CN114675458A - High-performance hydrogen bond organic framework material electrochromic device - Google Patents

High-performance hydrogen bond organic framework material electrochromic device Download PDF

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CN114675458A
CN114675458A CN202210299874.6A CN202210299874A CN114675458A CN 114675458 A CN114675458 A CN 114675458A CN 202210299874 A CN202210299874 A CN 202210299874A CN 114675458 A CN114675458 A CN 114675458A
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organic framework
framework material
film
tio
hydrogen bond
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王诗铭
金远航
刘琳
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Liaoning University
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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
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Abstract

The invention discloses an electrochromic device of a high-performance hydrogen bond organic framework material. Comprises a working electrode, an electrolyte and a counter electrode; the working electrode is characterized in that a conductive substrate is coated with an electrochromic layer, and the electrochromic layer is a hydrogen bond organic framework material film; the electrolyte is ionic liquid; the counter electrode is a composite film prepared by compounding polyoxometallate and transition metal oxide, and a charge balance layer is coated on a conductive substrate. The invention improves the electrochromic performance of the device by changing the mode of the counter electrode, the device has excellent performances on light modulation, response time and coloring efficiency, and can be colored and faded under the same polarity voltage range, thereby achieving the purpose of energy conservation.

Description

High-performance hydrogen bond organic framework material electrochromic device
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a high-performance hydrogen bond organic framework material electrochromic device
Background
With the continuous consumption of energy, the development of new energy-saving devices is the focus of current research. The electrochromic material is used as a photoelectric material, and the color and the transmittance of the material can be changed when voltage changes, so that the material is an energy-saving material with better performance. The traditional electrochromic material has the defects of poor optical performance, slow color transition, poor radiation resistance, weak adhesion to a glass substrate and the like. As a new electrochromic material, the hydrogen bond organic framework material has the characteristics of high porosity, adjustable structure, easy modification and the like, so that how to obtain a high-performance hydrogen bond organic framework material electrochromic device is always a hot point of research.
Disclosure of Invention
In order to solve the problem of preparing a high-performance hydrogen bond organic framework material electrochromic device, the invention improves the electrochromic performance of the device by improving the counter electrode.
The technical scheme adopted by the invention is as follows: a high-performance hydrogen bond organic framework material electrochromic device comprises a working electrode, electrolyte and a counter electrode; the working electrode is characterized in that a conductive substrate is coated with an electrochromic layer, and the electrochromic layer is a hydrogen bond organic framework material film; the electrolyte is ionic liquid; the counter electrode is a composite film prepared by compounding polyoxometallate and transition metal oxide, and a charge balance layer is coated on a conductive substrate.
Preferably, in the electrochromic device with the high-performance hydrogen bond organic framework material, the hydrogen bond organic framework material is selected from PFC materials.
Preferably, in the electrochromic device with the high-performance hydrogen bond organic framework material, the ligand of the PFC material is H4TBAPy、H4TBAPy-CH3、H4TBAPy-Cl or H4TBAPy-NO2。
Preferably, the above electrochromic device is an electrochromic device made of high-performance hydrogen bond organic framework materials, and the ionic liquid is [ BMIM ] TF 2N.
Preferably, in the electrochromic device with the high-performance hydrogen bond organic framework material, the composite film is a transition metal oxide TiO prepared by a spin coating method2Depositing a layer of polyoxometallate PW on the film by an electrodeposition method12Film-produced TiO2-PW12Compounding film; the TiO is2The thickness of the film is 350 to 500 nm.
Preferably, in the electrochromic device with the high-performance hydrogen bond organic framework material, the conductive substrate is FTO glass.
A preparation method of a high-performance hydrogen bond organic framework material electrochromic device comprises the following steps:
1) preparation of a working electrode: ultrasonically dispersing PFC powder in dichloromethane to serve as a deposition solution, taking two pieces of FTO glass, immersing the two pieces of FTO glass into the deposition solution at an interval of 1cm, respectively connecting two electrodes of an electrophoretic deposition instrument with the two pieces of FTO glass, and depositing for 6 minutes to obtain a hydrogen bond organic framework material PFC membrane at the positive electrode;
2) preparing a counter electrode: adding TiO with ethanol2Diluting the solution into a titanium dioxide nano particle solution with the mass fraction of 20-40%, spin-coating the solution on FTO glass, and annealing the FTO glass at 500 ℃ for 30min to obtain TiO2A film; subjecting PW to12Dissolving in deionized water as electrodeposition liquid, TiO2The film is used as a working electrode, the platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, and the electrodeposition is carried out by utilizing cyclic voltammetry to obtain TiO2-PW12Compounding film;
3) and (3) assembling the working electrode, [ BMIM ] TF2N as electrolyte and a counter electrode into an electrochromic device.
Preferably, the above preparation method, the preparation method of PFC powder comprises the steps of: sequentially adding a phenylboronic acid compound, 1,3,6, 8-tetrabromopyrene, tetrakis (triphenylphosphine) palladium and cesium fluoride into 1, 4-dioxane, reacting at 85 ℃ for 3 days, adding an ice water mixture to precipitate a solid, performing suction filtration, and drying to obtain a solid; adding the obtained solid and KOH into a mixed solution of THF, 1, 4-dioxane and deionized water, and reacting at 85 ℃ for 24h to obtain a ligand; dispersing the obtained ligand in DMF, adding methanol, stirring for 1 minute, standing at room temperature to obtain PFC crystals, and grinding.
Preferably, in the above preparation method, the phenylboronic acid compound is 4- (methoxycarbonyl) phenylboronic acid, (4- (methoxycarbonyl) -2-methylphenyl) boronic acid, 2-chloro-4- (methoxycarbonyl) phenylboronic acid or 4-methoxycarbonyl-2-nitrophenylboronic acid.
Preferably, in the above preparation method, step 2), the electrodeposition conditions using cyclic voltammetry are as follows: the deposition voltage is-1.5-0.2V, and the sweep rate is 100mV s-1The number of deposition cycles was 5.
The invention has the beneficial effects that:
1. according to the invention, the electrochromic material of the high-performance electrochromic device is a hydrogen bond organic framework material, and charged particles can be formed in the protonation and deprotonation processes, so that the electrochromic material can be deposited on FTO glass in an electrophoretic deposition mode.
2. The invention, using TiO2-PW12The composite film is used as a charge balance layer, so that the light modulation of a device is enlarged, the response time is shortened, the coloring efficiency is improved, the voltage range is narrowed, and the purpose of saving energy is achieved.
3. The invention has the advantages of simple preparation process of the working electrode and the counter electrode, easy operation and low cost.
4. According to the invention, the electrochromic performance of the device is improved by changing the mode of the counter electrode. The device has excellent performances on light modulation, response time and coloring efficiency, and can be colored and faded under the same polarity voltage range, thereby achieving the purpose of energy conservation.
Drawings
FIG. 1 shows TiO of different thicknesses prepared in examples 1 to 42Cross-sectional scanning electron micrographs of the film.
FIG. 2 is an assembly diagram of an electrochromic device made of high-performance hydrogen bonding organic framework material.
FIG. 3 shows the transmittance change of the ECD-1p prepared in example 1 at an ultraviolet/visible wavelength of 600nm and an applied voltage of 0 to 2.5V.
FIG. 4 is the ECD-2p-CH prepared in example 23The transmittance change condition when the ultraviolet visible wavelength is 600nm and the applied voltage is 0-2.5V.
FIG. 5 shows the transmittance of the ECD-3p-Cl prepared in example 3 at a UV/visible wavelength of 600nm and a voltage of 0-2.5V.
FIG. 6 is the ECD-4p-NO prepared in example 42The transmittance change condition when the ultraviolet visible wavelength is 600nm and the applied voltage is 0-2.5V.
Detailed Description
To highlight the technical advantages and excellent performance of the present invention, the following description will be made with reference to the accompanying drawings and specific examples. The following specific examples are provided only for the present invention, and the specific implementation process can be adjusted according to the understanding and practical situation of the skilled person.
EXAMPLE 1 high Performance Hydrogen bonding organic framework materials electrochromic device (ECD-1p)
The preparation method comprises
1. Preparation of working electrode
Preparation of hydrogen bond organic framework material
1, 4-dioxane pretreatment: 150mL of 1, 4-dioxane was subjected to solvent evaporation at 102 ℃ and then nitrogen was introduced to remove dissolved oxygen.
5g of 4- (methoxycarbonyl) phenylboronic acid, 2.85g of 1,3,6, 8-tetrabromopyrene, 0.1g of tetrakis (triphenylphosphine) palladium and 1g of cesium fluoride are added into the pretreated 1, 4-dioxane, the mixture is reacted at 85 ℃ for 3 days, an ice-water mixture is added to precipitate a solid, and the solid is filtered by suction and dried to obtain 3.7g of a yellow solid. 1g of yellow solid and 1g of KOH are added to a mixed solution of 100mL of THF, 1, 4-dioxane and deionized water (volume ratio of 2:1:1) and reacted at 85 ℃ for 24H to obtain H4TBAPy ligand, H4The structural formula of the TBAPy ligand is as follows:
Figure BDA0003565122310000031
150mg H was sonicated4Dispersing TBAPy ligand in 22.5mL DMF, adding 90mL methanol and stirring for 1 minute, standing at room temperature to obtain crystal, and grinding into powder to obtain hydrogen bond organic framework material labeled as PFC-1.
Preparation of PFC-1 film
Ultrasonically dispersing 4mg of PFC-1 powder in 40mL of dichloromethane to serve as a deposition solution, taking two pieces of FTO glass, immersing the two pieces of FTO glass into the deposition solution at an interval of 1cm, respectively connecting two electrodes of an electrophoretic deposition instrument with the two pieces of FTO glass, and depositing for 6 minutes to obtain the PFC-1 membrane at the positive electrode.
2. Preparation of counter electrode
①TiO2Preparation of the film
Adding TiO with ethanol2Diluting to 20% by mass of titanium dioxide nanoparticle solution, spin-coating on FTO glass for 2 times, and annealing at 500 deg.C for 30min to obtain TiO2And (3) a membrane. As shown in (1) in FIG. 1, TiO2The film thickness was 360 nm.
②TiO2-PW12Preparation of composite membranes
Take 0.1g of PW12Dissolving in 10mL deionized water as electrodeposition solution, TiO2The film is used as a working electrode, the platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, electrodeposition is carried out by utilizing cyclic voltammetry, the deposition voltage is-1.5-0.2V, and the sweep rate is 100mV s-1Deposition cycle number 5 times in TiO2Electrodepositing a layer of PW on the film12Film to obtain TiO2-PW12Composite membrane, labeled 1 p. Deposition of PW12After TiO 22The film thickness was unchanged.
3. Electrochromic device ECD-1p assembly
Using PFC-1 film as working electrode, TiO2-PW12The composite membrane is a counter electrode, [ BMIM]TF2N is electrolyte, and is assembled into an electrochromic device, which is marked as ECD-1p, and the structure is shown in figure 2.
(II) Performance testing
In the prepared device ECD-1p, a working electrode is a positive electrode, a counter electrode is a negative electrode, the applied voltage is 0-2.5V, the period is 60s, the positive voltage and the negative voltage are applied for the same time, the wavelength is 600nm when the device is tested in an ultraviolet visible spectrophotometer, the transmittance of the device is changed as shown in figure 3, as can be seen from figure 3, the transmittance is reduced from the initial 99.6% to 52.6% with the application of the positive voltage, and the transmittance returns to the initial 99.6% with the application of the 0V voltage. The light modulation of the device was 47%, the fade time was 2.1s, the coloration time was 3.8s, and the coloration efficiency was 222.73cm2 C-1. TiO for the device2-PW12Thin film, but PW12And TiO2As a charge balance layer with improved electrochromic properties, PW12The layer can receive both the glass from the FTO and the TiO2Electrons of the layer.
Example 2 high Performance Hydrogen bonding organic framework materials electrochromic device (ECD-2 p-CH)3)
The preparation method comprises
1. Preparation of working electrode
Preparation of hydrogen bond organic framework material
1, 4-dioxane pretreatment: 150mL of 1, 4-dioxane was subjected to solvent evaporation at 102 ℃ and then nitrogen was introduced to remove dissolved oxygen.
5g of (4- (methoxycarbonyl) -2-methylphenyl) boric acid, 2.85g of 1,3,6, 8-tetrabromopyrene, 0.1g of tetrakis (triphenylphosphine) palladium and 1g of cesium fluoride were added to the pretreated 1, 4-dioxane, reacted at 85 ℃ for 3 days, an ice-water mixture was added to precipitate a solid, and the solid was dried after suction filtration to obtain 3.7g of a yellow solid. 1g of yellow solid and 1g of KOH are added into a mixed solution of 100mL of THF, 1.4-dioxane and deionized water (volume ratio is 2:1:1) and reacted at 85 ℃ for 24H to obtain H4TBAPy-CH3Ligand, H4TBAPy-CH3The structural formula of the ligand is as follows:
Figure BDA0003565122310000051
150mg H was sonicated4TBAPy-CH3Dispersing ligand in 22.5mL DMF, adding 90mL methanol, stirring for 1 min, standing at room temperature to obtain crystal, grinding into powder to obtain hydrogen bond organic skeleton material labeled as PFC-CH3。
②PFC-CH3Preparation of the film
4mg of PFC-CH3Ultrasonically dispersing the powder in 40mL of dichloromethane to obtain a deposition solution, immersing two pieces of FTO glass into the deposition solution at an interval of 1cm, respectively connecting two electrodes of an electrophoretic deposition instrument with the two pieces of FTO glass, depositing for 6 minutes, and obtaining PFC-CH at the positive electrode3And (3) a membrane.
2. Preparation of counter electrode
①TiO2Preparation of the film
Adding TiO with ethanol2Diluting to be titanium dioxide nano particle solution with mass fraction of 30%, spin-coating on FTO glass for 1 time, and annealing at 500 ℃ for 30min to obtain TiO2And (3) a membrane. TiO, as shown in (2) in FIG. 12The film thickness was 400 nm.
②TiO2-PW12Preparation of composite membranes
Take 0.1g of PW12Dissolving in 10mL deionized water as electrodeposition solution, TiO2The film is used as a working electrode, the platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, electrodeposition is carried out by utilizing cyclic voltammetry, the deposition voltage is-1.5-0.2V, and the sweep rate is 100mV s-1Deposition cycle number 5 times in TiO2Electrodepositing a layer of PW on the film12Film to obtain TiO2-PW12Composite membrane, labeled 2 p. Deposition of PW12After TiO 22The film thickness was unchanged.
3. Electrochromic device ECD-2p-CH3Assembling
With PFC-CH3The membrane being the working electrode, TiO2-PW12The composite membrane is a counter electrode, [ BMIM]TF2N is electrolyte, and is assembled into electrochromic device, marked as ECD-2p-CH3. The structure is shown in fig. 2.
(II) Performance testing
The prepared device ECD-2p-CH3In the method, a working electrode is a positive electrode, a counter electrode is a negative electrode, the applied voltage is 0-2.5V, the period is 60s, the positive voltage and the negative voltage are applied for the same time, the wavelength is 600nm when the working electrode and the counter electrode are tested in an ultraviolet visible spectrophotometer, the transmittance of the device changes as shown in figure 4, as can be seen from figure 4, the transmittance decreases from the initial 100% to 32.5% when the positive voltage is applied, and the transmittance returns to the initial 100% when the 0V voltage is applied. The light modulation of the device was 67.5%, the fade time was 5.1s, the coloration time was 3.6s, and the coloration efficiency was 373.28cm2 C-1. The device has excellent electrochemical performance and different PW contents12And TiO of different thickness2With different effects on the electrochemical behaviour of the device, TiO 400nm2-PW12The film is most suitable for hydrogen bonding organic framework material electrochromic devices.
Example 3 high Performance Hydrogen bonding organic framework materials electrochromic device (ECD-3p-Cl)
The preparation method comprises
1. Preparation of working electrode
Preparation of hydrogen bond organic skeleton material
1, 4-dioxane pretreatment: 150mL of 1, 4-dioxane was subjected to solvent evaporation at 102 ℃ and then nitrogen was passed to remove dissolved oxygen.
5g of 2-chloro-4- (methoxycarbonyl) phenylboronic acid, 2.85g of 1,3,6, 8-tetrabromopyrene, 0.1g of tetrakis (triphenylphosphine) palladium and 1g of cesium fluoride are added into the pretreated 1, 4-dioxane, reacted at 85 ℃ for 3 days, an ice-water mixture is added to precipitate a solid, and the solid is dried after suction filtration to obtain 3.7g of a yellow solid. Adding 1g of yellow solid and 1g of KOH into a mixed solution of 100mL of THF, 1.4-dioxane and deionized water (the volume ratio is 2:1:1), and reacting at 85 ℃ for 24H to obtain H4TBAPy-Cl ligand, H4The structural formula of the TBAPy-Cl ligand is as follows:
Figure BDA0003565122310000061
150mg H was sonicated4Dispersing TBAPy-Cl ligand in 22.5mL DMF, adding 90mL methanol, stirring for 1 min, standing at room temperature to obtain crystal, and grinding into powder to obtain hydrogen bond organic framework material labeled as PFC-Cl.
Preparation of PFC-Cl film
Ultrasonically dispersing 4mg of PFC-Cl powder in 40mL of dichloromethane to serve as a deposition solution, taking two pieces of FTO glass, immersing the two pieces of FTO glass into the deposition solution at an interval of 1cm, respectively connecting two electrodes of an electrophoretic deposition instrument with the two pieces of FTO glass, depositing for 6 minutes, and obtaining the PFC-Cl membrane at the positive electrode.
2. Preparation of counter electrode
①TiO2Preparation of the film
Adding TiO with ethanol2Diluting to be titanium dioxide nano particle solution with mass fraction of 30%, spin-coating on FTO glass for 2 times, and annealing at 500 ℃ for 30min to obtain TiO2And (3) a membrane. As shown in (3) in FIG. 1, TiO2The film thickness was 448 nm.
②TiO2-PW12Preparation of composite film
Take 0.1g of PW12Dissolving in 10mL deionized water as electrodeposition solution, TiO2The membrane being the working electrode, platinumThe filament is used as a counter electrode, Ag/AgCl is used as a reference electrode, electrodeposition is carried out by cyclic voltammetry, the deposition voltage is-1.5-0.2V, and the sweep rate is 100mV s-1Deposition cycle number 5 times in TiO2Electrodepositing a layer of PW on the film12Film to obtain TiO2-PW12Composite membrane, labelled 3 p. Deposition of PW12After TiO 22The film thickness was unchanged.
3. Electrochromic device ECD-3p-Cl assembly
Using PFC-Cl film as working electrode and TiO2-PW12The composite membrane is a counter electrode, [ BMIM]TF2N is electrolyte, and is assembled into an electrochromic device, and is marked as ECD-3 p-Cl. The structure is shown in fig. 2.
(II) Performance testing
In the prepared device ECD-3p-Cl, a working electrode is a positive electrode, a counter electrode is a negative electrode, the applied voltage is 0-2.5V, the period is 60s, the application time of the positive voltage is the same as that of the negative voltage, the wavelength is 600nm when the device is tested in an ultraviolet visible spectrophotometer, the transmittance of the device is changed as shown in figure 5, as can be seen from figure 5, the transmittance is reduced to 38% from the initial 98.1% with the application of the positive voltage, and the transmittance returns to the initial 98.1% with the application of the 0V voltage. The light modulation of the device was 60.1%, the fade time was 4.6s, the coloration time was 2.1s, and the coloration efficiency was 390.73cm2 C-1. TiO at 448nm thickness2-PW12The composite film as a charge balance layer has promotion effect on electrochromic performance of devices, and the effect of the charge balance layer and the PW12Content of (2) and TiO2Is related to the thickness of PW12Content of (2) and TiO2Increased thickness, increased charge balance, but too thick TiO2The conductivity is low, and the conductivity is poor, so that the electrochemical performance of the device can be influenced.
Example 4 high Performance Hydrogen bonding organic framework materials electrochromic device (ECD-4 p-NO)2)
The preparation method comprises
1. Preparation of working electrode
Preparation of hydrogen bond organic skeleton material
1, 4-dioxane pretreatment: 150mL of 1, 4-dioxane was subjected to solvent evaporation at 102 ℃ and then nitrogen was introduced to remove dissolved oxygen.
5g of 4-methoxycarbonyl-2-nitrophenylboronic acid, 2.85g of 1,3,6, 8-tetrabromopyrene, 0.1g of tetrakis (triphenylphosphine) palladium and 1g of cesium fluoride are added to the pretreated 1, 4-dioxane, the mixture is reacted at 85 ℃ for 3 days, an ice-water mixture is added to precipitate a solid, and the solid is dried after suction filtration to obtain 3.7g of a yellow solid. Adding 1g of yellow solid and 1g of KOH into a mixed solution of 100mL of THF, 1.4-dioxane and deionized water (the volume ratio is 2:1:1), and reacting at 85 ℃ for 24H to obtain H4TBAPy-NO2Ligand, H4TBAPy-NO2The structural formula of the ligand is as follows:
Figure BDA0003565122310000081
150mg H was sonicated4TBAPy-NO2Dispersing ligand in 22.5mL DMF, adding 90mL methanol, stirring for 1 min, standing at room temperature to obtain crystal, grinding into powder to obtain hydrogen bond organic skeleton material labeled as PFC-NO2。
②PFC-NO2Preparation of the film
4mg of PFC-NO2Ultrasonically dispersing the powder in 40mL of dichloromethane to obtain a deposition solution, immersing two pieces of FTO glass into the deposition solution at an interval of 1cm, respectively connecting two electrodes of an electrophoretic deposition instrument with the two pieces of FTO glass, depositing for 6 minutes, and obtaining PFC-NO at the positive electrode2And (3) a membrane.
2. Preparation of counter electrode
①TiO2Preparation of the film
Adding TiO with ethanol2Diluting to be titanium dioxide nano particle solution with mass fraction of 40%, spin-coating on FTO glass for 1 time, and annealing at 500 ℃ for 30min to obtain TiO2And (3) a membrane. TiO, as shown in (4) in FIG. 12The film thickness was 477 nm.
②TiO2-PW12Preparation of composite membranes
Take 0.1g of PW12Dissolved in 10mL of deionized water asElectrodeposition baths, TiO2The film is used as a working electrode, the platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, electrodeposition is carried out by utilizing cyclic voltammetry, the deposition voltage is-1.5-0.2V, and the sweep rate is 100mV s-1Deposition cycle number 5 times in TiO2Electrodepositing a layer of PW on the film12Film to obtain TiO2-PW12Composite membrane, labelled 4 p. Deposition of PW12After TiO 22The film thickness was unchanged.
3. Electrochromic device ECD-4p-NO2Assembly
With PFC-NO2The membrane being the working electrode, TiO2-PW12The membrane sample was the counter electrode, [ BMIM]TF2N is electrolyte, and is assembled into electrochromic device marked as ECD-4p-NO2. The structure is shown in fig. 2.
(II) Performance testing
The prepared device ECD-4p-NO2In the test, the working electrode is the positive electrode, the counter electrode is the negative electrode, the applied voltage is 0-2.5V, the period is 60s, the positive voltage and the negative voltage are applied for the same time, the wavelength is 600nm when the test is carried out in an ultraviolet visible spectrophotometer, the transmittance of the device changes as shown in figure 6, as can be seen from figure 6, the transmittance decreases from the initial 100% to 57.2% when the positive voltage is applied, and the transmittance returns to the initial 100% when the 0V voltage is applied. The light modulation of the device was 44.2%, the fade time was 3.1s, the coloration time was 2s, and the coloration efficiency was 228.18cm2 C-1。

Claims (10)

1. A high-performance hydrogen bond organic framework material electrochromic device is characterized in that: the high-performance hydrogen bond organic framework material electrochromic device comprises a working electrode, electrolyte and a counter electrode; the working electrode is characterized in that a conductive substrate is coated with an electrochromic layer, and the electrochromic layer is a hydrogen bond organic framework material film; the electrolyte is ionic liquid; the counter electrode is a composite film prepared by compounding polyoxometallate and transition metal oxide, and a charge balance layer is coated on a conductive substrate.
2. The electrochromic device of high-performance hydrogen bond organic framework material according to claim 1, characterized in that: the hydrogen bond organic framework material is selected from PFC materials.
3. The electrochromic device of high-performance hydrogen bond organic framework material according to claim 2, characterized in that: the ligand of the PFC material is H4TBAPy、H4TBAPy-CH3、H4TBAPy-Cl or H4TBAPy-NO2。
4. The electrochromic device of high-performance hydrogen-bonding organic framework material according to claim 1, 2 or 3, characterized in that: the ionic liquid is [ BMIM ] TF 2N.
5. The electrochromic device of high-performance hydrogen-bonding organic framework material according to claim 1, 2 or 3, characterized in that: the composite film is transition metal oxide TiO prepared by a spin coating method2Depositing a layer of polyoxometallate PW on the film by an electrodeposition method12Film produced TiO2-PW12Compounding film; the TiO is2The thickness of the film is 350 to 500 nm.
6. The electrochromic device of high-performance hydrogen-bonding organic framework material according to claim 1, 2 or 3, characterized in that: the conductive substrate is FTO glass.
7. A preparation method of a high-performance hydrogen bond organic framework material electrochromic device is characterized by comprising the following steps: the method comprises the following steps:
1) preparation of a working electrode: ultrasonically dispersing PFC powder in dichloromethane to serve as a deposition solution, taking two pieces of FTO glass, immersing the two pieces of FTO glass into the deposition solution at an interval of 1cm, respectively connecting two electrodes of an electrophoretic deposition instrument with the two pieces of FTO glass, and depositing for 6 minutes to obtain a hydrogen bond organic framework material PFC membrane at the positive electrode;
2) preparing a counter electrode: adding TiO with ethanol2Diluted to 20-40% by massSpin-coating titanium dioxide nanoparticle solution on FTO glass for 1-2 times, and annealing at 500 deg.C for 30min to obtain TiO2A film; subjecting PW to12Dissolving in deionized water as electrodeposition liquid, TiO2The film is used as a working electrode, the platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, and the electrodeposition is carried out by utilizing cyclic voltammetry to obtain TiO2-PW12Compounding film;
3) the working electrode, [ BMIM ] TF2N as electrolyte and the counter electrode were assembled into an electrochromic device.
8. The method of claim 7, wherein: the preparation method of the PFC powder comprises the following steps: sequentially adding a phenylboronic acid compound, 1,3,6, 8-tetrabromopyrene, tetrakis (triphenylphosphine) palladium and cesium fluoride into 1, 4-dioxane, reacting at 85 ℃ for 3 days, adding an ice water mixture to precipitate a solid, performing suction filtration, and drying to obtain a solid; adding the obtained solid and KOH into a mixed solution of THF, 1, 4-dioxane and deionized water, and reacting at 85 ℃ for 24h to obtain a ligand; dispersing the obtained ligand in DMF, adding methanol, stirring for 1 minute, standing at room temperature to obtain crystals, and grinding.
9. The method of claim 8, wherein: the phenylboronic acid compound is 4- (methoxycarbonyl) phenylboronic acid, (4- (methoxycarbonyl) -2-methylphenyl) boric acid, 2-chloro-4- (methoxycarbonyl) phenylboronic acid or 4-methoxycarbonyl-2-nitrobenzeneboronic acid.
10. The method of claim 7, wherein: in the step 2), the conditions for performing electrodeposition by cyclic voltammetry are as follows: the deposition voltage is-1.5-0.2V, and the sweep rate is 100mV s-1The number of deposition cycles was 5.
CN202210299874.6A 2022-03-25 2022-03-25 High-performance hydrogen bond organic framework material electrochromic device Pending CN114675458A (en)

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