钨酸盐纳米材料的制备及其在电致变色领域的研究进展

doi:10.11949/0438-1157.20241283

摘要/Abstract

摘要：

电致变色是指在外加电场下，材料的光学性质（如透过率、反射率等）发生稳定可逆变化的技术，电致变色智能窗在建筑节能领域具有广阔的应用前景，助力我国碳达峰、碳中和目标的实现。钨酸盐纳米材料是一种极具潜力的无机电致变色材料，具有材料来源广泛、合成工艺简单、种类丰富、结构可调等诸多优点。采用钨酸盐纳米材料制备的电致变色器件，光谱调制范围广、响应时间短、着色效率高、循环稳定性良好，在智能窗和建筑节能中的应用潜力巨大。综述了钨酸盐纳米材料的结构特点和制备方法，详细阐述了其在电致变色领域的国内外研究进展，并展望了其未来研究与发展前景。

关键词: 电致变色, 纳米材料, 钨酸盐, 纳米技术, 制备

Abstract:

Electrochromism refers to the technology in which the optical properties of materials (such as transmittance, reflectance, etc.) undergo stable and reversible changes under an applied electric field. Electrochromic smart windows have broad application prospects in the field of building energy conservation, helping China achieve its carbon peak and carbon neutrality goals. Tungstate nanomaterials, as promising inorganic electrochromic materials, offer numerous advantages including abundant sources, simple synthesis processes, diverse types, and tunable structures. Electrochromic devices made from tungstate nanomaterials exhibit a wide spectral modulation range, short response time, high coloration efficiency, and excellent cycling stability, demonstrating immense potential for applications in smart windows and building energy conservation. This review summarizes the structural characteristics and preparation methods of tungstate nanomaterials, elaborates on the research progress in the field of electrochromism both domestically and internationally, and discusses future research and development prospects.

Key words: electrochromism, nanomaterials, tungstate, nanotechnology, preparation

中图分类号:

TB 34

彭健, 沈鲁恺, 王立坤, 忻利宏, 刘涌, 赵高凌, 马赛男, 韩高荣. 钨酸盐纳米材料的制备及其在电致变色领域的研究进展[J]. 化工学报, 2025, 76(6): 2451-2468.

Jian PENG, Lukai SHEN, Likun WANG, Lihong XIN, Yong LIU, Gaoling ZHAO, Sainan MA, Gaorong HAN. Preparation of tungstate nanomaterials and research progress in electrochromic field[J]. CIESC Journal, 2025, 76(6): 2451-2468.

图/表 14

图1 已报道的过渡金属氧化物电致变色材料分布

Fig.1 Reported distribution of transition metal oxide electrochromic materials

图2 WO3随温度变化的晶型、晶面取向、空间群的变化[16]

Fig.2 Changes in crystal form, crystal plane orientation, and space group of WO3 with temperature variation[16]

图3 不同制备方法制备的各类WO3的纳米形貌

Fig.3 Nano morphologies of various WO3 prepared by different preparation methods

表1 不同纳米结构WO3薄膜的电致变色性能

Table 1 Electrochromic properties of WO3 thin films with different nanostructures

纳米结构	制备方法	光调制幅度（波长/nm）	响应时间 T_c、T_b/s	着色效率/ (cm²·C^-1)	循环次数/次	电解液及浓度/ (mol·L^-1)	对电极	文献
纳米片	液相剥离	62.57%（700）	10.74/6.97 @700 nm	—	1000（6%调制衰减）	LiClO₄-PC(1)	Pt	[13]
纳米棒	气相沉积	61%（680）	2.05/0.74 @680 nm	174 @680 nm	1000（5%调制衰减）	LiClO₄-PC(1)	NiO	[15]
纳米棒	气相沉积	89%（1000）	0.85/1.0 @1000 nm	386 @1000 nm	1000（5%调制衰减）	LiClO₄-PC(1)	NiO	[15]
纳米线	水热法	66%（650）	1.2/2 @650 nm	115.2 @650 nm	10000（1.6%调制衰减）	KOH水溶液(3)	Pt	[17]
纳米花	溶剂热法	41.43%（700）	6.67/1.54 @700 nm	—	4000（2.25%调制衰减）	LiClO₄-PC(1)	碳棒	[26]
纳米孔网络	阳极氧化	75%（750）	2.5/16.6 @750 nm	141.5 @750 nm	2000	H₂SO₄水溶液(0.1)	Pt	[27]
纳米颗粒	电沉积法	88.51%（555）	5.1/3.7 @632.8 nm	137 @555 nm	—	LiClO₄-PC(0.5)	ITO	[28]

图4 (a)各类无机材料论文在电致变色领域的占比；(b)2014—2024年钨基化合物在电致变色领域发表论文的数量趋势

Fig.4 (a) The proportion of various inorganic material papers in the field of electrochromism; (b) The trend of the number of published papers on tungsten based compounds in the field of electrochromism from 2014 to 2024

图5 钨酸盐纳米材料的常见制备方法

Fig.5 Common preparation methods of tungstate nanomaterials

表2 常见钨酸盐纳米材料制备方法优缺点对比

Table 2 Comparison of advantages and disadvantages of common preparation methods for tungstate nanomaterials

制备方法	制备难度	优点	缺点
高温固相法^[42-44]	较低	适用于大规模生产，操作简单；产物结晶度高，稳定性好	需要高温条件，能耗大；颗粒易团聚，形貌可控性差
沉淀法^[47,50-52]	较低	工艺简单，设备要求低；适合大规模制备，成本低	颗粒尺寸不均匀，形貌难以控制；处理工艺复杂，产品纯度低
水热法^[53-55,74]	中等	简单易行，成本较低；反应条件温和（低温高压）	颗粒尺寸较大，难以精确控制；产率受限，安全性要求高
溶剂热法^[61,75]	中等	颗粒尺寸较小，形貌可控；溶剂种类多样，反应环境易调控	反应条件复杂（高温高压）；有机溶剂昂贵且对环境可能有污染
溶胶-凝胶法^[66-67,76]	较低	可在低温进行，适合大规模生产；多组分掺杂，均匀性较好	工艺较复杂，难以控制凝胶的均匀性；产物颗粒易团聚
电化学沉积法^[68-69,72]	较高	颗粒形貌可控；可实现薄膜制备	设备复杂，对电极材料要求高；需严格控制电化学参数，技术难度高
喷雾热解法^[70-71,73]	较高	参数可控，生产效率高；产物纯度高，粒径分布均匀	前体溶液分散性、稳定性要求高；设备成本高，能耗较高

图6 (a)Li掺杂NWO薄膜和WO3薄膜在300~1500 nm的透过率曲线；(b)器件在不同偏压下的300~1000 nm的透过率曲线；(c)静置不同时间后器件在300~1500 nm的透过率曲线；(d)器件电荷密度随循环次数的时间变化曲线；(e)器件CV曲线随循环次数的变化曲线；(f)器件透过率随循环次数在300~1000 nm的变化曲线[81]

Fig.6 (a) Transmittance curves of Li doped NWO and WO3 films at 300—1500 nm; (b) Transmittance curves of the device at 300—1000 nm under different biases; (c) Transmittance curves of the device at 300—1500 nm after being left to stand for different periods of time; (d) Time variation curve of device charge density with the number of cycles; (e) The variation curve of the device CV curve with the number of cycles; (f) The variation curve of device transmittance with the number of cycles at 300—1000 nm[81]

图7 (a)六方钠钨青铜的晶体结构；(b)钠钨青铜的透射电镜照片；(c)钠钨青铜在褪色和着色状态下的透射光谱（附图为数码照片）；(d)钠钨青铜在褪色和着色状态下的XRD谱图；(e)钠钨青铜在褪色和着色状态下的傅里叶红外光谱图[19]

Fig.7 (a) Crystal structure of hexagonal sodium tungsten bronze; (b) Transmission electron microscopy image of sodium tungsten bronze; (c) Transmission spectra of sodium tungsten bronze in bleached and colored states (digital photo attached); (d) XRD patterns of sodium tungsten bronze in bleached and colored states; (e) Fourier transform infrared spectra of sodium tungsten bronze in bleached and colored states[19]

图8 (a)H2W2O7、WO3·H2O、WO3结构示意图；(b)扫描速度分别为50、100、200、500、1000 mV·s-1下的CV曲线；(c)H2W2O7的扫描电镜照片；(d)H2W2O7的原位拉曼光谱曲线；(e)H2W2O7在原位拉曼光谱过程中收集的数码照片[89]

Fig.8 (a) Schematic diagram of H2W2O7, WO3·H2O, and WO3 structures; (b) CV curves at scanning speeds of 50, 100, 200, 500, and 1000 mV·s-1; (c) Scanning electron microscopy image of H2W2O7; (d) In situ Raman spectroscopy curve of H2W2O7; (e) Digital photos collected during in situ Raman spectroscopy of H2W2O7[89]

图9 (a)Cs3W11O35的晶体结构；(b)不同层数Cs3W11O35的透过率和反射率曲线；(c)Cs3W11O35的透射电镜照片；(d)热屏蔽测试的可见光和红外图像[94]

Fig.9 (a) Crystal structure of Cs3W11O35; (b) Transmittance and reflectance curves of Cs3W11O35 with different layers; (c) Transmission electron microscopy image of Cs3W11O35; (d) Visible and infrared images for thermal shielding test[94]

图10 (a) WO3结构示意图；(b) Nb18W16O93结构示意图；(c) Nb2O5结构示意图；(d) 扫描速度20 mV·s-1下的CV曲线；(e) 633 nm处的原位透过率-电压曲线；(f) 300~1600 nm的透过率曲线（插图为相应照片）；(g) 633 nm处施加方波电势的原位透过率曲线；(h) 不同电压下的透过率曲线；(i) 633 nm处的着色效率[39]

Fig.10 (a) Schematic diagram of WO3 structure; (b) Schematic diagram of Nb18W16O93 structure; (c) Schematic diagram of Nb2O5 structure; (d) CV curve at a scanning speed of 20 mV·s-1; (e) In situ transmittance voltage curve at 633 nm; (f) Transmittance curve of 300—1600 nm (corresponding photo in the illustration); (g) In situ transmittance curve with a square wave potential applied at 633 nm; (h) Transmittance curves at different voltages; (i) Coloring efficiency at 633 nm[39]

图11 (a) Ce4W9O33电极在不同施加电位下的透过率曲线；(b) Ce4W9O33电极的电致变色照片；(c) Ce4W9O33电极在不同施加电位下的太阳光辐照光谱；(d) 633 nm时施加方波电势的原位透过率曲线；(e) 1200 nm时施加方波电势的原位透过率曲线；(f)Ce4W9O33电极的循环性能[40]

Fig.11 (a) Transmittance curves of Ce4W9O33 electrode under different applied potentials; (b) Electrochromic photo of Ce4W9O33 electrode; (c) Solar irradiation spectra of Ce4W9O33 electrode under different applied potentials; (d) In situ transmittance curve with a square wave potential applied at 633 nm; (e) In situ transmittance curve with a square wave potential applied at 1200 nm; (f) The cycling performance of Ce4W9O33 electrode[40]

表3 常见钨基纳米薄膜的电致变色性能

Table 3 The electrochromic properties of common tungstate nanofilms

纳米材料	制备方法	光调制幅度(波长/nm)	响应时间 T_c、T_b/s	着色效率/(cm²·C^-1)	循环次数/次	电解液及浓度/ (mol·L^-1)	对电极	文献
WO₃·0.1H₂O	光沉积法	55.1%（633）	11.4/23.9 @633 nm	47.7 @633 nm	—	ZnSO₄ 水溶液(1)	Zn	[99]
WO₃·0.5H₂O	光沉积法	69.0%（633）	7.0/3.4 @633 nm	61.9 @633 nm	13000（3%调制衰减）	ZnSO₄ 水溶液(1)	Zn	[99]
WO₃·H₂O	溶胶-凝胶法	82%（900）	12.0/6.0 @900 nm	97.8 @650 nm	1000（13%调制衰减）	LiClO₄/SPE	FTO	[17]
WO₃·H₂O	电沉积法	59%（1200）	<15	96.2 @1200 nm	—	LiClO₄-PC(1)	Li	[100]
WO₃·H₂O	电沉积法	59%（1200）	<15	96.2 @1200 nm	—	TBAClO₄-PC(0.1)	Pt	[100]
Ni-W@Li	磁控溅射法	75%（550）	—	115.2 @650 nm	1000	LiClO₄-PC(0.5)	WO₃	[81]
Bi₂Na_0.5La_0.5TiWO₉	高温固相法	30.3%（555）	—	37.1 @555 nm	—	H₂SO₄水溶液(0.2)	Pt	[88]
Nb₁₈W₁₆O₉₃	溶胶-凝胶法	53.1%（633）	4.7/4.0 @633 nm	46.57 @633 nm	8000（21.9%调制衰减）	LiClO₄-PC(0.5)	FTO	[97]
Nb₁₈W₁₆O₉₃	水热法	49.4%（633）	12.0/2.6 @633 nm	33.7 @633 nm	600（35%调制衰减）	LiClO₄-PC(0.5)	Pt	[38]
Nb₁₈W₁₆O₉₃	水热法	90.5%（1600）	6.5/6.1 @1600 nm	66.1 @1600 nm	600（35%调制衰减）	LiClO₄-PC(0.5)	Pt	[38]
Nb₁₈W₁₆O₉₃	溶胶-水热法	93%（633）	10.1/12.7 @633 nm	105.6 @633 nm	1000（16.5%调制衰减）	LiClO₄/PMMA(0.3)	NiO	[39]
Nb₁₈W₁₆O₉₃	溶胶-水热法	89%（1200）	7.4/5.4 @1200 nm	105.6 @633 nm	6000（33.6%调制衰减）	LiClO₄/PMMA(0.3)	NiO	[39]
Ce₄W₉O₃₃	水热法	74.7%（633）	10.5/4.5 @633 nm	98.3 @1200nm	500（11.1%调制衰减）	ZnSO₄ 水溶液(0.5)	NiO	[40]
Ce₄W₉O₃₃	水热法	85.8%（1200）	6.5/4.1 @1200 nm	98.3 @1200nm	500（11.1%调制衰减）	ZnSO₄ 水溶液(0.5)	NiO	[40]

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