A New Broadband and Strong Absorption Performance FeCO₃/RGO Microwave Absorption Nanocomposites

Abstract

A novel composite of FeCO₃ nanoparticles, which are wrapped with reduced graphene oxide (RGO), is fabricated using a facile one-spot solvothermal method. The composite consists of a substrate of RGO and FeCO₃ nanoparticles that are embedded in the RGO layers. The experimental results for the FeCO₃/RGO composite reveal a minimum refection loss (−44.5 dB) at 11.9 GHz when the thickness reaches 2.4 mm. The effective bandwidth is 7.9 GHz between 10.1 and 18 GHz when the refection loss was below −10 dB. Compared to GO and RGO, this type of composite shows better microwave absorption thanks to improved impedance matching. Overall, this thin and lightweight FeCO₃/RGO composite is a promising candidate for absorbers that require both strong and broad absorption.

1. Introduction

Because of the ubiquity of electronic devices, electromagnetic radiation, and, in particular, signal interference have become a global problem [1,2,3]. As a result, big efforts have been made to reduce electromagnetic pollution and other related problems. One promising approach is the use of high-performance microwave absorbing materials (MAMs). Graphene, a relatively new carbon-based material, has excellent properties such as high electron mobility, high permittivity and a high specific surface area, which can dampen electromagnetic waves effectively using polarization relaxation [4,5,6,7]. However, pure graphene can reflect most of the electromagnetic waves, resulting in being unsuitable for MAM due to their poor impedance matching.

Fortunately, it is possible through to combine graphene with magnetic materials to overcome this problem [8,9]. Most of the related studies are focused on soft magnetic materials, which have high magnetic loss due to natural resonance, and they can produce better results as compounded with graphene. For example, Cui et al. [10] prepared a hollow Fe₃O₄@RGO composite by a facile route. The minimum reflection loss is −41.89 dB at 6.7 GHz. In the range of 1–4 mm, the reflection loss of nanocomposite thickness is less than −10 dB at 3.4 GHz to 13.6 GHz. Wang et al. [11] loaded MnFe₂O₄ nanoparticles on RGO sheets by one-step hydrothermal method. The minimum reflection loss of MnFe₂O₄/RGO is −32.8 dB at 8.2 GHz with the thickness of 3.5 mm, and the absorption bandwidth with the reflection loss below-10 dB is up to 4.8 GHz (from 7.2 to 12 GHz). Feng et al. [12] synthesized ZnFe₂O₄@SiO₂@RGO core-shell microspheres by “coating-coating” method. The minimum reflection loss of the sample with a thickness of 2.8 mm can reach −43.9 dB at 13.9 GHz. In recent years, the composite of paramagnetic FeCO₃ and RGO has shown great brilliance in the field of batteries due to its excellent electrochemical properties [13,14,15]. However, as far as we know, the microwave absorption properties of FeCO₃/RGO, especially its magnetic loss characteristic spectrum, have not been investigated.

Therefore, FeCO₃/RGO composites were synthesized using a one-pot solvothermal method. To reveal the microwave absorption mechanism of the FeCO₃/RGO composite, the frequency dependence of both complex permittivity and the reflection-loss formation were studied and compared with GO and RGO. The outcome of this study can aid the development of light-weight and broadband electromagnetic-wave absorbers.

2. Experimental

10.8 g FeCl₃·6H₂O, 7.2 g urea, 5 g PVP and 1.2 g nano-iron powder were added into a 400 mL graphene-oxide slurry (purchased from Qitaihe Baotailong New Materials Co., Ltd. (Qitaihe, China) Containing GO 3.3 mg/mL). The mixture was dispersed, aided by ultrasonic treatment for 30 min, to form a homogeneous solution, and subsequently put into a 500 mL Teflon-lined stainless-steel autoclave, where it was kept at 200 °C for 12 h. After cooling to room temperature, the reaction products were washed with deionized water and alcohol, three times. Finally, the reaction products were dried in a vacuum furnace at 60 °C for 24 h.

The morphology, structure, surface elements, and the electromagnetic parameters were analyzed using SEM, TEM, XRD, XPS, and VNA, field emission scanning electron microscopy (FE-SEM, Nava Nano FE-SEM450/650, Eindhoven, Netherlands), transmission electron microscopy (TEM, LI-BRA200, Oberkochen, German), X-ray diffraction (XRD, D/MAX-2500PC, Rigaku, Tokyo, Japan), X-ray photoelectron spectroscopy (XPS, PHI5300, Ulvac-Phi, Tokyo, Japan), and Vector network analyzer (VNA, PNA-N5244A, AGILENT, Santa Clara, CA, USA),respectively. The electromagnetic parameters of the measured samples were prepared by mixing the products (60%) with molten paraffin wax (40%) and placing them into a toroidal mold (Φ_in = 3 mm, Φ_out = 7 mm) with a thickness of 2.0–3.0 mm. The test software (AGILENT, Santa Clara, CA, USA) is 85071 and the calibration part is 85050D. Before the test, the permittivity of air was measured as an evaluation of the calibration effect.

3. Results and Discussion

Figure 1a shows the XRD patterns of GO, RGO, and the FeCO₃/RGO composite. There is a broad peak at 13.4° in GO (pattern a), which corresponds to the (001) reflection of GO [16]. The broad peak at 25.2° and the disappearance of the peak at 13.4° (pattern b) indicate that GO was reduced to RGO. The XRD patterns of the FeCO₃/RGO composite (pattern c) show that all the diffraction peaks match JCPS No.29-0696, which confirms that the FeCO₃/RGO composite was indeed obtained. The disappearance of the RGO peaks in FeCO₃/RGO [17] due to the uniform distribution of FeCO₃ particles between graphene layers (Figure 2), which prevents the interlayer aggregation of RGO sheets, causes the diffraction intensity, i.e., the RGO peak, to be much smaller than for FeCO₃.

The XPS survey spectrum of FeCO₃/RGO (Figure 1b) shows that the composite consists of Fe, O, C, and N. Four peaks were detected (284.4 eV, 285.8 eV, 287.7 eV, 289.2 eV) in C1s spectrum (Figure 1c), which correspond to C=C/C–C, C–O, C=O, and FeCO₃ [13], respectively. As shown in Figure 1d (Fe2p), two peaks appear at 710.1 eV and 723.4 eV, which correspond to Fe2p_3/2 and Fe2p_1/2. Furthermore, a satellite peak of Fe2p_3/2 appears at 714.1 eV [18]. These characteristic peaks confirm the presence of FeCO₃/RGO. The formation of FeCO₃ can be derived from the following chemical equations:

$$CO{(N{H}_2)}_2+3H_{2}O\stackrel{}{\to }2N{H}_4{}^{+}+C{O}_2+2O{H}^{-}$$

(1)

$$C{O}_2+2O{H}^{-}\stackrel{}{\to }C{O}_3{}^{2-}+H_{2}O$$

(2)

$$2F{e}^{3+}+Fe\stackrel{}{\to }3F{e}^{2+}$$

(3)

$$F{e}^{2+}+C{O}_3{}^{2-}\stackrel{}{\to }FeC{O}_3$$

(4)

Figure 2 shows the SEM, TEM, and HRTEM images of FeCO₃/RGO. Polyhedron-like FeCO₃ nanoparticles with a diameter of 20~40 nm were evenly embedded in layers of lamellar RGO. The formation of FeCO₃ can be also proved by Figure 2c, and the space between two lattice fringes is 0.279 nm, corresponding to (104) plane of FeCO₃. During the reduction process, the uniform distributions of nanoparticles in the RGO layers can prevent GO from agglomerating and the formation of a FeCO₃-RGO conductive network, which might help facilitate dielectric loss.

Figure 3 shows the frequency-dependent electromagnetic properties of GO, RGO, and FeCO₃/RGO between 2 and 18 GHz. Figure 3a,b illustrate the associated real (ε′) and imaginary (ε″) complex permittivity. The values of ε′ show the same trend, ε′ decreases with increasing frequency. Furthermore, the ε′ of FeCO₃/RGO is higher than for both GO and RGO due to the enhanced polarization characteristics. Also, the ε″ of FeCO₃/RGO is larger than for both GO and RGO due to higher conductivity [19]. Figure 3c,d depict the real (μ′) and imaginary (μ″) complex permeability of the composites. The complex permeability of GO and RGO varies similarly with frequency, indicating that there is little effect of the reduction reaction on the magnetic properties of GO. However, the observed trend for FeCO₃/RGO is different from GO and RGO. The complex permeability of FeCO₃/RGO varies greatly between 10 GHz and 16 GHz because the magnetic FeCO₃ nanoparticles can produce natural resonance loss and exchange resonance loss (due to size effect, surface effect, and spin wave excitation) [20,21,22,23].

As well known, reflection loss (R_L) can assess and characterize microwave absorption performance. According to the transmission line model, R_L of a metal-backed microwave absorption layer can be calculated by the following formulas [24]:

$$R_{\mathrm{L}}=20\lg \left|\frac{Z_{\mathrm{in}}-Z_0}{Z_{\mathrm{in}}+Z_0}\right|$$

(5)

$$Z_{\mathrm{in}}=\sqrt{\frac{{\mu }_{\mathrm{r}}}{{\epsilon }_{\mathrm{r}}}}\tanh [j\frac{2\pi df}{c}\sqrt{{\mu }_{\mathrm{r}}{\epsilon }_{\mathrm{r}}}]$$

(6)

Here, Z_in is the input impedance of the absorber, Z₀ is the impedance of free space (Z₀ is generally 1), ε_r and μ_r are the complex permittivity and permeability, c is the speed of light in vacuum, d is the thickness of the absorber, and f is the microwave frequency. 3D theoretical R_L plots of the composites are shown in Figure 4a–c. It can be observed that with the reduction of GO and the introduction of FeCO₃, the microwave absorption properties improves significantly. FeCO₃/RGO nanocomposites show excellent microwave absorption properties as the thickness between 2 mm and 3 mm. R_L curves of composites versus frequency is shown in Figure 4d. R_L(min) appears in X and Ku band as thickness in the range of 2–3 mm and shifts to lower frequency with increasing thickness. When the thickness is 2.4 mm, FeCO₃/RGO shows optimal microwave absorption and reaches a R_L(min) of −44.5 dB, while the corresponding bandwidth is less than −10 dB is 7.9 GHz (10.1~18 GHz). It is noteworthy that the effective bandwidth of FeCO₃/RGO can reach up to 6 GHz and keep steadily when the thickness is 2~3 mm.

Table 1. Microwave absorption performances of the soft magnetic material-based, graphene material-based composite compared with FeCO₃/reduced graphene oxide (RGO).

Sample	RL (dB)	Effective Bandwidth (GHz) (RL < −10 dB)	Thickness (mm)	Wt. (%)	Reference
Fe3O4/RGO	−41.89	4.2	2.5	50	[10]
Fe3O4@SnO2/RGO	−45.5	3	4.5	50	[25]
MnFe2O4/RGO	−29	4.88	3	10	[1]
NiFe2O4/RGO	−58	4.08	2.7	27	[26]
RGO/MWCNTs/ZnFe2O4	−23.8	2.6	1.5	50	[27]
RGO/MWCNTs/CoFe2O4	−46.8	3.4	1.6	50	[28]
RGO/Cu2O/Cu	−51.8	4.1	1.3	50	[29]
CoS2/RGO	−56.9	4.1	2.2	50	[30]
FeCO3/RGO	−44.5	7.9	2.4	60	This work

lists some reported microwave absorption composites of soft magnetic based material, graphene-based material, and FeCO₃/RGO composite prepared in this work. Notably, FeCO₃/RGO composite not only displays a promising negative R_L value, but also has a wide effective absorption bandwidth due to the good impedance matching.

4. Conclusions

The FeCO₃/RGO composite produced and investigated in this study is a novel material with excellent microwave absorption. The composite can not only effectively facilitate electromagnetic loss but also improve impedance matching. Specifically, the refection loss at 11.9 GHz, when the composite thickness is 2.4 mm, reaching a minimum of −44.5 dB, and the effective bandwidth is 7.9 GHz (from 10.1 to 18 GHz). In addition, we observed very stable broad characteristics for a thickness range of 2–3 mm. Because of the good properties mentioned above, this composite is can be regarded as an excellent microwave absorber with the potential for many commercial applications.