carbon atom is resumed, ID/IGIntensity increase is consistent.I in the Raman spectrogram of three kinds of composites in Fig. 2 (d), 2 (e) and 2 (f)D/
IGBeing respectively 1.21:1,1.22:1,1.16:1, this shows that iron-nickel alloy nano-cluster-Graphene prepared by the embodiment of the present invention is multiple
Graphite oxide in condensation material is preferably reduced.
Electron microscopy image analysis
Fig. 3 (a) is the TEM figure of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 1 preparation；Fig. 3
B () is the HRTEM figure of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 1 preparation.As can be seen from the figure
Iron-nickel alloy nanocrystal size is homogeneous, does not has obvious agglomeration, is grown in uniformly on graphene film, nanocrystal
Size is about 3nm.It can be seen that iron-nickel alloy nanocrystal spacing of lattice is 0.204nm from the upper left corner illustration of Fig. 3 (b),
This is consistent with the diffraction maximum d value of (111) crystal face in XRD figure spectrum.Lower right corner illustration in Fig. 3 (b) is prepared by the embodiment of the present invention 1
SAED (Selected Area Electron Diffraction, the constituency of iron-nickel alloy nano-cluster-graphene composite material
Electronic diffraction) figure, as can be seen from the figure the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 1 preparation
There are obvious diffraction lattice and the most sharp-pointed ring, show that the alloy nano particle obtained is polycrystalline structure, it was demonstrated that alloy is received
The crystallinity of meter Jing Ti is good.Fig. 3 (c) is the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 1 preparation
SEM schemes；Fig. 3 (d) is the carbon analysis chart of scanning electron microscope corresponding for Fig. 3 (c)；Fig. 3 (e) is the scanning electron microscope that Fig. 3 (c) is corresponding
Ferrum element analysis chart；Fig. 3 (f) is the nickel element analysis chart of scanning electron microscope corresponding for Fig. 3 (c)；These several figures show the present invention
There is nickel in carbon, ferrum and nickel element, and composite in the iron-nickel alloy nano-cluster-graphene composite material of embodiment 1 preparation
Content apparently higher than the content of ferrum.
Fig. 4 (a) and Fig. 4 (d) is the SEM of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 2 preparation
Figure；Fig. 4 (b) is the TEM figure of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 2 preparation.From Fig. 4 (a), 4
B () and 4 (d), it can be seen that the iron-nickel alloy nanoparticle growth of a large amount of size uniformity is on graphene film, is uniformly dispersed, and
Do not observe iron-nickel alloy nanocrystal and graphene film individualism or the phenomenon of reunion, it was demonstrated that all iron-nickel alloy nanometers
Crystal has been grown on graphene film completely.From Fig. 4 (b), it can also be seen that the size of iron-nickel alloy nanocrystal is about 60
～between 100nm.Fig. 4 (c) is the HRTEM of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 2 preparation
Figure, it can be seen that the spacing of lattice of the nanoparticle being attached on Graphene is 0.206nm from the illustration in Fig. 4 (c) upper right corner,
During this composes with the XRD figure of cubic closest packing alloy, (111) face diffraction maximum d value is consistent.Lower right corner illustration in Fig. 4 (c) is this
The SAED figure of the iron-nickel alloy nano-cluster-graphene composite material of bright embodiment 2 preparation, alloy nano as can be seen from the figure
Granule has obvious lattice diffraction ring, it was demonstrated that generate the iron-nickel alloy nanocrystal that crystallinity is good.Fig. 4 (e) is Fig. 4
The carbon analysis chart of d scanning electron microscope that () is corresponding；Fig. 4 (f) is the ferrum element analysis chart of scanning electron microscope corresponding for Fig. 4 (d)；Figure
4 (g) is the nickel element analysis chart of scanning electron microscope corresponding for Fig. 4 (d)；These several figures show ferrum nickel prepared by the embodiment of the present invention 2
Alloy nanocluster-graphene composite material exists in carbon, ferrum and nickel element, and composite the content of nickel apparently higher than ferrum
Content.
Fig. 5 (a) and Fig. 5 (d) is the SEM of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 3 preparation
Figure；Fig. 5 (b) is the TEM figure of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 3 preparation.From Fig. 5 (a), 5
B () and 5 (d) is it can be seen that the iron-nickel alloy nanoparticle growth of a large amount of size uniformity is on graphene film, and be uniformly dispersed not
Have agglomeration, still further it can be seen that the spherical iron-nickel alloy of nanometer be about by diameter 10～20nm iron-nickel alloy nanocrystal
Composition.Fig. 5 (c) is the HRTEM figure of the iron-nickel alloy nano-cluster-graphene composite material of the embodiment of the present invention 3 preparation；From Fig. 5
It can be seen that iron-nickel alloy nanocrystal spacing of lattice is 0.217nm in (c).Upper left corner illustration in Fig. 5 (c) is that the present invention is real
Execute the SAED figure of the iron-nickel alloy nano-cluster-graphene composite material of example 3 preparation, alloy nanoparticle as can be seen from the figure
There is obvious lattice diffraction ring, it was demonstrated that generate the iron-nickel alloy nanocrystal that crystallinity is good.Fig. 5 (e) is Fig. 5 (d)
The carbon analysis chart of corresponding scanning electron microscope；Fig. 5 (f) is the ferrum element analysis chart of scanning electron microscope corresponding for Fig. 5 (d)；Fig. 5
G () is the nickel element analysis chart of scanning electron microscope corresponding for Fig. 5 (d)；Fig. 5 (h) is that the iron-nickel alloy of the embodiment of the present invention 3 preparation is received
The EDS figure of rice bunch-graphene composite material；Can obtain Fe:Ni mol ratio from Fig. 5 (h) and be about 1:3.5, this closes with ferrum nickel
The atom number of gold, than basic coupling, in conjunction with Fig. 5 (e), the elementary analysis of 5 (f) and 5 (g), may certify that the embodiment of the present invention 3
It is successfully generated iron-nickel alloy nano-cluster-graphene composite material.
The absorbing property result of iron-nickel alloy nano-cluster-graphene composite material
For comparing and evaluate the microwave suction of iron-nickel alloy nano-cluster-graphene composite material prepared according to the methods of the invention
Receiving performance, three kinds of iron-nickel alloy nano-cluster-graphene composite materials that above-described embodiment is prepared uniformly mix (its with paraffin
In, iron-nickel alloy nano-cluster-graphene composite material mass fraction in the mixture is 60%, and paraffin does not has electromagnetic wave to inhale
Receive), it is assembled into an electro-magnetic wave absorption device, the external diameter of this device and internal diameter are 7.00nm and 3.04nm respectively, use
Agilent E8362B vector network analyzer, tests, reflection magnetic loss value (RL) of all samples in the range of 1-18GHz,
It is under given frequency and thickness of sample, theoretical according to microwave transmission, use below equation to obtain:
RL (dB)=20log | (Zin-Z0)/(Zin+Z0)| (2)
In above formula (1) and (2), ZinRepresent the input impedance of wave-absorber, Z0Represent air impedance, μrRepresent relative magnetic permeability
Rate, εrRepresenting relative dielectric constant, j represents the imaginary part of symbol of plural number, and f represents microwave frequency, d representative sample thickness, and c represents electricity
Electromagnetic wave propagation speed.
Test result is as shown in Figure 6.Fig. 6 is that three kinds of iron-nickel alloy nano-cluster-Graphenes prepared by the embodiment of the present invention are multiple
The microwave reflection rate loss value of condensation material and the graph of a relation of thickness of sample, wherein, (a) is the graph of a relation of embodiment 1 correspondence, (b)
For the graph of a relation of embodiment 2 correspondence, (c) is the graph of a relation of embodiment 3 correspondence.By Fig. 6 it is found that working as thickness of sample is 3mm
Time, the maximum reflection loss of the iron-nickel alloy nano-cluster-graphene composite material of embodiment 2 preparation is-21.5dB, at 9.2GHz
(Mid Frequency), the maximum reflection loss of the iron-nickel alloy nano-cluster-graphene composite material of embodiment 3 preparation is-17.1dB,
7.1GHz (Mid Frequency).When thickness is 4mm, the maximum of the iron-nickel alloy nano-cluster-graphene composite material of embodiment 2 preparation
Reflection loss is-23.1dB, at 6.6GHz (Mid Frequency), the iron-nickel alloy nano-cluster-graphene composite material of embodiment 3 preparation
Maximum reflection loss for-14.8dB, in 5.7GHz (low-frequency range).When thickness is 5mm, the iron-nickel alloy of embodiment 2 preparation
The maximum reflection loss of nano-cluster-graphene composite material is-28.2dB, in 4.9GHz (low-frequency range), and (high at 16.9GHz
Frequency range) also there is the reflection loss less than-10dB, for-15.1dB；Iron-nickel alloy nano-cluster-the Graphene of embodiment 3 preparation is combined
The maximum reflection loss of material is-17.2dB, in 4.1GHz (low-frequency range), and also has less than-10dB at 13.5GHz (high band)
Reflection loss, for-12.6dB；Iron-nickel alloy nano-cluster-the graphene composite material of now embodiment 1 preparation is at 15.7GHz
The reflection loss of (high band) is-28.8dB.This absorbing property test result shows, ferrum nickel prepared according to the methods of the invention closes
Gold nanoclusters-graphene composite material has preferable absorbing property.
It should be noted that in this article, the relational terms of such as first and second or the like is used merely to a reality
Body or operation separate with another entity or operating space, and deposit between not necessarily requiring or imply these entities or operating
Relation or order in any this reality.
Above iron-nickel alloy nano-cluster-graphene composite material provided by the present invention, Preparation Method And The Use are entered
Go and be discussed in detail.Principle and the embodiment of the present invention are set forth by specific embodiment used herein, above reality
The explanation executing example is only intended to help to understand method and the central idea thereof of the present invention.It should be pointed out that, for this area is common
For technical staff, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out some improvement and modification, these
Improve and modify the protection also falling into the claims in the present invention.
Claims (10)
1. the method preparing iron-nickel alloy nano-cluster-graphene composite material, it is characterised in that comprise the following steps:
1), graphite oxide joined in the first organic solvent and disperse；
2), add ferric acetyl acetonade, nickel acetylacetonate and 18-amine., in inertia protective gas, heat the mixture to 100
DEG C～150 DEG C, maintain 20～50min, then heat to solution boiling reflux, maintain 1～5h；
Described graphite oxide is 0.2～0.3 with the mass ratio of described ferric acetyl acetonade；Described graphite oxide and described acetylacetone,2,4-pentanedione
The mass ratio of nickel is 0.1～0.2；Described graphite oxide is 1:80～1:40 with the mass ratio of described 18-amine.；
3), add the second organic solvent and stop sudden for reaction, isolate product, wash and be dried described product.
2. the method for claim 1, it is characterised in that step 1) in the first organic solvent be 2-Pyrrolidone, N-
At least one in methyl pyrrolidone and oleyl amine.
3. the method for claim 1, it is characterised in that step 1) described in graphite oxide and described first organic solvent
Mass volume ratio be 0.8mg/mL～1.2mg/mL.
4. the method for claim 1, it is characterised in that step 1) in be separated into ultrasonic disperse.
5. the method for claim 1, it is characterised in that step 2) in inertia protective gas be argon or nitrogen.
6. the method for claim 1, it is characterised in that step 2) in be heated to 110～130 DEG C.
7. the method for claim 1, it is characterised in that step 3) in the second organic solvent be ethanol.
8. the method for claim 1, it is characterised in that step 3) middle normal hexane, acetone alternately washing, and in 40 DEG C
It is vacuum dried described product.
9. the iron-nickel alloy nano-cluster-Graphene composite wood prepared by the method according to any one of claim 1～8
Material.
10. iron-nickel alloy nano-cluster-graphene composite material as claimed in claim 9 is for the purposes of electromagnetic wave absorption.
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