CN116088240A - High performance electrochromic-energy storage devices based on polyoxometallates and cobalt doped manganese dioxide - Google Patents

High performance electrochromic-energy storage devices based on polyoxometallates and cobalt doped manganese dioxide Download PDF

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Publication number
CN116088240A
CN116088240A CN202310103140.0A CN202310103140A CN116088240A CN 116088240 A CN116088240 A CN 116088240A CN 202310103140 A CN202310103140 A CN 202310103140A CN 116088240 A CN116088240 A CN 116088240A
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China
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energy storage
electrochromic
high performance
polyoxometallate
storage device
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Inventor
王诗铭
王锴华
金远航
卢天洋
周璐
刘琳
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Liaoning University
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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
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • 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
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • G02F2001/1557—Side by side arrangements of working and counter electrodes

Abstract

The invention discloses a high performance electrochromic-energy storage device based on polyoxometallate and cobalt doped manganese dioxide. Comprises a working electrode, an electrolyte and a counter electrode. The working electrode is formed by coating an electrochromic layer on a conductive substrate, and the electrochromic layer is polyoxometallate. The electrolyte is 1M LiClO 4 PC solution. The counter electrode is a conductive substrate coated with a charge balance layer. The charge balance layer is Co doped MnO 2 A film. The invention is realized by the method that the catalyst is prepared by the steps of 2 After the thin film is doped with metal Co, the device has excellent performances in light modulation, capacitance and conductivity, has larger optical modulation capability in the same voltage range, and achieves the purpose of energy conservation.

Description

High performance electrochromic-energy storage devices based on polyoxometallates and cobalt doped manganese dioxide
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a high-performance electrochromic-energy storage device based on polyoxometallate and cobalt-doped manganese dioxide.
Background
With the continuous generation of fossil energyExhaustion, continuous consumption of natural resources, and development of energy-saving materials and energy-saving devices with multiple functions. The polyoxometallate as an emerging electrochromic material has excellent electrochemical performance, good ultraviolet stability, wide optical modulation range and high chemical stability. However, in electrochromic devices, the lack of ion storage capability of the counter electrode results in long color change response time of polyoxometallate, low coloring efficiency and ineffective performance. MnO (MnO) 2 Because of its own physical and chemical properties, it has become one of the most attractive inorganic materials, and is widely used in the fields of catalysis, biosensors, supercapacitors, etc., but there are problems of lower conductivity and lower capacitance in electrochromic devices.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-performance electrochromic-energy storage device based on polyoxometallate and cobalt-doped manganese dioxide, and electrochromic and energy storage performances of the device are improved by improving a counter electrode.
The technical scheme adopted by the invention is as follows: a high performance electrochromic-energy storage device based on polyoxometallate and cobalt doped manganese dioxide includes a working electrode, an electrolyte and a counter electrode; the working electrode is formed by coating an electrochromic layer on a conductive substrate, wherein the electrochromic layer is polyoxometallate; the electrolyte contains active Li + A solution of ions; the counter electrode is a conductive substrate covered with a charge balance layer, and the charge balance layer is Co doped MnO 2 A film.
Further, the polyoxometalates are POMs.
Further, the POMs are P 2 W 18 。
Further, the active Li-containing alloy contains + The ionic solution was 1M LiClO 4 PC solution.
Further, the conductive substrate is FTO glass.
A method for preparing a high performance electrochromic-energy storage device based on polyoxometallate and cobalt doped manganese dioxide, comprising the steps of:
1) Preparation of working electrode: by spin coating 2 W 18 Spin coating liquid is spin coated on the FTO glass to obtain P 2 W 18 A film.
2) Preparation of the counter electrode: depositing on FTO glass by constant current deposition to obtain Co doped MnO 2 A film.
3) Working electrode, 1M LiClO 4 The PC solution is used as an electrolyte and a counter electrode to assemble a high-performance electrochromic-energy storage device.
Further, the step 1) specifically comprises: adding polyvinyl alcohol into deionized water, magnetically stirring at 120deg.C to obtain polyvinyl alcohol crosslinking agent solution, and adding P 2 W 18 Adding into polyvinyl alcohol cross-linking agent solution, stirring uniformly to obtain P 2 W 18 Spin coating liquid; will P 2 W 18 The spin coating solution was spin coated on the FTO glass in two steps, the first step at 1000rpm for 15s and the second step at 2000rpm for 20s.
Further, the step 2) specifically comprises: FTO glass is used as a working electrode, pt wire is used as a counter electrode, ag/AgCl is used as a reference electrode, and 0.2M MnSO is used 4 、1.1M H 2 SO 4 And 0.025-0.1M Co (NO) 3 ) 2 ·H 2 The mixed solution of O is used as electrolyte for electrodeposition at 3mA/cm 2 Is deposited at a current density of 60s.
The beneficial effects of the invention are as follows:
1. the invention utilizes cobalt to dope MnO 2 The film is used as a charge balance layer, so that the conductivity and the capacitance of the film are improved, the energy level is more matched, the electron transition potential barrier is reduced, the film has larger optical modulation under the same voltage, the coloring efficiency is improved, and the purpose of energy conservation is achieved.
2. The invention has the advantages of simple preparation process of the working electrode and the counter electrode, easy operation and low cost.
Drawings
FIG. 1 shows the transmittance change at 580nm of the visible ultraviolet wavelength of EESD1 prepared in example 1, with applied voltages of 2 to-0.5V, 2 to-0.8V, 2 to-1.2V, 2 to-1.6V, and 2 to-2V.
FIG. 2 shows the transmittance change at 580nm of the visible ultraviolet wavelength of EESD2 prepared in example 2, with voltages of 2-0.5V, 2-0.8V, 2-1.2V, 2-1.6V, and 2-2V.
FIG. 3 shows the transmittance change at 580nm of the visible ultraviolet wavelength of EESD3 prepared in example 3, with applied voltages of 2 to-0.5V, 2 to-0.8V, 2 to-1.2V, 2 to-1.6V, and 2 to-2V.
FIG. 4 shows the transmittance change at 580nm of the visible ultraviolet wavelength of EESD4 prepared in example 4, with applied voltages of 2 to-0.5V, 2 to-0.8V, 2 to-1.2V, 2 to-1.6V, and 2 to-2V.
Detailed Description
In order to highlight the technical advantages and the excellent performance of the present invention, further description will be made with reference to the accompanying drawings and specific examples. The following embodiments are provided for the purpose of illustrating the invention and may be modified in practice by those skilled in the art.
Example 1 preparation of high Performance electrochromic-energy storage device (EESD 1) based on polyoxometallate and cobalt doped manganese dioxide
1. Preparation of working electrode
P 2 W 18 Is prepared from the following steps: 300g of Na 2 WO 4 Slowly adding into 300mL deionized water, dissolving, adding 250mL HCl with concentration of 4mol/L, generating milky white precipitate during the adding process, stirring vigorously, adding 250mL H with concentration of 4mol/L after the precipitate is dissolved 3 PO 4 A pale yellow solution was obtained. Reflux-heating for 24 hr, cooling to room temperature, stirring at room temperature, adding 150g KCl to obtain yellow precipitate, and air-drying for 2 hr to obtain P 2 W 18 。
0.3g of polyvinyl alcohol is added into 10mL of deionized water, and magnetically stirred at 120 ℃ to obtain a polyvinyl alcohol cross-linking agent solution, and then 3g P is added 2 W 18 Adding the mixture into a polyvinyl alcohol cross-linking agent solution, and uniformly stirring to obtain 0.3g/mL of P 2 W 18 Spin coating liquid; will P 2 W 18 Spin coating liquid is spin coated on FTO in two stepsThe glass is spin-coated for 15s at 1000rpm in the first step and for 20s at 2000rpm in the second step to obtain P 2 W 18 A film.
2. Preparation of counter electrode
Using constant current deposition, using FTO glass as a working electrode, pt wire as a counter electrode, ag/AgCl as a reference electrode, and 0.2M MnSO 4 、1.1M H 2 SO 4 And 0.025M Co (NO) 3 ) 2 ·H 2 The O mixed solution is used as an electrolyte for electrodeposition, and is 3mA/cm 2 Is deposited for 60s under the current density to obtain Co doped MnO 2 A film.
3. Preparation of electrolyte
1.06g LiClO 4 Dissolving in 10mL PC solution under magnetic stirring at room temperature, and obtaining 1MLiClO after complete dissolution 4/ PC solution.
4. Device assembly
With P 2 W 18 The film is a working electrode, 1M LiClO 4 The PC solution is electrolyte, co doped MnO 2 The thin film is the counter electrode, assembled into a high performance electrochromic-energy storage device, labeled EESD1.
(II) Performance test
In the prepared device EESD1, the working electrode is the positive electrode, the electrode is the negative electrode, and the test is carried out, and the applied voltages are respectively 2-0.5V, 2-0.8V, 2-1.2V, 2-1.6V and 2-2V. The transmittance change of the device, as shown in FIG. 1, was 9.1% at a voltage of 2 to-0.5V, 33.2% at a voltage of 2 to-0.8V, 48.8% at a voltage of 2 to-1.2V, 62.1% at a voltage of 2 to-1.6V, and 72.6% at a voltage of 2 to-2V, when measured in an ultraviolet-visible spectrophotometer at a wavelength of 580 nm.
Example 2 preparation of high Performance electrochromic-energy storage device (EESD 2) based on polyoxometallate and cobalt doped manganese dioxide (I)
1. Preparation of working electrode
Same as in example 1
2. Preparation of counter electrode
Using constant current deposition, taking FTO glass as a working electrode and Pt wire asCounter electrode, ag/AgCl as reference electrode, 0.2M MnSO 4 、1.1M H 2 SO 4 And 0.05MCo (NO) 3 ) 2 ·H 2 The O mixed solution is used as an electrolyte for electrodeposition, and is 3mA/cm 2 Is deposited for 60s under the current density to obtain Co doped MnO 2 A film.
3. Preparation of electrolyte
Same as in example 1
4. Device assembly
With P 2 W 18 The film is a working electrode, liClO 4 The PC solution is electrolyte, co doped MnO 2 The thin film is the counter electrode, assembled into a high performance electrochromic-energy storage device, labeled EESD2.
(II) Performance test
In the prepared device EESD2, the working electrode is the positive electrode, the electrode is the negative electrode, and the test is carried out, and the applied voltages are respectively 2-0.5V, 2-0.8V, 2-1.2V, 2-1.6V and 2-2V. The wavelength is 580nm, the transmittance change of the device is shown in figure 2, delta T is 8.8% under the voltage of 2 to-0.5V, delta T is 44% under the voltage of 2 to-0.8V, delta T is 64% under the voltage of 2 to-1.2V, delta T is 64.7% under the voltage of 2 to-1.6V, and delta T is 69.7% under the voltage of 2 to-2V.
Example 3 preparation of high Performance electrochromic-energy storage device (EESD 3) based on polyoxometallate and cobalt doped manganese dioxide (II)
1. Preparation of working electrode
Same as in example 1
2. Preparation of counter electrode
Using constant current deposition, using FTO glass as a working electrode, pt wire as a counter electrode, ag/AgCl as a reference electrode, and 0.2M MnSO 4 、1.1M H 2 SO 4 And 0.075MCo (NO) 3 ) 2 ·H 2 The O mixed solution is used as an electrolyte for electrodeposition, and is 3mA/cm 2 Is deposited for 60s under the current density to obtain Co doped MnO 2 A film.
3. Preparation of electrolyte
Same as in example 1
4. Device assembly
With P 2 W 18 The film is a working electrode, liClO 4 The PC solution is electrolyte, co doped MnO 2 The thin film is the counter electrode, assembled into a high performance electrochromic-energy storage device, labeled EESD3.
(II) Performance test
In the prepared device EESD3, the working electrode is the positive electrode, the electrode is the negative electrode, and the test is carried out, and the applied voltages are respectively 2-0.5V, 2-0.8V, 2-1.2V, 2-1.6V and 2-2V. The transmittance change of the device, as shown in FIG. 3, was 5.7% at a voltage of 2 to-0.5V, 22.9% at a voltage of 2 to-0.8V, 47.6% at a voltage of 2 to-1.2V, 65.5% at a voltage of 2 to-1.6V, and 59.6% at a voltage of 2 to-2V, when measured in an ultraviolet-visible spectrophotometer at a wavelength of 580 nm.
Example 4 preparation of high Performance electrochromic-energy storage device (EESD 4) based on polyoxometallate and cobalt doped manganese dioxide
1. Preparation of working electrode
Same as in example 1
2. Preparation of counter electrode
Using constant current deposition, using FTO glass as a working electrode, pt wire as a counter electrode, ag/AgCl as a reference electrode, and 0.2M MnSO 4 、1.1M H 2 SO 4 And 0.1M Co (NO) 3 ) 2 ·H 2 The O mixed solution is used as an electrolyte for electrodeposition, and is 3mA/cm 2 Is deposited for 60s under the current density to obtain Co doped MnO 2 A film.
3. Preparation of electrolyte
Same as in example 1
4. Device assembly
With P 2 W 18 The film is a working electrode, liClO 4 The PC solution is electrolyte, co doped MnO 2 The thin film is the counter electrode, assembled into a high performance electrochromic-energy storage device, labeled EESD4.
(II) Performance test
In the prepared device EESD4, the working electrode is the positive electrode, the electrode is the negative electrode, and the test is carried out, and the applied voltages are respectively 2-0.5V, 2-0.8V, 2-1.2V, 2-1.6V and 2-2V. The transmittance change of the device, as shown in FIG. 4, was 7.1% at a voltage of 2 to-0.5V, 21.8% at a voltage of 2 to-0.8V, 54.5% at a voltage of 2 to-1.2V, 69.1% at a voltage of 2 to-1.6V, and 77.4% at a voltage of 2 to-2V, when measured in an ultraviolet-visible spectrophotometer at a wavelength of 580 nm.

Claims (8)

1. A high performance electrochromic-energy storage device based on polyoxometallate and cobalt doped manganese dioxide, characterized in that the high performance electrochromic-energy storage device comprises a working electrode, an electrolyte and a counter electrode; the working electrode is formed by coating an electrochromic layer on a conductive substrate, wherein the electrochromic layer is polyoxometallate; the electrolyte contains active Li + A solution of ions; the counter electrode is a conductive substrate covered with a charge balance layer, and the charge balance layer is Co doped MnO 2 A film.
2. The high performance electrochromic-energy storage device according to claim 1, wherein the polyoxometallate is POMs and cobalt doped manganese dioxide.
3. The high performance electrochromic-energy storage device based on polyoxometallate and cobalt doped manganese dioxide of claim 2, wherein the POMs are P 2 W 18 。
4. A high performance electrochromic-energy storage device based on polyoxometallate and cobalt doped manganese dioxide according to claim 1, 2 or 3, characterized in that the active Li-containing + The ionic solution was 1M LiClO 4 PC solution.
5. A high performance electrochromic-energy storage device based on polyoxometallate and cobalt doped manganese dioxide according to claim 1, 2 or 3, characterized in that the conductive substrate is FTO glass.
6. A method for preparing a high performance electrochromic-energy storage device based on polyoxometallate and cobalt doped manganese dioxide, the method comprising the steps of:
1) Preparation of working electrode: the P is applied by spin coating 2 W 18 Spin coating liquid is spin coated on the FTO glass to obtain P 2 W 18 A film;
2) Preparation of the counter electrode: depositing on FTO glass by constant current deposition to obtain Co doped MnO 2 A film;
3) Working electrode, 1M LiClO 4 The PC solution is used as an electrolyte and a counter electrode to assemble a high-performance electrochromic-energy storage device.
7. The method of manufacturing according to claim 6, wherein: the step 1) is specifically as follows: adding polyvinyl alcohol into deionized water, magnetically stirring at 120deg.C to obtain polyvinyl alcohol crosslinking agent solution, and adding P 2 W 18 Adding into polyvinyl alcohol cross-linking agent solution, stirring uniformly to obtain P 2 W 18 Spin coating liquid; will P 2 W 18 The spin coating solution was spin coated on the FTO glass in two steps, the first step at 1000rpm for 15s and the second step at 2000rpm for 20s.
8. The method of manufacturing according to claim 6, wherein: the step 2) is specifically as follows: FTO glass is used as a working electrode, pt wire is used as a counter electrode, ag/AgCl is used as a reference electrode, and 0.2M MnSO is used 4 、1.1M H 2 SO 4 And 0.025-0.1MCo (NO) 3 ) 2 ·H 2 The mixed solution of O is used as electrolyte for electrodeposition at 3mA/cm 2 Is deposited at a current density of 60s.
CN202310103140.0A 2023-02-13 2023-02-13 High performance electrochromic-energy storage devices based on polyoxometallates and cobalt doped manganese dioxide Pending CN116088240A (en)

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