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Progress in Chemistry 2019, Vol. 31 Issue (12): 1712-1728 DOI: 10.7536/PC190527 Previous Articles   Next Articles

Thermochromic Smart Coatings

Rui Sun1,2, Lin Yao2, Junhui He2,**(), Jie Liang1   

  1. 1. College of Chemistry and Environmental Engineering, China University of Mining and Technology(Beijing),Beijing 100083, China
    2. Technical Institute of Physics and Chemistry,Chinese Academy of Sciences, Beijing 100190, China
  • Received: Online: Published:
  • Contact: Junhui He
  • About author:
    ** E-mail:
  • Supported by:
    National Key Research and Development Program of China(2017YFA0207102); National Natural Science Foundation of China(21571182); National Natural Science Foundation of China(21271177); Key Laboratory of Photochemical Conversion and Optoelectronic Materials, CAS
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The current situation of energy and environment makes it urgent to develop a new generation of intelligent building windows with energy-saving features to effectively reduce building energy consumption. Thermochromic materials can change their optical characteristics according to changes in external temperature, and intelligently adjust the solar radiation energy entering the room without consuming other energy sources, which makes it a great potential application in building energy conservation. In recent years, an increasing number of research works in regard to thermochromic materials have been carried out, including hydrogels, ionic liquids, perovskites, metamaterials, liquid crystals and VO2. Among them, VO2 is one of the ideal candidates because its transmittance decreases obviously in the near infrared region before and after the phase transition and remains unchanged in the visible light range. This review outlines the principles, construction methods, and recent progress in thermochromic smart window coating related materials. Firstly, the structural characteristics, phase transition mechanism and research progress of various thermochromic materials are introduced in detail. Then, taking VO2 as a vital example, the surface engineering design and optimization of smart window coating is clarified and the influence of different construction methods on optical performance is discussed deeply. Finally, the challenges and future development direction of thermochromic smart coatings is presented.

Key words: smart coatings, surface engineering, thermochromic materials, VO2
Fig. 1 (a) Characteristics of solar spectrum[10];(b) intelligent window mechanism[25]
Table 1 Common thermochromic materials and their discoloration principle mechanisms[16]
Thermochromic
materials		 Discoloration principle Phase transition temperature
PNIPAm hydrogels Critical temperature
hydrophilic hydrophobic
phase transition		 32 ℃
IL-Ni-Cl Ionic liquid Complex structure
phase transition		 Dark green(T>80 ℃) ? Light brown(T<20 ℃)
VO,VO2,VnO2n-1
(n=2~6,8)
Ti2O3,TinO2n-1
(n=3~6)
NbO2, Fe3O4,
MnO2, CuO		 xM++AOy+xe-? MxAOy
(M=H, Li, Na; A=metal)		 Yellow(T>68 ℃) ? Fuscous(T<6 ℃)
Anatase ? Rutile(486~580 ℃)
Ag2S
NiS		 Still unknown Monoclinic variant ? Equiaxed variant
(179 ℃)
cryogenic β phase ? α phase 397 ℃
Ge-Te-Sb-S Vitreous ? Crystal transfer
Ge-S-Se, As-Se-
(Ag,Cu)
Cu2[HgI4]
Ag2[HgI4]		 Metal transfer in an
uncertain structure
structural change		 Red(T>69 ℃) ? Dark purple(T<6 ℃)
Yellow(T>48 ℃) ? Red(T< 5 ℃)
Fig. 2 Schematic representation of the lower critical solution temperature(LCST) reversible demixing phase transition of polymers in water[42]
Fig. 3 (a)Schematic diagram of the PNIPAm hydrogel smart window sandwich structure;(b)transmittance spectrum of 200 μm PNIPAm hydrogel thin film;(c)optical properties of integrated visible transmittance(Tlum), calculated solar energy modulation(ΔTsol), infrared modulation(ΔTIR), and integrated visible light modulation(ΔTlum) of 200 μm PNIPAm film;(d)the insets(left and right) are the 200 μm demonstration devices at 20 and 80℃, respectively[42];(a~d) reproduced with permission;(e)optical transmittance spectra of 25 μm HPCA, W-VO2, and W-VO2 with HPCA microgel samples[37]
Fig. 4 (a)Transmittance spectrum over the UV-Vis-NIR regions of pure IL-Ni-Cl film, VO2 nanoparticles, and VO2/IL-Ni-Cl hybrid film at 20 and 80 ℃;(b) demonstrations of pure IL-Ni-Cl film, VO2 nanoparticle film, and VO2/IL-Ni-Cl hybrid film at 20 and 80 ℃[47].(a、b) Reproduced with permission.(c)Schematic illustration of thermochromic optical transmittance change upon variation in temperature
Fig. 5 (a) Transmittance spectrum over the UV-Vis-NIR region of ionogel at various temperatures ranging from 15 to 60 ℃;(b) the photographs of transparent, translucent, and opaque states of the ionogel, respectively[52]
Fig. 6 (a)Schematic illustration of kiri-kirigami structure with notches on both sides. The upper part(green) has reversed patterned notches compared with the lower part(yellow).(b) Optical images of the deformed kiri-kirigami structure with identical design to(a) upon uniaxial stretching.(c) Experimental demonstrations of thermal activation and orientation switch of kiri-kirigami paper metamaterials at various temperatures[60]
Fig. 7 (a) Schematic of transmittance modulation methods based on(1) reconfigurable metamaterials,(2) active LSPR, and(3) the integration of active LSPR and reconfigurable metamaterials.(b)Photographs of the roll-up process of the yellow-brown composite film from figures on the left to right(1~6).(c)SEM-simulated strain distributions of the kirigami VO2-PDMS film and the magnified strain contour on a cut tip area as the inset[61]
Fig. 8 Schematic of the orientation-dependent optical behavior of cholesteric liquid crystalline materials:(a)Planar orientation;(b) focal conic orientation;(c) homeotropic orientation[64]
Fig. 9 (a)Schematic of the smectic A(SmA) to chiral nematic(N*) phase transition in a cell containing the LCs and ITO NCs;(b)the as-made film can reversibly change between transparent and opaque state in response to temperature;(c) the transmittance spectra of the initial film(black line) and the film after 300 cycles(red line);(d) temperature dependence of the transmittance of the smart films containing 0% ITO/SiO2 and 5.0 wt% ITO/SiO2[68]
Fig. 10 (a)The structure of rutile VO2(left) and monoclinic VO2(right)[73];(b)Standard solar spectra[92];(c) Representative XRD peaks at several temperatures.(d) Relative monoclinic portion as a function of temperature, estimated from XRD peak analysis in(c)[75]
Fig. 11 SEM images of samples prepared at different temperatures(a) 160℃ and(b) 180℃.Typical FE-SEM images of products obtained with different vanadium precursor concentrations.(c) 0.17 M,(d) 0.25 M,(e) 1.0 M[93]
Fig. 12 (a)Side and top elevations of a nanotextured surface with hexagonally arranged circular paraboloid cones;(b) Three-dimensional illustration of the VO2-coated nipple arrays used in the simulation;(c) the calculated ΔTsol map based on the FDTD parameter search[96]. Reproduced with permission from Ref[96]Copyright The Optical Society;(d) AFM images of AR samples with different periods;(e) Transmittance spectra measured at 25/90 ℃ for planner and AR samples with 140 nm thickness[112]
Fig. 13 (a) The preparation process of different periodical VO2 nanostructures; SEM images of patterned VO2 film prepared by the PS sphere with diameter of 160 nm;(b) Calculated(dashed lines) and measured(solid lines) transmittance spectra of nanoparticle arrays with diameters of 67, 125, and 287 nm, respectively;(c) the transmittance spectra at 20 and 95 ℃[114].(d) The preparation process of hollow-structured honeycomb-structured VO2 films via fully solution-based spontaneous self-template and assembly during the dual-phase transformation process[116]
Fig. 14 (a) VO2@TiO2 composite[120];(b)TEM images of TLHNs structure[121].(c) TEM images of VO2@ZnO core-shell structure[122]. Reproduced with permission from Ref[120~122]. Copyright(2013) Nature,(2018)Wiley,(2017) ACS;(d) Schematic diagram of VO2 @ZnS core-shell nanoparticles[123];(e,f) VO2 with /without good dispersion and their corresponding transmittance spectra, respectively[124];(g,h)Transmittance spectra of VO2@SiO2 nanoparticles and nanorods, respectively[125].Reproduced with Permission from Ref[123~125]. Copyright(2017)Elsevier,(2015)ACS,(2013)Nanoscale
Fig. 15 (a) Preparation of VO2 nanoparticle-based mixture from commercial V2O5;(b) photograph of large-scale VO2-PVP coatings[129]. Copyright(2018) RSC.(c) optical transmittance spectra of hybrid samples with different W-VO2 NPs content at 20 ℃ and 55 ℃, respectively;(d) optical modulation modes of composite films in response to different stimuli;(e) transmittance of samples with different W-VO2 NPs content during heating and cooling cycles. Reproduced with permission from Ref[133]. Copyright(2017) ACS
Fig. 16 (a)Solar modulation mechanism of the VO2/hydrogel hybrid[35].(b)Photographs of NIT and composite films at 20 and 80 ℃, respectively. Transmittance spectra of(c) NIT coating;(d) VO2 single layer film;(e) VO2/NIT composite film. Reproduced with permission from Ref[135]. Copyright(2018) Elsevier
Fig. 17 (a~c) Schematic illustration of the separated modulation of visible and NIR light transmittance working in passive mode(in response to environmental temperature);(d~f) Schematic illustration of the modulation of solar light transmittance from a transparent state to a blocking state working in active mode 1(in response to input voltage);(g and h) Schematic illustration of turning the device from an opaque state into a transparent state in response to the applied electric field(working in active mode 2)[136]
Table 2 Summary of research results of VO2 coating surface engineering
Approach Tlum(%) ΔTsol(%) Structure
Periodical patterned films 43.6/59.9 19.4 Moth-eye structure[111, 96]
43.9/42.2 14.3 Periodic micro-patterned VO2 thin films[137]
95.4#/- 5.5 Honeycomb-structured VO2(M) films[116]
46/45.8 13.2 2D periodical structure with d=160 nm[114]
70.2#/- 7.9 Ordered porous structure introduced by PS template[110]
75.5/73.8 7.7 Double-sided island structure[138]
55.6 8.42 VO2/SiO2 periodical structure[63]
core-shell structure 62.2/57.4 14.6 SiO2@VO2 core-shell structure[124]
62.6 18.54 VO2@SiO2 nano-rods[127]
71.02/56.5 14.31 VO2@SiO2 core-shell structure[139]
51/- 19 VO2@ZnO core-shell structure[122]
- - VO2@ZnS core-shell structure[123]
74 12 SiO2/TiO2/VO2 hollow core-shell nanospheres structure
61.8 12.6 VO2@SiO2 hollow core-shell sphere structure[127]
Integrated techniques - 12.9 VO2 dispersed in PVP[129]
43/- 11.3 SiO2-VO2 composite film[140]
57.8/-
73.3/68.71		 34.6
18.19		 Embedding VO2 NPs into LCs matrix[131]
67.3/36.2 27.3 Hybrid of VO2 and nickel(II)-based ligand[135]
VO2/hydrogel hybrid film[35]
62.6/43.2 34.7
80/33 36 VO2 /microgels hybrid[37]
55.3 40.9 PC-LCs/VO2/graphene composite structure[137]
35.2 37.7 Kirigami Metamaterials[61]
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[1] Zhang Haixuan1,2 Meng Xun1,2 Li Ping1**. Light and Thermal-stimuli Responsive Materials [J]. Progress in Chemistry, 2008, 20(05): 657-672.
[2]

Lv Weihua|Wang Rongmin**|He Yufeng|Zhang Huifang

. Preparation and Application of Smart Coatings [J]. Progress in Chemistry, 2008, 20(0203): 351-361.
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Abstract

Thermochromic Smart Coatings