CN104004496B - The preparation method of a kind of redox graphene/nickel oxide composite wave-suction material - Google Patents
The preparation method of a kind of redox graphene/nickel oxide composite wave-suction material Download PDFInfo
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- CN104004496B CN104004496B CN201410173989.6A CN201410173989A CN104004496B CN 104004496 B CN104004496 B CN 104004496B CN 201410173989 A CN201410173989 A CN 201410173989A CN 104004496 B CN104004496 B CN 104004496B
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Abstract
The invention discloses a kind of redox graphene/nickel oxide composite wave-suction material, particle diameter is evenly distributed on graphene nanometer sheet at the NiO nanoparticle of 1-100nm.Does this composite wave-suction material have superior microwave absorbing property: best reflection loss is low to moderate-55.5dB, lower than the absorption band below-10dB up to 6.7? GHz; In addition, this composite wave-suction material quality is light, meets the feature of microwave absorbing material high-strength light.The invention also discloses the preparation method of this composite wave-suction material, this composite wave-suction material is first dissolved in graphene oxide solution by nickelous acetate, lyophilize, then by the high temperature pyrolysis and obtained under argon atmosphere of the sample after lyophilize, this preparation method is easy, environmental protection, cost are low.
Description
Technical field
The present invention relates to microwave absorption Material Field, be specifically related to the preparation method of a kind of redox graphene/nickel oxide composite wave-suction material.
Background technology
Stealth material is referred to as absorbing material again, and its effect is that external hertzian wave material is converted to heat energy, reduces reflection intensity of wave, reaches stealthy effect.Electromagnetic-wave absorbent due to be widely used in radar, space flight, microwave communication and electronic countermeasure, electronics compatibility the field such as absorption shielding and cause the extensive concern of people.
Nickel oxide is a kind of typical metal oxide, and it has potential using value in ultracapacitor, lithium ion battery, catalyzer etc.
C-base composte material has very superior microwave absorbing property and they can also meet other advantages required for absorbing material, and such as quality is light, and specific inductivity is high.Graphene is a kind of novel carbon-based material, since finding, has caused the extensive concern of people and has been used in the fields such as field-effect transistor, ultracapacitor, lithium ion battery, gas sensing and chemical sensor from 2004.In the recent period, scientists finds that the redox graphene prepared by chemical process and the matrix material based on it have excellent microwave absorbing property.Such as Bietal. (J.Appl.Phys., 2012,111,07A522) is at the bowl-shape ferriferrous oxide nano-particle of graphenic surface load; Guanetal.(Appl.Phys.Lett., 2012,101,153108) at the two-sided load Z 250 of Graphene, and form superstructure; Chenetal.(J.Mater.Chem., 2012,22,15190 – 15197) loaded metal nickel on Graphene; Yuetal.(J.Mater.Chem., 2012,22,21679 – 21685) load polyaniline nano-rod array etc. on Graphene.Quetal. the Graphene of (PhysicalChemistryChemicalPhysics, 2013,15, the 13038-13043) three-dimensional structure that utilized hydrothermal method to prepare and four ferric oxide composite wave-suction materials; The Graphene of three-dimensional structure that this project team system is standby and a-Fe
2o
3(JournalofMaterialsChemistryA, 2013,1,8547-8552), Graphene and V
2o
5(ChemPhysChem, 2014,15,366-373) Graphene and Fe
3o
4(RSCAdv, 2014,4,14441-14446) composite aquogel; Liuetal.(MaterialsLetters, 2013,107,166 – 169) supported cobaltosic oxide nano particle on Graphene; Wangetal.(MaterialsScienceandEngineeringB, 2013,178,1403 – 1409) prepared Fe doping NiOSiO
2Graphene and NiO nanometer sheetSiO
2Graphene (RSCAdv., 2013,3,23290 – 23295) composite nano materials; Etc..These matrix materials based on Graphene all show good microwave absorbing property.But after mixing solutions lyophilize, and then the composite wave-suction material utilizing the method for high temperature pyrolysis to prepare Graphene and nickel oxide have not been reported.
Summary of the invention
The problem that the present invention solves is to provide the preparation method of a kind of redox graphene/nickel oxide composite wave-suction material, and the method is easy, environmental protection, and cost is low, and material has good microwave absorption performance.
For achieving the above object, the technical solution used in the present invention is as follows:
A preparation method for redox graphene/nickel oxide composite wave-suction material, comprises the following steps:
(1) graphene oxide is soluble in water, and ultrasonic disperse is even, obtains the aqueous solution of graphene oxide;
(2) in the aqueous solution of graphene oxide in step (1), add nickelous acetate under magnetic stirring and dissolve fully, obtaining mixing solutions;
(3) above-mentioned mixing solutions is dry;
(4) by above-mentioned dried product high temperature pyrolysis in tube furnace;
(5) after question response terminates, room temperature is cooled to, collecting reaction product.
In described step (1), the concentration of graphene oxide is 1-10mg/mL, and the ultrasonic disperse time is 0.5-5h.
In described step (2) mixing solutions, the concentration of nickelous acetate is 0.1-20mM.
The drying mode of described step (3) mixing solutions is lyophilize.
In described step (4), high temperature pyrolysis carries out in argon atmosphere.
In described step (4), the temperature of high temperature pyrolysis is 300-800 DEG C.
In described step (4), the heat-up rate of high temperature pyrolysis is 1-10 DEG C/min.
1-10h is incubated after reaching top temperature during high temperature pyrolysis in described step (4).
Described NiO nanoparticle size is 1-100nm, and it is evenly dispersed on graphene nanometer sheet.
Beneficial effect of the present invention:
In redox graphene prepared by the present invention/nickel oxide composite wave-suction material, the content of nickel oxide reaches 40wt%-90wt%, and the content of Graphene reaches 10wt%-60wt%.
The present invention has prepared redox graphene/nickel oxide composite wave-suction material under high temperature pyrolysis condition.NiO nanoparticle is dispersed on graphene nanometer sheet uniformly, changes the electromagnetic parameter of matrix material, reduces the specific inductivity of matrix material, achieves impedance matching, improves the reflection loss of matrix material.And Graphene quality is light, thus effectively reduces the quality of composite wave-suction material, has possessed the feature of stealth material high-strength light.In the present invention, the redox graphene/nickel oxide composite wave-suction material of preparation, at the absorption band of below reflection loss-10dB up to 6.7GHz, and minimum reflection loss reaches-55.5dB.And now in the sample of microwave test, the quality of redox graphene/nickel oxide composite wave-suction material only accounts for 8wt%, the thickness also only 2mm of test sample, meets the requirement of absorbing material high-strength light completely.
accompanying drawing explanationfig. 1 is the XRD figure of redox graphene/nickel oxide composite wave-suction material prepared by embodiment 1.
Fig. 2 is that redox graphene/nickel oxide composite wave-suction material SEM prepared by embodiment 1 schemes.
Fig. 3 is that redox graphene/nickel oxide composite wave-suction material TEM prepared by embodiment 1 schemes.
Fig. 4 is the reflection loss extinction curve of redox graphene/nickel oxide composite wave-suction material when different thickness prepared by embodiment 1.
Embodiment
In order to understand the present invention further, below in conjunction with specific embodiment, the present invention is described further.Should be appreciated that these embodiments are only not limited to scope of the present invention for illustration of the present invention.
Embodiment 1
1, graphene oxide is prepared
The Hummers method improved is adopted to prepare graphene oxide, as the precursor liquid of composite wave-suction material.
Concrete preparation method is: the graphite taking 3g, the mixing of the SODIUMNITRATE of 1.5g, and the sulfuric acid measuring 150mL slowly adds in above-mentioned solid, ice bath and add the potassium permanganate of 9.0g under magnetic stirring slowly, and this process lasts is at about 2h; Remove ice bath, 35 DEG C of water-baths about 5 days, slowly add the water of 140mL, add the water of 350mL after 30min again, slowly drip the hydrogen peroxide of 20mL30%, solution becomes deep yellow gradually; By above-mentioned solution centrifugal and washed several times with water, get the ultrasonic 2h of subnatant, then 8000 turns of centrifuging and taking upper liquid, dialyse 15 days, lyophilize.
The preparation of 1, graphene oxide/nickelous acetate mixture
(1) take 100mg graphene oxide, ultrasonic disperse in the water of 25mL, and is made into the aqueous solution of 4mg/mL;
(2) take the nickel acetate tetrahydrate of 50mg, add under magnetic agitation in above-mentioned solution and also fully dissolve;
(3) after fully dissolving, ultrasonic half an hour;
(4) the freezing rear drying of the mixing solutions obtained.
The preparation of 3, graphene oxide/nickel oxide composite wave-suction material
Graphene oxide after above-mentioned lyophilize/nickelous acetate mixture is taken out, puts into porcelain boat, heat in tube furnace argon atmosphere.Temperature rise rate is 3 DEG C/min, is incubated 2h, then lowers the temperature with the speed of 3 DEG C/min when being warming up to 500 DEG C.After being down to room temperature, collect sample.
Embodiment 2
1, the preparation of graphene oxide is with embodiment 1.
The preparation of 2, graphene oxide/nickelous acetate mixture
(1) take 100mg graphene oxide, ultrasonic disperse in the water of 50mL, and is made into the aqueous solution of 2mg/mL;
(2) take the nickel acetate tetrahydrate of 100mg, add under magnetic agitation in above-mentioned solution and also fully dissolve;
(3) after fully dissolving, ultrasonic half an hour;
(4) the freezing rear drying of the mixing solutions obtained.
The preparation of 3, graphene oxide/nickel oxide composite wave-suction material
Graphene oxide after above-mentioned lyophilize/nickelous acetate mixture is taken out, puts into porcelain boat, heat in tube furnace argon atmosphere.Temperature rise rate is 5 DEG C/min, is incubated 2h, then lowers the temperature with the speed of 5 DEG C/min when being warming up to 400 DEG C.After being down to room temperature, collect sample.
Embodiment 3
1, the preparation of graphene oxide is with embodiment 1.
The preparation of 2, graphene oxide/nickelous acetate mixture
(1) take 100mg graphene oxide, ultrasonic disperse in the water of 50mL, and is made into the aqueous solution of 2mg/mL;
(2) take the nickel acetate tetrahydrate of 50mg, add under magnetic agitation in above-mentioned solution and also fully dissolve;
(3) after fully dissolving, ultrasonic half an hour;
(4) the freezing rear drying of the mixing solutions obtained.
The preparation of 3, graphene oxide/nickel oxide composite wave-suction material
Graphene oxide after above-mentioned lyophilize/nickelous acetate mixture is taken out, puts into porcelain boat, heat in tube furnace argon atmosphere.Temperature rise rate is 3 DEG C/min, is incubated 2h, then lowers the temperature with the speed of 3 DEG C/min when being warming up to 600 DEG C.After being down to room temperature, collect sample.
Claims (6)
1. redox graphene/nickel oxide composite material is as a purposes for absorbing material, it is characterized in that: the preparation method of material comprises the following steps:
(1) graphene oxide is soluble in water, and ultrasonic disperse is even, obtains the aqueous solution of graphene oxide;
(2) in the aqueous solution of graphene oxide in step (1), add nickelous acetate under magnetic stirring and dissolve fully, the concentration of nickelous acetate is 0.1-20mM, obtains mixing solutions;
(3) by above-mentioned mixing solutions lyophilize;
(4) by above-mentioned dried product high temperature pyrolysis in tube furnace;
(5) after question response terminates, room temperature is cooled to, collecting reaction product; In reaction product, NiO nanoparticle size is 1-100nm, is evenly dispersed on graphene nanometer sheet.
2. redox graphene/nickel oxide composite material, as a purposes for absorbing material, is characterized in that as claimed in claim 1: in described step (1), the concentration of graphene oxide is 1-10mg/mL, and the ultrasonic disperse time is 0.5-5h.
3. redox graphene/nickel oxide composite material, as a purposes for absorbing material, is characterized in that as claimed in claim 1: in described step (4), high temperature pyrolysis carries out in argon atmosphere.
4. redox graphene/nickel oxide composite material, as a purposes for absorbing material, is characterized in that as claimed in claim 1: in described step (4), the temperature of high temperature pyrolysis is 300-800 DEG C.
5. redox graphene/nickel oxide composite material, as a purposes for absorbing material, is characterized in that as claimed in claim 1: in described step (4), the heat-up rate of high temperature pyrolysis is 1-10 DEG C/min.
6., it is characterized in that as a purposes for absorbing material as weighed redox graphene/nickel oxide composite material as described in 1: after reaching top temperature during high temperature pyrolysis in described step (4), be incubated 1-10h.
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| CN104690289A (en) * | 2015-01-12 | 2015-06-10 | 冯丹 | Graphene-nano-nickel wave-absorbing material |
| CN105023762B (en) * | 2015-08-10 | 2017-11-14 | 安徽建筑大学 | A kind of foliaceous CuO NiO composite construction nano materials and preparation method thereof |
| CN109054710A (en) * | 2018-07-05 | 2018-12-21 | 广东石成科技有限公司 | A kind of graphene composite material and preparation method and its application as magnetic-conductive adhesive |
| CN111218189B (en) * | 2018-11-26 | 2022-07-08 | 西安光启尖端技术研究院 | Resistive film and preparation method and application thereof |
| CN112165848A (en) * | 2020-09-27 | 2021-01-01 | 晋中学院 | Composite wave-absorbing material with magnetic metal or oxide thereof loaded on graphene and preparation method thereof |
| CN113823919B (en) * | 2021-09-24 | 2023-01-03 | 中南大学 | Light nickel/nickel oxide assembled graphene-based composite low-frequency wave-absorbing foam and preparation method thereof |
| CN114784227B (en) * | 2022-04-12 | 2024-03-29 | 中国科学院电工研究所 | Graphene/metal oxide composite nano material, preparation method and application thereof, electrode plate and application thereof |
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| CN102184781A (en) * | 2011-03-03 | 2011-09-14 | 上海大学 | Nano-nickel oxide/graphene composite material and preparation method thereof |
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| CN101733985A (en) * | 2009-12-23 | 2010-06-16 | 天津大学 | Graphene/nickel oxide laminated-structure composite film and preparation method thereof |
| CN102184781A (en) * | 2011-03-03 | 2011-09-14 | 上海大学 | Nano-nickel oxide/graphene composite material and preparation method thereof |
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| Bifunctional Reduced Graphene Oxide/V2O5 Composite Hydrogel: Fabrication, High Performance as Electromagnetic Wave Absorbent and Supercapacitor;Hui Zhang，等;《ChemPhysChem》;20131206;第15卷(第2期);第366-373页 * |
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