Multilevel Heterogeneous Interfaces Enhanced Polarization Loss of 3D-Printed Graphene/NiCoO2/Selenides Aerogels for Boosting Electromagnetic Energy Dissipation.

Heterointerface engineering is an attractive approach to modulating electromagnetic (EM) parameters and EM wave absorption performance. However, the weak interfacial interactions and poor impedance matching would lead to unsatisfactory EM absorption performance due to the limitation of the construction materials and design strategies. Herein, multilevel heterointerface engineering is proposed by in situ growing nanosheet-like NiCoO2 and selenides with abundant interface structures on 3D-printed graphene aerogel (GA) skeletons, which strengthens the interfacial effect and improves the dielectric polarization loss. Benefiting from the features of substantially enhanced polarization loss and optimized impedance matching, the graphene/S-NiCoO2/selenides (G/S-NCO/Se) have achieved brilliant EM wave absorption performance with a strong reflection loss (RL) value of -60.7 dB and a broad effective absorption bandwidth (EAB) of 8 GHz, which is about six times greater than that of the graphene aerogel (-9.8 dB). Moreover, it is further confirmed by charge density differences and off-axis electron holography that a large amount of polarized charge accumulates at the interface, leading to significant polarization relaxation behaviors. This work provides a deep understanding of the effect of a multilevel heterogeneous interface on dielectric polarization loss, which injects a fresh and infinite vitality for designing high-efficiency EM wave absorbers.

Manipulation of Impedance Matching toward 3D-Printed Lightweight and Stiff MXene-Based Aerogels for Consecutive Multiband Tunable Electromagnetic Wave Absorption.

Highly conductive MXene material exhibits outstanding dissipation capability of electromagnetic (EM) waves. However, the interfacial impedance mismatch due to high reflectivity restricts the application of MXene-based EM wave absorbing materials. Herein, a direct ink writing (DIW) 3D printing strategy to construct lightweight and stiff MXene/graphene oxide aerogels (SMGAs) with controllable fret architecture is demonstrated, exhibiting tunable EM wave absorption properties by manipulating impedance matching. Noteworthy, the maximum reflection loss variation value (ΔRL) of SMGAs is -61.2 dB by accurately modulating the width of the fret architecture. The effective absorption region (fE) of SMGAs exhibits consecutive multiband tunability, and the broadest tunable fE (Δf) is 14.05 GHz, which could be continuously tuned in the whole C- (4-8 GHz), X- (8-12 GHz), and Ku-bands (12-18 GHz). Importantly, the hierarchical structures and the orderly stacking of filaments endow lightweight SMGAs (0.024 g cm-3) with a surprising compression resistance, which can withstand 36 000 times its own weight without obvious deformation. Finite element analysis (FEA) further indicates that the hierarchical structure facilitates stress dispersion. The strategy developed here provides a method for fabricating tunable MXene-based EM wave absorbers that are lightweight and stiff.

Interfacial π-π Interactions Induced Ultralight, 300 °C-Stable, Wideband Graphene/Polyaramid Foam for Electromagnetic Wave Absorption in Both Gigahertz and Terahertz Bands.

High-performance electromagnetic wave-absorbing (EMA) materials used in high-temperature environments are of great importance in both civil and military fields. Herein, we have developed the ultralight graphene/polyaramid composite foam for wideband electromagnetic wave absorption in both gigahertz and terahertz bands, with a higher service temperature of 300 °C. It is found that strong interfacial π-π interactions are spontaneously constructed between graphene and polyaramids (PA), during the foam preparation process. This endows the foam with two advantages for its EMA performance. First, the π-π interactions trigger the interfacial polarization for enhanced microwave dissipation, as confirmed by the experimental and simulation results. The composite foam with an ultralow density (0.0038 g/cm3) shows a minimum reflection loss (RL) of -36.5 dB and an effective absorption bandwidth (EAB) of 8.4 GHz between 2 and 18 GHz band. Meanwhile, excellent terahertz (THz) absorption is also achieved, with EAB covering the entire 0.2-1.6 THz range. Second, the interfacial π-π interactions promote PA to present a unique in-plane orientation configuration along the graphene surface, thus making PA the effective antioxidation barrier layer for graphene at high temperatures. The EMA performance of the foam could be completely preserved after 300 °C treatment in air atmosphere. Furthermore, the composite foam exhibits multifunctions, including good compressive, thermal insulating, and flame-retardant properties. We believe that this study could provide useful guidance for the design of next-generation EMA materials used in harsh environments.

Ionic Liquid Gating Enhanced Photothermoelectric Conversion in Three-Dimensional Microporous Graphene.

The photothermoelectric (PTE) effect can effectively convert light into electricity through photothermal and thermoelectric processes and has great potential applications in light energy harvesting and bandgap-independent photodetection. It is particularly applicable for the terahertz (THz) range featuring low photon energy but has not been well established due to lack of high-performance PTE materials in this range. Three-dimensional microporous graphene (3DMG) foam possesses ultrahigh THz absorptivity and outstanding photothermal conversion and can serve as a promising candidate. Here, enhancement of the THz PTE response of 3DMG foam by fine-tuning its thermoelectric properties using the ionic liquid electric double layer (EDL) technique was demonstrated. Continuous and reversible control of the Seebeck coefficient of 3DMG highlights the effectiveness of EDL gating in manipulating the electronic structures of such bulk and porous material. An approximate 1 order of magnitude enhancement in the Seebeck coefficient as well as the PTE responsivity was observed. In addition, a double-cell 3DMG EDL device with a p-n junction like channel configuration enabled further improvement of the photoresponse. This work opens a new avenue to optimize the PTE performance of 2D nanosheet-assembled 3D porous materials for highly efficient energy harvesting and detection of THz radiation.

Compressible Highly Stable 3D Porous MXene/GO Foam with a Tunable High-Performance Stealth Property in the Terahertz Band.

In this work, a three-dimensional (3D) porous MXene/GO foam (MGOF) was successfully synthesized and exhibited an excellent terahertz stealth property covering a whole measurement frequency of 0.2-2.0 THz. This is due to the ingenious assembly of two functional two-dimensional materials that have different advantages. The multiscale micro-nanostructure constructed with the 3D porous MGOF can effectively increase the terahertz scattering and refraction. Furthermore, MXene sheets with high conductivity can enhance the responsiveness to the terahertz wave. By adjusting the content of MXene in the MGOF, it exhibits a maximum reflection loss (RL) of 37 dB with a 100% qualified frequency bandwidth (RL > 10 dB), which is the most outstanding result in the available reference. In addition, the optimal average terahertz RL values of MGOF were up to 30.6 dB, which is 100% higher than the best data presented in previous work. Benefitting from an ultralow density, a high RL value, and a wide bandwidth, the maximum specific average terahertz absorption performance can reach 4.6 × 104 dB g-1 cm3, which is more than 4000 times that of other materials. In addition, the regulation of the terahertz absorption property through microstructure and morphology control is reported for the first time.

Annealing Temperature-Dependent Terahertz Thermal-Electrical Conversion Characteristics of Three-Dimensional Microporous Graphene.

Three-dimensional microporous graphene (3DMG) possesses ultrahigh photon absorptivity and excellent photothermal conversion ability and shows great potential in energy storage and photodetection, especially for the not well-explored terahertz (THz) frequency range. Here, we report on the characterization of the THz thermal-electrical conversion properties of 3DMG with different annealing treatments. We observe distinct behavior of bolometric and photothermoelectric responses varying with annealing temperature. Resistance-temperature characteristics and thermoelectric power measurements reveal that marked charge carrier reversal occurs in 3DMG as the annealing temperature changes between 600 and 800 °C, which can be well explained by Fermi-level tuning associated with oxygen functional group evolution. Benefiting from the large specific surface area of 3DMG, it has an extraordinary capability of reaching thermal equilibrium quickly and exhibits a fast photothermal conversion with a time constant of 23 ms. In addition, 3DMG can serve as an ideal absorber to improve the sensitivity of THz detectors and we demonstrate that the responsivity of a carbon nanotube device could be enhanced by 12 times through 3DMG. Our work provides new insight into the physical characteristics of carrier transport and THz thermal-electrical conversion in 3DMG controlled by annealing temperature and opens an avenue for the development of highly efficient graphene-based THz devices.

Consecutively Strong Absorption from Gigahertz to Terahertz Bands of a Monolithic Three-Dimensional Fe3O4/Graphene Material.

With the booming microwave and terahertz technology for communication, detection, and healthcare, the consequently increasingly complicated electromagnetic environment is in urgent need of high-performance microwave and terahertz absorption materials. However, it is still a huge challenge to achieve consecutively strong absorption in both microwave and terahertz regimes. Herein, an ultra-broadband and highly efficient absorber for both microwave and terahertz bands based on the monolithic three-dimensional cross-linked Fe3O4/graphene material (3DFG) is first reported. The 3DFG shows an incredible wide qualified absorption bandwidth (with reflection loss less than -10 dB) from 3.4 GHz to 2.5 THz, which is the best result in this area by far. Furthermore, the remarkable absorption performance can be maintained under oblique incidence, different compressive strains, and even after 200 compression/release cycles. The designed highly porous structure for minimizing surface reflection combined with the micro-macro integrated high lossy framework results in the excellent absorptivity, as verified by the terahertz time-domain spectroscopy technique. With these, the 3DFG achieves an unprecedentedly average absorption intensity of 38.0 dB, which is the maximum value among the broadband absorbers. In addition, its specific average microwave and terahertz absorption value is over 2 orders of magnitude higher than other kinds of reported materials. The results provide new insights for developing novel ultra-broadband absorbers with stronger reflection loss and wider absorption bandwidth.