多孔NiMn-LDH纳米片薄膜的溶剂热生长及其电致变色性能

doi:10.15541/jim20240137

摘要/Abstract

摘要：

具有动态变色和调光特性的电致变色材料在汽车防眩后视镜、智能窗、低功耗显示、电子纸等领域具有潜在的应用价值, 引起了人们的极大兴趣。NiO和MnO₂是为数不多的具有中性色调的阳极着色材料。然而, 单一的NiO和MnO₂薄膜褪色态透过率较低, 导致其光调制幅度较小。本研究以NiCl₂·6H₂O作为镍源、MnSO₄·H₂O作为锰源, 采用溶剂热法直接在氟掺杂氧化锡(FTO)导电玻璃基底上生长多孔镍锰层状双氢氧化物(NiMn-LDH)电致变色薄膜。通过X射线衍射仪(XRD)和场发射扫描电子显微镜(FESEM)表征所制备的NiMn-LDH薄膜的晶相和微观形貌, 并用紫外-可见-近红外分光光度计和电化学工作站研究其电致变色和电化学性能。结果表明: 溶剂热法生长的薄膜是由NiMn-LDH纳米片组成, 表面呈多孔结构, 在550 nm处具有61.9%的光调制幅度, 着色时间和褪色时间分别为15.8和13.2 s, 着色效率为 63.1 cm²·C^-1, 在160次着色和褪色循环后的光调制幅度仍可以保持初始值的87.0%。此外, NiMn-LDH薄膜在0.1 mA·cm^-2电流密度下的面电容为10.0 mF·cm^-2。本研究制备的NiMn-LDH薄膜电极在电致变色和储能领域具有良好的应用前景。

关键词: NiMn-LDH, 电致变色, 纳米片, 溶剂热

Abstract:

Electrochromic materials with dynamic color change and optical modulation have potential applications in the fields of automotive anti-glare mirror, smart window, low-power display, and electronic paper, attracting worldwide attention. NiO and MnO₂ are typical anodic coloration materials with a comfortable neutral tone. However, the low transmittance of single NiO or MnO₂ films in bleaching states leads to small optical modulation. Herein, a porous nickel-manganese layered double hydroxide (NiMn-LDH) film with neutral color for visible electrochromic application was prepared. The NiMn-LDH films were grown directly on fluorine-doped tin oxide (FTO) conductive glass substrates by a one-step solvothermal method using NiCl₂·6H₂O and MnSO₄·H₂O as the raw materials. The crystalline phase and micromorphology of the as-grown NiMn-LDH films were characterized and the electrochromic and electrochemical performances were also investigated. The results indicate that the film grown by solvothermal method is composed of NiMn-LDH nanosheets with porous surface morphology, leading to a large optical modulation of 61.9% at 550 nm. The coloration and bleaching time are calculated to be 15.8 and 13.2 s, respectively. A high coloration efficiency of 63.1 cm²·C^-1 is also achieved for the as-grown NiMn-LDH nanosheet film. Meanwhile, the NiMn-LDH film electrode demonstrates good cycle stability, retaining 87.0% of its maximum optical modulation after 160 cycles. Furthermore, the NiMn-LDH film electrode delivers an area capacitance of 10.0 mF·cm^-2 at a current density of 0.1 mA·cm^-2. These results consolidate that the as-prepared NiMn-LDH film electrode is a promising candidate for both electrochromic and energy-storage applications.

Key words: NiMn-LDH, electrochromic, nanosheet, solvothermal

中图分类号:

TQ174

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.

FENG Xingzhe, MA Dongyun, WANG Jinmin. Porous NiMn-LDH Nanosheets Film: Solvothermal Growth and Electrochromic Properties[J]. Journal of Inorganic Materials, 2024, 39(12): 1391-1396.

图/表 6

图1 NiMn-LDH薄膜XRD谱图

Fig. 1 XRD pattern of the NiMn-LDH film

图2 (a)高、(b)低分辨率下NiMn-LDH薄膜的FESEM照片

Fig. 2 FESEM images of as-grown NiMn-LDH film at (a) low- and (b) high-magnification

图3 NiMn-LDH薄膜的电化学性能

Fig. 3 Electrochemical properties of the NiMn-LDH film (a) CV curve scanned at 5 mV·s-1; (b) CV curves at different scanning rates; (c) GCD curves at different current densities; (d) Specific capacitance variations with respect to the current density

图4 NiMn-LDH薄膜的数码照片

Fig. 4 Digital photos of the NiMn-LDH film (a) Bleached state; (b) Colored state

图5 NiMn-LDH薄膜的电致变色性能

Fig. 5 Electrochromic properties of the NiMn-LDH film (a) Transmittance spectra in the colored and bleached states; (b) Time-current curve measured at -1.2 V for 25 s and 1.0 V for 25 s; (c) Real-time transmittance change; (d) Optical density variations with respect to the charge density at 550 nm

图6 NiMn-LDH薄膜在550 nm处的循环稳定性

Fig. 6 Cycle performance of the NiMn-LDH film recorded at a wavelength of 550 nm

参考文献 33

[1]	WANG J L, SHENG S Z, HE Z, et al. Self-powered flexible electrochromic smart window. Nano Letters, 2021, 21(23):9976.
[2]	MA D Y, EH A L S, CAO S, et al. Wide-spectrum modulated electrochromic smart windows based on MnO₂/PB films. ACS Applied Materials and Interfaces, 2022, 14(1):1443.
[3]	CAI G F, WANG J X, LEE P S. Next-generation multifunctional electrochromic devices. Accounts of Chemical Research, 2016, 49(8):1469. DOI PMID
[4]	ZHOU K L, WANG H, ZHANG Q Q, et al. Dynamic process of ions transport and cyclic stability of WO₃electrochromic film. Journal of Inorganic Materials, 2021, 36(2):152.
[5]	WANG J M, YU H Y, MA D Y, et al. Progress in the preparation and application of nanostructured manganese dioxide. Journal of Inorganic Materials, 2020, 35(12):1307. DOI
[6]	TUTEL Y, DURUKAN M B, HACIOGLU S O, et al. Cobalt-doped MoO₃ thin films and dual-band electrochromic devices with excellent cyclic stability. Applied Materials Today, 2023, 35: 101924.
[7]	GAO G, TAO X J, HE Y, et al. Electrochromic composites films composed of MoO₃ doped by tungsten atoms with remarkable response speed and color rendering efficiency via electrochemical deposition. Applied Surface Science, 2023, 640(15):158346.
[8]	HE Y C, LI T Z, ZHONG X L, et al. Lattice and electronic structure variations in critical lithium doped nickel oxide thin film for superior anode electrochromism. Electrochimica Acta, 2019, 316(1):143.
[9]	HU F, YAN B, SUN G, et al. Conductive polymer nanotubes for electrochromic applications. ACS Applied Nano Materials, 2019, 2(5):3154. DOI
[10]	FANG X J, WANG C W, TIAN Q Y, et al. Based on triphenylamine-imidazole skeleton electro-fluorochromic small organic molecules: synthesis and electrofluorochromic properties. Materials Letters, 2023, 333(15):133659.
[11]	QIU M J, ZHOU F W, SUN P, et al. Unveiling the electrochromic mechanism of Prussian blue by electronic transition analysis. Nano Energy, 2020, 78: 105148.
[12]	MA Q, CHEN J X, ZHANG H, et al. Dual-function self-powered electrochromic batteries with energy storage and display enabled by potential difference. ACS Energy Letters, 2022, 8(1):306.
[13]	RAO T K, ZHOU Y L, JIANG J, et al. Low dimensional transition metal oxide towards advanced electrochromic devices. Nano Energy, 2022, 100: 107479.
[14]	GUO J J, WANG M, DONG G B, et al. Mechanistic insights into the coloration, evolution, and degradation of NiO_x electrochromic anodes. Inorganic Chemistry, 2018, 57(15):8874.
[15]	KANDPAL S, BANSAL L, GHANGHASS A, et al. Bifunctional solid state electrochromic device using WO₃/WS₂ nanoflakes for charge storage and dual-band color modulation. Journal of Materials Chemistry C, 2023, 11(37):12590.
[16]	DONG D M, DJAOUED H, VIENNEAU G, et al. Electrochromic and colorimetric properties of anodic NiO thin films: uncovering electrochromic mechanism of NiO. Electrochimica Acta, 2020, 335(1):35648.
[17]	YANG H, YU J H, SEO H J, et al. Improved electrochromic properties of nanoporous NiO film by NiO flake with thickness controlled by aluminum. Applied Surface Science, 2018, 461(15):88.
[18]	TIAN M H, LIU X Q, DIAO X G, et al. High performance PANI/MnO₂ coral-like nanocomposite anode for flexible and robust electrochromic energy storage device. Solar Energy Materials and Solar Cells, 2023, 253: 112239.
[19]	WANG S M, JIN Y H, WANG T, et al. Polyoxometalate-MnO₂ film structure with bifunctional electrochromic and energy storage properties. Journal of Materiomics, 2023, 9(2):269.
[20]	HU J, TANG X M, DAI Q, et al. Layered double hydroxide membrane with high hydroxide conductivity and ion selectivity for energy storage device. Nature Communications, 2021, 12(1):3409. DOI PMID
[21]	KUMAR J, NEIBER R R, ABBAS Z, et al. Hierarchical NiMn- LDH hollow spheres as a promising pseudocapacitive electrode for supercapacitor application. Micromachines, 2023, 14(2):482.
[22]	GUO X L, LIU X Y, HAO X D, et al. Nickel-manganese layered double hydroxide nanosheets supported on nickel foam for high- performance supercapacitor electrode materials. Electrochimica Acta, 2016, 194(10):179.
[23]	TANG Y Q, SHEN H M, CHENG J Q, et al. Fabrication of oxygen-vacancy abundant NiMn-layered double hydroxides for ultrahigh capacity supercapacitors. Advanced Functional Materials, 2020, 30(11):1908223.
[24]	BAIG M M, GUL I H, AHMAD R, et al. One-step sonochemical synthesis of NiMn-LDH for supercapacitors and overall water splitting. Journal of Materials Science, 2021, 56(33):18636.
[25]	BAIG M M, MEHRAN M T, KHAN R, et al. Direct chemical synthesis of interlaced NiMn-LDH nanosheets on LSTN perovskite decorated Ni foam for high-performance supercapacitors. Surface and Coatings Technology, 2021, 421(15):127455.
[26]	ZHANG B, YANG Y, CAI J L, et al. Mg doping of NiMn-LDH with a three-dimensional porous morphology for an efficient supercapacitor. Dalton Transactions, 2023, 52(30):10557.
[27]	SUN J W, WAN X Y, YANG T, et al. Preparation and electrochromic properties of Ti₂Nb₁₀O₂₉films. Journal of Inorganic Materials, 2023, 38(12):1434.
[28]	MURUGAN E, GOVINDARAJU S, SANTHOSHKUMAR S. Hydrothermal synthesis, characterization and electrochemical behavior of NiMoO₄ nanoflower and NiMoO₄/rGO nanocomposite for high-performance supercapacitors. Electrochimica Acta, 2021, 392(1):138973.
[29]	NIU H B, HUANG J H, LI Q W, et al. Directly hydrothermal growth and electrochromic properties of porous NiMoO₄ nanosheet films. Journal of Inorganic Materials, 2023, 38(12):1427.
[30]	REN Y, ZHOU X G, ZHANG H, et al. Preparation of a porous NiO array-patterned film and its enhanced electrochromic performance. Journal of Materials Chemistry C, 2018, 6(18):4952.
[31]	ZHAO L L, CHEN Z M, PENG Y Q, et al. High-performance complementary electrochromic energy storage device based on tungsten trioxide and manganese dioxide films. Sustainable Materials and Technologies, 2022, 32: e00445.
[32]	ZHOU D, CHE B Y, LU X H. Rapid one-pot electrodeposition of polyaniline/manganese dioxide hybrids: a facile approach to stable high-performance anodic electrochromic materials. Journal of Materials Chemistry C, 2017, 5(7):1758.
[33]	CHAVAN H S, HOU B, JO Y, et al. Optimal rule-of-thumb design of nickel-vanadium oxides as an electrochromic electrode with ultrahigh capacity and ultrafast color tunability. ACS Applied Materials and Interfaces, 2021, 13(48):57403.