2.1. Morphology and Structure
Figure 1 shows the schematic synthesis process of Co-embedded porous carbon composites.
The X-ray diffraction technique was used to verify the crystalline and phase composition of SC and Co/C composites. As shown in
Figure 2(a), different proportions of precursors have no obvious influence on the composition of Co/C composites, reflecting nearly the same peaks on the patterns. Specifically, all the Co/C samples have three strong diffraction peaks located at 44.3°, 51.6°, 75.9°, which can be indexed to the (111), (200) and (220) planes of face-centered cubic cobalt (JCPDS No. 15-0806), respectively. The results confirm the in-situ reduction of Co
2+ to Co metal during the calcination process. The sharp peak of SC pattern located at 26.6° responds to the graphitized crystal plane (002) of carbon, indicating that SC has certain graphitized carbon domains. Whereas, the diffraction peak of Co/C composites at 26.6° becomes much fainter compared with SC, which is the direct evidence of reaction between SC and cobalt nitrate hexahydrate in the pyrolysis process. Particularly, there also appear other peaks except for 26.6° and 44.6°. This is consistent with our previous research results that SC not only contains C but also includes other elements such as O, N, Fe, Mn, Ni, etc. These components are the source of other peaks [
11]. The existence of these elements also contributes to dipole and interface polarization, which is conducive to the enhancement of microwave absorption.
Raman spectroscopy was further used to investigate the effect of cobalt salt on the carbon graphitization degree during the carbonization process, as illustrated in
Figure 2(b). There are two characteristic peaks in each sample, which are roughly at 1350 cm
−1 (D-band) and 1580 cm
−1 (G-band). The local defect and the disordered carbon are represented by the D-band, whereas the graphited C atoms observed for sp
2 carbon domains are represented by the G-band. The peak intensity of D-band to G-band (I
D/I
G) is usually used to evaluate the degree of graphitization of carbon-based materials [
36,
37]. As shown in
Figure 2(b), the Co/C composites exhibit a much higher I
D/I
G than that of SC (0.83). Since cobalt salt could catalyze the graphitization of carbon, the increased I
D/I
G value could be attributed to the transitional stage from amorphous carbon to nanocrystalline graphite according to the phenomenological three-stage model proposed by Ferrari and Roberston [
38]. Due to the nano size of crystalline graphite, the I
D/I
G values show a decline tendency. In addition, the higher the content of the cobalt salt precursor, the higher the I
D/I
G value. Specifically, the I
D/I
G value rises from 0.95 to 0.97 for Co/C-0.75 and Co/C-2. The enhancement of nanocrystalline graphite would promote conductivity and polarization capability, which is in favor of conductive loss and polarization loss for better microwave absorption.
Thermogravimetric analysis (TGA) was carried out to determine the accurate content of Co nanoparticles in Co/SC composites.
Figure 2(c) displays the thermogravimetric curves of Co/C composites in air atmosphere. The samples were heated to 100 °C and kept for 30 min for the removal of adsorbed water. The samples were kept for 4 h at 700 °C then for the sufficient redox reaction. The weight fluctuation of the samples mainly originated from the oxidation of Co nanoparticles to Co
3O
4, the combustion of carbon to CO
2 or other carbon oxides and the splitting of other components such as O, N. The weight increase from 100 °C to ~440 °C is mainly attributed to the oxidation of Co to Co
3O
4 while the sharp decline from ~440 °C to ~580 °C are primarily ascribed to carbon consumption. The weight percentage was finally constant at 42.83 %, 47.39 %, 53.57 % and 59.87 %, respectively. The content of Co in the Co/C composites can be evaluated via the following formula:
where
represents the content of Co in the Co/C composites, R stands for the residual weight percentage after the reaction.
M(Co) and
M(Co
3O
4) represent the molecular weights of Co and Co
3O
4 respectively [
39]. Hence, the content of Co nanoparticles in Co/C-0.75, Co/C-1, Co/C-1.5 and Co/C-2 composites was determined to be 31.48 wt%, 34.83 wt%, 39.37 wt% and 44.00 wt%, respectively. The above results illustrate that the Co content in Co/C composites has positive correlation with the doping of cobalt salt.
The chemical state information on the surface of the samples was characterized by XPS.
Figure 2(d) shows the survey spectra of SC and Co/C composites. The Co/C composites show three typical peaks located at 282 eV, 529 eV and 776 eV, corresponding to C 1s, O 1s and Co 2p respectively, which demonstrate the existence of C, O and Co elements in Co/C composites. The high-resolution C 1s XPS spectrum (
Figure 2e) of Co/C-1 consists of three deconvoluted peaks at 284.8 eV, 286.4 eV, 288.9 eV, corresponding to C−C/C=C, C−O and C=C functional groups respectively. Four different Co species types are visible in the high-resolution Co 2p XPS spectra. The peaks at 780.8 eV and 795.6 eV correspond to Co 2p
3/2 and Co 2p
1/2 respectively, while the peaks at 784.8 eV and 803.3 eV are the satellite peaks of Co 2p from Co metal. The results are consistent with the analysis of XRD that Co metal is the main existence state [
38].
The magnetic properties of all the samples were measured at 300 K. As shown in
Figure 3, all the Co/C composites exhibit typical ferromagnetic characteristics with magnetic hysteresis loops. Co/C composites have considerably superior magnetic characteristics than that of SC (
Figure S2), suggesting that magnetic elements were successfully incorporated during the carbonization process. The saturation magnetization (Ms) values of the Co/C composite increase with the elevated Co doping, which is consistent with the TGA results for increased Co content from Co/C-0.75 to Co/C-2. Specifically, the Ms values of Co/C-0.75, Co/C-1, Co/C-1.5 and Co/C-2 are 34.93 emu/g, 40.83 emu/g, 45.78 emu/g and 56.44 emu/g respectively. Noteworthy, Co/C-1 displays the highest coercive forces (Hc, 138 Oe) than those of other Co/C composites, which is attributed to its peculiar microstructure for shape anisotropy. The results demonstrate that these Co/C composites with various morphology and dimension possess tailorable intrinsic dielectric properties and magnetic response abilities.
The morphologies and structures were characterized by SEM, as shown in
Figure 4. The composites inherited plenty of pores from SC (
Figure S1). Abundant spherical, quasi-spherical and irregular Co particles distribute in the pores and walls of SC, resulting in a sharp decrease of the pores compared with SC. Different Co doping has a significant effect on the size and distribution of Co nanoparticles. The size and distribution of Co particles were measured via the Nano measurer software from the SEM images. Co/C-2 possesses the biggest Co mean size of ~150 nm and the widest distribution. In contrast, the mean size of Co/C-1 and Co/C-1.5 is relatively small at ~100 nm and ~60 nm respectively. Remarkably, Co/C-1 shows a wider distribution than other Co/C composites, combined with its dynamic spherical, quasi-spherical and irregular shapes, contributing to a better shape anisotropy. The results illustrate that the precursors would participate in the reaction process, thus influencing the growth of grains, dynamic sizes and distributions. According to our previous analysis, possible reactions in the annealing process are listed as follows:
The EDS mapping of Co/C-1 composites was performed to observe the elemental distribution. As shown in
Figure 4(i), Co, O, and C atoms uniformly distribute in the composites, indicating that the Co nanoparticles embedded in porous carbon composites were successfully fabricated.
2.2. Microwave Absorption Performance
The EM absorption performance of the as-prepared composites was studied through the calculated RL value according to the following equations:
where
is the air impedance,
is the input impedance,
d is the thickness of the absorbers,
f represents the microwave frequency and
c is the velocity of light in free space.
and
stand for the complex permittivity and complex permeability, respectively. The RL value below −10 dB is regarded as an effective microwave absorption, which mean more than 90% of the electromagnetic energy can be attenuated, and the corresponding frequency range is called the effective absorption bandwidth (EAB). The RL curves and the 3D plots of SC and Co/C composites in the range of 2−18 GHz are displayed in
Figure 5. As shown in
Figure 5, all the Co/C composites show an enhanced MA compared with SC, demonstrating that the Co incorporation has a significant effect on the composition, structure, and electromagnetic parameters, which endows the composites with improved MA performance. The RL
min of SC is far below −10 dB at the calculated matching thicknesses. Although Co/C-0.75 has the strongest absorbing ability with the RL
min value of −38.33 dB, the matching thickness is as high as 5.0 mm, which is disadvantageous for practical applications. Co/C-1exhibits the moderate RL
min of −33.45 dB at a thickness of 4.0 mm. The EAB of Co/C-1 is 3.47 GHz (10.15−13.62 GHz) at 2.0 mm in thickness. The RL
min of Co/C-1.5 and Co/C-2 show a declining tendency compared with Co/C-1, which indicates that different compositions, sizes and microstructures of Co/C composites would influence the electromagnetic parameters and thus diverse MA performances.
The complex permittivity (ε
r =ε′−jε′′) and permeability (μ
r =μ′−jμ′′) are the primarily determinants for the EM properties. ε′ and μ′ denote the ability to store electric and magnetic energies respectively, while ε′′ and μ′′ represent the ability to dissipate the electric and magnetic energies respectively. To further investigate the relationship between the complex permittivity, complex permeability and the MA performances, the frequency dependences of permittivity and permeability are depicted, as shown in
Figure 6. In
Figure 6(a), all the samples display a downward tendency with the increased frequency, which can be attributed to dielectric polarization relaxation behavior of Co/C -paraffin hybrids. The ε′ and ε′′ values of SC fluctuate from 3.74 to 3.45 and 0.65 to 0.35 respectively, which are much lower than those of Co/C composites. This is attributed to the fact that SC has the inferior storage capability of electric field, indicating that the electrical conductivity and graphitization are not satisfactory. The electric storage and dissipation abilities are attributed to carbon and Co for Co/C composites. Among the Co/C composites, Co/C-1 exhibits outstanding electric storage and attenuation capabilities, which is mainly ascribed to its peculiar microstructure. Although the graphitization degree of Co/C-1 is moderate, the variform Co nanoparticles and the resulting abundant pores made more prominent contribution to the conductivity and polarization capabilities than its counterparts, bringing about higher ε′ (12.08−10.49) and ε′′ (3.44−2.90). Whereas, more and bigger Co particles would restrict the polarization of dipoles for better electric storage capability, thus exhibit a decrease for Co/C-2. The incorporation of magnetic Co nanoparticles greatly enhanced the magnetic storage and attenuation capabilities, showing much higher μ′ and μ′′ for the Co/C composites compared with SC. Noteworthy, Co/C-1 exhibits the lowest μ′ and μ′′, this could be ascribed to its highest Hc, as shown in the previous VSM analysis. A high Hc mean more difficult magnetizability for magnetic energies storage and dissipation capabilities, resulting in the lowest μ′ and μ′′ for Co/C-1. In addition, dielectric loss and magnetic loss tangent (tanδ
ε =ε''/ε', tanδ
µ =μ''/μ') are crucial parameters to determine the dominant loss mechanism in the MA mechanism. As shown in
Figure 6 (c) and (f), dielectric loss is the main contribution to the MA performance of Co/C-1 because the tanδɛ value (above 0.24) are larger than the tanδμ values (below 0.2) in almost the entire frequency ranges, demonstrating that the dielectric loss is the dominant loss mechanism for the attenuation of electromagnetic waves [
40].
To further investigate the existence of dielectric polarization and the related relaxation, the relationship between ε′ and ε″ was analyzed based on the Debye relaxation theory:
In the curve of ε′~ε′′, an approximate semicircle (Cole-Cole semicircle) represents one Debye relaxation process. The polarization in the tested frequency range mainly includes interfacial polarization and dipolar polarization. The Cole-Cole plots are shown in
Figure 7. As shown in
Figure 7(a)-(e), Co/C composites exhibit more semicircles compared with SC, which is attributed to the introduction of multiple nano-heterointerfaces due to the incorporation of Co nanoparticles and Co embedding into the pores of SC. Specifically, SC shows five distinct semicircles, while the Co/C composites exhibit seven distinct semicircles except Co/C-2. Remarkably, Co/C-2 exhibits six distinct semicircles and a longer tail than other Co/C composites. The tail is the symbol of conductive loss, suggesting that Co/C-2 possess stronger conductive ability [
41].
The magnetic loss mechanism was analyzed. The following formula is usually used to analyze the eddy current effect on the EM absorbing performance:
If
is constant in the curve of
, the eddy current loss is considerable. As shown in
Figure 7(f),
C0 almost fluctuates in the whole tested frequency. The
C0 value falls dramatically with increasing frequency below 8 GHz and then continuously changes in 8–18 GHz. Therefore, eddy current loss is not the dominant magnetic loss mechanism in 2−18 GHz. Natural resonance is represented by the fluctuating peaks at lower frequencies, whereas exchange resonance is represented by the peaks at higher frequencies.
To further investigate the influence of impedance matching and microwave attenuation capability on the MA performances, the calculated attenuation constant (α) and impedance matching are shown in
Figure 8. The higher α value means stronger attenuation capability of an absorber to dissipate the EM energies. If the input impedance of an absorber is equal to that of the free space, the value of |Z
in/Z
0| is 1. The closer of |Z
in/Z
0| value to 1 means more input EM waves would enter the interior of an absorber and be dissipated. A high α and benign impedance matching capability are two prominent factors for favorable MA performances. As shown in
Figure 8, SC exhibits the lowest α compared with Co/C composites, indicating the weakest EM attenuation capability, meanwhile, the value of |Z
in/Z
0| is far less than 1, which manifests the inferior impedance matching performance. Among the Co/C composites, Co/C-1 exhibits the highest α and the best impedance matching abilities, which is the prerequisite for favorable MA performance. The results are consistent with the calculated RL results.