CN114752210A - Ultraviolet curing electrolyte, preparation method of electrolyte membrane and electrochromic device - Google Patents
Ultraviolet curing electrolyte, preparation method of electrolyte membrane and electrochromic device Download PDFInfo
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- CN114752210A CN114752210A CN202210521157.3A CN202210521157A CN114752210A CN 114752210 A CN114752210 A CN 114752210A CN 202210521157 A CN202210521157 A CN 202210521157A CN 114752210 A CN114752210 A CN 114752210A
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- curing agent
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- electrolyte
- electrolyte membrane
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 72
- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000001723 curing Methods 0.000 claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 25
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000007784 solid electrolyte Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 16
- -1 1- (2, 4-difluorophenyl) -3-pyrrolyl Chemical group 0.000 claims description 14
- 239000004925 Acrylic resin Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 11
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
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- 238000010521 absorption reaction Methods 0.000 claims description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 238000003848 UV Light-Curing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 3
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- CGWGNMXPEVGWGB-UHFFFAOYSA-N 2-hydroxy-1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=C(CCO)C=C1 CGWGNMXPEVGWGB-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
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- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
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- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- OWNSEPXOQWKTKG-UHFFFAOYSA-M lithium;methanesulfonate Chemical compound [Li+].CS([O-])(=O)=O OWNSEPXOQWKTKG-UHFFFAOYSA-M 0.000 claims description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
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- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 4
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- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- JTOZNOWMMLUVTP-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine;thiophene Chemical compound C=1C=CSC=1.O1CCOC2=CSC=C21 JTOZNOWMMLUVTP-UHFFFAOYSA-N 0.000 description 1
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- 238000010505 homolytic fission reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- G02F1/1533—Constructional details structural features not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention discloses an ultraviolet curing electrolyte, which comprises the following raw material components: acrylic acid UV resin, epoxy resin, active diluent, curing agent, ionic liquid, lithium salt, the curing agent contains the photocuring agent, and the raw material components still include epoxy resin. The ultraviolet curing electrolyte has excellent light transmittance, electrolyte membrane strength and room temperature ionic conductivity. The invention also discloses a preparation method of the electrolyte membrane and an electrochromic device.
Description
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to an ultraviolet curing electrolyte, a preparation method of an electrolyte membrane and an electrochromic device.
Background
Electrochromism refers to a phenomenon that optical properties (reflectivity, transmittance, extraction rate and the like) of a material are subjected to stable and reversible color change under the action of an external electric field, and the electrochromism is represented by reversible changes of color and transparency in appearance. As an important component of an electrochromic device, an electrolyte has been a difficulty in implementing the electrochromic device, and electrolytes in a solid form include a gel electrolyte and a solid electrolyte.
The gel electrolyte is formed by compounding a solid polymer and a liquid electrolyte, and has the following technical defects: firstly, the mass proportion of the electrolyte is often larger (>80 wt%), which results in poor mechanical properties of the electrolyte; secondly, when the polymer proportion is increased, the ionic conductivity is sharply reduced, so that the color change performance of the electrochromic device is reduced; third, liquid solvents and the like contained in the gel electrolyte are volatile, and the failure of the device due to electrolyte volatilization and stripping is easily caused in the using process.
The solid electrolyte comprises an inorganic solid electrolyte and a solid polymer electrolyte, the inorganic solid electrolyte has the defects of low membrane conductivity, difficult large-area membrane formation, easy short circuit failure of a device and the like, and the solid polymer electrolyte mainly has the defects of low ionic conductivity and easy phase separation between ionic salt and polymer to cause device failure.
The ionic liquid modified solid electrolyte is called as a quasi-solid electrolyte, and a quasi-solid electrolyte system in the prior art has the defect that at least one of light transmittance, electrolyte membrane strength and room-temperature ionic conductivity is poor or unstable, so that the cycling stability of an electrochromic device is deteriorated.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides an ultraviolet curing electrolyte which can ensure the optical transmittance and improve the strength of an electrolyte membrane; the electrolyte membrane and the color-changing material layer are tightly bonded, and the electrolyte membrane has the characteristics of high room-temperature ionic conductivity and low interface impedance, and is favorable for the circulation stability of the device.
In order to achieve the purpose, the technical scheme of the invention is as follows: an ultraviolet curing electrolyte comprises the following raw material components: acrylic UV resin, epoxy resin, reactive diluent, curing agent, organic and/or inorganic ion salt, lithium salt, the curing agent contains light curing agent.
The preferable technical scheme is that the coating mainly comprises the following components in percentage by mass:
acrylic UV resin 10-25%
10 to 30 percent of epoxy resin
5 to 15 percent of active diluent
35 to 55 percent of organic and/or inorganic ion salt
5 to 10 percent of lithium salt
The mass of the curing agent is 1-5%, preferably 1-3%, and more preferably 2% of the sum of the mass of the acrylic UV resin, the mass of the epoxy resin and the mass of the reactive diluent. The sum of the mass percentages of the acrylic UV resin, the epoxy resin and the reactive diluent is 30-70%, preferably 40-60%, and more preferably 40-50%.
The mass percent of the organic and/or inorganic ion salt is 35-55%, preferably 35-40%, and more preferably 37.5%; the mass percent of the lithium salt is 5% to 10%, preferably 8% to 10%, and more preferably 10%.
The preferable technical scheme is that the viscosity of the epoxy resin is 25-40 Pa.S at 25 ℃, and the acid value is 3-5 mgKOH/g; and/or the viscosity range of the acrylic UV resin at 25 ℃ is 10-15 Pa.S. The practical operation mode is mainly knife coating, certain requirements on uniformity and knife coating thickness are met, viscosity is too low, the fluidity of the mixed solution is extremely high, so that the film layer is extremely thin, electrolyte transmission ion/electron channels are insufficient, the conveying capacity is reduced, and the conductivity is influenced; the viscosity is too high to facilitate the operation.
The preferable technical scheme is that the curing agent comprises a first curing agent and a second curing agent;
the first curing agent is one or more selected from bis (1- (2, 4-difluorophenyl) -3-pyrrolyl) dicyclopentadiene, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, benzoin dimethyl ether, methyl o-benzoylbenzoate and 2-hydroxy-4' - (2-hydroxyethyl) -2-methyl propiophenone; considering the irradiation wavelength range of the UV lamp, selecting a corresponding curing agent, wherein the curing agent has an effective absorption peak value within a wider absorption range (350 nm-400 nm), and can generate one or more free radicals after irradiation to initiate crosslinking polymerization and accelerate the curing efficiency; the optical bleaching/coating layer is required to have the non-yellowing characteristic, so that the interference of electrochromism is avoided; after absorbing light energy, initiator molecules jump to an excited singlet state and jump to an excited triplet state through intersystem leap, and when the initiator molecules are in the excited singlet state or the excited triplet state, the molecular structure is in an unstable state, weak bonds in the initiator molecules can generate homolytic cleavage, primary active free radicals are generated, and the oligomer and the active diluent are initiated to be polymerized and crosslinked.
And/or the second curing agent is one or more selected from alpha-hydroxyisobutyrophenone, 1-hydroxycyclohexyl phenyl ketone, 4- (p-tolylthio) benzophenone and ethyl 4-dimethylaminobenzoate. The ultraviolet light penetrates through the resin to generate phenomena such as light absorption and scattering, and the received light intensity is different along with the difference of the upper surface distance. The near-surface region generates high-concentration free radicals in a short time, so that the resin of the near-surface region is quickly cured, and the sample is unevenly cured to generate internal stress; the second curing agent makes up the defect that the deep layer may be incompletely cured, and has the advantages of wide applicability and economy.
The preferable technical scheme is that the mass of the first curing agent and the mass of the second curing agent are respectively 0.5-2.5% of the sum of the mass of the acrylic UV resin, the mass of the epoxy resin and the mass of the reactive diluent.
The preferable technical scheme is that the epoxy resin is one or more selected from polyphenol type glycidyl ether epoxy resin, modified epoxy acrylate resin and aliphatic glycidyl ether epoxy resin; the polyphenol type glycidyl ether epoxy resin is a multifunctional epoxy resin, has more than two epoxy groups in the molecule, and has high crosslinking density; the modified epoxy acrylate resin has good water solubility and dryness, and better stability compared with other epoxy resins; the epoxy group of the aliphatic epoxy resin is directly connected to the alicyclic ring, a compact rigid molecular structure can be formed, the crosslinking density is increased after curing, the tensile strength is high, no benzene ring is contained, and the weather resistance is good.
And/or the acrylic UV resin is one or more selected from aliphatic polyurethane acrylate oligomer, polyurethane epoxy acrylate oligomer, vinyl diacrylate and bifunctional polyester acrylic resin. The selected acrylic UV resin has medium and high functionality, is water white transparent viscous liquid, has obvious oxygen inhibition, can improve the surface defects of a system such as leveling, pocking marks and the like, and has excellent adhesive force to a PET film.
The preferable technical scheme is that the organic and/or inorganic ion salt is one or more selected from 1-butyl-3-methylimidazole dinitrile amine salt, 1-vinyl-3-ethylimidazole bistrifluoromethane yellow imide salt, 1-butyl-3-methylimidazole hexafluorophosphate and 1-butyl-3-methylimidazole tetrafluoroborate;
and/or the lithium salt is one or more of lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) amide, lithium methylsulfonate, lithium perchlorate and lithium tetrafluoroborate.
The preferable technical scheme is that the reactive diluent is one or more selected from ethylene glycol diglycidyl ether, 1, 6-hexanediol diacrylate, methoxy polyethylene glycol (350) monoacrylate, methoxy polyethylene glycol (550) monomethacrylate and beta-hydroxyethyl methacrylate. The methacrylate is a free radical type reactive diluent, contains an epoxy group, can participate in the curing reaction of the epoxy resin, and becomes a part of a cross-linked network structure; low molecular weight, low viscosity of prepolymer, no influence on the performance of cured film layer and toughening effect.
The invention also aims to provide a preparation method of the electrolyte membrane, which is based on the ultraviolet curing electrolyte and comprises the following steps:
s1: the curing agent is dissolved in the active diluent;
s2: sequentially adding the acrylate resin and the epoxy resin into the mixed system obtained in the step S1 according to the proportion, and uniformly mixing;
s3: dissolving lithium salt in organic and/or inorganic ion salt to obtain an ionic liquid mixed solution, adding the ionic liquid mixed solution into the mixed system obtained in S2, and uniformly mixing and defoaming;
s4: and (4) coating the mixed solution obtained in the step (S3) on the surface of a substrate, and carrying out anaerobic UV curing and drying to obtain the solid electrolyte membrane.
When the curing agent which is solid at normal temperature has low solubility in the reactive diluent, the mixed system can be optionally heated, and/or the dissolution of the curing agent can be further accelerated by stirring. The heating temperature of the electrolyte membrane preparation method S1 is preferably 40-60 ℃. The curing agent has a certain solubility in the diluent, and the solubility is related to the solute, namely the curing agent, and is influenced by the temperature. The crystal is adhered to the bottom of the container, and is easy to separate out when the temperature is too high; if the temperature is too low, the solubility is not high, and residual curing agent powder exists, which wastes materials.
The preferable technical proposal is that the absorption wavelength in UV curing is 350nm to 400 nm; the lamp power is 250w, and the illumination time is 30-300 s. The UV curing process parameters are inherent in the device, and the curing agent absorption effective peak is not in the device beyond/below the wave band range, namely the curing agent absorption effective peak is not adaptive, and the energy cannot be absorbed to generate transition.
It is a further object of the present invention to provide an electrochromic device comprising a solid electrolyte membrane made of the above-mentioned uv-curable electrolyte. The thickness of the electrolyte membrane ranges from 30 μm to 50 μm. The electrolyte film is too thin, the interface adhesive force is insufficient, phase separation can occur, ion/electron transmission channels are few, and the fading and coloring efficiency is influenced; and the electrolyte membrane is too thick, and the transmission path is too long, which also influences the conductivity.
The electrochromic device comprises a transparent electrode, a color-changing material layer, a solid electrolyte membrane, a counter electrode and a transparent electrode which are sequentially stacked, wherein the color-changing material of the color-changing material layer is a dioxythiophene conductive polymer.
The invention has the advantages and beneficial effects that:
the ultraviolet curing electrolyte has good fluidity before curing, is beneficial to increasing the wetting fusion between the color-changing material layer and the electrolyte, is fully contacted between layers, and has positive influence on the performance of a device;
organic and/or inorganic ion salt components in the ultraviolet curing electrolyte component not only provide the function of ion salt, but also have the function of dissociating lithium salt, the good ionic conductivity is shown at different temperatures, the service life of the device is favorably prolonged, the response time of the electrochromic device is short, the color change speed of reversible change between transparent and blue is fast, the response time of the conversion from the fading state to the coloring state and from the coloring state to the fading state is fast, and the actually measured conversion time of pinching the surface is less than 5 s;
the electrolyte generates binding power during ultraviolet curing, so that the assembly and packaging integration of the all-solid-state electrochromic device is realized, and a new idea is provided for large-area assembly of the electrochromic device; the all-solid-state electrochromic device prepared by adopting the ultraviolet curing electrolyte has excellent interlayer bonding force and is beneficial to improving the overall stability of the device;
the processing mode of ultraviolet curing of the quasi-solid electrolyte layer enables the electrolyte preparation process to be simpler, has low cost and short preparation period, has no special requirements on equipment, is suitable for mass production, and provides a foundation for industrialization of large-area electrochromic devices.
Drawings
FIG. 1 is an optical photograph of a UV-curable electrolyte membrane according to example 1 of the present invention;
FIG. 2 is a SEM scan of a UV cured electrolyte membrane of example 1 of the present invention;
FIG. 3 is a graph showing a visible light optical transmittance test of an UV-curable electrolyte membrane according to example 1 of the present invention;
FIG. 4 is a graph showing the conductivity test of the UV-curable electrolyte membrane at different temperatures according to example 2 of the present invention;
FIG. 5 is a graph showing the transmittance of visible light of an electrochromic device in a colored state and a discolored state according to example 2 of the present invention;
FIG. 6 is a sectional scanning test chart of the UV curable electrolyte membrane and the color-changing material layer according to example 3 of the present invention;
FIG. 7 is a stress strain plot of a UV cured electrolyte membrane according to example 3 of the present invention;
FIG. 8 is a rheological graph of a UV curable electrolyte raw material mixing system according to example 3 of the present invention;
FIG. 9 is a graph of the electrochemical window range of a UV cured electrolyte membrane of example 3 of the present invention;
fig. 10 is a graph showing the results of the optical cycle stability test of the electrochromic device of example 3 of the present invention.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
Example 1 a method for preparing a uv curable electrolyte membrane was:
s1: taking 0.2% of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide powder of the total system, adding the 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide powder into methoxypolyethylene glycol (350) monoacrylate (accounting for 8% of the total system), heating and stirring the mixture at the same time until the powder is completely dissolved, sucking and dripping alpha-hydroxyisobutyrylbenzene (accounting for 0.2% of the total system), and slightly stirring the mixture for later use;
s2: sampling the aliphatic polyurethane acrylate oligomer accounting for 16 percent of the total system and the modified epoxy acrylate resin accounting for 16 percent of the total system according to the proportion, sequentially dripping the mixture obtained in the step S1, and uniformly stirring to obtain first mixed slurry; the mass ratio of the methoxy polyethylene glycol (350) monoacrylate to the aliphatic polyurethane acrylate oligomer to the modified epoxy acrylate resin is 1: 2: 2, accounting for 40 percent of the total system. The sum of the two curing agents is 1 percent of the sum of the mass of the three components.
S3: adding lithium salt LiTFSI powder accounting for 8 percent of the total system into organic and/or inorganic ion salt [ BMim ]]PF6Then, the mixture is mixed with the first mixed slurry obtained in step S2, and the mixture is stirred to obtain a clear and transparent mixed liquid with good compatibility. Sealing, and ultrasonically treating for 3-5 min to remove bubbles. In this example, [ BMim]PF6Accounting for 51.6 percent of the total system, and the stirring speed is not specially specified. The total system is the ultraviolet curing electrolyte membrane system, and the same is applied below.
S4: 0.3ml to 0.5ml of the mixed liquid is absorbed by a dropper, a 50-mesh wire rod is used for quickly and slowly coating the mixed liquid on a PET sheet material, and another flat and clean sheet material is taken to cover a coating to avoid oxidation. And in UV curing, the absorption wavelength is 393nm, the lamp power is 250w, and UV illumination is carried out for 5min to obtain a transparent solid electrolyte membrane.
Example 1 test results of solid electrolyte membrane:
1.1 photograph of solid electrolyte membrane referring to fig. 1, the thickness of the solid electrolyte membrane was 32 μm;
1.2 the surface of the solid electrolyte membrane of example 1 was subjected to an electron scanning test, and the SEM image is shown in FIG. 2. The surface of the solid electrolyte membrane is rough but has no hole state, and the continuous fold state presents a hilly-like shape which is formed due to a cross-linking structure in the polymer; in addition, the highly compact micro-morphology indicates that the electrolyte membrane is uniform and has no significant phase separation;
1.3 testing the visible light transmittance of the electrolyte membrane by using an ultraviolet spectrophotometer: as shown in fig. 3, within the wavelength range of 350nm to 800nm, the visible light transmittance reaches more than 92 percent, which greatly meets the use requirements of electrochromic devices;
1.4 testing the conductivity of the electrolyte membrane by Electrochemical Impedance (EIS): the solid electrolyte membrane has an ionic conductivity of not less than 2.91X 10 at 25 deg.C-4S·cm-1The conductivity is higher;
and 1.5, performing cyclic voltammetry by adopting Zennium EL 101, wherein the voltage scanning range is-1-6V, and the scanning speed is 1mv/s, so that the electrochemical window range of the solid electrolyte membrane is obtained. The experimental result shows that the electrochemical window of the solid electrolyte membrane of the example 1 is wider and is not lower than 4.8V.
Example 2
Example 2 a method of preparing a uv curable electrolyte membrane was:
s1: adding a proper amount of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide powder into methoxy polyethylene glycol (350) monoacrylate accounting for 10% of the total system, heating to 60 ℃, rapidly stirring, sucking and dropwise adding alpha-hydroxyisobutyrophenone equivalent to the first curing agent at room temperature after the powder is completely dissolved, slightly stirring, and standing for later use;
s2: respectively adding 10% of aliphatic polyurethane acrylate oligomer and 30% of modified epoxy acrylate resin to the mixture obtained in S1, and uniformly stirring to obtain a first mixture; in this embodiment, the mass ratio of the methoxypolyethylene glycol (350) monoacrylate to the aliphatic urethane acrylate oligomer to the modified epoxy acrylate resin is 1: 1: 3, accounting for 50 percent of the total system. The total amount of the two curing agents accounts for 2 percent of the sum of the mass of the three components, namely 1 percent of the total system.
S3: adding 9% of LiTFSI powder to organic and/or inorganic ion salt BMim]PF6And (4) stirring to obtain an ionic liquid mixed solution, mixing the ionic liquid mixed solution with the premix obtained in the step S2, and stirring uniformly until the mixed solution is transparent. Sealing, performing ultrasonic treatment for 3-5 min, and defoaming. The ionic liquid mixed solution in this example accounts for 49% of the total system.
S4: the preparation method of the ultraviolet curing electrolyte membrane is the same as the example 1, and the different process parameters are as follows: UV light for 4 min.
Preparing a solid electrochromic device:
a transparent Indium Tin Oxide (ITO) conductive film coating, namely commonly known PET-ITO, is sputtered on a PET material, the thickness of the coating is 0.175mm, the surface resistance is less than 100 omega, the PET material belongs to an upper transparent electrode part and a lower transparent electrode part in a device, electrochromic poly (3, 4-ethylenedioxythiophene) thiophene conductive polymers are coated on the transparent electrode layers in a blade mode, a solid electrolyte film layer is added, and the all-solid-state device is assembled.
Example 2 test results of solid electrolyte membranes and solid electrochromic devices:
2.1 example 2 the electrolyte membrane had a thickness of 34 μm;
2.2 testing the visible light transmittance: the electrolyte membrane of the embodiment 2 has the visible light transmittance of more than 91.7 percent at the wavelength of 350-800 nm;
2.3 the conductivity of the solid electrolyte membrane of example 2 was tested under different temperature conditions: fig. 4 shows a graph of change in conductivity with temperature, and the solid electrolyte membrane provided in example 2 exhibits good ionic conductivity at different temperatures, which can reach 3.58 × 10 at room temperature-4S·cm-1；
2.4 example 2 the light transmission curves of the electrochromic device in the tinted and bleached states are shown in fig. 5: when a forward voltage of 2.3V is applied to the electrochromic device, the device is in a fading state, and the transmittance of the device at a wavelength of 580nm is high and reaches 57.98%; when a negative voltage of 2.3V was applied to the prepared electrochromic, the device was in a colored state, and its transmittance at a wavelength of 580m was 15.78%.
Example 3
Example 3 the electrolyte membrane was prepared by the following method:
s1: adding 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide powder into methoxy polyethylene glycol (350) monoacrylate, heating to 50 ℃, rapidly stirring, sucking and dropwise adding alpha-hydroxyisobutyrophenone at room temperature after the powder is completely dissolved, slightly stirring, and standing for later use; the mass ratio of the two curing agents is 1: 1.
S2: respectively adding the aliphatic polyurethane acrylate oligomer and the modified epoxy acrylate resin to the mixture obtained in S1, and uniformly stirring to obtain a first mixture; in this embodiment, the mass ratio of the methoxypolyethylene glycol (350) monoacrylate to the aliphatic urethane acrylate oligomer to the modified epoxy acrylate resin is 1: 2: 2, accounting for 50 percent of the total system. The total amount of the two curing agents accounts for 5 percent of the sum of the mass of the three components, namely 2.5 percent of the total system.
S3: 10% (of the total system) of the LiTFSI powder was added to the ionic liquid, i.e. [ BMim ] selected]PF6After stirring, the mixture was mixed with the premix obtained in S2 and stirred until the mixture was transparent. Sealing, performing ultrasonic treatment for 3-5 min, and defoaming. The ionic liquid state (ionic liquid mixed solution) in this example accounts for 47.5% of the total system.
S4: the ultraviolet curing electrolyte membrane was prepared in the same manner as in example 1; the solid state electrochromic device was prepared as in example 2.
Example 3 test results of solid electrolyte membranes and solid electrochromic devices:
3.1 example 3 the electrolyte membrane thickness was 35 μm;
3.2 the section of the UV-cured electrolyte membrane of this example 3 was subjected to an electronic scanning test, and the results are shown in FIG. 6, where the polymer-based solid electrolyte membrane did not delaminate significantly;
3.3 fig. 7 is a stress strain plot of the uv cured electrolyte membrane of example 3. The result shows that the tensile deformation can reach 45%, the tensile stress is 25KPa at the moment, and the electrolyte membrane has good strength;
3.4 FIG. 8 is a rheological profile of the UV curable electrolyte raw material mixed system of example 3 at a shear rate of 0.6s-1When the viscosity of the electrolyte raw material mixed system reaches 80Pa & lts & gt, the fluidity is lost, and the state is very stable;
3.5 the electrochromic device of example 3 was subjected to cyclic voltammetry tests. The voltage scanning range is-1 to 6V, the scanning speed is 1mv/s, and the electrochemical window range of the ultraviolet curing electrolyte membrane is obtained. FIG. 9 shows that the electrochemical window of the electrochromic device of example 3 is wide, which can reach 5.2V;
3.6 results of optical cycling stability test of electrochromic device are shown in fig. 10, and the cycling curves show that the solid state electrochromic device can still maintain the optical modulation range of 71.7% of the initial state after the solid state device is cycled for 100 times.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (12)
1. The ultraviolet curing electrolyte is characterized by comprising the following raw material components: acrylic UV resin, epoxy resin, reactive diluent, curing agent, organic and/or inorganic ion salt, lithium salt, the curing agent contains light curing agent.
2. The ultraviolet-curable electrolyte according to claim 1, which is characterized by mainly consisting of, in mass percent:
acrylic UV resin 10-25%
10 to 30 percent of epoxy resin
5 to 15 percent of active diluent
35 to 55 percent of organic and/or inorganic ion salt
5 to 10 percent of lithium salt
The mass of the curing agent is 1-5% of the sum of the mass of the acrylic UV resin, the mass of the epoxy resin and the mass of the reactive diluent.
3. The ultraviolet curable electrolyte according to claim 1, wherein the epoxy resin has a viscosity of 25 to 40pa.s at 25 ℃ and an acid value in a range of 3 to 5 mgKOH/g; and/or the viscosity range of the acrylic UV resin at 25 ℃ is 10-15 Pa.S.
4. The ultraviolet curable electrolyte of claim 1, wherein the curing agent comprises a first curing agent and a second curing agent;
the first curing agent is one or more selected from bis (1- (2, 4-difluorophenyl) -3-pyrrolyl) dicyclopentadiene, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, benzoin dimethyl ether, methyl o-benzoylbenzoate and 2-hydroxy-4' - (2-hydroxyethyl) -2-methyl propiophenone;
and/or the second curing agent is one or more selected from alpha-hydroxyisobutyrophenone, 1-hydroxycyclohexyl phenyl ketone, 4- (p-tolylthio) benzophenone and ethyl 4-dimethylaminobenzoate.
5. The ultraviolet curing electrolyte of claim 3, wherein the mass of the first curing agent and the mass of the second curing agent are respectively 0.5-2.5% of the sum of the mass of the acrylic UV resin, the mass of the epoxy resin and the mass of the reactive diluent.
6. The ultraviolet curable electrolyte according to claim 1 or 3, wherein the epoxy resin is one or more selected from the group consisting of a polyphenol type glycidyl ether epoxy resin, a modified epoxy acrylate resin, and an aliphatic glycidyl ether epoxy resin;
and/or the acrylic UV resin is one or more selected from aliphatic polyurethane acrylate oligomer, polyurethane epoxy acrylate oligomer, vinyl diacrylate and bifunctional polyester acrylic resin.
7. The uv-curable electrolyte according to claim 1, wherein the organic and/or inorganic ionic salt is one or more selected from the group consisting of 1-butyl-3-methylimidazolium dinitrile amine salt, 1-vinyl-3-ethylimidazolium bistrifluoromethane succinimide salt, 1-butyl-3-methylimidazolium hexafluorophosphate salt, 1-butyl-3-methylimidazolium tetrafluoroborate salt;
and/or the lithium salt is one or more of lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) amide, lithium methylsulfonate, lithium perchlorate and lithium tetrafluoroborate.
8. The UV-curable electrolyte according to claim 1, wherein the reactive diluent is one or more selected from the group consisting of ethylene glycol bisglycidyl ether, 1, 6-hexanediol diacrylate, methoxypolyethylene glycol (350) monoacrylate, methoxypolyethylene glycol (550) monomethacrylate, and beta-hydroxyethyl methacrylate.
9. A method for producing an electrolyte membrane, based on the ultraviolet-curable electrolyte of any one of claims 1 to 8, comprising the steps of:
s1: the curing agent is dissolved in the active diluent;
s2: sequentially adding the acrylate resin and the epoxy resin into the mixed system obtained in the step S1 according to the proportion, and uniformly mixing;
s3: dissolving lithium salt in organic and/or inorganic ion salt to obtain an ionic liquid mixed solution, adding the ionic liquid mixed solution into the mixed system obtained in S2, and uniformly mixing and defoaming;
s4: and (4) coating the mixed solution obtained in the step (S3) on the surface of a base material, and carrying out anaerobic UV curing and drying to obtain the solid electrolyte membrane.
10. The method for producing a solid electrolyte membrane according to claim 10, wherein the absorption wavelength in UV curing is 350nm to 400 nm; the lamp power is 250w, and the illumination time is 30-300 s.
11. An electrochromic device characterized by comprising a solid electrolyte membrane made of the ultraviolet-curable electrolyte according to any one of claims 1 to 8.
12. The electrochromic device according to claim 11, wherein the electrochromic device comprises a transparent electrode, a color-changing material layer, a solid electrolyte membrane, a counter electrode and a transparent electrode, which are sequentially stacked, wherein the color-changing material of the color-changing material layer is a dioxythiophene type conductive polymer.
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| CN115820109A (en) * | 2022-12-29 | 2023-03-21 | 安徽精卓光显技术有限责任公司 | Preparation method and application of coatable solid electrolyte |
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