基于WO3·xH2O与可逆金属电沉积的无色/黑色转换电致变色器件

doi:10.15541/jim20250017

摘要/Abstract

摘要：

可逆金属电沉积器件(Reversible Metal Electrodeposition Device, RMED)的电致变色(Electrochromic, EC)智能窗为动态调节光和热的传输提供了一个极具吸引力的替代方案。本工作通过在氟掺杂氧化锡(Fluorine-doped Tin Oxide, FTO)透明导电玻璃上电沉积WO₃·xH₂O薄膜, 再利用Bi/Cu的可逆金属电沉积来构建电致变色器件(Electrochromic Device, ECD)。电解质由CuCl₂、BiCl₃、KCl和HCl水溶液组成, 为电化学过程和电沉积过程提供必要的成分。该器件可在无色和黑色状态之间快速转换, 在570 nm波长处实现了77.0%的光调制幅度。在黑色状态下, ECD在400~1100 nm范围内呈现出接近零的透过率。此外, 经历60000 s的着色/褪色循环后, 该器件能够维持其初始光调制幅度的96.6%, 展现出良好的循环稳定性。所制备的RMED在开路电压下具有相对较高的稳定性, 还拥有出色的隔热性能。这些研究结果为克服RMED循环稳定性差以及提高ECD的光调制幅度提供了一种解决方案。

关键词: 可逆金属电沉积, 电致变色, WO₃·xH₂O

Abstract:

Electrochromic (EC) smart windows utilizing a reversible metal electrodeposition device (RMED) offer a compelling alternative for dynamically regulating transmissions of optical and thermal energy. An EC device (ECD) is constructed by reversible metal electrodeposition (RME) of Bi/Cu on WO₃·xH₂O film electrodeposited onto fluorine-doped tin oxide (FTO) transparent conductive glass. The electrolyte consists of CuCl₂, BiCl₃, KCl and HCl aqueous solution, supplying necessary components for both electrochemical and electrodeposition processes. The ECD shows ability to rapidly transition between colorless and black states, which achieves a large optical modulation of 77.0% at 570 nm. In the black state, the ECD exhibits a near-zero transmittance in the wavelength range of 400-1100 nm while maintaining 96.6% of its initial optical modulation after coloration/bleaching cycling of 60000 s, exhibiting good cyclic stability. This RMED has relatively high stability under open-circuit voltage and also possesses excellent heat insulation performance. The results offer a solution to overcome the poor cyclic stability of RMEDs and improve the optical modulation of ECDs.

Key words: reversible metal electrodeposition, electrochromic, WO₃·xH₂O

中图分类号:

TQ174

宛心怡, 王文奇, 李加诚, 赵俊亮, 马董云, 王金敏. 基于WO₃·xH₂O与可逆金属电沉积的无色/黑色转换电致变色器件[J]. 无机材料学报, 2025, 40(10): 1163-1174.

WAN Xinyi, WANG Wenqi, LI Jiacheng, ZHAO Junliang, MA Dongyun, WANG Jinmin. Colorless/Black Switching Electrochromic Device Based on WO₃·xH₂O and Reversible Metal Electrodeposition[J]. Journal of Inorganic Materials, 2025, 40(10): 1163-1174.

图/表 11

Fig. 1 Schematic illustration and photos of the RMED (a, b) Schematic diagrams of the RMED in the (a) bleached state and (b) colored state; (c, d) Photos of the RMED (c) after 40 s of metal stripping at 1.0 V and (d) after 30 s of metal electrodeposition at -3.0 V

Fig. 2 Mechanism of stripping reactions in the Bi/Cu halide electrolyte

Fig. 3 Mechanisms of chemical and electrochemical reactions in the RMED during operation (a) Colored state (metal electrodeposition); (b) Bleached state (metal stripping)

Fig. 4 GIXRD patterns of the Bi/Cu electrodeposited on the WO3·xH2O film

Fig. 5 SEM images and EDS mappings (a, b) SEM images of (a) WO3·xH2O film and (b) Bi/Cu nanoparticles; (c-f) EDS mappings of Bi/Cu nanoparticles

Fig. 6 Electrochemical behavior of the WO3·xH2O film (a) CV curve at a scan rate of 10 mV·s-1; (b) CV curves at different scan rates; (c) Linear relationship between lgi and lgv; (c, d) Contribution of surface capacitance to total charge storage (shaded area) in CV curves at scan rates of (d) 10 and (e)100 mV·s-1; (f) Proportion of charge storage attributed to diffusion-controlled and surface capacitance characteristics at various scan rates. Colorful figures are available on website

Fig. 7 Optical characteristics of the RMED (a) Transmission spectra at the colored and bleached states measured at -3.0 and 1.0 V, respectively; (b) Solar irradiance spectra of the colored and bleached states measured at -3.0 and 1.0 V, respectively. Colorful figures are available on website

Fig. 8 Electrochemical and EC properties of the RMED (a) Duration needed for the RMED to go from coloration to bleaching at a wavelength of 570 nm when operating at open circuit voltage; (b) Real-time transmittance curve of the RMED recorded at 570 nm by applying a square wave potential of -3.0 V for 30 s and 1.0 V for 40 s; (c) Optical density variations with respect to charge density; (d) Cyclic performance of the RMED measured by applying -3.0 V for 30 s and 1.0 V for 40 s

Fig. 9 Infrared blocking performance of the RMED smart window in a model house (a) Schematic diagram of the indoor temperature change experiment using the model house; (b) Indoor temperature change curves of each mode during heating process of the house; (c) Physical pictures of the house during heating and heating-stopping simulation; (d) Indoor temperature change curves of each mode during the heating-stopping process

Fig. S1 Real-time transmittance curves at 570 nm for RMEDs with different metal atomic ratios under coloration (-3.0 V) and bleaching (1.0 V) conditions (a) Cu:Bi = 5 : 1; (b) Cu:Bi = 4 : 1; (c) Cu:Bi = 2 : 1; (d) Cu:Bi = 1 : 1; (e) Cu:Bi = 1 : 2; (f) Cu:Bi = 1 : 3

Fig. S2 Electrochromic properties of the RMED without WO3·xH2O film (a) Transmission spectra in the colored (-3.0 V for 30 s) and bleached (1.0 V for 40 s) states; (b) Real-time transmittance curve at 570 nm

参考文献 42

[1]	KHANDEKAR M L, MURTY T S, CHITTIBABU P. The global warming debate: a review of the state of science. Pure Appl. Geophys., 2005, 162(8/9): 1557.
[2]	GRANQVIST C G. Transparent conductors as solar energy materials: a panoramic review. Sol. Energy Mater. Sol. Cells, 2007, 91(15): 1529.
[3]	SUMBOJA A, LIU J M, ZHENG W G, et al. Electrochemical energy storage devices for wearable technology: a rationale for materials selection and cell design. Chem. Soc. Rev., 2018, 47(15): 5919. DOI PMID
[4]	KIM H, SON M, AHN S H, et al. Comparison of electrochromic characteristics of electrochromic device upon various sintering methods of Sol-Gel based WO₃ electrode. Curr. Appl. Phys., 2020, 20(6): 782.
[5]	EH A L S, TAN A W M, CHENG X, et al. Recent advances in flexible electrochromic devices: prerequisites, challenges, and prospects. Energy Technol., 2018, 6(1): 33.
[6]	ZHANG R C, ZHANG Z B, HAN J C, et al. Advanced liquid crystal-based switchable optical devices for light protection applications: principles and strategies. Light Sci. Appl., 2023, 12(1): 11.
[7]	GLOGIC E, FUTSCH R, THENOT V, et al. Development of eco-efficient smart electronics for anticounterfeiting and shock detection based on printable inks. ACS Sustain. Chem. Eng., 2021, 9(35): 11691.
[8]	WANG J L, LIU J W, SHENG S Z, et al. Manipulating nanowire assemblies toward multicolor transparent electrochromic device. Nano Lett., 2021, 21(21): 9203.
[9]	ALCARAZ G K A, JUAREZ-ROLON J S, BURPEE N A, et al. Thermally-stable dynamic windows based on reversible metal electrodeposition from aqueous electrolytes. J. Mater. Chem. C, 2018, 6(8): 2132.
[10]	ARAKI S, NAKAMURA K, KOBAYASHI K, et al. Electrochemical optical-modulation device with reversible transformation between transparent, mirror, and black. Adv. Mater., 2012, 24(23): 122.
[11]	EH A L S, CHEN J, ZHOU X, et al. Robust trioptical-state electrochromic energy storage device enabled by reversible metal electrodeposition. ACS Energy Lett., 2021, 6(12): 4328.
[12]	ZIEGLER J P. Status of reversible electrodeposition electrochromic devices. Sol. Energy Mater. Sol. Cells, 1999, 56(3/4): 477.
[13]	LAIK B, CARRIÈRE D, TARASCON J M. Reversible electrochromic system based on aqueous solution containing silver. Electrochim. Acta, 2001, 46(13/14): 2203.
[14]	BARILE C J, SLOTCAVAGE D J, HOU J Y, et al. Dynamic windows with neutral color, high contrast, and excellent durability using reversible metal electrodeposition. Joule, 2017, 1(1): 133.
[15]	BARILE C J. Electrolyte dynamics in reversible metal electrodeposition for dynamic windows. J. Appl. Electrochem., 2018, 48(4): 443.
[16]	HOWARD B M, ZIEGLER J P. Optical properties of reversible electrodeposition electrochromic materials. Sol. Energy Mater. Sol. Cells, 1995, 39(2/3/4): 309.
[17]	ISLAM S M, FINI C N, BARILE C J. Dynamic windows based on reversible metal electrodeposition with enhanced functionality. J. Electrochem. Soc., 2019, 166(8): D333.
[18]	JEONG K R, LEE I, PARK J Y, et al. Enhanced black state induced by spatial silver nanoparticles in an electrochromic device. NPG Asia Mater., 2017, 9: e362.
[19]	LUO G, SHEN L Y, ZHENG J M, et al. A europium ion doped WO₃ film with the bi-functionality of enhanced electrochromic switching and tunable red emission. J. Mater. Chem. C, 2017, 5(14): 3488.
[20]	DOV N E, SHANKAR S, COHEN D, et al. Electrochromic metallo-organic nanoscale films: fabrication, color range, and devices. J. Am. Chem. Soc., 2017, 139(33): 11471. DOI PMID
[21]	ASSIS L M N, LEONES R, KANICKI J, et al. Prussian blue for electrochromic devices. J. Electroanal. Chem., 2016, 777: 33.
[22]	ZHI M Y, HUANG W X, SHI Q W, et al. Enhanced electrochromic performance of vanadium pentoxide/reduced graphene oxide nanocomposite film prepared by the Sol-Gel method. J. Electrochem. Soc., 2016, 163(10): H891.
[23]	QIU M J, SUN P, ZHANG B, et al. Reliable information encryption and digital display applications based on multistate smart windows. Adv. Opt. Mater., 2018, 6(22): 1800338.
[24]	SUI C X, PU J K, CHEN T H, et al. Dynamic electrochromism for all-season radiative thermoregulation. Nat. Sustain., 2023, 6(4): 428.
[25]	JIA Z F, SUI Y M, QIAN L, et al. Electrochromic windows with fast response and wide dynamic range for visible-light modulation without traditional electrodes. Nat. Commun., 2024, 15(1): 6110. DOI PMID
[26]	ZHANG Y X, XU B, HUANG B K, et al. Color-neutral smart window enabled by gradient reversible alloy deposition. ACS Energy Lett., 2024, 9(8): 4162.
[27]	NGUYEN T V, DO H, GUO W W, et al. Tungsten oxide-modified ITO electrode for electrochromic window based on reversible metal electrodeposition. Electron. Mater. Lett., 2022, 18(1): 36.
[28]	SHENG K, XUE B, ZHENG J M, et al. A transparent to opaque electrochromic device using reversible Ag deposition on PProDOT- Me₂ with robust stability. Adv. Opt. Mater., 2021, 9(11): 2002149.
[29]	ZHANG X Q, SUI Y M, YEASMIN S, et al. Fast-switching electrochromic device enabled by Fe²⁺-mediated MnO₂/Mn²⁺ redox reactions. ACS Appl. Electron. Mater., 2024, 6(11): 8163.
[30]	EVANS R C, AUSTIN R, MILLER R C, et al. Surface-facet- dependent electrochromic properties of WO₃ nanorod thin films: implications for smart windows. ACS Appl. Nano Mater., 2021, 4(4): 3750.
[31]	LI Y Q, MCMASTER W A, WEI H, et al. Enhanced electrochromic properties of WO₃ nanotree-like structures synthesized via a two-step solvothermal process showing promise for electrochromic window application. ACS Appl. Nano Mater., 2018, 1(6): 2552.
[32]	ZHOU Z Q, CHEN Z, MA D Y, et al. Porous WO₃·2H₂O film with large optical modulation and high coloration efficiency for electrochromic smart window. Sol. Energy Mater. Sol. Cells, 2023, 253: 112226.
[33]	ISLAM S M, HERNANDEZ T S, MCGEHEE M D, et al. Hybrid dynamic windows using reversible metal electrodeposition and ion insertion. Nat. Energy, 2019, 4(3): 223.
[34]	HERNANDEZ T S, BARILE C J, STRAND M T, et al. Bistable black electrochromic windows based on the reversible metal electrodeposition of Bi and Cu. ACS Energy Lett., 2018, 3(1): 104.
[35]	EH A L S, LIN M F, CUI M Q, et al. A copper based reversible electrochemical mirror device with switchability between transparent, blue, and mirror states. J. Mater. Chem. C, 2017, 5(26): 6547.
[36]	GUPTA S, SINGH R, ANOOP M D, et al. Electrochemical sensor for detection of mercury (II) ions in water using nanostructured bismuth hexagons. Appl. Phys. A, 2018, 124(11): 737.
[37]	ZHANG C, LI S, WU R, et al. Robust MnO₂-WO₃ complementary electrochromic device enabled by reversible electrodeposition of MnO₂. Nano Lett., 2024 24(51): 16360.
[38]	YUAN Y L, LU Y D, JIA B E, et al. Integrated system of solar cells with hierarchical NiCo₂O₄ battery-supercapacitor hybrid devices for self-driving optical-emitting diodes. Nano-Micro Lett., 2019, 11(1): 42.
[39]	SUN J W, WAN X Y, YANG T, et al. High-performance tungsten- niobium bimetallic oxide films with designable electrochromic properties. Sol. Energy Mater. Sol. Cells, 2023, 256: 112318.
[40]	CHO S M, KIM S, KIM T Y, et al. New switchable mirror device with a counter electrode based on reversible electrodeposition. Sol. Energy Mater. Sol. Cells, 2018, 179: 161.
[41]	TAO X, LIU D Q, LIU T W, et al. A bistable variable infrared emissivity device based on reversible silver electrodeposition. Adv. Funct. Mater., 2022, 32(32): 2202661.
[42]	PENG Y C, FAN L L, JIN W L, et al. Coloured low-emissivity films for building envelopes for year-round energy savings. Nat. Sustain., 2021, 5(4): 339.

基于WO₃·xH₂O与可逆金属电沉积的无色/黑色转换电致变色器件

Colorless/Black Switching Electrochromic Device Based on WO₃·xH₂O and Reversible Metal Electrodeposition

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 42

相关文章 15

编辑推荐

Metrics

本文评价

[1]	杨光, 张楠, 陈舒锦, 王义, 谢安, 严育杰. 基于多孔ITO电极的WO₃薄膜的制备及其电致变色性能[J]. 无机材料学报, 2025, 40(7): 781-789.
[2]	甄明硕, 刘晓然, 范向前, 张文平, 严东东, 刘磊, 李晨. 电致变色型智能可视化湿度系统[J]. 无机材料学报, 2024, 39(4): 432-440.
[3]	冯星哲, 马董云, 王金敏. 多孔NiMn-LDH纳米片薄膜的溶剂热生长及其电致变色性能[J]. 无机材料学报, 2024, 39(12): 1391-1396.
[4]	牛海滨, 黄佳慧, 李倩文, 马董云, 王金敏. 多孔NiMoO₄纳米片薄膜的直接水热生长及其电致变色性能[J]. 无机材料学报, 2023, 38(12): 1427-1433.
[5]	孙佳伟, 宛心怡, 杨婷, 马董云, 王金敏. Ti₂Nb₁₀O₂₉薄膜的制备及其电致变色性能[J]. 无机材料学报, 2023, 38(12): 1434-1440.
[6]	陈长, 赵若伊, 韩少杰, 王焕燃, 杨群, 高彦峰. 纳米晶液相镀膜制备WO₃电致变色薄膜研究和性能优化[J]. 无机材料学报, 2023, 38(11): 1355-1363.
[7]	张家强, 邹馨蕾, 王能泽, 贾春阳. 两步电沉积法制备Zn-Fe PBA薄膜及其在电致变色器件中的性能研究[J]. 无机材料学报, 2022, 37(9): 961-968.
[8]	张笑宇, 刘永盛, 李然, 李耀刚, 张青红, 侯成义, 李克睿, 王宏志. 基于Cu₃(HHTP)₂薄膜的离子液体电致变色电极[J]. 无机材料学报, 2022, 37(8): 883-890.
[9]	黄郅航, 滕官宏伟, 铁鹏, 范德松. 钙钛矿陶瓷薄膜的电致变色特性[J]. 无机材料学报, 2022, 37(6): 611-616.
[10]	王金敏, 后丽君, 马董云. 氧化钼电致变色材料与器件[J]. 无机材料学报, 2021, 36(5): 461-470.
[11]	张翔, 李文杰, 王乐滨, 陈曦, 赵九蓬, 李垚. 无机电致变色材料反射特性研究进展[J]. 无机材料学报, 2021, 36(5): 451-460.
[12]	武琦, 丛杉, 赵志刚. 多彩氧化钨薄膜的红外电致变色性能研究[J]. 无机材料学报, 2021, 36(5): 485-491.
[13]	王天悦, 王梦颖, 黄庆姣, 杨佳明, 王顺花, 刁训刚. 溶胶-凝胶旋涂法制备电致变色智能窗用钛酸锂薄膜[J]. 无机材料学报, 2021, 36(5): 471-478.
[14]	贾汉祥, 邵泽伟, 黄爱彬, 金平实, 曹逊. 光学设计用于全固态电致变色器件的高溅射效率三明治结构电解质[J]. 无机材料学报, 2021, 36(5): 479-484.
[15]	方华靖, 赵泽天, 武文婷, 汪宏. 柔性电致变色器件研究进展[J]. 无机材料学报, 2021, 36(2): 140-151.