High-conductivity Hydrophobic Fumed-SiO2 Composite Gel Electrolyte for High Performance Electrochromic Devices

doi:10.15541/jim20200376

Abstract

Abstract:

Gel electrolytes are chemically stable, nonflammable and easy to encapsulate, however, their moderate ionic conductivity (10^-4-10^-5S?cm^-1) hinders their further development for the usage in electrochromic devices (ECDs). Here, we developed a highly conductive hydrophobic SiO₂/PMMA/PC/LiClO₄ gel polymer electrolyte (H-SiO₂ GPE). Electrochemical behaviors of ECDs were characterized by electrochemical impedance spectroscope (EIS), cyclic voltammetry (CV) and chronoamperometry (CA). Systematic analyses show that the ionic conductivity of the H-SiO₂ GPE can reach 5.14 mS?cm^-1 (at 25 ℃) by introducing only 0.5wt% hydrophobic fumed SiO₂. This increase is due to the good compatibility and hydrophobic-hydrophobic attractions between SiO₂ additive and organic electrolyte, which promotes the dissociation of lithium perchlorate. Additionally, the viscosity as a function of shear rate for GPE with various fumed silica contents shows the behavior of shear thinning, which indicates the formation of a three-dimensional network structure. This structure provides ion transport channels, leading to a clearly improved switching speed for ECDs assembled with hydrophobic SiO₂ GPEs (t_bleaching=4 vs 8 s and t_coloring=14 vs 16 s). Similarly, the investigation of hydrophobic fumed SiO₂ in liquid electrolyte is demonstrated that the ionic conductivity of LiClO₄/PC liquid electrolyte without and with hydrophobic fumed SiO₂ increases from 6.94 to 7.58 mS?cm^-1, respectively. Therefore, hydrophobic fumed SiO₂ as a filler has a positive effect on electrolytes, and the proposal of the H-SiO₂ GPE provides a new idea for offsetting the trade-off between a high ionic conductivity and easy leakage when applied in ECDs.

Key words: gel electrolyte, electrochromic, hydrophobic, SiO₂

CLC Number:

TQ174

ZHAO Qi, QIAO Ke, YAO Yongji, CHEN Zhang, CHEN Dongchu, GAO Yanfeng. High-conductivity Hydrophobic Fumed-SiO₂ Composite Gel Electrolyte for High Performance Electrochromic Devices[J]. Journal of Inorganic Materials, 2021, 36(2): 161-167.

Figures/Tables 9

Fig. S1 Static water contact angle (CA) of hydrophobic fumed SiO2

Fig. S2 Particle size of hydrophobic fumed silica (a) and hydrophilic fumed silica (b) in PC

Fig. 1 FT-IR spectrum of hydrophobic fumed SiO2

Electrolyte	Ionic conductivity/(mS·cm^-1)
PMMA/LiClO₄/hydrophobic SiO₂(This work)	5.14
PMMA/LiClO₄/hydrophilic SiO₂^[1]	3.8
P(BMA-St)/hydrophilic SiO₂^[2]	2.15
PEO/LiCF₃SO₃/TiO₂^[3]	0.16
PVDF/LiClO₄/palygorskite^[4]	0.12
PMMA/LiClO₄/[Emim]BF₄^[5]	2.9
PVB/LiClO₄^[6]	0.04
PVDF-HFP/LiCF₃SO₃/ZrO₂^[7]	1.78
PAN/LiClO₄/Li_0.33La_0.557TiO₃^[8]	0.0605

Fig. S3 SEM images of pure GPEs (a) and 0.5wt% H-SiO2 GPEs (b)

Fig. S4 XRD patterns of the as-prepared WO3(a), SEM image of WO3 films coated on ITO substrates(b), TEM images of WO3 dispersion (c) and typical nanorod (d) with high magnification

Fig. 3 Schematic diagram of the transportation of Li+ ion through H-SiO2GPEs with three-dimensional structure

Fig. 4 Ionic conductivity of liquid electrolyte with 0, 0.2wt%, 0.5wt%, 0.8wt%, and 1.0wt% fumed SiO2 (a), and colored state Nyquist plots (b) and CV curves (c) of WO3 films in liquid electrolyte with 0, 0.2wt%, 0.5wt%, 0.8wt% and 1.0wt% fumed SiO2. Scan rate: 100 mV/s

References 27

[1]	PATEL K J, BHATT G G, RAY J R, et al. All-inorganic solid-state electrochromic devices: a review. Journal of Solid State Electrochemistry, 2016,21(2):1-11.
[2]	AGNIHOTRYA SA, SEKHON P SS. PMMA based gel electrolyte for EC smart windows. Electrochimica Acta, 1998,44:3121-3126.
[3]	LI H, WANG J, SHI Q, et al. Constructing three-dimensional quasi- vertical nanosheet architectures from self-assemble two-dimensional WO₃·2H₂O for efficient electrochromic devices. Applied Surface Science, 2016,380:281-287.
[4]	GROCE F, APPETECCHI G B, PERSI L, et al. Nanocomposite polymer electrolytes for lithium batteries. Nature, 1998,394:456.
[5]	AZIZ S B, WOO T J, KADIR M F Z,, et al. A conceptual review on polymer electrolytes and ion transport models. Journal of Science: Advanced Materials and Devices, 2018,3:1-17.
[6]	TAO C, GAO M, YIN B, et al. A promising TPU/PEO blend polymer electrolyte for all-solid-state lithium ion batteries. Electrochimica Acta, 2017,257:31-39.
[7]	JUNG H R, JU D H, LEE W J, et al. Electrospun hydrophilic fumed silica/polyacrylonitrile nanofiber-based composite electrolyte membranes. Electrochimica Acta, 2009,54:3630-3637.
[8]	KUPPU S V, JEYARAMAN A R, GURUVIAH P K, et al. Preparation and characterizations of PMMA-PVDF based polymer composite electrolyte materials for dye sensitized solar cell. Current Applied Physics, 2018,18:619-625.
[9]	ZHAI W, ZHU H, WANG L, et al. Study of PVDF-HFP/PMMA blended micro-porous gel polymer electrolyte incorporating ionic liquid [BMIM] BF₄ for lithium ion batteries. Electrochimica Acta, 2014,133:623-630.
[10]	VIGNAROOBAN K, DISSANAYAKE M A K L, ALBINSSON I, et al. Effect of TiO₂ nano-filler and EC plasticizer on electrical and thermal properties of poly(ethylene oxide)(PEO) based solid polymer electrolytes. Solid State Ionics, 2014,266:25-28.
[11]	VIJAYAKUMAR G, KARTHICK S N, SATHIYA PRIYA A R, et al. Effect of nanoscale CeO₂ on PVDF-HFP-based nanocomposite porous polymer electrolytes for Li-ion batteries. Journal of Solid State Electrochemistry, 2007,12:1135-1141.
[12]	CROCE F, SCROSATI B, MARIOTTO G. Electrochemical and spectroscopic study of the transport properties of composite polymer electrolytes. Chem. Mater., 1992,4:1134-1136.
[13]	YAO P, ZHU B, ZHAI H, et al. PVDF/palygorskite nanowire composite electrolyte for 4 V rechargeable lithium batteries with high energy density. Nano Letters, 2018,18:6113-6120.
[14]	AHMAD S, AHMAD S, AGNIHOTRY S A. Nanocomposite electrolytes with fumed silica in poly(methyl methacrylate): thermal, rheological and conductivity studies. Journal of Power Sources, 2005,140:151-156.
[15]	JITJAICHAM M, KUSUKTHAM B. Spinning of poly(ethylene terephthalate) fiber composites incorporated with fumed silica. Silicon, 2017,10:575-583.
[16]	WANG J, KHOO E, LEE PS, et al. Synthesis, assembly, and electrochromic properties of uniform crystalline WO₃ nanorods. J. Phys. Chem. C, 2008,112:14306-14312.
[17]	ZHAO Q, FANG Y, QIAO K, et al. Printing of WO₃/ITO nanocomposite electrochromic smart windows. Solar Energy Materials and Solar Cells, 2019,194:95-102.
[18]	EL-FATTAH M A, El SAEED A. M,et al. Chemical interaction of different sized fumed silica with epoxy via ultrasonication for improved coating. Progress in Organic Coatings, 2019,129:1-9.
[19]	PUGUAN J M C, CHUNG W J, KIM H, et al. Ion-conductive and transparent PVdF-HFP/silane-functionalized ZrO₂ nanocomposite electrolyte for electrochromic applications. Electrochimica Acta, 2016,196:236-244.
[20]	SAIKIA D, WU C G, FANG J, et al. Organic-inorganic hybrid polymer electrolytes based on polyether diamine, alkoxysilane, and trichlorotriazine: synthesis, characterization, and electrochemical applications. Journal of Power Sources, 2014,269(10):651-660.
[21]	TANG Q, LI H, YUE Y, et al. 1-Ethyl-3-methylimidazolium tetrafluoroborate-doped high ionic conductivity gel electrolytes with reduced anodic reaction potentials for electrochromic devices. Materials & Design, 2017,118:279-285.
[22]	LEONES R, SABADINI R C, SENTANIN F C, et al. Polymer electrolytes for electrochromic devices through solvent casting and Sol-Gel routes. Solar Energy Materials & Solar Cells, 2017,169:98-106.
[23]	ZHANG F, DONG G, LIU J, et al. Polyvinyl butyral-based gel polymer electrolyte films for solid-state laminated electrochromic devices. Ionics, 2017,23:1879-1888.
[24]	RAGHAVAN S R, RILEY M W, FEDKIW P S, et al. Composite polymer electrolytes based on poly(ethylene glycol) and hydrophobic fumed silica: dynamic rheology and microstructure. Chemistry of Materials, 1998,10(1):244-251.
[25]	ŠURCA VUK A, JOVANOVSKI V, POLLET-VILLARD A, et al. Imidazolium-based ionic liquid derivatives for application in electrochromic devices. Solar Energy Materials and Solar Cells, 2008,92(2):126-135.
[26]	BAE J, KIM H, MOON H C, et al. Low-voltage, simple WO₃-based electrochromic devices by directly incorporating an anodic species into the electrolyte. Journal of Materials Chemistry C, 2016,46(4):10887-10892.
[27]	CUI J, ZHOU Z, JIA M, et al. Solid polymer electrolytes with flexible framework of SiO₂ nanofibers for highly safe solid lithium batteries. Polymers, 2020,12:1324.

High-conductivity Hydrophobic Fumed-SiO₂ Composite Gel Electrolyte for High Performance Electrochromic Devices

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