CN115963665A - Self-healing hydrogel electrolyte for electrochromic energy storage dual-function device - Google Patents

Self-healing hydrogel electrolyte for electrochromic energy storage dual-function device Download PDF

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CN115963665A
CN115963665A CN202111189884.6A CN202111189884A CN115963665A CN 115963665 A CN115963665 A CN 115963665A CN 202111189884 A CN202111189884 A CN 202111189884A CN 115963665 A CN115963665 A CN 115963665A
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energy storage
electrochromic
polyvinyl alcohol
preparation
modified polyvinyl
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刘建
李小薇
马娜
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Nanjing Forestry University
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Nanjing Forestry University
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Abstract

The invention relates to a self-healing hydrogel electrolyte for an electrochromic energy storage dual-function device. The hydrogel takes a deionized water/glycerol mixture as a solvent, a polyvinyl alcohol and acrylamide graft copolymer as a main monomer, potassium salt and zinc salt as electrolytes and gelatin as an additive, and the hydrogel electrolyte with good self-healing and anti-freezing properties is prepared by adopting a circulating thawing method by adjusting the adding amount of the gelatin. The hydrogel electrolyte is further used for preparing an electrochromic energy storage dual-function device, shows good electrochromic and energy storage properties at a temperature range of-30 ℃, and is suitable for preparing flexible devices. The novel hydrogel electrolyte provided by the invention has the advantages of simple preparation method, cheap and easily-obtained raw materials, high ionic conductivity, high transparency and good self-healing performance, and has wide application prospects in the field of electrochromic energy storage.

Description

Self-healing hydrogel electrolyte for electrochromic energy storage dual-function device
Technical Field
The invention relates to preparation and application of a self-healing hydrogel electrolyte, in particular to preparation of a self-healing modified polyvinyl alcohol hydrogel electrolyte for an electrochromic energy storage dual-function device, and belongs to the technical field of electrochromic.
Background
Electrochromic phenomena have received much attention since their discovery in 1969, with potential applications in display and light emission and transmission management. The electrochromic glass can reduce energy consumption caused by building heating, air conditioning and ventilation, can reduce glare, does not damage natural lighting and brings higher indoor comfort level due to smooth vision, and has the characteristics of easiness in control, good energy-saving effect, color memory and the like. From the aspects of electrochemical principle and device structure, the electrochromic device not only has a device structure similar to that of energy storage devices such as batteries and super capacitors, but also has similar processes of charge transfer, storage and element valence state change. Through reasonable design, a dual-function device with energy storage and electrochromic functions can be developed, and the device has the function of energy storage while the color is changed. The electrochromic and energy storage dual-function device is used as a novel electrochemical device and has wide application prospect in the fields of energy conservation and energy storage.
In an electrochromic energy storage device, the traditional liquid electrolyte has the problems of easy leakage, difficult packaging and the like. The hydrogel is a functional polymer material with a three-dimensional network structure formed by hydrophilic polymers by using water as a dispersion medium, so that the problems are overcome. The hydrogel contains a large number of free water molecules, and generally has high ionic conductivity; the highly crosslinked polymer network in turn gives the hydrogel excellent mechanical properties and deformability. Therefore, the hydrogel electrolyte has wide application in electrochromic devices. Hydrogels with self-healing capabilities are of interest for their ability to heal spontaneously after being compromised in order to provide better stability and extended useful life. In general, the self-healing properties of polymer hydrogels result from dynamic covalent bonds and non-covalent interactions between polymer chains.
At present, the traditional polymer hydrogel electrolyte is generally used for manufacturing flexible electrochromic devices or energy storage devices, but when the flexible electrochromic devices or the energy storage devices are subjected to external mechanical damage or severe environments, the service life of the devices is severely limited due to the lack of self-healing characteristics. Therefore, it is of great significance to develop hydrogel electrolytes with significant self-healing properties that can be used in devices with both electrochromic and energy storage functions.
Disclosure of Invention
Aiming at the influence of the external environment on the electrolyte in the electrochromic energy storage dual-function device, the invention provides a preparation method of a self-healing hydrogel electrolyte for the electrochromic energy storage dual-function device.
The invention also aims to provide a simple and convenient manufacturing method of the electrochromic energy storage dual-function device, which comprises the steps of fixing a hollow separation groove between two electrodes by using 3M double faced adhesive tape, pouring a hydrogel solution into the hollow separation groove, and solidifying the hollow separation groove in the device under a circulating thawing condition; not only can ensure that the electrolyte layer is very thin, but also can prolong the service life of the device.
A self-healing hydrogel electrolyte for an electrochromic energy storage dual-function device and a device preparation method comprise the following steps:
(1) Preparation of modified polyvinyl alcohol: acrylamide (AM) was grafted onto polyvinyl alcohol (PVA) to prepare modified polyvinyl alcohol (PVA-g-AM). In the copolymerization reaction, PVA and AM are used as monomers in a nitrogen atmosphere to obtain a uniform PVA solution, AM is added, and a mixture of ammonium ceric nitrate and concentrated sulfuric acid is used as an initiator for initiation. After the reaction is finished, cooling the product to room temperature, then precipitating with acetone, washing with an acetone-water mixture for several times to remove a homopolymer, finally washing with pure acetone, and drying in an oven at 40 ℃ to finally obtain PVA-g-PAM;
(2) Preparation of hydrogel electrolyte: adding PVA-g-PAM into a mixed solvent of deionized water/glycerol at the temperature of 80 ℃, fully stirring and dissolving, sequentially adding potassium salt, zinc salt and an additive, and stirring and dissolving to obtain a hydrogel solution;
(3) Preparing an electrode material: depositing a Prussian blue film on the conductive glass by a constant current deposition method to be used as an anode of the electrochromic energy storage dual-function device; the zinc foil is used as a cathode of the electrochromic energy storage device;
(4) Manufacturing an electrochromic energy storage dual-function device: fixing a hollow separation groove between the two electrodes prepared in the step (2) by using a 3M double-sided adhesive, dropwise adding the hydrogel solution prepared in the step (1), and solidifying the hydrogel after circulating and thawing for three times to obtain the electrochromic energy storage dual-function device based on the modified polyvinyl alcohol self-healing hydrogel.
In the step (1), the concentration of PVA and AM is 0.1g/mL, the amount of ammonium ceric nitrate is 0.084mmol, the amount of concentrated sulfuric acid is 1.2mL, the reaction temperature is 85 ℃, and the reaction time is 12 hours.
The volume ratio of the deionized water to the glycerol in the mixed solvent of the deionized water and the glycerol in the step (1) is 2: 1.
In the step (2), the potassium salt is potassium chloride, and the concentration is 0.9mol/L; the zinc salt is one of zinc sulfate, zinc acetate or zinc trifluoromethanesulfonate, and the concentration is 0.1mol/L.
In the step (2), the additive is gelatin which is used as an interpenetrating network chain segment, and the mass ratio of the gelatin to PVA-g-PAM is 1: 1-6.
In the electrodeposition process in the step (3), ITO (indium tin oxide) conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, and a silver wire is used as a reference electrode.
In the device preparation process in the step (4), the thickness of the 3M double-sided adhesive tape is 400 μ M, and the thickness of the zinc foil is 80 μ M.
The invention has the following advantages:
the method for preparing the hydrogel electrolyte is simple and convenient, the hydrogel has self-healing performance, can keep complete morphological characteristics and high ionic conductivity within the range of minus 30-30 ℃, a device based on the hydrogel also has excellent electrochromic and energy storage performance within the range of minus 30-30 ℃, and has good application prospect in the fields of intelligent color-changing windows and flexible electronic equipment.
Drawings
Fig. 1 is a structural diagram of an electrochromic energy storage dual-function device.
FIG. 2 is the infrared spectrum of the graft copolymerization of PVA and PAM and the infrared spectrum of the hydrogel electrolyte prepared by using the same as the matrix. As can be seen from the figure, the characteristic functional groups of PVA and PAM can be embodied, and the successful graft copolymerization of PVA and PAM is proved; after addition of the additive, some characteristic peaks of the hydrogel shifted towards lower wavenumbers, indicating hydrogen bonding between PVA-g-PAM and the additive.
Fig. 3 is an optical microscope picture of the self-healing hydrogel electrolyte self-healing process.
FIG. 4 is the UV absorption spectrum and the coloring efficiency at room temperature after fabrication of an electrochromic energy storage device with the hydrogel of example 1; as can be seen, the maximum absorption wavelength of the device is 680nm, and at 680nm, the device has high coloring efficiency.
FIG. 5 is a constant current charging and discharging curve diagram of the electrochromic energy storage dual-function device; the results showed that the concentration of the compound was 0.02mA/cm at room temperature 2 Has a current density of 35.2mA · h/m at low current density discharge 2 Has a high coulombic efficiency of 97.6% at 0.8mA/cm 2 Can still provide 25.7 mA.h/m under the condition of high current density 2 The capacity of (a); meanwhile, the energy storage property is still kept at low temperature, and the capacity is 15.0 mA.h/m at-30 DEG C 2 。
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described below with reference to the following embodiments.
Example 1
(1) Preparation of modified polyvinyl alcohol:
the copolymerization of PVA with AM was carried out under nitrogen atmosphere. Adding 2.0g of PVA and 20mL of deionized water into a flask, completely dissolving the PVA at 85 ℃, adding 2.0g of AM into the solution, and finally adding 0.046g of ammonium ceric nitrate and 1.2mL of concentrated sulfuric acid as initiators to initiate and continue to react for 12 hours. After the reaction is finished, cooling the product to room temperature, then precipitating with 100mL of acetone, washing for 10 times with an acetone-water mixture (7: 3, volume ratio) to remove the homopolymer, finally washing with pure acetone, and drying in an oven at 40 ℃ to finally obtain PVA-g-PAM;
(2) Preparation of hydrogel electrolyte:
at the temperature of 80 ℃, 0.5g of PVA-g-PAM is added into 5mL of deionized water-glycerol (2: 1, volume ratio) mixed solvent, and stirred until the mixture is dissolved; 0.1g of gelatin is weighed into the solution and stirred for 20 minutes; then adding 0.9mol/L potassium chloride and 0.1mol/L zinc trifluoromethanesulfonate until the potassium chloride and the zinc trifluoromethanesulfonate are completely dissolved; stirring for 30 minutes to obtain a hydrogel solution;
(3) Preparing an electrode:
preparing a Prussian blue film by adopting a constant current deposition method, weighing 0.329g of potassium ferricyanide, 0.162g of ferric chloride, 0.746g of potassium chloride and 1mol/L of hydrochloric acid, dissolving in 100mL of deionized water to obtain an electrodeposition solution, and depositing at a constant current of 50 muA for 800 seconds; in the electrodeposition process, ITO conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, and a silver wire is used as a reference electrode;
(4) Preparing an electrochromic energy storage device:
fixing a hollow partition groove with a certain size and thickness on the ITO conductive glass deposited with the Prussian blue film by using a 3M double-sided adhesive, dripping the obtained uniform hydrogel solution into the partition groove, sticking the cut zinc foil onto the 3M double-sided adhesive, and circularly thawing for three times at the temperature of minus 20 ℃ and room temperature to solidify the hydrogel, thereby obtaining the electrochromic energy storage device based on the modified polyvinyl alcohol self-healing hydrogel.
Example 2
(1) Preparation of modified polyvinyl alcohol the same as in example 1
(2) Preparation of hydrogel electrolyte:
at the temperature of 80 ℃, 0.6g of PVA-g-PAM is added into 6mL of deionized water-glycerol (2: 1, volume ratio) mixed solvent, and stirred until the mixture is dissolved; 0.2g of gelatin is weighed into the solution and stirred for 20 minutes; then adding 0.9mol/L potassium chloride and 0.1mol/L zinc trifluoromethanesulfonate until the potassium chloride and the zinc trifluoromethanesulfonate are completely dissolved; stirring for 30 minutes to obtain a hydrogel solution;
(3) The electrodes and electrochromic energy storage devices were prepared in the same manner as in example 1.
Example 3
(1) Preparation of modified polyvinyl alcohol the same as in example 1
(2) Preparation of hydrogel electrolyte:
at the temperature of 80 ℃, 0.5g of PVA-g-PAM is added into 5mL of deionized water-glycerol (2: 1, volume ratio) mixed solvent, and stirred until dissolved; 0.1g of gelatin is weighed into the solution and stirred for 20 minutes; then adding 0.9mol/L potassium chloride and 0.1mol/L zinc sulfate until the potassium chloride and the zinc sulfate are completely dissolved; stirring for 30 minutes to obtain a hydrogel solution;
(3) The electrodes and electrochromic energy storage devices were prepared in the same manner as in example 1.
Example 4
(1) Preparation of modified polyvinyl alcohol the same as in example 1
(2) Preparation of hydrogel electrolyte:
at the temperature of 80 ℃, 0.5g of PVA-g-PAM is added into 5mL of deionized water-glycerol (2: 1, volume ratio) mixed solvent, and stirred until dissolved; 0.1g of gelatin is weighed into the solution and stirred for 20 minutes; then adding 0.9mol/L potassium chloride and 0.1mol/L zinc acetate until the mixture is completely dissolved; stirring for 30 minutes to obtain a hydrogel solution;
(3) The electrodes and electrochromic energy storage devices were prepared in the same manner as in example 1.
The above-described embodiments are intended to enable those skilled in the art to understand the disclosure of the present invention and to implement the same, and therefore should not be construed as limiting the scope of the present invention, but rather should be construed as covering equivalent variations or modifications within the spirit of the present invention.

Claims (8)

1. An electrochromic energy storage dual-function device based on modified polyvinyl alcohol self-healing hydrogel is characterized by comprising an ITO electrode deposited with electrochromic materials, a transparent self-healing hydrogel electrolyte and a zinc foil electrode.
2. The preparation method of the electrochromic energy storage dual-function device based on the modified polyvinyl alcohol self-healing hydrogel according to claim 1, wherein the preparation method comprises the following steps:
(1) Preparation of modified polyvinyl alcohol: acrylamide (AM) was grafted onto polyvinyl alcohol (PVA) to prepare modified polyvinyl alcohol (PVA-g-AM). In the copolymerization reaction, PVA and AM are used as precursors in a nitrogen atmosphere, an AM is added after a uniform PVA solution is obtained, and a mixture of ammonium ceric nitrate and concentrated sulfuric acid is used as an initiator for initiation. After the reaction is finished, cooling the product to room temperature, then precipitating with acetone, washing with an acetone-water mixture for several times to remove homopolymers, finally washing with pure acetone, and drying in a vacuum oven at 40 ℃ to finally obtain PVA-g-PAM;
(2) Preparation of hydrogel electrolyte: adding PVA-g-PAM into a deionized water/glycerol mixed solvent at the temperature of 80 ℃, fully stirring and dissolving, then sequentially adding potassium salt, zinc salt and an additive, and stirring and dissolving to obtain a hydrogel solution;
(3) Preparing an electrode material: depositing a Prussian blue film on the conductive glass by using a constant current deposition method to serve as an anode of the electrochromic energy storage device; the zinc foil is used as the cathode of the electrochromic energy storage device;
(4) Manufacturing an electrochromic energy storage dual-function device: and (3) fixing a hollow partition groove between the two electrodes prepared in the step (2) by using 3M double faced adhesive tape, dropwise adding the hydrogel solution prepared in the step (1), and solidifying the hydrogel after circulating and thawing for three times to obtain the electrochromic energy storage dual-function device based on the modified polyvinyl alcohol self-healing hydrogel.
3. The preparation method of the electrochromic energy storage dual-function device based on the modified polyvinyl alcohol self-healing hydrogel according to claim 2, wherein in the step (1), the concentrations of PVA and AM are both 0.1g/mL, the amount of ammonium ceric nitrate is 0.084mmol, and the amount of concentrated sulfuric acid is 1.2mL. The reaction temperature was 85 ℃ and the reaction time was 12 hours.
4. The preparation method of the electrochromic energy storage dual-function device based on the modified polyvinyl alcohol self-healing hydrogel according to claim 2, wherein a volume ratio of deionized water to glycerol in the mixed solvent of deionized water and glycerol in the step (1) is 2: 1.
5. The preparation method of the electrochromic energy storage bifunctional device based on the modified polyvinyl alcohol self-healing hydrogel according to claim 2, wherein in the step (2), the potassium salt is potassium chloride, and the concentration is 0.9mol/L; the zinc salt is one of zinc sulfate, zinc acetate or zinc trifluoromethanesulfonate, and the concentration is 0.1mol/L.
6. The preparation method of the electrochromic energy storage bifunctional device based on the modified polyvinyl alcohol self-healing hydrogel according to claim 2, wherein the additive in the step (2) is gelatin, the gelatin is used as an interpenetrating network chain segment, and the mass ratio of the gelatin to PVA-g-PAM is 1: 1-6.
7. The preparation method of the electrochromic energy storage dual-functional device based on the modified polyvinyl alcohol self-healing hydrogel according to claim 2, wherein in the electrodeposition process in the step (3), ITO (indium tin oxide) conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, and a silver wire is used as a reference electrode.
8. The preparation method of the electrochromic energy storage dual-function device based on the modified polyvinyl alcohol self-healing hydrogel according to claim 2, wherein in the preparation process of the device in the step (4), the thickness of the 3M double-sided adhesive tape is 400 μ M, and the thickness of the zinc foil is 80 μ M.
CN202111189884.6A 2021-10-12 2021-10-12 Self-healing hydrogel electrolyte for electrochromic energy storage dual-function device Pending CN115963665A (en)

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