CN107991819B - Method for improving Prussian blue electrochromic film on LiClO4Method for cyclic stability in PC electrolytes - Google Patents

Method for improving Prussian blue electrochromic film on LiClO4Method for cyclic stability in PC electrolytes Download PDF

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CN107991819B
CN107991819B CN201711223044.0A CN201711223044A CN107991819B CN 107991819 B CN107991819 B CN 107991819B CN 201711223044 A CN201711223044 A CN 201711223044A CN 107991819 B CN107991819 B CN 107991819B
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liclo
prussian blue
electrolyte
improving
electrolytes
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CN107991819A (en
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严辉
李梓同
周开岭
汪浩
刘晶冰
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Beijing University of Technology
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Beijing University of Technology
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F2001/1517—Cyano complex compounds, e.g. Prussian blue

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

Method for improving Prussian blue electrochromic film on LiClO4A method for the circulation stability in PC electrolyte, which belongs to the functional material technologyThe field of application. In-situ LiClO4Weak acid (selected from acetic acid, oleic acid, oxalic acid and the like) is dropped into the PC electrolyte, and the Prussian blue electrochromic film is put into the electrolyte for electrochromic. Can improve the circulation stability and prolong the service life.

Description

Method for improving Prussian blue electrochromic film on LiClO4Method for cyclic stability in PC electrolytes
Technical Field
The invention relates to how to improve the effect of Prussian blue film on LiClO4A method for prolonging the cycle life of PC electrolyte belongs to the technical application field of functional materials.
Background
At present, in China which continuously promotes urbanization, the energy consumption of buildings accounts for about 28% of the total social energy consumption, windows are the main ways of the energy consumption of the buildings, about 30% -50% of the energy is lost through the windows, meanwhile, the energy and environmental problems are increasingly highlighted, and the reduction of the energy consumption is imperative. The electrochromic material can generate reversible color change under the action of certain external voltage as a novel functional material, and is widely applied to the fields of airplane suspension windows, intelligent windows, automobile rearview mirrors, national defense and military camouflage and the like. Electrochromic materials are materials that can reversibly change their optical properties under the action of an applied voltage or current. Electrochromic materials are required to have good ionic and electronic conductivity, high contrast, high color change efficiency, cycle period and other electrochromic properties.
Among a plurality of electrochromic materials, prussian blue has the characteristics of high response speed, high color contrast, good film uniformity and low cost of preparation raw materials, and can change among three colors of colorless, blue and light green, so that the prussian blue is paid more and more attention by researchers. However, when researchers want to apply it in electrochromic devices, Prussian blue was found in LiClO4The circulation stability in the/PC electrolyte is poor, the circulation life is only about 100 circles, and obviously the circulation stability can not meet the practical application. Prussian blue in LiClO4Poor cycling stability and durability in the/PC electrolyte become problems to be solved urgently. Prussian blue in LiClO using the method of adding acetic acid as mentioned herein4The cycle life in the/PC electrolyte can be increased from 100 to 3000 cycles without significant decay occurring before and after cycling. Moreover, we consider thatSimilar effects can be achieved if other types of weak acids are added.
Disclosure of Invention
The Prussian Blue (PB) film with uniform texture is prepared mainly by an electrochemical deposition technology with low cost and simple operation. By adding into LiClO4The method of adding acetic acid into PC electrolyte improves the cycle life of the Prussian blue film from 100 circles to 3000 circles without obvious attenuation. It is believed that similar effects can be achieved if other types of weak acids are added.
Method for improving Prussian blue electrochromic film on LiClO4Method for the cycling stability in a PC electrolyte, characterized in that LiClO is arranged4Dripping weak acid into PC electrolyte; in LiClO4In PC electrolyte, LiClO4The molar ratio of the weak acid to the weak acid is 1:1.7 × 1-610×10-6Or the volume ratio of the PC to the weak acid is 500: 1-5, and the Prussian blue electrochromic film is placed into the electrolyte for electrochromic.
The weak acid can be one or more selected from acetic acid, oleic acid, oxalic acid, etc., preferably acetic acid, and more preferably glacial acetic acid.
A three-electrode system is adopted, and a Princeton electrochemical workstation and an ultraviolet visible spectrophotometer are utilized to carry out timing current and transmittance tests in two electrolytes. The blue color of the PB film is in a coloring state, and the colorless state is a fading state. The method of the invention ensures that the Prussian blue electrochromic film has stable transmittance, does not change and attenuate with time increase or lapse, and has good cycle stability and long service life.
Drawings
FIG. 1 photo of a uniformly textured PB film
FIG. 2 shows a PB film on LiClO4(ii) a PC electrolyte (a) and a solution of acetic acid + LiClO4Transmittance curve in PC electrolyte (b).
Detailed Description
The essential features and the remarkable advantages of the present invention will be further clarified in the following description taken in conjunction with the accompanying drawings, which are not to be construed as limiting the invention to other embodiments in any wayWeak acids of the kind added to LiClO4The same guidance was found in the case of the/PC electrolyte.
Example 1
(1) Preparing PB precursor solution required by electrodeposition: 0.05mM K3Fe(CN)6、0.05mM FeCl3Dissolving 0.1M KCl in deionized water, magnetically stirring for 5min, adjusting pH to 2.0 with concentrated hydrochloric acid, and magnetically stirring for 5 min.
(2) Before the ITO conductive glass is used, the ITO conductive glass needs to be sequentially subjected to ultrasonic cleaning by acetone, ethanol and deionized water, and the glass is wiped dry after cleaning. Coating with a potentiostat, performing electrodeposition with a three-electrode system in constant current mode, connecting ITO conductive glass with working electrode, using platinum sheet as counter electrode, Ag/KCl electrode as reference electrode, and measuring current density at 10 μ A/cm2The electrodeposition time under the condition is 15 min. The working electrode and the counter electrode are arranged in parallel and symmetrically.
(3) The deposited film is washed by deionized water and then is placed in room temperature air for 12 hours.
(4) Preparing an electrolyte solution: 50ml of 1mol/L LiClO were prepared4[ PC ] electrolyte (LiClO)4And an electrolyte solution of PC, LiClO4Concentration of 1mol/L) and 2 drops of glacial acetic acid are added after complete dissolution, so that LiClO is obtained4The molar ratio of the weak acid to the weak acid is 1:1.7 × 10-6～3×10-6。
(5) Preparing LiClO at the same time4Comparative test was carried out with PC electrolyte. If additional weak acid is added, the test can be performed as a volume ratio of PC to weak acid.
(6) Putting the prepared film into an electrolyte solution, adopting a three-electrode system in the step (3), and respectively carrying out timing current (set to be-0.05V and 0.5V) and transmittance tests in two electrolytes by utilizing a Princeton electrochemical workstation and an ultraviolet visible spectrophotometer to obtain a PB film in LiClO4(ii) a PC electrolyte (a) and a solution of acetic acid + LiClO4The transmission test conditions in the/PC electrolyte (b) were identical, and the results are shown in particular in FIG. 2.

Claims (3)

1. Method for improving Prussian blue electrochromic film on LiClO4Propylene carbonateA method of cycling stability in an alkenyl ester (PC) electrolyte, characterized in that LiClO is disposed4And (2) dripping weak acid into Propylene Carbonate (PC) electrolyte, and putting the Prussian blue electrochromic film into the electrolyte for electrochromic, wherein the weak acid is selected from glacial acetic acid.
2. The method for improving the electrochromism of prussian blue on LiClO according to claim 14Method for cyclic stability in Propylene Carbonate (PC) electrolytes, characterized in that LiClO4The molar ratio of the weak acid to the weak acid is 1:1.7 × 10-6~10×10-6。
3. The method for improving the electrochromism of prussian blue on LiClO according to claim 14A method for cycling stability in Propylene Carbonate (PC) electrolytes, characterized in that the volume ratio of Propylene Carbonate (PC) to weak acid is 500: 1 to 5.
CN201711223044.0A 2017-11-23 2017-11-23 Method for improving Prussian blue electrochromic film on LiClO4Method for cyclic stability in PC electrolytes Active CN107991819B (en)

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CN109537016B (en) * 2018-11-28 2020-11-03 浙江大学 Regeneration method of tungsten trioxide electrochromic film
CN111381412A (en) * 2020-04-01 2020-07-07 宁波祢若电子科技有限公司 Complementary electrochromic device and preparation method thereof
CN113777856B (en) * 2021-08-24 2023-08-29 同济大学 Method for regulating nonlinear absorption performance of Prussian blue film and Prussian blue film
CN114907025B (en) * 2022-06-23 2024-02-20 广西大学 Preparation method of single-component multicolor display dual-band electrochromic film

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KR100740324B1 (en) * 2006-03-06 2007-07-18 에스케이씨 주식회사 Preparation of prussian blue coating film for electrochromic device
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US8945756B2 (en) * 2012-12-12 2015-02-03 Aquion Energy Inc. Composite anode structure for aqueous electrolyte energy storage and device containing same
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