CN107991819A - One kind improves Prussian blue electrochomeric films in LiClO4The method of cyclical stability in/PC electrolyte - Google Patents

One kind improves Prussian blue electrochomeric films in LiClO4The method of cyclical stability in/PC electrolyte Download PDF

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Publication number
CN107991819A
CN107991819A CN201711223044.0A CN201711223044A CN107991819A CN 107991819 A CN107991819 A CN 107991819A CN 201711223044 A CN201711223044 A CN 201711223044A CN 107991819 A CN107991819 A CN 107991819A
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China
Prior art keywords
electrolyte
liclo
prussian blue
electrochomeric films
acid
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CN201711223044.0A
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CN107991819B (en
Inventor
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

One kind improves Prussian blue electrochomeric films in LiClO4The method of cyclical stability in/PC electrolyte, belongs to functional material technical applications.In the LiClO of configuration4Weak acid (optional acetic acid, oleic acid, oxalic acid etc.) is instilled in/PC electrolyte, Prussian blue electrochomeric films are put into electrolyte and carry out electrochromism.Cyclical stability can be improved, improves the service life.

Description

One kind improves Prussian blue electrochomeric films in LiClO4Circulation in/PC electrolyte The method of stability
Technical field
Present invention relate to how to improve Prussian blue film in LiClO4The method of the cycle life of/PC electrolyte, belongs to Functional material technical applications.
Background technology
At present in the China of continuous Promoting Urbanization, the energy consumption of building accounts for 28% or so of social total energy consumption, window It is the main path of building energy consumption, about 30%~50% energy is lost in by window, while the energy and environmental problem also day Benefit highlights, and it is imperative to reduce energy consumption.Electrochromic material can be crossed certain outer as a kind of new function material Making alive effect is lower to occur reversible color change, is widely used to aircraft and hangs window, smart window, automobile rearview mirror, national defence troops The fields such as thing camouflage.Electrochromic material refers to reversibly change its optical property under the action of applied voltage or electric current Material.Electrochromic material requires good ion and electron conduction, higher contrast, becomes colour efficiency and circulation The electrochromic properties such as cycle.
It is Prussian blue that there is fast response time, color contrast height, uniformity of film in numerous electrochromic materials Well, the characteristics of cost of raw material is low is prepared, and can be changed between colourless, blue, three kinds of colors of light green color, therefore is got over Carry out more researcher's concerns.But when researcher is intended to be applied in electrochromic device, it has been found that it is Prussian blue LiClO4Cyclical stability in/PC electrolyte is poor, its cycle life only has 100 circles or so, it is clear that cannot meet in practice Application.It is Prussian blue in LiClO4Cyclical stability, durability difference become urgent problem to be solved in/PC electrolyte.Use The method referred to herein for adding acetic acid, it is Prussian blue in LiClO4Cycle life in/PC electrolyte can be improved from 100 circles Obvious decay is occurred without to 3000 circles and before and after circulating.And, it is believed that it can also reach if adding the weak acid of other species Similar effect.
The content of the invention
The present invention prepares homogeneous Pu Lu mainly by relatively low, the easy to operate electrochemical deposition technique of cost Scholar's indigo plant (PB) film.By in LiClO4In/PC electrolyte add acetic acid method, by the cycle life of Prussian blue film from 100 circles improve to 3000 circles and occur without obvious decay.It is considered that if the weak acid for adding other species can also reach similar Effect.
One kind improves Prussian blue electrochomeric films in LiClO4The method of cyclical stability in/PC electrolyte, its It is characterized in that, in the LiClO of configuration4Weak acid is instilled in/PC electrolyte；In LiClO4In/PC electrolyte, LiClO4With weak acid Molar ratio is 1: 1.7 × 1-610×10-6Or the volume ratio of PC and weak acid is 500: 1~5, by Prussian blue electrochomeric films It is put into electrolyte and carries out electrochromism.
Above-mentioned weak acid may be selected from the one or more in acetic acid, oleic acid, oxalic acid etc., preferably acetic acid, further preferred ice Acetic acid.
Using three-electrode system, using Princeton electrochemical workstation and ultraviolet-uisible spectrophotometer in two kinds of electrolysis Chrono-amperometric and transmission measurement are carried out in matter.PB films blueness is coloured state, and colourless is colour fading state.Method using the present invention So that Prussian blue electrochomeric films transmitance is stablized, do not increase with the time or elapse and change and decay, good cycling stability, Long lifespan.
Brief description of the drawings
Homogeneous PB film photos prepared by Fig. 1
Fig. 2 is PB films in LiClO4/ PC electrolyte (a) and in acetic acid+LiClO4Transmitance in/PC electrolyte (b) is bent Line.
Embodiment
With reference to the accompanying drawings and detailed description, the substantive distinguishing features and remarkable advantage that the present invention is furture elucidated, this Invention is limited only to by no means following embodiments, which is added to LiClO for the weak acid of other species4Have in/PC electrolyte There is identical directive function.
Embodiment 1
(1) PB precursor liquids needed for electro-deposition are prepared：By 0.05mM K3Fe(CN)6、0.05mM FeCl3, 0.1M KCl dissolve in In deionized water, magnetic agitation 5min, its pH=2.0, then magnetic agitation 5min are adjusted with concentrated hydrochloric acid.
(2) ITO electro-conductive glass needs successively by acetone, ethanol, deionized water ultrasonic cleaning before use, will after cleaning Glass is dried.Plated film is carried out using potentiostat, under constant current mode, electro-deposition, ITO conduction glass are carried out using three-electrode system Glass connects working electrode, using platinized platinum as, as reference electrode, being 10 μ A/cm in current density to electrode, Ag/KCl electrodes2 Under the conditions of electrodeposition time be 15min.Working electrode and to electrode runs parallel symmetric arrays.
(3) film for depositing completion is placed on 12h in air at room temperature with deionized water rinsing.
(4) electrolyte solution is configured：Prepare the LiClO of the 1mol/L of 50ml4/ PC electrolyte (LiClO4With the electricity of PC compositions Solve liquid, LiClO4Concentration be 1mol/L), dissolve completely after add 2 drop glacial acetic acid so that LiClO4Molar ratio with weak acid is 1 ∶1.7×10-6~3 × 10-6。
(5) while LiClO is prepared4/ PC electrolyte does contrast test.Can be by PC and the body of weak acid if adding other weak acid Product ratio is tested.
(6) film prepared is put into electrolyte solution, using step (3) three-electrode system, utilizes Princeton Electrochemical workstation and ultraviolet-uisible spectrophotometer carried out respectively in two kinds of electrolyte chrono-amperometric (be set to -0.05V and 0.5V) and transmission measurement, PB films are in LiClO4/ PC electrolyte (a) and in acetic acid+LiClO4It is saturating in/PC electrolyte (b) It is identical to cross rate test condition, is as a result specifically shown in Fig. 2.

Claims (5)

1. one kind improves Prussian blue electrochomeric films in LiClO4Cyclical stability in/propene carbonate (PC) electrolyte Method, it is characterised in that in the LiClO of configuration4Weak acid is instilled in/PC electrolyte, Prussian blue electrochomeric films are put Enter into electrolyte and carry out electrochromism.
2. a kind of Prussian blue electrochomeric films of raising described in accordance with the claim 1 are in LiClO4Circulation in/PC electrolyte The method of stability, it is characterised in that LiClO4Molar ratio with weak acid is 1: 1.7 × 10-6~10 × 10-6。
3. a kind of Prussian blue electrochomeric films of raising described in accordance with the claim 1 are in LiClO4Circulation in/PC electrolyte The method of stability, it is characterised in that the volume ratio of PC and weak acid is 500: 1~5.
4. a kind of Prussian blue electrochomeric films of raising described in accordance with the claim 1 are in LiClO4Circulation in/PC electrolyte The method of stability, it is characterised in that one or more of the weak acid in glacial acetic acid, oleic acid, oxalic acid.
5. a kind of Prussian blue electrochomeric films of raising described in accordance with the claim 1 are in LiClO4Circulation in/PC electrolyte The method of stability, it is characterised in that weak acid is glacial acetic acid.
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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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109537016A (en) * 2018-11-28 2019-03-29 浙江大学 A kind of regeneration method of Tungsten Trioxide Electrochromic Films
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
CN113777856A (en) * 2021-08-24 2021-12-10 同济大学 Method for regulating and controlling non-linear absorption performance of Prussian blue film and Prussian blue film
CN114907025A (en) * 2022-06-23 2022-08-16 广西大学 Preparation method of single-component multi-color display dual-waveband electrochromic film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61213828A (en) * 1985-03-19 1986-09-22 Hitachi Maxell Ltd Electrochromic display element
CN101293961A (en) * 2008-04-08 2008-10-29 浙江工业大学 Electrochromic polymeric compounds, preparing method and application thereof
CN101395244A (en) * 2006-03-06 2009-03-25 Skc株式会社 Preparation of prussian blue coating film for electrochromic device
CN104871349A (en) * 2012-12-12 2015-08-26 亚奎尼能源公司 Composite anode structure for aqueous electrolyte energy storage and device containing same
CN106681078A (en) * 2016-12-21 2017-05-17 北京工业大学 Large-area, uniform and fast-responding WO3 electrochromic device and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61213828A (en) * 1985-03-19 1986-09-22 Hitachi Maxell Ltd Electrochromic display element
CN101395244A (en) * 2006-03-06 2009-03-25 Skc株式会社 Preparation of prussian blue coating film for electrochromic device
CN101293961A (en) * 2008-04-08 2008-10-29 浙江工业大学 Electrochromic polymeric compounds, preparing method and application thereof
CN104871349A (en) * 2012-12-12 2015-08-26 亚奎尼能源公司 Composite anode structure for aqueous electrolyte energy storage and device containing same
CN106681078A (en) * 2016-12-21 2017-05-17 北京工业大学 Large-area, uniform and fast-responding WO3 electrochromic device and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109537016A (en) * 2018-11-28 2019-03-29 浙江大学 A kind of regeneration method of Tungsten Trioxide Electrochromic Films
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
CN113777856A (en) * 2021-08-24 2021-12-10 同济大学 Method for regulating and controlling non-linear absorption performance of Prussian blue film and Prussian blue film
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
CN114907025A (en) * 2022-06-23 2022-08-16 广西大学 Preparation method of single-component multi-color display dual-waveband electrochromic 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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