CN116239855B - Transparent polymer network skeleton composite gel electrolyte film and preparation method and application thereof - Google Patents

Transparent polymer network skeleton composite gel electrolyte film and preparation method and application thereof Download PDF

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CN116239855B
CN116239855B CN202211641649.2A CN202211641649A CN116239855B CN 116239855 B CN116239855 B CN 116239855B CN 202211641649 A CN202211641649 A CN 202211641649A CN 116239855 B CN116239855 B CN 116239855B
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polymer network
electrolyte film
network skeleton
gel electrolyte
lithium
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CN116239855A (en
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刘涌
周昼
曾宇
程子强
赵方园
孙梦涛
韩高荣
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Shanxi Zhejiang University Institute Of New Materials And Chemical Industry
Zhejiang University ZJU
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Shanxi Zhejiang University Institute Of New Materials And Chemical Industry
Zhejiang University ZJU
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Abstract

The invention discloses a transparent polymer network skeleton composite gel electrolyte film, a preparation method and application thereof, and belongs to the field of electrochromic devices, wherein the composite gel electrolyte film comprises a polymer network skeleton, and strong polar plastic crystals, mixed plasticizers and metal lithium salts which are uniformly distributed in the polymer network skeleton, wherein the polymer network skeleton is formed by in-situ thermal triggering and crosslinking of polymer monomers, and the mass ratio of the polymer monomers, the strong polar plastic crystals, the mixed plasticizers and the metal lithium salts is 13-24:8-32:15-33:1. The preparation method of the transparent polymer network skeleton composite gel electrolyte film is simple, raw materials are easy to obtain, large-scale production is easy to realize, and the transparent polymer network skeleton composite gel electrolyte film has the characteristics of high visible light transparency, high ion conductivity and good mechanical strength.

Description

Transparent polymer network skeleton composite gel electrolyte film and preparation method and application thereof
Technical Field
The invention relates to the field of electrochromic devices, in particular to a transparent polymer network skeleton composite gel electrolyte film, a preparation method and application thereof.
Background
The polymer electrolyte has good mechanical property, high transparency and easy realization, can be used as an ion storage layer material of an electrochromic device, but has low ion conductivity and large interface impedance at normal temperature, and still needs to be further improved to meet the actual use requirement. The research work shows that the problems of low ionic conductivity and large interfacial resistance can be effectively improved by adding the plasticizer into the polymer matrix, and the common liquid plasticizers such as ethylene carbonate, propylene carbonate and the like have low viscosity and insufficient polarity, and the interfacial resistance and the ionic conductivity are improved to a certain extent, but the mechanical properties of the polymer electrolyte are reduced, so that the film formation is not facilitated. Therefore, it is difficult to raise the ionic conductivity of the polymer electrolyte to a desired level only by adding an appropriate amount of plasticizer, thereby satisfying the response speed required for electrochromic devices.
The inorganic filler Succinonitrile (SN) is a strong polar small molecular plastic crystal, is waxy at room temperature, and can further improve mechanical properties compared with a liquid plasticizer under the same volume. At present, main researches focus on storing an electrolyte mixed solution containing SN in micropores of a polymer substrate with high toughness, and cooperatively building a three-dimensional lithium ion channel, for example, chinese patent literature with publication number of CN115051028A discloses a nanofiber-based composite solid electrolyte, which is obtained by taking a conductive polymer nanofiber membrane with a three-dimensional intercommunication network structure as a substrate, coating an electrolyte solution (a mixture of succinonitrile, lithium salt and ionic liquid) on the surface of the nanofiber membrane and penetrating the electrolyte solution into the micropores of the nanofiber membrane of the three-dimensional intercommunication network. However, in the above method, SN cannot completely permeate the whole membrane, and interface transmission resistance between different phases has an inhibition effect on ion conductivity, and in addition, a product film is opaque, so that the method is difficult to apply to electrochromic devices.
The invention discloses an all-solid-state plastic crystal flexible electrolyte film, which is prepared by taking high molecular compounds such as polyvinyl alcohol, polyvinyl butyral and the like as a matrix, lithium salt as alkali metal salt and inorganic nano particles (nano ZrO 2 or nano Ta 2O5) as electrolyte additives and adopting two preparation methods of a casting method or a melt extrusion method, wherein the problems that the solvent volatilization process is long and the electrolyte cannot be uniformly dispersed are likely to exist.
Disclosure of Invention
In order to solve the problems of low ion mobility and low transparency caused by phase separation in the prior art, the invention provides a transparent polymer network skeleton composite gel electrolyte film which has a structure of being locked with electrolyte in a three-dimensional cross-linked skeleton, can be self-healed, has high viscoelasticity, uniform plastic crystal distribution, and has high visible light transparency, high ion conductivity and good mechanical strength.
The technical scheme adopted is as follows:
The transparent polymer network skeleton composite gel electrolyte film comprises a polymer network skeleton, and strong polar plastic crystals, mixed plasticizers and metal lithium salts which are uniformly distributed in the polymer network skeleton, wherein the polymer network skeleton is formed by in-situ thermal triggering and crosslinking of polymer monomers, and the mass ratio of the polymer monomers to the strong polar plastic crystals to the mixed plasticizers to the metal lithium salts is 13-24:8-32:15-33:1.
The strong polar plastic crystal comprises succinonitrile;
the mixed plasticizer comprises at least two of propylene carbonate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, dimethylformamide, r-butyrolactone, PEG400 (polyethylene glycol), PPG1000 (polypropylene glycol), methyl formate, methyl acetate, tetrahydrofuran and 1, 2-dimethoxyethane;
The polymer monomers include, but are not limited to, methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, butyl methacrylate, and the like;
The metal lithium salt comprises at least one of lithium perchlorate, lithium hexafluorophosphate, lithium difluorooxalato borate, lithium bistrifluoromethylsulfonyl imide, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium dioxaoxalato borate and lithium trifluoromethane sulfonate.
The invention also provides a preparation method of the transparent polymer network skeleton composite gel electrolyte film, which comprises the following steps:
(1) Preparing a precursor solution by taking a polymer monomer, an initiator, a cross-linking agent, strong polar plastic crystals, a mixed plasticizer and metal lithium salt as raw materials;
(2) And thermally crosslinking the precursor solution to obtain the transparent polymer network skeleton composite gel electrolyte film.
The invention prepares a polymer cross-linked network with uniform structure by utilizing the interaction between the strong polar plastic crystal, the mixed plasticizer and the polymer unit through in-situ thermal trigger polymerization, so that the plastic crystal is uniformly distributed in the cross-linked network to form an effective ion transmission channel.
Preferably, the initiator is added in an amount of 0.1 to 0.5 weight percent and the crosslinking agent is added in an amount of 1 to 5 weight percent based on 100 weight percent of the polymer monomer; the initiator comprises at least one of azodiisobutyronitrile, benzoyl peroxide and benzophenone, and the cross-linking agent is an organosilicon cross-linking agent.
In the step (2), the transparent polymer network skeleton composite gel electrolyte film can be prepared by adopting one-step thermal crosslinking, and can also be prepared by adopting two-step thermal crosslinking, and when the one-step thermal crosslinking method is adopted, the parameters of the thermal crosslinking are as follows: when a two-step thermal crosslinking method is adopted at 50-70 ℃ for 2-6h, the parameters of the first step of crosslinking are as follows: the temperature is 50-60 ℃ and 0.5-2 h, and the parameters of the second step of crosslinking are as follows: 60-70 ℃ for 2-4 h.
The invention also provides an electrochromic device, and the structure comprises the transparent polymer network skeleton composite gel electrolyte film. Preferably, the structure of the electrochromic device comprises the following components stacked in sequence: the electrolyte comprises a basal layer, a current collecting layer, an electrochromic layer, the transparent polymer network skeleton composite gel electrolyte film, an ion storage layer, a current collecting layer and a basal layer.
The electrochromic device prepared by the composite gel electrolyte film has low interface impedance and good cycle performance, and meanwhile, the mechanical property and the heat resistance of the electrochromic device are enhanced due to the excellent elasticity, toughness and thermosetting property of the composite gel electrolyte film.
The transparent polymer network skeleton composite gel electrolyte film has high ion conductivity, is mainly used for transmitting lithium ions between positive and negative electrodes, has high visible light transparency, and does not influence the change of an electrochromic layer.
The preparation method of the electrochromic device comprises the following steps:
(1) Preparing a precursor solution by taking a polymer monomer, an initiator, a cross-linking agent, strong polar plastic crystals, a mixed plasticizer and metal lithium salt as raw materials;
(2) The precursor solution is subjected to first-step crosslinking for 0.5 to 2 hours at the temperature of 50 to 60 ℃ to prepare a pre-crosslinked gel electrolyte film;
(3) And (3) sequentially assembling the pre-crosslinked gel electrolyte film obtained in the step (2) with the basal layer, the current collecting layer, the electrochromic layer and the ion storage layer, then reinforcing, vacuumizing and packaging to obtain an electrochromic element, and performing second-step crosslinking on the electrochromic element at 60-70 ℃ for 2-4 hours to obtain the electrochromic device.
In the process of preparing the electrochromic device, the transparent polymer network skeleton composite gel electrolyte film is formed by two-step thermal crosslinking, and the thermal crosslinking is carried out in two steps, wherein the pre-crosslinked gel electrolyte film with a certain crosslinking degree is obtained in the first step, and is further cured after being assembled into the device in the second step, so that the influence of the thermal gelation effect is effectively avoided, and the electrolyte film is well contacted with the electrode. If the uncrosslinked solution is directly injected into a device for heating and curing, uneven distribution of polymer electrolyte can be caused by a thermal gel effect, and uneven contact with an electrode can affect the color changing effect and the circulation stability; if the completely crosslinked gel electrolyte film is assembled with a device, the problem of poor contact exists, and the polymer electrolyte film cannot be cooled to form a film after being melted again by heating after the assembly is completed like a common polymer electrolyte because of the special heat curing property of a crosslinked network structure, so that the polymer electrolyte film can be in good contact with an electrode.
Preferably, the vacuum degree range is less than 133MPa during the assembly of the electrochromic device.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention utilizes polymer monomer solution to perform in-situ thermal trigger free radical polymerization to form a three-dimensional crosslinked network structure, strong-polarity plastic crystals are uniformly distributed in the polymer network skeleton, a three-dimensional lithium ion conducting channel is built together, and simultaneously, lithium ion active conductive liquid is blocked by utilizing gel swelling characteristics of the three-dimensional crosslinked network. The three-dimensional cross-linked network structure improves the mechanical strength of the transparent polymer network skeleton composite gel electrolyte film, and realizes the self-healing high viscoelasticity of flexibility. In addition, the preparation method of the transparent polymer network skeleton composite gel electrolyte film is simple, raw materials are easy to obtain, mass production is easy, and the transparent polymer network skeleton composite gel electrolyte film has the characteristics of high visible light transparency, high ion conductivity and good mechanical strength.
(2) Compared with the traditional tape casting method adopting a strong polar solvent to dissolve polymer matrix particles, the preparation method disclosed by the invention has the advantages that solvent volatilization is not needed, on one hand, the procedure is simplified, and on the other hand, the problem that high-concentration plastic crystals and electrolyte cannot be uniformly dispersed due to the solvent volatilization process is avoided, so that the performance of an electrochromic device prepared by the method is improved, and the space-selective electrochromic imaging defect generated in the working process of the electrochromic device is avoided.
(3) The invention uses the pre-crosslinked gel electrolyte film to be assembled into the electrochromic element preliminarily, and then carries out the second step of crosslinking treatment to obtain the electrochromic device, thereby replacing the direct solution filling thermal initiation film forming in the electrochromic device and improving the problems of uneven reaction caused by gel effect and poor contact of two sides of the electrolyte layer.
Drawings
FIG. 1 shows the AC impedance spectra of the product films of example 1 and comparative example 1, wherein A is example 1 (PMMA/PC/SN) and B is comparative example 1 (PMMA/PC).
FIG. 2 is a graph of current versus time for the product films of example 1 and comparative example 1.
FIG. 3 is a voltammogram of a transparent polymer network backbone composite gel electrolyte film of example 1.
FIG. 4 is a graph showing the transmission spectrum of the electrochromic device of example 5.
Fig. 5 is an optical image of the electrochromic device of example 5 before and after color change in different electrochemical states, where a is before color change and B is after color change.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
Example 1 preparation of transparent Polymer network skeleton composite gel electrolyte film
S1, mixing MMA (methyl methacrylate), AIBN (azobisisobutyronitrile) and EDGMA (ethylene glycol dimethacrylate) according to a mass ratio of 1:0.03:0.3 (6 g MMA monomer solution, 0.018g AIBN and 0.18g EDGMA) into a three-necked flask, stirring by an intelligent digital display magnetic stirrer until a clear and transparent solution is formed in the three-necked flask, wherein the stirring temperature is 30 ℃ and the stirring speed is 600rpm; 3.5g PC (propylene carbonate), 4.0g EC (ethylene carbonate) and 2.5g SN (succinonitrile) are further added into the clear and transparent solution, and the mixture is stirred uniformly under the conditions; adding 0.3g LiClO 4 min, sweeping with nitrogen, and stirring for 6h under the above conditions to fully dissolve and ionize the active lithium salt in the solution to obtain precursor solution;
S2, preparing a transparent polymer network skeleton composite gel electrolyte film: and naturally casting the precursor solution into a mould, putting the mould into an oven for crosslinking for 2 hours at 60 ℃ to enable SN and PC, EC, liClO 4 to be orderly and uniformly dispersed in a three-dimensional ion-conducting network constructed by a polymer formed by crosslinking MMA monomers, thus obtaining the transparent polymer network skeleton composite gel electrolyte film.
Example 2 preparation of transparent Polymer network skeleton composite gel electrolyte film
The preparation method of the transparent polymer network skeleton composite gel electrolyte film in this example is different from that in example 1 only in that the succinonitrile added amount in step S1 is 3.5g.
Example 3 preparation of transparent Polymer network skeleton composite gel electrolyte film
The preparation method of the transparent polymer network skeleton composite gel electrolyte film in this example is different from that in example 1 only in that the succinonitrile added amount in step S1 is 6.5g.
Example 4 preparation of transparent Polymer network skeleton composite gel electrolyte film
The preparation method of the transparent polymer network skeleton composite gel electrolyte film in the embodiment is different from that in the embodiment 1 only in that in the step S1, the polymer monomer is butyl acrylate, the metal lithium salt is lithium fluorophosphate, the addition amount is 0.25g, and in the step S2, the transparent polymer network skeleton composite gel electrolyte film is placed into an oven to be crosslinked for 0.5h at 50 ℃ and then crosslinked for 2h at 70 ℃.
Comparative example 1
The gel polymer electrolyte membrane in this comparative example is different from the transparent polymer network skeleton composite gel electrolyte membrane in example 1 only in that succinonitrile is not added in step S1.
Comparative example 2
The gel polymer electrolyte thin film in this comparative example was different from the transparent polymer network skeleton composite gel electrolyte thin film in example 1 in that in step S1, 6g mma monomer solution, 0.018g AIBN and 0.18g EDGMA were not added, but 6.18gPMMA g polymer was added, dissolved in 25g acetone, and further a polar plastic crystal, mixed plasticizer and metal lithium salt were added as in example 1 to prepare a precursor solution; in the step S2, the precursor solution is baked for 24 hours in a vacuum oven at 60 ℃ to obtain the gel polymer electrolyte film.
Example 5 preparation of electrochromic device
In this embodiment, the method for manufacturing an electrochromic device includes the steps of:
S1, mixing MMA (methyl methacrylate), AIBN (azobisisobutyronitrile) and EDGMA (ethylene glycol dimethacrylate) according to a mass ratio of 1:0.03:0.3 (6 g MMA monomer solution, 0.018g AIBN and 0.18g EDGMA) into a three-necked flask, stirring by an intelligent digital display magnetic stirrer until a clear and transparent solution is formed in the three-necked flask, wherein the stirring temperature is 30 ℃ and the stirring speed is 600rpm; 3.5g PC (propylene carbonate), 4.0g EC (ethylene carbonate) and 6.5g SN (succinonitrile) are further added into the clear and transparent solution, and the mixture is stirred uniformly under the conditions; adding 0.3g LiClO 4 min, sweeping with nitrogen, and stirring for 6h under the above conditions to fully dissolve and ionize the active lithium salt in the solution to obtain precursor solution;
S2, preparing a transparent polymer network skeleton composite gel electrolyte film: and naturally casting the precursor solution into a mould, putting the mould into an oven at 60 ℃ for pre-crosslinking for 1h, and orderly and uniformly dispersing SN and PC, EC, liClO 4 into a three-dimensional ion-conducting network constructed by a polymer formed by crosslinking MMA monomers to obtain the transparent polymer network skeleton composite gel electrolyte film.
S3, preparing an electrochromic device: the transparent polymer network skeleton composite gel electrolyte film prepared by cutting S2 by a microtome is a square slice with the thickness of 10cm multiplied by 10cm, and positive and negative electrodes with the thickness of 10cm multiplied by 10cm are assembled into a structure that: and (3) vacuum sealing the device, placing the device in a vacuum oven, and curing and crosslinking at 60 ℃ for 4 hours to obtain the device prototype of the composite gel electrolyte film/NiO/ITO/glass prepared by glass/ITO/WO 3/S2.
Comparative example 3 preparation of electrochromic device
The preparation method of the electrochromic device in this example is different from that in example 5 only in that the electrochromic device is assembled by using the gel polymer electrolyte film prepared in comparative example 2, and the electrochromic device is obtained by vacuum-sealing the device and then placing the device in a vacuum oven and heating at 140 ℃ for 0.5 h.
Sample analysis
1. Ion conductivity
The alternating current impedance spectrum test is to clamp the electrolyte film of the product to be tested between the blocking electrodes, and use the electrochemical workstation of the Netherlands IVIUM to test the ionic conductivity of the composite gel electrolyte films prepared in examples 1-4 and the gel polymer electrolyte films prepared in comparative examples 1-2, wherein the variables in examples 1-3 are the volume ratio of added SN and carbonate plasticizer, and the ionic conductivity of the composite gel electrolyte films in examples is higher than that in comparative example 1, the alternating current impedance spectra of the product films in example 1 and comparative example 1 are respectively shown as A and B in figure 1, and when the SN addition amount is 6.5g, the ionic conductivity can reach 1.2X10 -2 S/cm at room temperature, which is obviously higher than that of comparative examples 1 and 2.
2. Lithium ion mobility test
Lithium ion mobility test the electrolyte films of the products to be tested were sandwiched between blocking electrodes, and the electrolyte films of the products prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to a current time-dependent curve test under constant voltage using an electrochemical workstation of Shanghai Chenhua CHI 604B. The current-time curves of the product films of example 1 and comparative example 1 are shown in fig. 2, and it can be seen from the graph that the lithium ion mobility of the composite gel electrolyte film of example 1 is about 0.35, and the lithium ion mobility of the gel polymer electrolyte film of comparative example 1 is about 0.2, which shows that the addition of succinonitrile can effectively improve the lithium ion transmission efficiency.
3. Electrochemical window testing
Electrochemical window test the voltammogram of the transparent polymer network backbone composite gel electrolyte film of example 1 was shown in figure 3 using the Shanghai Chenhua CHI604B electrochemical workstation with the electrolyte film of the product to be tested sandwiched between the blocking electrodes. The graph shows that the composite gel electrolyte film is in a stable state within +/-4V and has good electrochemical stability.
4. Electrochromic device testing
The electrochromic device performance test adopts an ultraviolet spectrophotometer and an electrochemical workstation, and the transmission spectrum of the electrochromic device in the test example 5 is shown in fig. 4, the electrochemical stability of the electrochromic device in the test example 5 is higher, the device is in a fading state at-3.5V, is in a dark blue coloring state at 3.5V, and the modulation amplitude at 695nm is 50%; fig. 5 is an optical picture of the electrochromic device before and after color change in different electrochemical states, wherein a is before color change and B is after color change, indicating that the electrochromic device has good color change performance. In comparative example 3, the device assembled by the film directly prepared by PMMA has uneven discoloration due to poor contact, and meanwhile, the cyclic stability is poor, which is difficult to realize practical application.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.

Claims (4)

1. An electrochromic device, wherein the structure of the electrochromic device comprises the following components which are sequentially stacked: the electrolyte comprises a basal layer, a current collecting layer, an electrochromic layer, a transparent polymer network skeleton composite gel electrolyte film, an ion storage layer, a current collecting layer and a basal layer;
The transparent polymer network skeleton composite gel electrolyte film comprises a polymer network skeleton, and strong polar plastic crystals, mixed plasticizers and metal lithium salts which are uniformly distributed in the polymer network skeleton, wherein the polymer network skeleton is formed by in-situ thermal triggering and crosslinking of polymer monomers, and the mass ratio of the polymer monomers to the strong polar plastic crystals to the mixed plasticizers to the metal lithium salts is 13-24:8-32:15-33:1;
the preparation method of the electrochromic device comprises the following steps:
(1) Preparing a precursor solution by taking a polymer monomer, an initiator, a cross-linking agent, strong polar plastic crystals, a mixed plasticizer and metal lithium salt as raw materials;
(2) The precursor solution is subjected to first-step crosslinking for 0.5 to 2 hours at the temperature of 50 to 60 ℃ to prepare a pre-crosslinked gel electrolyte film;
(3) And (3) sequentially assembling the pre-crosslinked gel electrolyte film obtained in the step (2) with the basal layer, the current collecting layer, the electrochromic layer and the ion storage layer, then reinforcing, vacuumizing and packaging to obtain an electrochromic element, and performing second-step crosslinking on the electrochromic element at 60-70 ℃ for 2-4 hours to obtain the electrochromic device.
2. The electrochromic device according to claim 1, wherein said strongly polar plastic crystals comprise succinonitrile; the mixed plasticizer comprises at least two of propylene carbonate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, dimethylformamide, r-butyrolactone, polyethylene glycol, polypropylene glycol, methyl formate, methyl acetate, tetrahydrofuran and 1, 2-dimethoxyethane.
3. The electrochromic device according to claim 1, wherein said polymer monomer comprises methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate or butyl methacrylate; the metal lithium salt comprises at least one of lithium perchlorate, lithium hexafluorophosphate, lithium difluorooxalato borate, lithium bistrifluoromethylsulfonyl imide, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium dioxaoxalato borate and lithium trifluoromethane sulfonate.
4. The electrochromic device according to claim 1, wherein the initiator is added in an amount of 0.1 to 0.5wt% and the crosslinking agent is added in an amount of 1 to 5wt%, based on 100% by weight of the polymer monomer; the initiator comprises at least one of azodiisobutyronitrile, benzoyl peroxide and benzophenone, and the cross-linking agent is an organosilicon cross-linking agent.
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