CN102604593A - Cubic-phase nickel nanostructure-graphene complex and preparation method thereof - Google Patents

Cubic-phase nickel nanostructure-graphene complex and preparation method thereof Download PDF

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CN102604593A
CN102604593A CN2012100717246A CN201210071724A CN102604593A CN 102604593 A CN102604593 A CN 102604593A CN 2012100717246 A CN2012100717246 A CN 2012100717246A CN 201210071724 A CN201210071724 A CN 201210071724A CN 102604593 A CN102604593 A CN 102604593A
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nickel
cubic
gn
graphene
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CN102604593B (en
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杨晓晶
孙根班
陈婷婷
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北京师范大学
北京师大科技园科技发展有限责任公司
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Abstract

The invention provides a magnetic nanomaterial-graphene complex, in particular to a cubic-phase nickel nanostructure-graphene complex, the chemical formula of which is c-Ni/GN. A preparation method for the cubic-phase nickel nanostructure-graphene complex includes the following steps that: (a) graphite oxide is dissolved in 2-pyrrolidone or N-methylpyrrolidone, so that brown solution is obtained; (b) acetylacetone nickel and octadecylamine are added into the brown solution, the brown solution is heated to 110 DEG C to 140 DEG C under the protection of nitrogen, and the temperature is kept for 20 to 40 minutes, then increased to 202 DEG C and kept for 1.5 to 2.5 hours; (c) organic solvent is added to suddenly stop reaction, and the temperature of the reaction system is rapidly decreased to the room temperature; (d) reaction product is separated out, washed and dried. The cubic-phase nickel nanostructure-graphene complex provided by the invention is a novel electromagnetic wave-absorbing material, and enhances the wave-absorbing property of nickel, so that nickel has good electromagnetic wave-absorbing property. The preparation method for the cubic-phase nickel nanostructure-graphene complex is simple, convenient and quick, the effect of reduction is good, the raw materials are easy to obtain, and the cost is low.

Description

立方相镍纳米结构-石墨烯复合体及其制备方法 Ni nanostructured cubic phase - graphene composite material and its preparation method

技术领域 FIELD

[0001] 本发明涉及电磁波吸收材料领域,具体涉及一种立方相镍纳米结构-石墨烯复合体及其制备方法。 [0001] The present invention relates to the field of electromagnetic wave absorbing material, in particular, to a Ni nanostructured cubic phase - graphene composite material and its preparation method.

背景技术 Background technique

[0002] 近年来,无线通讯技术在商业、工业以及军事行业中快速发展,为我们的生活带来便利的同时也带来了电磁波的危害,这使得制备能吸收电磁波的装置和研究吸收电磁波的材料的任务变得更加紧迫。 [0002] In recent years, the rapid development of wireless communication technology in commercial, industrial and military sectors, bring convenience to our lives has brought harm of electromagnetic waves, which makes the device research and preparation can absorb electromagnetic wave absorption of electromagnetic waves material becomes more urgent task. 因此,对电磁波具有宽吸收范围、高吸收容量、低密度、热稳性好、抗氧化能力好的材料的研究引起了人们的极大关注。 Thus, an electromagnetic wave having a broad absorption range, high absorption capacity, low density, good thermal stability, good material research antioxidant capacity aroused great concern.

[0003] 金属镍是一种典型的磁性材料,其在氢存储材料、催化剂、磁传感器和电磁波吸收材料等方面具有很好的潜在应用。 [0003] Nickel is typically a magnetic material, in which a hydrogen storage material, a catalyst, a magnetic sensor and an electromagnetic wave absorbing material and so has a very good potential applications.

[0004] 石墨烯(GN)由于具有良好的导电性、大的比表面积、柔韧性和化学稳定性等许多优良的性质,所以常常被用来作为承载其他活性材料的基底。 [0004] Graphene (GN) due to good electrical conductivity, a large specific surface area of ​​many excellent properties, flexibility and chemical stability, it is often used as the base carrier of other active materials. 自2004年Geim等人发现石墨烯以来,石墨烯与其他纳米材料复合体的研究引起了人们的极大关注,其中这些纳米材料主要包括各种纳米粒子,例如,Mn3O4, MoS2, Fe3O4, Co、Co3O4, Co (OH)2, CoFe2O4, Ni (OH)2 纳米粒子以及NiO纳米粒子。 Since 2004 Geim, who discovered graphene, graphene research and other nano-composite body aroused great concern among these nanomaterials include a variety of nanoparticles, for example, Mn3O4, MoS2, Fe3O4, Co, Co3O4, Co (OH) 2, CoFe2O4, Ni (OH) 2 and NiO nanoparticles nanoparticles. 由于石墨烯具有很高的导电率,同时金属镍纳米粒子具有良好的磁性,如果能将金属镍纳米粒和石墨烯制成复合体,那么这种复合材料必将具有良好的电磁波吸收效应。 Since graphene has high electrical conductivity, while nickel has good magnetic nanoparticles, nickel nanoparticles can if graphene composite is made, then this composite material will have good electromagnetic wave absorption effect. 此外,与传统的吸波材料相比,石墨烯具有密度小、抗腐蚀性好、柔性较大以及成本低等优点,所以这使得对于金属镍-石墨烯吸收电磁波材料的研究更具有现实意义。 Further, compared with conventional absorbers, graphene having a low density, good corrosion resistance, low cost, and greater flexibility, this makes for a nickel - is more practical significance of the graphene material absorbing electromagnetic waves.

发明内容 SUMMARY

[0005] 本发明解决的问题在于提供一种立方相镍纳米结构-石墨烯复合体,具有良好的电磁波吸收性能。 [0005] The present invention solves the problem to provide a Ni nanostructured cubic phase - graphene composite body having excellent electromagnetic wave absorption performance. 本申请还提供该立方相镍纳米结构-石墨烯复合体的制备方法,简便,快速,还原效果好。 The present application also provides the Ni nanostructured cubic phase - Preparation graphene composite is simple, rapid, reducing effect.

[0006] 为了解决上述技术问题,本发明的技术方案为: [0006] To solve the above technical problem, the technical solution of the present invention is:

[0007] 一种磁性纳米材料-石墨烯复合体,其特征在于,化学式为c-Ni/GN。 [0007] A magnetic nanomaterial - graphene composite, wherein the formula c-Ni / GN.

[0008] 一种以上所述的磁性纳米材料-石墨烯复合体的制备方法,包括: [0008] The one or more magnetic nanomaterial - Preparation graphene composite body, comprising:

[0009] a)将氧化石墨溶于2-吡咯烷酮或N-甲基吡咯烷酮,得到棕色溶液; [0009] a) the graphite oxide was dissolved in N- methylpyrrolidone or 2-pyrrolidone, to give a brown solution;

[0010] b)将乙酰丙酮镍和十八胺加入上述棕色溶液中,在氮气保护下加热至110°C〜 140°C维持20min〜40min,再升温至202°C并维持I. 5h〜2. 5h ; [0010] b) The nickel acetylacetonate and octadecyl amine was added to the brown solution, was heated to 110 ° C~ 140 ° C 20min~40min maintained under nitrogen, then heated to 202 ° C and maintained I. 5h~2 . 5h;

[0011] c)加入有机溶剂将反应猝停,使反应体系的温度迅速降至室温; [0011] c) an organic solvent was added and the reaction is quenched, the temperature of the reaction system was rapidly cooled to room temperature;

[0012] d)分离反应产物,洗涤后干燥,得到c-Ni/GN。 [0012] d) separation of the reaction product was washed and dried to give c-Ni / GN.

[0013] 作为优选,所述氧化石墨溶于2-吡咯烷酮或N-甲基吡咯烷酮得到的溶液中氧化石墨的浓度为O. 8g/L〜I. 5g/L。 [0013] Advantageously, the concentration of 2-pyrrolidone dissolved in the graphite oxide or graphite oxide solution obtained is N- methylpyrrolidone O. 8g / L~I. 5g / L.

[0014] 作为优选,所述氧化石墨与乙酰丙酮镍的质量比为I : 35〜45。 [0014] Advantageously, the graphite oxide and nickel acetylacetonate mass ratio of I: 35~45. [0015] 作为优选,所述氧化石墨与十八胺的质量比为I : 90〜120。 [0015] Advantageously, octadecylamine oxide and graphite mass ratio of I: 90~120.

[0016] 作为优选,所述c)中的有机溶剂为醇类。 [0016] Advantageously, the c) the organic solvent is an alcohol.

[0017] 作为优选,所述d)中洗涤为使用正己烷、丙酮交替洗涤。 [0017] Advantageously, said d) is washed with n-hexane as, alternately washed with acetone.

[0018] 作为优选,所述d)中干燥为在40°C真空下干燥。 [0018] Advantageously, said d) is dried under vacuum dried at 40 ° C.

[0019] 本发明提供的立方相镍纳米结构-石墨烯复合体是一种新型的电磁波吸收材料, 使得镍的吸波性能得到提高,具有良好的电磁波吸收性能。 [0019] Ni nanostructured cubic phase present invention provides - graphene composite is a novel electromagnetic wave absorbing material, so that the absorbing performance of nickel is improved, having good electromagnetic wave absorption performance. 该立方相镍纳米结构-石墨烯复合体的制备方法具有简便,快速,还原效果好,原材料易得,成本低等优点。 The Ni nanostructured cubic phase - Preparation graphene composite is simple, rapid, reducing effect, readily available raw materials, low cost.

附图说明 BRIEF DESCRIPTION

[0020] 图I为本发明实施例中用到的石墨(a)、制备的GO (b)、GN (c)和c_Ni (2_P) / GN (d)、c-Ni (NMP) /GN (e)的XRD 图; [0020] FIG oriented graphite I (a) used in Example embodiment of the invention, GO (b) preparation, GN (c) and c_Ni (2_P) / GN (d), c-Ni (NMP) / GN ( e) the XRD pattern;

[0021] 图2为本发明实施例制备的石墨烯的TEM(a)、HRTEM(b)、和SAED(C)照片; TEM (a) [0021] FIG graphene prepared in Example 2 of the present embodiment of the invention, HRTEM (b), and SAED (C) photographs;

[0022] 图3为本发明实施例制备的c-Ni (2-P) /GN的TEM(a_c)、HRTEM(d)和FFT (d中插图)图; c-Ni (2-P) [0022] Preparation Example 3 of the present invention / GN of TEM (a_c), HRTEM (d) and FFT (d inset) FIG;

[0023] 图4为本发明实施例制备的c-Ni (NMP)的TEM图(a、b),c-Ni (NMP) /GN的TEM图(c、d)、HRTEM图(e、f)、高分辨晶格相(f中上端插图)、FFT图(f中下端插图); [0023] FIG 4 c-Ni (NMP) TEM image (a, b) prepared in the Examples of the present invention, c-Ni (NMP) / GN TEM images (c, d), HRTEM FIG. (E, f ), high resolution lattice phase (f in the upper illustration), an FFT pattern (f the lower illustration);

[0024]图 5 为本发明实施例制备的c-Ni (2-P)、c_Ni (2_P) /GN、c_Ni (NMP) ,c-Ni (NMP) /GN 在3mm厚度时的微波反射率损耗值图。 [0024] FIG. 5 embodiment of the present invention prepared in Example c-Ni (2-P), c_Ni (2_P) / GN, c_Ni (NMP), c-Ni (NMP) / GN microwave reflectivity loss of 3mm thickness value chart.

具体实施方式 Detailed ways

[0025] 为了进一步了解本发明,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。 [0025] To further understand the present invention, the following preferred embodiments of the present invention will be described in conjunction with embodiments, it is to be understood that the description merely to further illustrate the features and advantages of the present invention, and not limit the claims of the invention.

[0026] 本发明提供一种磁性纳米材料-石墨烯复合体,为立方相镍纳米结构-石墨烯复合体,化学式为c-Ni/GN。 [0026] The present invention provides a magnetic nanomaterial - graphene composite, a nickel nanostructured cubic phase - graphene complex, of the formula c-Ni / GN.

[0027] 本发明提供的c-Ni/GN的制备方法包括以下步骤: [0027] c-Ni / GN production method according to the present invention comprises the steps of:

[0028] a)将氧化石墨(GO)溶于2_吡咯烷酮(2_P)或N-甲基吡咯烷酮(NMP),得到棕色溶液,氧化石墨的浓度为O. 8g/L〜I. 5g/L,氧化石墨通过改进的Hmnmers方法制备; [0028] a) The graphite oxide (GO) was dissolved 2_ pyrrolidinone (2_P) or N- methylpyrrolidone (NMP), to give a brown solution, the concentration of graphite oxide is O. 8g / L~I. 5g / L, graphite oxide prepared by the improved method Hmnmers;

[0029] b)将乙酰丙酮镍和十八胺加入上述棕色溶液中,在氮气保护下加热至110°C〜 140°C维持20min〜40min,再升温至202°C并维持I. 5h〜2. 5h ;溶液中氧化石墨与乙酰丙酮镍的质量比为I : 35〜45,氧化石墨与十八胺的质量比为I : 90〜120 ; [0029] b) The nickel acetylacetonate and octadecyl amine was added to the brown solution, was heated to 110 ° C~ 140 ° C 20min~40min maintained under nitrogen, then heated to 202 ° C and maintained I. 5h~2 . 5h; mass of graphite oxide solution and nickel acetylacetonate ratio of I: 35~45, graphite octadecylamine oxide mass ratio of I: 90~120;

[0030] c)加入有机溶剂将反应猝停,使反应体系的温度迅速降至室温,有机溶剂可使用醇类,如乙醇; [0030] c) an organic solvent was added and the reaction is quenched, the temperature of the reaction system was rapidly cooled to room temperature, the organic solvent may be an alcohol, such as ethanol;

[0031] d)分离反应产物后进行洗涤,可通过离心的方式分离,优选使用正己烷、丙酮交替洗涤产物,然后干燥,优选40°C真空下干燥,得到c-Ni/GN。 [0031] d) after separation of the reaction product was washed, it can be isolated by centrifugation manner, preferably n-hexane, the product is washed alternately with acetone, and then dried, preferably 40 ° C under vacuum and dried to give c-Ni / GN.

[0032] 其中,当使用2-吡咯烷酮(2-P)为溶剂时制备的c-Ni/GN为球状面心立方金属镍-石墨烯复合体,本文中记为c-Ni(2-P)/GN ;当使用N-甲基吡咯烷酮(NMP)为溶剂时制备的c-Ni/GN为花状面心立方金属镍-石墨烯复合体,本文中记为c-Ni (NMP)/GN。 [0032] wherein, when a 2-pyrrolidone (2-P) c-Ni is prepared in solvent / GN spherical face centered cubic nickel - graphene composite, herein referred to as c-Ni (2-P) / GN; when using N- methylpyrrolidone (NMP) c-Ni is prepared in solvent / GN as a flower-like face centered cubic nickel - graphene composite, herein referred to as c-Ni (NMP) / GN.

[0033] 与上述制备复合体的方法类似,如果不引入石墨烯,即可以制备球状面心立方相金属镍单质和花状面心立方相金属镍。 [0033] The above-described method for preparing a composite with a similar, if not the graphene is introduced, which can be prepared with the spherical face centered cubic metals and elemental nickel face-centered cubic flower-shaped metallic nickel.

[0034] 实施例: [0034] Example:

[0035] I、制备氧化石墨 [0035] I, Preparation of graphite oxide

[0036] 采用改进的Hummers方法制备氧化石墨,做为制备立方相金属镍_石墨烯复合体的原料。 [0036] The improved process for preparing graphite oxide Hummers method, as a starting material was prepared cubic nickel _ graphene composite.

[0037] 称取5g石墨粉,5gNaN03,和230mL浓H2SO4,置于冰水浴中,边搅拌边缓慢加入30gKMn04,此过程大约15分钟。 [0037] Weigh 5g of graphite powder, 5gNaN03, and 230mL of concentrated H2SO4, placed in an ice water bath, was added slowly with stirring 30gKMn04, this process takes about 15 minutes.

[0038] 撤去冰水浴,放入35°C水浴中,缓慢加入460mL蒸馏水,此过程约30分钟,产物由黑色渐渐变为褐色。 [0038] The ice-water bath was removed, placed in 35 ° C water bath, was slowly added to 460mL of distilled water, this process for about 30 minutes, the product gradually from black to brown.

[0039] 之后放于98°C油浴中保温15分钟。 After [0039] placed in an oil bath at 98 ° C incubated for 15 min.

[0040] 撤出油浴后,加入1400mL温水,搅拌,加入IOOmLH2O2,此时产物变为金黄色。 [0040] After withdrawal of the oil bath, was added 1400mL heated, with stirring, was added IOOmLH2O2, this time the product becomes golden yellow. 过滤, 用质量分数为5%的稀HCl溶液洗涤,至滤液中无S042_为止。 Filtered, washed with a mass fraction of 5% diluted HCl solution to the filtrate till no S042_. 所得产物于70°C空气中干燥。 The resulting product was dried at 70 ° C in air.

[0041] 2、制备球状面心立方金属镍-石墨烯复合体 [0041] 2. Preparation of the spherical face centered cubic nickel - graphene composite

[0042] 将20mgG0加入20mL2_吡咯烷酮中,超声分散,得到棕色溶液。 [0042] The 20mgG0 20mL2_ pyrrolidone was added, ultrasonic dispersion, to give a brown solution.

[0043] 接下来,将2mmol乙酰丙酮镍和2g十八胺加入上述棕色溶液中,先将混合物加热到120°C并在此温度维持30min,然后升高温度到202°C,在此温度维持2h,整个反应过程在氮气的保护下进行,并一直保持磁力搅拌。 [0043] Next, 2mmol nickel acetylacetonate and 2g octadecylamine was added to the brown solution, and the mixture was heated first to 120 ° C and maintained at this temperature for 30min, then the temperature is raised to 202 ° C, maintained at this temperature 2h, the entire reaction is carried out under the protection of nitrogen, and kept stirred magnetically.

[0044] 反应停止后,加入20mL乙醇将反应猝停,使反应体系的温度迅速降低至室温。 [0044] After the reaction stopped, 20mL of ethanol was added and the reaction is quenched, the temperature of the reaction system is rapidly lowered to room temperature.

[0045] 最后,通过离心的方式分离出反应产物,并用正己烷、丙酮交替洗涤,产物于40°C 真空干燥,制得c-Ni (2-P) /GN。 [0045] Finally, by centrifugally separated reaction product, and washed with hexane, washed with acetone and alternately, the product was dried in vacuo at 40 ° C, to obtain c-Ni (2-P) / GN.

[0046] 3、制备花状面心立方金属镍-石墨烯复合体 [0046] 3. Preparation of flower-like face centered cubic nickel - graphene composite

[0047] 与制备c-Ni (2-P)/GN相似,只是将溶剂由2_吡咯烷酮改为N-甲基吡咯烷酮,制得c-Ni(NMP)/GN。 [0047] Preparation c-Ni (2-P) / GN is similar, except that the solvent was changed to N- methylpyrrolidone 2_ pyrrolidone to prepare c-Ni (NMP) / GN.

[0048] 另外,用同样的方法但不引入石墨烯,制备出立方相金属镍单质c-Ni (2-P)和c-Ni(NMP)。 [0048] Further, using the same method without introducing graphene prepared cubic elemental nickel metal c-Ni (2-P), and c-Ni (NMP).

[0049] 对产物的表征: [0049] The characterization of the product:

[0050] I、对实施例中用到的石墨、制备的G0、GN、c-Ni (2_P)/GN和c_Ni (NMP)/GN进行表征,请参考图1,图I为本发明实施例中用到的石墨(8)、制备的60(13)、6^(3)和C-Ni (2-P)/ GN (d)、c-Ni (NMP) /GN (e)的XRD 图。 [0050] I, graphite used in embodiment embodiment, the G0 prepared, GN, c-Ni (2_P) / GN and c_Ni (NMP) / GN characterization, please refer to FIG. 1, an embodiment of the present invention, FIG. I the graphite used in (8), prepared from 60 (13), 6 ^ (3) and C-Ni (2-P) / GN (d), c-Ni (NMP) / GN (e) of FIG XRD .

[0051] 由图(a)可见,所选用的石墨原料结晶性良好,在2 Θ = 26. 5°处出现(002)晶面的衍射峰,对应的层间距为O. 34nm。 [0051] As seen, the choice of raw material graphite with good crystallinity FIG (A), appear at 2 Θ = 26. 5 ° a diffraction peak at a (002) plane, corresponding to the interlayer spacing O. 34nm. 经氧化之后,所得产物GO依然具有很好的结晶性,而且保持层状结构,但是衍射峰向低角度移动,在2 Θ =10.9°处出现衍射峰,对应层间距为 After oxidation by, GO resulting product still has good crystallinity, and holding the layered structure, but moves to the low angle diffraction peak at 2 Θ = 10.9 ° of the diffraction peak appears, corresponding to the interlayer spacing

O. 76nm,见图(b),石墨被氧化后引入含氧官能团,从而引起层间距的增大。 O. 76nm, Figure (B), the oxygen-containing functional group is introduced after the graphite is oxidized, thereby causing an increase in the layer spacing. 图(c)为氧化石墨还原后所得产物GN的XRD图,从图中未观察到层间距为O. 76nm的衍射峰,并且在2 Θ = 23. 5°有一个弱的且宽化的衍射峰出现,表明GO已经被还原,并且石墨烯的层状结构被破坏。 FIG (c) is obtained after reduction of graphite oxide product GN XRD pattern was not observed from the drawing into a layer spacing of 76nm O. diffraction peaks, and there is a weak and a width of diffraction in 2 Θ = 23. 5 ° peak, indicating that the GO has been reduced, and the graphene layer structure is destroyed. 图(d)(e)的XRD衍射图谱均与JCPDS card 65-2865吻合,表明所得金属Ni为面心立方结构(a = b = c = 3. 524nm)。 FIG. (D) (e) are the XRD patterns consistent with the JCPDS card 65-2865, showed that the resulting metal is Ni face centered cubic structure (a = b = c = 3. 524nm). 此外,与图(c)类似,由于加入了氧化石墨,图(d) (e)中均观察到2 Θ =23.5°处的弱的且宽化的衍射峰出现,但是未出现层间距为O. 76nm的衍射峰,表明在金属Ni生成的过程中已经将GO还原为石墨稀。 Further, FIG. (C) Similarly, due to the addition of graphite oxide, FIG. (D) (e) was observed in both weak and width of the diffraction peak of 2 Θ = 23.5 ° at the emergence, but the layer spacing does not appear to O diffraction peak. 76 nm, indicating that the process of Ni has been generated as graphene GO restored. [0052] 2、请参考图2,图2为本发明实施例制备的石墨烯的TEM(透射电子显微镜,a)、 HRTEM(高分辨透射电子显微镜,b)、和SAED(选区电子衍射,c)照片。 [0052] 2, refer to FIG. 2, FIG. 2 of the TEM graphene prepared in the Examples of the present invention (transmission electron microscope, a), HRTEM (high resolution transmission electron microscopy, b), and SAED (selected area electron diffraction, C )photo. 图a为由氧化石墨还原得到石墨烯的TEM图,从中可以看出,经过氧化和还原之后,石墨的层状结构被破坏,但是所得石墨烯仍保持片状结构,同时观察到一些褶皱,可能是因为石墨烯太薄的原因。 FIG reduction of graphite oxide obtained by a graphene TEM image, it can be seen, after oxidation and reduction, the layered structure of graphite is destroyed, but still maintaining the resulting graphene sheet structure, while the number of wrinkles observed, may the reason is because graphene is too thin. 图b 和c分别为石墨烯的HRTEM照片和SAED图谱,从图b中可以看出,所得石墨烯为单层,层板厚度为O. 34nm,这与石墨(002)面的层间距为O. 34nm对应。 FIGS b and c are the HRTEM images of graphene and SAED pattern, it can be seen from Figure b, resulting in a single layer of graphene, ply thickness O. 34nm, (002) plane of graphite which is O . 34nm counterparts. 从图c中可以看出,石墨烯中碳原子采取sp2杂化,为平面蜂窝状结构,具有完整的晶体结构。 Can be seen from Figure c, graphene taken sp2 hybridized carbon atoms, a planar honeycomb structure, having a completely crystalline structure.

[0053] 3、请参考图3,图3为本发明实施例制备的c-Ni (2-P) /GN的TEM(a_c)、HRTEM(d) 和FFT (快速傅里叶转换,d中插图)图。 [0053] 3, refer to FIG. 3, FIG. 3 embodiment of the present invention prepared in Example c-Ni (2-P) / GN of TEM (a_c), HRTEM (d) and FFT (Fast Fourier Transform, d in inset) Fig. 由图a和b可以看出,制备的立方相镍(c-Ni)呈球状,直径尺寸在50到200nm之间,这些纳米球随机的分布在石墨烯片层上。 As can be seen from the diagrams a and B, a nickel cubic phase (c-Ni) prepared in spherical, the diameter between 50 to 200 nm, these nanospheres randomly distributed on the graphene sheet. 此外,从图c 中可以观察到石墨烯被镍纳米粒子腐蚀的边缘,表明c-Ni纳米球深深的“镶嵌”在石墨烯中,而且这些直径为200nm的纳米球是由一些直径在10到20nm之间的纳米颗粒组成的二次粒子。 Further, it can be observed from Figure c the graphene nanoparticles edge corrosion of nickel, indicating that c-Ni nanospheres deep "mosaic" in the graphene, and the diameter of the nanospheres 200nm in diameter by some 10 secondary particles to between 20nm nanoparticles thereof. 图d中可以观察到石墨烯的边缘,其中金属镍的晶格间距为O. 203nm,与立方相金属镍XRD图谱中(111)面衍射峰的d值吻合。 D can be observed in FIG graphene edge, wherein the nickel lattice spacing XRD pattern with nickel (111) plane diffraction peak d anastomosis is O. 203nm, and cubic. 图d内插图为石墨烯的二维FFT (快速傅立叶转换)图,表现为典型石墨烯的六方衍射晶格,从而进一步证明所得产物为金属镍和石墨烯的复合体。 A two-dimensional FFT (Fast Fourier Transform) FIG, hexagonal diffraction grating is a typical manifestation of graphene, whereby the resultant product is further proof of metallic nickel and graphene composite inset within FIG d graphene.

[0054] 4、请参考图4,图4为本发明实施例制备的c-Ni (NMP)的TEM图(a、b),c_Ni (NMP) / GN的TEM图(c、d)、HRTEM图(e、f)、高分辨晶格相(f中上端插图)、FFT图(f中下端插图)。 [0054] 4, refer to FIG. 4, FIG. 4 c-Ni (NMP) TEM image (a, b) of the invention prepared in Example, c_Ni (NMP) / GN TEM images (c, d) oriented, HRTEM FIG. (e, f), high resolution lattice phase (f in the upper illustration), FFT pattern (f in the lower illustration). 用与制备c-Ni (NMP)/GN相似的方法,只是不引入石墨烯,可以制得花状面心立方相金属镍c-Ni (NMP),图a、b为c-Ni (NMP)的TEM图,从图中可以看出,所得产物为花状。 With the preparation of c-Ni (NMP) / GN similar manner, but without introducing the graphene can be prepared popcorn face-centered cubic nickel c-Ni (NMP), FIG. A, b are c-Ni (NMP) TEM images, it can be seen from the figure, the resulting product is a flower. 此外, 从高倍率TEM照片b中可以看出,这些花状镍纳米粒子实际上是由直径在10-20nm之间的小纳米颗粒组成的二次粒子。 Further, it can be seen from the high-magnification TEM photograph (b), these flower-like nickel nanoparticles are actually small secondary particles having a diameter between 10-20nm nanoparticles thereof. 图c、d中可以看出,花状镍纳米粒子均匀的附着在石墨烯上, 并且可以清晰的看到二者的边缘,如图中箭头方向所示。 FIG c, d can be seen, even the flower-like nickel nanoparticles deposited on the graphene, and can clearly see both edges, the direction of the arrow shown in FIG. 图e中可以观察到石墨烯被金属镍腐蚀的边缘,表明镍纳米粒子紧紧的镶嵌在石墨烯中。 E can be observed in FIG graphene edge corrosion of metallic nickel, nickel nanoparticles show tightly embedded in the graphene. 图f中可以看到c-Ni (NMP)规整的晶格边缘以及石墨烯中碳sp2杂化的六方晶格相。 F can be seen in FIG c-Ni (NMP) and regular lattice fringes graphene carbon sp2 hybridized with a hexagonal lattice. 此外,从高分辨TEM图中可以测量出镍的晶格间距为O. 203nm,对应立方相镍的(111)面,与之前的XRD结果一致。 In addition, the high resolution TEM images of the nickel can be measured lattice spacing O. 203nm, corresponding to the (111) plane of the cubic phase of nickel, consistent with previous results of XRD.

[0055] 5、为了评估c-Ni (2_P)/GN、c-Ni (NMP)/GN复合体的电磁波吸收性能,进行了相关复合磁导率和介电常数测试。 [0055] 5, an electromagnetic wave in order to assess c-Ni (2_P) / GN, c-Ni (NMP) / GN composite absorbent properties were related complex permittivity and permeability testing. 测试在固定的频率和样品厚度下进行,反射率损耗值(RL)依据传送线理论进行计算,公式如下: Tests were conducted at a fixed frequency and sample thickness, the reflectance loss value (RL) is calculated based on transmission line theory, the following formula:

Figure CN102604593AD00061

[0058] 其中f代表微波频率,d代表吸收剂的厚度,c代表光速,Zin表示吸收剂的输入阻抗。 [0058] where f is the frequency of the microwave, d for absorbent thickness, c the velocity of light, Zin denotes an input impedance of the absorbent.

[0059] 在I. 0-18. OGHz频率范围内测定相关复合磁导率和介电常数,结果如图5所示,图5 为本发明实施例制备的c-Ni (2-P) ,c-Ni (2_P)/GN、c_Ni (NMP) ,c-Ni (NMP)/GN 在3_ 厚度时的微波反射率损耗值图。 [0059] Determination of Related Complex permittivity and permeability within OGHz frequency range I. 0-18, the results shown in FIG. 5, FIG. 5 c-Ni prepared in Example (2-P) embodiment of the present invention, c-Ni (2_P) / GN, c_Ni (NMP), c-Ni (NMP) / GN FIG microwave reflectivity loss value at 3_ thickness. 由图可见,所制备的两种镍和石墨烯的立方相复合体都表现出比相对应镍单体更好的电磁波吸收效率。 It is seen from the figure, a cubic phase and the two nickel complex prepared graphene showed better than the corresponding electromagnetic wave absorption of nickel monomer efficiency. 例如,c-Ni (2-P)纳米球在I. 0-18. OGHz频率范围内观察到两处吸收峰,分别在9. OGHz和12. 8GHz处,对应的RL分别为-2. 4dB和-3. IdB, c-Ni (2-P)/GN复合体在9. OGHz处有明显吸收,对应RL为-9. OdB,相比镍单质有增强吸收;对于c-Ni (NMP)花状纳米粒子及其复合体而言,在I. 0-18. OGHz频率范围内也观测到两处宽范围的吸收峰吸收,分别在8. OGHz和9. 2GHz处,对应的RL分别为-I. 9dB和-9. OdB0从上述结果中可以看出,c-Ni/GN复合体具有更好的电磁性能,因而表现出更强的电磁波吸收能力,从而使其有望做为微波屏蔽装置的吸波材料。 For example, c-Ni (2-P) nanospheres. OGHz frequency within the range observed in I. 0-18 to two absorption peaks, respectively at 9. OGHz and 12. 8GHz, respectively corresponding RL -2. 4dB . and -3 IdB, c-Ni (2-P) / GN complexes have significant absorption at 9. OGHz the corresponding RL is -9 OdB, compared to elemental nickel reinforcing absorption; for c-Ni (NMP) its flower-like nanoparticle composite, in I. 0-18. OGHz within the frequency range of the absorption peak was also observed two broad absorption range, respectively 8. OGHz 9. 2GHz and at respectively corresponding RL -I. 9dB and -9. OdB0 can be seen from the above results, c-Ni / GN composite having better electromagnetic performance, and therefore show stronger electromagnetic wave absorption capability, so that it is expected as a microwave shielding device absorbing materials.

[0060] 以上对本发明所提供的立方相镍纳米结构-石墨烯复合体及其制备方法进行了详细介绍。 [0060] The foregoing Ni nanostructured cubic phase present invention provides - graphene composite material and its preparation method are described in detail. 本文中应用了具体个例对本发明的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。 Herein through specific examples and embodiments of the principles of the present invention are set forth in the above described embodiments are only used to help understand the method and core idea of ​​the present invention. 应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。 It should be noted that those of ordinary skill in the art, in the present invention without departing from the principles of the premise, may also be a number of modifications and improvements of the present invention, and these improvements and modifications also fall within the scope of the claims of the invention.

Claims (8)

1. 一种磁性纳米材料-石墨烯复合体,其特征在于,化学式为C-Ni/GN。 A magnetic nanomaterial - graphene composite, wherein the formula C-Ni / GN.
2. —种权利要求I所述的纳米材料-石墨烯复合体的制备方法,其特征在于,包括:a)将氧化石墨溶于2-吡咯烷酮或N-甲基吡咯烷酮,得到棕色溶液;b)将乙酰丙酮镍和十八胺加入上述棕色溶液中,在氮气保护下加热至110°C〜140°C 维持20min〜40min,再升温至202°C并维持I. 5h〜2. 5h ;c)加入有机溶剂将反应猝停,使反应体系的温度迅速降至室温;d)分离反应产物,洗涤后干燥,得到c-Ni/GN。 2. - I nanomaterial according to claim Species - Preparation of graphene composite body, characterized by comprising: a) graphite oxide was dissolved in N- methylpyrrolidone or 2-pyrrolidone, to give a brown solution; b) the nickel acetylacetonate and octadecyl amine was added to the brown solution, was heated to 110 ° C~140 ° C 20min~40min maintained under nitrogen, then heated to 202 ° C and maintained I. 5h~2 5h;. c) organic solvent is added and the reaction is quenched, the temperature of the reaction system was rapidly cooled to room temperature; D) reaction product is isolated, washed and dried to give c-Ni / GN.
3.根据权利要求2所述的制备方法,其特征在于,所述氧化石墨溶于2-吡咯烷酮或N-甲基吡咯烷酮得到的溶液中氧化石墨的浓度为O. 8g/L〜I. 5g/L。 3. The production method according to claim 2, characterized in that the graphite oxide Graphite oxide concentration in the solution is dissolved in 2-pyrrolidone or N- methylpyrrolidone was obtained O. 8g / L~I. 5g / L.
4.根据权利要求2所述的制备方法,其特征在于,所述氧化石墨与乙酰丙酮镍的质量比为I : 35〜45。 4. The production method according to claim 2, wherein said mass of graphite oxide and nickel acetylacetonate ratio of I: 35~45.
5.根据权利要求2所述的制备方法,其特征在于,所述氧化石墨与十八胺的质量比为I : 90 〜120。 The production method according to claim 2, wherein said graphite octadecylamine oxide mass ratio of I: 90 ~120.
6.根据权利要求2所述的制备方法,其特征在于,所述c)中的有机溶剂为醇类。 6. The production method according to claim 2, wherein said c) the organic solvent is an alcohol.
7.根据权利要求2所述的制备方法,其特征在于,所述d)中洗涤为使用正己烷、丙酮交替洗涤。 7. The production method according to claim 2, characterized in that the washing d) as n-hexane, acetone washed alternately.
8.根据权利要求2所述的制备方法,其特征在于,所述d)中干燥为在40°C真空下干燥。 8. The production method according to claim 2, wherein said d) is dried under vacuum dried at 40 ° C.
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