CN104004496A - Preparation method of reduced graphene oxide/nickel oxide composite wave absorbing material - Google Patents
Preparation method of reduced graphene oxide/nickel oxide composite wave absorbing material Download PDFInfo
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Abstract
The invention discloses a reduced graphene oxide/nickel oxide composite wave absorbing material. Nickel oxide nanoparticles with the particle size of 1-100nm are uniformly distributed on a graphene nanosheet. The composite wave absorbing material has superior microwave absorbing performances: the lowest optimum reflection loss is -55.5dB, and the highest absorption frequency band below -10dB is 6.7GHz. The composite wave absorbing material has a light weight, and can meet the characteristics of light weight and high strength of wave absorbing materials. The invention discloses a preparation method of the composite wave absorbing material. The preparation method comprises the following steps: dissolving nickel acetate in a graphene oxide solution, freeze-drying, and carrying out high temperature pyrolysis on the obtained freeze-dried sample in argon atmosphere to prepare the wave absorbing material. The preparation method has the advantages of simplicity, environmental protection and low cost.
Description
Technical field
The present invention relates to microwave absorption Material Field, be specifically related to a kind of preparation method of redox graphene/nickel oxide composite wave-suction material.
Background technology
Stealth material is referred to as again absorbing material, 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 has caused people's extensive concern owing to being widely used in the fields such as absorption shielding of radar, space flight, microwave communication and electronic countermeasure, electronics compatibility.
Nickel oxide is a kind of typical metal oxide, and it has potential using value at aspects such as ultracapacitor, lithium ion battery, catalyzer.
C-base composte material has very superior microwave absorbing property and they can also meet needed other advantages of absorbing material, and for example quality is light, and specific inductivity is high.Graphene is a kind of novel carbon-based material, since 2004 find, has caused people's extensive concern and has been used in the fields such as field-effect transistor, ultracapacitor, lithium ion battery, gas sensing and chemical sensor.In the recent period, scientists is found the redox graphene that chemical process is prepared and be take that it has excellent microwave absorbing property as basic matrix material.For example Bi et al. (J. Appl. Phys., 2012,111,07A522) at the bowl-shape ferriferrous oxide nano-particle of Graphene area load; Guan et al. (Appl. Phys. Lett., 2012,101,153108) is at the two-sided load Z 250 of Graphene, and forms superstructure; Chen et al.(J. Mater. Chem., 2012,22,15190 – 15197) loaded metal nickel on Graphene; Yu et al.(J. Mater. Chem., 2012,22,21679 – 21685) load polyaniline nano-rod array etc. on Graphene.Qu et al. (Physical Chemistry Chemical Physics, 2013,15,13038-13043) utilize hydrothermal method to prepare Graphene and the four ferric oxide composite wave-suction materials of three-dimensional structure; Graphene and the a-Fe of three-dimensional structure prepared in this seminar
2o
3(Journal of Materials Chemistry A, 2013,1,8547-8552), Graphene and V
2o
5(ChemPhysChem, 2014,15,366-373) Graphene and Fe
3o
4(RSC Adv, 2014,4,14441-14446) composite aquogel; Liu et al. (Materials Letters, 2013,107,166 – 169) supported cobaltosic oxide nano particle on Graphene; Wang et al.(Materials Science and Engineering B, 2013,178,1403 – 1409) prepared the NiO@SiO of Fe doping
2@Graphene and NiO nanometer sheet@SiO
2@Graphene (RSC Adv., 2013,3,23290 – 23295) composite nano materials; Etc..These be take Graphene and all show good microwave absorbing property as basic matrix material.But by after mixing solutions lyophilize, and then the composite wave-suction material that utilizes 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 a kind of preparation method 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 being uniformly dispersed, obtain the aqueous solution of graphene oxide;
(2) under magnetic agitation, in the aqueous solution of graphene oxide in step (1), add nickelous acetate 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 finishes, be cooled to room temperature, collecting reaction product.
In described step (1), the concentration of graphene oxide is 1-10 mg/mL, and ultrasonic jitter time is 0.5-5 h.
In described step (2) mixing solutions, the concentration of nickelous acetate is 0.1-20 mM.
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 ℃.
In described step (4), the heat-up rate of high temperature pyrolysis is 1-10 ℃/min.
After reaching top temperature during the middle high temperature pyrolysis of described step (4), be incubated 1-10 h.
Described NiO nanoparticle size is 1-100 nm, and it is evenly dispersed on graphene nanometer sheet.
Beneficial effect of the present invention:
In the prepared redox graphene/nickel oxide composite wave-suction material of the present invention, 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, has changed the electromagnetic parameter of matrix material, has reduced the specific inductivity of matrix material, has realized impedance matching, has improved the reflection loss of matrix material.And Graphene quality is light, thereby effectively reduce the quality of composite wave-suction material, possessed the feature of stealth material high-strength light.In the present invention, redox graphene/nickel oxide composite wave-suction material of preparation, the absorption band below the dB of reflection loss-10 is up to 6.7 GHz, and minimum reflection loss reaches-55.5 dB.And now in the sample of microwave test, the quality of redox graphene/nickel oxide composite wave-suction material only accounts for 8 wt %, the thickness of test sample is 2mm only also, has met 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 of embodiment 1 preparation.
Fig. 2 is redox graphene/nickel oxide composite wave-suction material SEM figure of embodiment 1 preparation.
Fig. 3 is redox graphene/nickel oxide composite wave-suction material TEM figure of embodiment 1 preparation.
Fig. 4 is redox graphene/nickel oxide composite wave-suction material of embodiment 1 preparation reflection loss extinction curve when different thickness.
Embodiment
In order further to understand the present invention, below in conjunction with specific embodiment, the present invention is described further.Should be appreciated that these embodiment are only not limited to scope of the present invention for the present invention is described.
Embodiment 1
1, prepare graphene oxide
Adopt improved Hummers method to prepare graphene oxide, as the precursor liquid of composite wave-suction material.
Concrete preparation method is: take the graphite of 3g, the SODIUMNITRATE of 1.5g is mixed, and the sulfuric acid that measures 150mL slowly adds in above-mentioned solid, ice bath and add slowly the potassium permanganate of 9.0g under magnetic agitation, and this process continues in 2h left and right; Remove ice bath, 35 ℃ 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 20mL 30%, and solution becomes deep yellow gradually; By above-mentioned solution centrifugal washed several times with water, get the ultrasonic 2h of subnatant, then 8000 turn centrifuging and taking upper strata liquid, dialyse 15 days, lyophilize.
1, the preparation of graphene oxide/nickelous acetate mixture
(1) take 100 mg graphene oxides, in the ultrasonic water that is dispersed in 25 mL, and be made into the aqueous solution of 4 mg/mL;
(2) take the nickel acetate tetrahydrate of 50 mg, under magnetic agitation, add in above-mentioned solution and fully and dissolve;
(3) after fully dissolving, ultrasonic half an hour;
(4) mixing solutions obtaining is freezing rear dry.
3, the preparation of graphene oxide/nickel oxide composite wave-suction material
Graphene oxide/nickelous acetate mixture after above-mentioned lyophilize is taken out, put into porcelain boat, in tube furnace argon atmosphere, heat.Temperature rise rate is 3 ℃/min, is incubated 2 h while being warming up to 500 ℃, then lowers the temperature with the speed of 3 ℃/min.After being down to room temperature, collect sample.
Embodiment 2
1, the preparation of graphene oxide is with embodiment 1.
2, the preparation of graphene oxide/nickelous acetate mixture
(1) take 100 mg graphene oxides, in the ultrasonic water that is dispersed in 50 mL, and be made into the aqueous solution of 2 mg/mL;
(2) take the nickel acetate tetrahydrate of 100 mg, under magnetic agitation, add in above-mentioned solution and fully and dissolve;
(3) after fully dissolving, ultrasonic half an hour;
(4) mixing solutions obtaining is freezing rear dry.
3, the preparation of graphene oxide/nickel oxide composite wave-suction material
Graphene oxide/nickelous acetate mixture after above-mentioned lyophilize is taken out, put into porcelain boat, in tube furnace argon atmosphere, heat.Temperature rise rate is 5 ℃/min, is incubated 2 h while being warming up to 400 ℃, then lowers the temperature with the speed of 5 ℃/min.After being down to room temperature, collect sample.
Embodiment 3
1, the preparation of graphene oxide is with embodiment 1.
2, the preparation of graphene oxide/nickelous acetate mixture
(1) take 100 mg graphene oxides, in the ultrasonic water that is dispersed in 50 mL, and be made into the aqueous solution of 2 mg/mL;
(2) take the nickel acetate tetrahydrate of 50 mg, under magnetic agitation, add in above-mentioned solution and fully and dissolve;
(3) after fully dissolving, ultrasonic half an hour;
(4) mixing solutions obtaining is freezing rear dry.
3, the preparation of graphene oxide/nickel oxide composite wave-suction material
Graphene oxide/nickelous acetate mixture after above-mentioned lyophilize is taken out, put into porcelain boat, in tube furnace argon atmosphere, heat.Temperature rise rate is 3 ℃/min, is incubated 2 h while being warming up to 600 ℃, then lowers the temperature with the speed of 3 ℃/min.After being down to room temperature, collect sample.
Claims (9)
1. a preparation method for redox graphene/nickel oxide composite wave-suction material, is characterized in that comprising the following steps:
(1) graphene oxide is soluble in water, and ultrasonic being uniformly dispersed, obtain the aqueous solution of graphene oxide;
(2) under magnetic agitation, in the aqueous solution of graphene oxide in step (1), add nickelous acetate 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 finishes, be cooled to room temperature, collecting reaction product.
2. the preparation method of redox graphene/nickel oxide composite wave-suction material according to claim 1, is characterized in that: in described step (1), the concentration of graphene oxide is 1-10 mg/mL, and ultrasonic jitter time is 0.5-5h.
3. the preparation method of redox graphene/nickel oxide composite wave-suction material according to claim 1, is characterized in that: in described step (2) mixing solutions, the concentration of nickelous acetate is 0.1-20 mM.
4. the preparation method of redox graphene/nickel oxide composite wave-suction material according to claim 1, is characterized in that: the drying mode of described step (3) mixing solutions is lyophilize.
5. the preparation method of redox graphene/nickel oxide composite wave-suction material according to claim 1, is characterized in that: in described step (4), high temperature pyrolysis carries out in argon atmosphere.
6. the preparation method of redox graphene/nickel oxide composite wave-suction material according to claim 1, is characterized in that: in described step (4), the temperature of high temperature pyrolysis is 300-800 ℃.
7. the preparation method of redox graphene/nickel oxide composite wave-suction material according to claim 1, is characterized in that: in described step (4), the heat-up rate of high temperature pyrolysis is 1-10 ℃/min.
8. the preparation method of redox graphene/nickel oxide composite wave-suction material according to claim 1, is characterized in that: after reaching top temperature during the middle high temperature pyrolysis of described step (4), be incubated 1-10 h.
9. the preparation method of redox graphene/nickel oxide composite wave-suction material according to claim 1, is characterized in that: described NiO nanoparticle size is 1-100 nm, and it is evenly dispersed on graphene nanometer sheet.
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Cited By (7)
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| CN104690289A (en) * | 2015-01-12 | 2015-06-10 | 冯丹 | Graphene-nano-nickel wave-absorbing material |
| CN105023762A (en) * | 2015-08-10 | 2015-11-04 | 安徽建筑大学 | Foliated CuO-NiO composite structure nano-material 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 |
| CN111218189A (en) * | 2018-11-26 | 2020-06-02 | 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 |
| CN113823919A (en) * | 2021-09-24 | 2021-12-21 | 中南大学 | Light nickel/nickel oxide assembled graphene-based composite low-frequency wave-absorbing foam and preparation method thereof |
| CN114784227A (en) * | 2022-04-12 | 2022-07-22 | 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104690289A (en) * | 2015-01-12 | 2015-06-10 | 冯丹 | Graphene-nano-nickel wave-absorbing material |
| CN105023762A (en) * | 2015-08-10 | 2015-11-04 | 安徽建筑大学 | Foliated CuO-NiO composite structure nano-material and preparation method thereof |
| 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 |
| CN111218189A (en) * | 2018-11-26 | 2020-06-02 | 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 |
| CN113823919A (en) * | 2021-09-24 | 2021-12-21 | 中南大学 | Light nickel/nickel oxide assembled graphene-based composite low-frequency wave-absorbing foam and preparation method thereof |
| CN114784227A (en) * | 2022-04-12 | 2022-07-22 | 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 |
| 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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