Metal sulfides based composites as promising efficient microwave absorption materials: A review

doi:10.1016/j.jmst.2021.06.065

Abstract

Abstract:

The increasingly severe electromagnetic microwave pollution raises higher requirements for the development of efficient microwave absorption (MA) materials. Metal sulfides are regarded as potential robust MA materials because of their unique optical, thermal, electrical, and magnetic properties, as well as the controllable microstructures. However, due to the limited MA performances of unary metal sulfides, morphology regulations and foreign materials hybridizations are adopted as effective strategies to improve their MA performances. Recent years witnessed the fast research progresses on the metal sulfides based MA materials and thus, a systematic literature survey on the materials design, fabrication, characterizations, MA behaviors, and the mechanisms behind is, highly desirable to summarize the rapid progress of this hot research area so as to provide guidance for the future development trend. This review firstly reviewed the research background, research progress, and basic principles of MA materials. Subsequently, the present synthetic methods and performance improvement strategies of metal sulfides based MA materials are systematically introduced. Then, by comparing the MA properties of one-dimensional, two-dimensional, and three-dimensional metal sulfides based composites, the influence of dimensionality and morphology on the MA properties are analyzed. By summarizing the research process of metal sulfides/dielectrics composites, metal sulfides/magnets composites, and metal sulfides/dielectrics/magnets composites MA materials, the influence of foreign materials hybridizations on the loss mechanisms and impedance matching conditions of metal sulfides based composites are revealed. Finally, the challenges and development prospects of metal sulfides based MA materials are presented. This review would provide a comprehensive understanding and insightful guidance for the exploration and development of efficient MA materials with thin thickness, light weight, wide absorption bandwidth, and strong absorption intensity.

Key words: Metal sulfides, Microwave absorption, Structure regulation, Materials hybridization, Impedance matching

Bin Li, Fenglong Wang, Kejun Wang, Jing Qiao, Dongmei Xu, Yunfei Yang, Xue Zhang, Longfei Lyu, Wei Liu, Jiurong Liu. Metal sulfides based composites as promising efficient microwave absorption materials: A review[J]. J. Mater. Sci. Technol., 2022, 104: 244-268.

Figures/Tables 19

Fig. 1. Schematic of modification strategies of metal sulfides based MA materials. Reproduced with permission from Refs. [34,[39], [40], [41], [42], [43]].

Fig. 2. Schematic illustration of the working mechanisms of MA materials.

Fig. 3. Schematic of synthesis methods of metal sulfides: (a) solvothermal approaches; (b) gas-solid reaction; (c) microwave-assisted synthesis; (d) ultrasonic spray methods; (e) high energy ball milling methods. Reproduced with permission from Refs. [66,73,38,79,80].

Table 1 Summary of synthetic methods of metal sulfides based materials.

Method	Description	Advantages	Disadvantages
Solvothermal /hydrothermal approaches	In a closed system, a chemical reaction is carried out with water or other reagents as a solvent at a certain temperature and pressure.	Mild reaction conditions Low energy consumption	Low purity Polluting waste
Gas-solid reaction	The precursors are vulcanized by sulfur-containing gases to obtain the corresponding metal sulfides.	Flexible operation Desirable crystallinity	High reaction temperature Large energy consumption
Microwave-assisted synthesis	The vulcanization reaction process is accelerated by the polarization interaction between microwaves and materials during the microwave heating.	Achieving rapid and uniform volume heating	Narrow application range
Ultrasonic spray	The precursors are ultrasonic nebulized and reacts rapidly in a vacuum and high temperature condition.	Rapid reaction High uniformity	Low output Large energy consumption Harsh reaction condition
High-energy ball milling	The precursors are crushed into nanoparticles and induced into chemical reactions.	Low cost High output High uniformity	Low purity

Fig. 4. SEM images and particle size distributions of (a) R-Sb2S3, and (b) S-Sb2S3; (c) the permittivity of R-Sb2S3 and S-Sb2S3; (d) 3D RL values of R-Sb2S3; (e) the Cole-Cole plots of R-Sb2S3 and S-Sb2S3; (f) schematic diagram of charge density distribution. Reproduced with permission from Ref. [39].

Fig. 5. (a) Schematic of the exfoliation method of MoS2-NS; (b), (c) SEM images of MoS2-Bulk; (d), (e) SEM images of MoS2-NS; (f) permittivity of MoS2-Bulk/wax and MoS2-NS/wax with different loading contents; (g) RL of MoS2-Bulk/wax and MoS2-NS/wax with 60 wt% at different thicknesses; (h) MA mechanism diagram of MoS2-NS MA materials. Reproduced with permission from Ref. [40].

Fig. 6. (a) Schematic illustration of NixCo3-xS4 hollow nanosphere; TEM images of NixCo3-xS4 sample prepared at various times: (b, c) 3 h; (d, e) 5 h; (f, g) 8 h; (h, i) HR-TEM images of NixCo3-xS4 (x = 1.0); RL curves for NixCo3-xS4 products (j) x = 0, (k) x = 0.3, (l) x = 0.6, (m) x = 1.0. Reproduced with permission from Ref. [102].

Fig. 7. (a) Schematic synthetic route of the CMM absorber; SEM images of as obtained materials: (b, e) CFs; (c, f) CM, (d, g) CMM; (h) ε′, (i) ε′′, (j) dielectric loss tangent of CMM samples; (k) optimal RL value of the materials; (l) MA mechanisms of the CMM system. Reproduced with permission from Ref. [45].

Fig. 8. TEM images of (a) WS2, (b) rGO, (c) WS2-rGO; (d) ε′ and (e) ε″ of WS2 and WS2-RGO; RL profiles and 3D maps of (f) pristine WS2 and (g) WS2-rGO; (h) MA mechanisms of WS2-rGO heterostructure nanosheets. Reproduced with permission from Ref. [93].

Fig. 9. (a) Schematic synthetic route of Cu9S5/C; SEM images of the intermediate Cu/C composites (b, c) CSC1, (d,e) CSC2, (f, g) CSC3, and (h, i) pure C; (j) the permittivity and tanδE for CS, CSC1, CSC2, CSC3 and C; simulated electric field distribution in carbon skeleton (k1) and Cu9S5/C (k2), magnetic field distribution in carbon skeleton (k3) and Cu9S5/C (k4); (l) schematic diagram of the MA mechanism. Reproduced with permission from Ref. [116].

Fig. 10. (a) Illustration of the preparation of WS2/NiO hybrids; TEM images of (b) WS2, (c) NiO, and (d) WS2/NiO composites; (e) the permittivity of WS2/NiO composites; (f) RL curves of WS2/NiO/wax composites; (g) illustration of loss mechanisms for WS2/NiO composites. Reproduced with permission from Ref. [18].

Fig. 11. (a) Synthesis process of CuS/Ag2S composite; SEM images of (b) CuS, (c) CuS/Ag2S (30:1), (d) CuS/Ag2S (5:1), (e) CuS/Ag2S (2:1); (f, g) TEM images of CuS/Ag2S composite with Cu:Ag mole ratio of 5:1; (h) ε′, (i) ε″ and (j) tan δe for CuS and CuS/Ag2S composites; (k) schematic diagram of the MA mechanism. Reproduced with permission from Ref. [35].

Fig. 12. (a) TEM image of the MoS2/FeS2 composite; (b) off-axis electron holograms; (c) electric potential diagram; (d) charge density distribution; (e) local electric field distribution; (f) the profile of charge density and local electrical field. Reproduced with permission from Ref. [126].

Fig. 13. (a) Illustration of the preparation of PPy@MoS2 composite; (b, c) SEM of PPy@MoS2 composite; (d) the permittivity of the PPy, MoS2 and PPy@MoS2 composite; (e) MA mechanisms for PPy@MoS2. Reproduced with permission from Ref. [135].

Fig. 14. SEM images of (a) Fe2O3 micro-sheet, (b) Fe-500, (c) Fe-650, (d) Fe2O3@MoS2, (e) Fe@MoS2-500 and (f) Fe@MoS2-650; (g) XRD patterns of (1) Fe2O3 micro-sheets, (2) Fe-500, (3) Fe-650, (4) Fe@MoS2-500 and (5) Fe@MoS2-650; (h-k) electromagnetic parameters of samples; the RL of coin-like (l) Fe@MoS2-500 and (m) Fe@MoS2-650. Reproduced with permission from Ref. [143].

Fig. 15. (a) Synthesis process of FeCo@MoS2 nanoflowers; SEM images of (b, d) S1, (c, e) S2, (f, h) S3, and (g, i) S4; (j) electromagnetic parameters measured from S1 to S4; (k) schematic illustration of MA mechanisms for the FeCo@MoS2. Reproduced with permission from Ref. [66].

Fig. 16. (a) Synthesis process for the Fe3O4/Fe3S4 composites; SEM images of (b) S1, (c) S2, (d) S3, (e) S4; (f) electromagnetic parameters of samples; RL values for S3 with loading content of 60 wt% at different thickness; (g) 3D plots, (h) 2D plots and (i) the minimum RL value at the matching thickness; (j) schematic illustration of MA mechanisms for the Fe3O4/Fe3S4 composites. Reproduced with permission from Ref. [42].

Fig. 17. (a) Synthesis process of CoFe2O4@1T/2H-MoS2 composites; SEM image of (b) pure CoFe2O4, (c) pure 1T/2H-MoS2, (d) a single nest-like pure 1T/2H-MoS2 particle, (e) sample S1, (f) sample S2, and (g) sample S3; (h) electromagnetic parameter of samples; (i) 3D contour maps of RL for S2; (j) EAB of S2; (k) schematic illustration of MA mechanism of CoFe2O4@1T/2H-MoS2 composites. Reproduced with permission from Ref. [150].

Table 2 Comparison of MA performances of different kinds of metal sulfides based MA materials.

Classify	Sample	Loading content (wt%)	RL_min		EAB		Refs.
Classify	Sample	Loading content (wt%)	Value (dB)	Thickness (mm)	Value (GHz)	Thickness (mm)	Refs.
1D metal sulfides MA materials	CoS nanorods	5	-43.0	4.3	-	-	[87]
	Sb₂S₃ nanorods	75	-65.9	3.8	9.5	3.8	[39]
	porous Ni_xS_y	30	-35.6	2.7	14.5	2.0-5.0	[90]
	Ni_xCo_3-_xS₄ nanoprisms	50	-13.5	2.0	5.6	2.0	[89]
	Co₉S₈ nanotubes	20	-46.7	2.8	4.0	2.8	[86]
2D metal sulfides MA materials	WS₂ nanosheets	40	-15.5	5.5	3.5	2.5	[93]
	CoS nanoplates	30	-14.0	2.9	0.5	2.9	[94]
	MoS₂ nanosheets	60	-44.4	3.0	0.4	3.0	[97]
	MoS₂ nanosheets	60	-38.4	2.4	4.1	2.4	[40]
	MoS₂ nanosheets	60	-47.8	2.2	5.2	1.9	[98]
3D metal sulfides MA materials	flower-like CuS	20	-17.4	1.9	3.6	1.9	[35]
	flower-shaped MoS₂	30	-39.2	2.4	7.6	3.0	[34]
	flower-like CuS	5	-102	3.5	4-18	2-5	[30]
	hollow Co_1-_xS microspheres	3	-46.1	2.5	5.6	2.5	[101]
	Ni_xCo_3-_xS₄ hollow spheres	50	-23.7	1.4	3.8	1.3	[102]
Metal sulfides/ dielectrics composites	CFs/Co₉S₈	15	-46.8	4.8	5.4	2.0	[106]
	CFs@MXene@MoS₂	20	-61.5	2.1	7.6	2.1	[45]
	MoS₂/CNTs	30	-47.9	3.8	5.6	2.4	[13]
	CoS₂/CNTs	50	-65.0	1.6	6.2	1.6	[111]
	MoS₂/U-CNTs	30	-38.3	3.5	5.4	2.5	[14]
	SnS/GO	45	-41.2	3.2	3.7	-	[113]
	EG/MoS₂ nanosheets	7	-52.3	15.1	4.1	1.6	[114]
	WS₂/rGO	40	-41.5	2.7	3.5	1.7	[93]
	FeS₂@carbon	55	-45.0	1.5	15.4	1.2-5	[41]
	Fe₇S₈/C	65	-68.9	1.3	4.6	1.5	[73]
	Cu₉S₅/C	45	-62.3	1.3	4.7	1.3	[116]
	CC@NPC/CoS₂	30	-59.6	2.8	9.2	2.5-2.8	[117]
	Co₉S₈/C/Ti₃C₂T_x	33	-50.1	2.5	4.2	2.5	[120]
	CoS@Ti₃C₂T_x	40	-59.2	2.0	4.2	2.0	[121]
	CuS/Ti₃C₂T_x	35	-45.3	3.5	5.2	2.0	[122]
	MoS₂/Co₃O₄	40	-43.6	4.0	4.8	2.0	[123]
	WS₂/NiO	40	-53.3	4.3	4.9	2.2	[18]
	CuS@ZnO	40	-40.5	1.5	4.1	1.5	[124]
	ZnO/MoS₂	30	-35.8	2.5	10.2	2.5	[125]
	CuS/Ag₂S	20	-47.2	2.9	4.4	2.9	[35]
	MoS₂/FeS₂	50	-60.2	3.0	6.5	2.0	[126]
	CuS@CoS₂ nanoboxes	20	-58.6	2.5	8.2	2.2	[130]
	NiS/Ni₃S₄	30	-43.0	2.4	4.2	1.8	[36]
	CoS@PPy	15	-29.2	4.0	3.0	4.0	[134]
	PANI/CoS/C	30	-24..0	3.0	0.6	3.0	[20]
	PPy@MoS₂ nanotubes	40	-49.1	5.0	6.4	2.5	[135]
Metal sulfides/ magnets composites	Ni/MoS₂	60	-55.0	3.0	4.0	1.5	[140]
	MoS₂@Ni	20	-22.0	2.0	2.8	2.0	[141]
	Ni/ZnS	70	-25.8	2.7	4.7	2.7	[142]
	Fe@MoS₂	60	-37.0	2.0	4.7	2.0	[143]
	Fe-doped NiS₂/NiS	20	-61.7	1.7	3.8	1.7	[144]
	FeCo@MoS₂ nanoflowers	45	-64.6	2.0	7.2	2.0	[66]
	Cu₉S₅/Fe₃O₄	50	-39.5	4.3	2-14	2.0-5.0	[10]
	sandwich-like Fe₃O₄/Fe₃S₄	60	-45.3	3.3	5.0	2.0	[42]
	Fe₃O₄/MoS₂	50	-64.0.	1.7	6.1	2.0	[11]
	ZnFe₂O₄@MoS₂	20	-61.8	3.0	6.0	2.0	[147]
	Co_0.6Fe_2.4O₄@ MoS₂	50	-79.9	2.7	6.0	2.3	[148]
	CoFe₂O₄@ 1T/2H-MoS₂	40	-68.5	1.8	4.6	1.6	[150]
Metal sulfides/ dielectrics/magnets composites	rGO/CoFe₂O₄/ ZnS	50	-43.2	1.8	5.5	2.0	[151]
	rGO@Ni-doped -MoS₂	40	-40.0	2.0	4.8	2	[152]
	Co/C/Co₉S₈	25	-21.5	4.0	8.2	2.2	[155]
	Co/C/Co₉S₈	30	-54.0	4.9	-	-	[155]
	PANI@MoS₂@Fe₃O₄ nanowires	30	-49.7	1.3	6.5	1.7	[156]

Table 2 Comparison of MA performances of different kinds of metal sulfides based MA materials.

Classify	Sample	Loading content (wt%)	RL_min		EAB		Refs.
Classify	Sample	Loading content (wt%)	Value (dB)	Thickness (mm)	Value (GHz)	Thickness (mm)	Refs.
1D metal sulfides MA materials	CoS nanorods	5	-43.0	4.3	-	-	[87]
	Sb₂S₃ nanorods	75	-65.9	3.8	9.5	3.8	[39]
	porous Ni_xS_y	30	-35.6	2.7	14.5	2.0-5.0	[90]
	Ni_xCo_3-_xS₄ nanoprisms	50	-13.5	2.0	5.6	2.0	[89]
	Co₉S₈ nanotubes	20	-46.7	2.8	4.0	2.8	[86]
2D metal sulfides MA materials	WS₂ nanosheets	40	-15.5	5.5	3.5	2.5	[93]
	CoS nanoplates	30	-14.0	2.9	0.5	2.9	[94]
	MoS₂ nanosheets	60	-44.4	3.0	0.4	3.0	[97]
	MoS₂ nanosheets	60	-38.4	2.4	4.1	2.4	[40]
	MoS₂ nanosheets	60	-47.8	2.2	5.2	1.9	[98]
3D metal sulfides MA materials	flower-like CuS	20	-17.4	1.9	3.6	1.9	[35]
	flower-shaped MoS₂	30	-39.2	2.4	7.6	3.0	[34]
	flower-like CuS	5	-102	3.5	4-18	2-5	[30]
	hollow Co_1-_xS microspheres	3	-46.1	2.5	5.6	2.5	[101]
	Ni_xCo_3-_xS₄ hollow spheres	50	-23.7	1.4	3.8	1.3	[102]
Metal sulfides/ dielectrics composites	CFs/Co₉S₈	15	-46.8	4.8	5.4	2.0	[106]
	CFs@MXene@MoS₂	20	-61.5	2.1	7.6	2.1	[45]
	MoS₂/CNTs	30	-47.9	3.8	5.6	2.4	[13]
	CoS₂/CNTs	50	-65.0	1.6	6.2	1.6	[111]
	MoS₂/U-CNTs	30	-38.3	3.5	5.4	2.5	[14]
	SnS/GO	45	-41.2	3.2	3.7	-	[113]
	EG/MoS₂ nanosheets	7	-52.3	15.1	4.1	1.6	[114]
	WS₂/rGO	40	-41.5	2.7	3.5	1.7	[93]
	FeS₂@carbon	55	-45.0	1.5	15.4	1.2-5	[41]
	Fe₇S₈/C	65	-68.9	1.3	4.6	1.5	[73]
	Cu₉S₅/C	45	-62.3	1.3	4.7	1.3	[116]
	CC@NPC/CoS₂	30	-59.6	2.8	9.2	2.5-2.8	[117]
	Co₉S₈/C/Ti₃C₂T_x	33	-50.1	2.5	4.2	2.5	[120]
	CoS@Ti₃C₂T_x	40	-59.2	2.0	4.2	2.0	[121]
	CuS/Ti₃C₂T_x	35	-45.3	3.5	5.2	2.0	[122]
	MoS₂/Co₃O₄	40	-43.6	4.0	4.8	2.0	[123]
	WS₂/NiO	40	-53.3	4.3	4.9	2.2	[18]
	CuS@ZnO	40	-40.5	1.5	4.1	1.5	[124]
	ZnO/MoS₂	30	-35.8	2.5	10.2	2.5	[125]
	CuS/Ag₂S	20	-47.2	2.9	4.4	2.9	[35]
	MoS₂/FeS₂	50	-60.2	3.0	6.5	2.0	[126]
	CuS@CoS₂ nanoboxes	20	-58.6	2.5	8.2	2.2	[130]
	NiS/Ni₃S₄	30	-43.0	2.4	4.2	1.8	[36]
	CoS@PPy	15	-29.2	4.0	3.0	4.0	[134]
	PANI/CoS/C	30	-24..0	3.0	0.6	3.0	[20]
	PPy@MoS₂ nanotubes	40	-49.1	5.0	6.4	2.5	[135]
Metal sulfides/ magnets composites	Ni/MoS₂	60	-55.0	3.0	4.0	1.5	[140]
	MoS₂@Ni	20	-22.0	2.0	2.8	2.0	[141]
	Ni/ZnS	70	-25.8	2.7	4.7	2.7	[142]
	Fe@MoS₂	60	-37.0	2.0	4.7	2.0	[143]
	Fe-doped NiS₂/NiS	20	-61.7	1.7	3.8	1.7	[144]
	FeCo@MoS₂ nanoflowers	45	-64.6	2.0	7.2	2.0	[66]
	Cu₉S₅/Fe₃O₄	50	-39.5	4.3	2-14	2.0-5.0	[10]
	sandwich-like Fe₃O₄/Fe₃S₄	60	-45.3	3.3	5.0	2.0	[42]
	Fe₃O₄/MoS₂	50	-64.0.	1.7	6.1	2.0	[11]
	ZnFe₂O₄@MoS₂	20	-61.8	3.0	6.0	2.0	[147]
	Co_0.6Fe_2.4O₄@ MoS₂	50	-79.9	2.7	6.0	2.3	[148]
	CoFe₂O₄@ 1T/2H-MoS₂	40	-68.5	1.8	4.6	1.6	[150]
Metal sulfides/ dielectrics/magnets composites	rGO/CoFe₂O₄/ ZnS	50	-43.2	1.8	5.5	2.0	[151]
	rGO@Ni-doped -MoS₂	40	-40.0	2.0	4.8	2	[152]
	Co/C/Co₉S₈	25	-21.5	4.0	8.2	2.2	[155]
	Co/C/Co₉S₈	30	-54.0	4.9	-	-	[155]
	PANI@MoS₂@Fe₃O₄ nanowires	30	-49.7	1.3	6.5	1.7	[156]

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