CN114752210B - 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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- CN114752210B CN114752210B CN202210521157.3A CN202210521157A CN114752210B CN 114752210 B CN114752210 B CN 114752210B CN 202210521157 A CN202210521157 A CN 202210521157A CN 114752210 B CN114752210 B CN 114752210B
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- curing agent
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- epoxy resin
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 65
- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000001723 curing Methods 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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
- 238000000016 photochemical curing Methods 0.000 claims abstract description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 32
- -1 1-butyl-3-methylimidazole dinitrile amine salt Chemical class 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000004925 Acrylic resin Substances 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 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 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
- 238000003848 UV Light-Curing Methods 0.000 claims description 6
- 238000010521 absorption reaction Methods 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
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 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 5
- 229910001410 inorganic ion Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 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 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-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
- 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
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 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
- 239000000758 substrate Substances 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 13
- 238000003756 stirring Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000004040 coloring Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010505 homolytic fission reaction Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- 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
-
- 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
- C08J2475/04—Polyurethanes
Abstract
The invention discloses an ultraviolet curing electrolyte, which comprises the following raw material components: acrylic acid UV resin, epoxy resin, reactive diluent, curing agent, ionic liquid and lithium salt, wherein the curing agent comprises a photo-curing agent and the raw material components further comprise epoxy resin. The ultraviolet curing electrolyte has excellent light transmittance, electrolyte membrane strength and room temperature ion 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 electrolyte, in particular to an ultraviolet curing electrolyte, a preparation method of an electrolyte membrane and an electrochromic device.
Background
Electrochromic refers to a phenomenon that optical properties (reflectivity, transmittance, drawing rate, etc.) of a material change in color stably and reversibly under the action of an applied electric field, and is represented as reversible changes in color and transparency in appearance. As an important component of electrochromic devices, electrolytes have been a difficulty in achieving application of electrochromic devices, and electrolytes exist in the form of solids including gel electrolytes and solid electrolytes.
The gel electrolyte is formed by compounding a solid polymer and a liquid electrolyte, and the following technical defects generally exist: firstly, the mass ratio of electrolyte is often larger (> 80 wt%), resulting in poor mechanical properties of the electrolyte; secondly, when the polymer duty ratio is increased, the ionic conductivity is rapidly reduced, so that the color changing performance of the electrochromic device is reduced; thirdly, the liquid solvent and the like contained in the gel electrolyte are easy to volatilize, and the device is easy to lose efficacy due to the volatilization and the film removal of the electrolyte in the use process.
The solid electrolyte comprises an inorganic solid electrolyte and a solid polymer electrolyte, wherein the inorganic solid electrolyte has the defects of low film conductivity, difficult large-area film formation, easy short-circuit failure of devices and the like, and the solid polymer electrolyte mainly has the defects of low ion conductivity and extremely easy phase separation between ion salt and polymers, so that the devices are invalid.
The ionic liquid modified solid electrolyte is called as "quasi-solid electrolyte", and the quasi-solid electrolyte system in the prior art has the defect of poor or unstable at least one of light transmittance, electrolyte membrane strength and room temperature ionic conductivity, which further leads to the deterioration of the cycling stability of the electrochromic device.
Disclosure of Invention
One of the purposes of the invention is to overcome the defects in the prior art, provide an ultraviolet curing electrolyte, and improve the strength of an electrolyte membrane while ensuring the optical transmittance; the electrolyte membrane is tightly adhered to the color-changing material layer, 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 above 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 ionic salt, lithium salt, said curing agent comprising photo curing agent.
The preferable technical proposal is that the main composition by mass percent is as follows:
10 to 25 percent of acrylic acid UV resin
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 three components of the acrylic UV resin, the epoxy resin and the reactive diluent, preferably 1-3%, more preferably 2%. The sum of the mass percentages of the three components of the acrylic acid UV resin, the epoxy resin and the reactive diluent is 30-70%, preferably 40-60%, more preferably 40-50%.
The mass percentage of the organic and/or inorganic ion salt is 35-55%, preferably 35-40%, more preferably 37.5%; the mass percentage of the lithium salt is 5% -10%, preferably 8% -10%, 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 range is 3-5 mg KOH/g; and/or the viscosity range of the acrylic acid UV resin at 25 ℃ is 10-15 Pa.S. The practical operation mode is mainly doctor-blading, certain requirements are met on uniformity and doctor-blading thickness, the viscosity is too low, the mixed liquid is extremely high, the film layer is extremely thin, the electrolyte is insufficient in ion/electron transmission channel, the transmission capacity is reduced, and the conductivity is influenced; the viscosity is too high, which is unfavorable for 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-diphenyl phosphine oxide, benzoin dimethyl ether, methyl o-benzoyl benzoate and 2-hydroxy-4' - (2-hydroxyethyl) -2-methylpropenyl acetone; considering the irradiation wavelength range of UV light, selecting a corresponding curing agent, wherein the curing agent has an effective absorption peak value in a wider absorption range (350-400 nm), and can generate one or more free radicals after irradiation to initiate crosslinking polymerization so as to accelerate the curing efficiency; the photo-bleaching/coating does not yellow, and avoids the interference of electrochromic; after absorbing light energy, the initiator molecule transitions to an excited singlet state, and transitions to an excited triplet state through intersystem crossing, and when the initiator molecule is in the excited singlet state or the excited triplet state, the molecular structure is in an unstable state, weak bonds in the initiator molecule can generate homolytic cleavage, primary active free radicals are generated, and the oligomer and the active diluent are polymerized and crosslinked.
And/or the second curing agent is one or more selected from alpha-hydroxy isobutyryl benzene, 1-hydroxy cyclohexyl benzene ketone, 4- (p-tolylthio) diphenyl ketone and 4-dimethyl amino ethyl benzoate. The ultraviolet light can be absorbed and scattered by the resin, and the received light intensity is different along with the difference of the distance between the upper surfaces. The near-surface region generates high concentration free radicals in a short time, so that the resin in the near-surface region is rapidly cured, and internal stress is generated due to uneven curing of the sample; the second curing agent makes up the defect that the deep layer is possibly 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 three components of the acrylic acid UV resin, the epoxy resin and 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, more than two epoxy groups are arranged in the molecule of the epoxy resin, and the crosslinking density of the epoxy resin is high; 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, so that a compact rigid molecular structure can be formed, the crosslinking density is increased after curing, the tensile strength is high, the epoxy resin does not contain benzene rings, and the epoxy resin has good weather resistance.
And/or the acrylic acid UV resin is one or more selected from aliphatic polyurethane acrylate oligomer, polyurethane epoxy acrylate oligomer, vinyl diacrylate and difunctional polyester acrylic resin. The selected acrylic acid UV resin has medium and high functionality, is water white transparent viscous liquid, has obvious oxygen polymerization inhibition, can improve surface defects such as leveling, pocking marks and the like of a system, and has excellent adhesive force to PET films.
The preferable technical scheme is that the organic and/or inorganic ionic salt is one or more selected from 1-butyl-3-methylimidazole dinitrile amine salt, 1-vinyl-3-ethylimidazole bistrifluoromethane Huang Xianya amine 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 methacrylic acid-beta-hydroxyethyl. Methacrylic esters are free radical reactive diluents containing epoxy groups which can participate in the curing reaction of epoxy resins and become part of a crosslinked network structure; the molecular weight is low, the viscosity of the prepolymer is reduced to be too high, the performance of the cured film layer is not affected, and the toughening effect can be achieved.
The second object of the present invention is to provide a method for preparing an electrolyte membrane, based on the above ultraviolet curing electrolyte, comprising the steps of:
s1: the curing agent is dissolved in the reactive diluent;
s2: sequentially adding acrylate resin and 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 ionic salt to obtain an ionic liquid mixed solution, adding the ionic liquid mixed solution into the mixed system obtained in the step S2, uniformly mixing and defoaming;
s4: and (3) coating the mixed solution obtained in the step (S3) on the surface of a substrate, and performing anaerobic UV curing and drying to obtain the solid electrolyte membrane.
The curing agent, which is solid at ordinary temperature, may be heated optionally when it is less soluble in the reactive diluent, and/or may be further accelerated by stirring. The heating temperature of the electrolyte membrane production method S1 is preferably 40 to 60 ℃. The curing agent has a certain solubility in the diluent, which is related to the solute, i.e. the curing agent itself, while being affected by temperature. The temperature is too high, the crystallization is easy to separate out, and the crystals adhere to the bottom of the container; the temperature is too low, the solubility is not high, and the residual curing agent powder exists, so that the material is wasted.
The preferable technical proposal is that the absorption wavelength in UV curing is 350 nm-400 nm; the power of the lamp is 250w, and the illumination time is 30 s-300 s. The UV curing process parameters are inherent to the device itself, outside/below the band range, and the curing agent absorption effective peak is not in it, i.e. is not adapted, and cannot absorb energy to undergo 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 membrane is too thin, the interface adhesion is insufficient, phase separation possibly occurs, the ion/electron transmission channels are few, and the fading and coloring efficiency are affected; and too thick electrolyte membrane, too long transmission path, also affects 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 laminated, wherein the color-changing material of the color-changing material layer is dioxythiophene type 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;
the organic and/or inorganic ionic salt component in the ultraviolet curing electrolyte component not only provides the effect of ionic salt, but also plays the role of dissociating lithium salt, and good ionic conductivity is shown at different temperatures, so that the service life of the device is prolonged, the response time of the electrochromic device is short, the color changing speed of reversible change between transparent and blue is high, the response time of switching from a color fading state to a coloring state and vice versa is high, and the actual measurement switching time of a table is less than 5s;
the electrolyte generates binding force during ultraviolet curing, is favorable for realizing the assembly and packaging integration of the all-solid-state electrochromic device, and provides a new idea for large-area assembly of the electrochromic device; the all-solid-state electrochromic device prepared by ultraviolet curing electrolyte has excellent interlayer binding force, and is beneficial to improving the overall stability of the device;
the processing mode of ultraviolet curing of the quasi-solid electrolyte layer ensures that the electrolyte preparation process is simpler, the cost is low, the preparation period is short, no special requirement is made on equipment, the method is suitable for mass production, and a foundation is provided for the industrialization of large-area electrochromic devices.
Drawings
FIG. 1 is an optical photograph of an ultraviolet-curable electrolyte membrane according to example 1 of the present invention;
fig. 2 is an SEM scan of the uv-cured electrolyte membrane according to example 1 of the present invention;
FIG. 3 is a graph showing the visible light transmittance test of the UV-cured electrolyte membrane according to example 1 of the present invention;
FIG. 4 is a graph showing the conductivity test of the UV-cured electrolyte membrane according to example 2 of the present invention at various temperatures;
fig. 5 is a graph showing the visible light transmittance test of the electrochromic device according to example 2 of the present invention in the colored state and the discolored state;
FIG. 6 is a sectional scan test chart of an ultraviolet cured electrolyte membrane and a color-changing material layer according to example 3 of the present invention;
FIG. 7 is a stress-strain diagram of an ultraviolet cured electrolyte membrane according to example 3 of the present invention;
FIG. 8 is a graph showing the rheology of the UV-cured electrolyte raw material mixture of example 3 of the present invention;
FIG. 9 is a graph showing the electrochemical window range of the ultraviolet-curable electrolyte membrane according to 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 describes the invention in further detail with reference to examples. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
Example 1 the method for preparing the uv-cured electrolyte membrane was:
s1: adding 0.2% of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide powder of the total system into methoxypolyethylene glycol (350) monoacrylate (accounting for 8% of the total system), heating and stirring until the powder is completely dissolved, sucking and dripping alpha-hydroxyisobutyryl benzene (accounting for 0.2% of the total system), slightly stirring uniformly, and keeping stand by;
s2: sampling aliphatic polyurethane acrylate oligomer accounting for 16% of the total system and modified epoxy acrylate resin accounting for 16% of the total system according to a proportion, sequentially dropwise adding 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, the aliphatic polyurethane acrylate oligomer and 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% of the total system to organic and/or inorganic ion salt [ BMim ]]PF 6 And then, the mixture is mixed with the first mixed slurry obtained in the step S2, and the mixture is stirred uniformly to obtain a transparent mixed liquid with good compatibility. Sealing, and removing bubbles by ultrasonic treatment for 3-5 min. [ BMim ] in the present embodiment]PF 6 The stirring rate is not specially defined and accounts for 51.6% of the total system. The total system represents an ultraviolet-curable electrolyte membrane system, and is the same as follows.
S4: the dropper sucks 0.3 ml-0.5 ml of the mixed liquid, and the mixed liquid is rapidly and gently scraped on the PET plate by a 50-mesh wire rod, and a flat and clean plate is additionally taken to cover the coating so as to avoid oxidization. The absorption wavelength in UV curing is 393nm, the lamp power is 250w, and UV illumination is carried out for 5min, so that a transparent solid electrolyte membrane is obtained.
Example 1 test results of solid electrolyte membrane:
1.1 Solid electrolyte membrane photograph referring to fig. 1, the solid electrolyte membrane has a thickness of 32 μm;
1.2 The surface of the solid electrolyte membrane of example 1 was subjected to an electron scan test, and the SEM image is shown in fig. 2. The solid electrolyte membrane has a rough but non-porous surface, and the continuous fold state presents a hilly morphology, which is formed due to the cross-linked structure in the polymer; in addition, the highly compact microscopic morphology demonstrates that the electrolyte membrane is uniform and has no significant phase separation;
1.3 The visible light transmittance of the electrolyte membrane was tested using an ultraviolet spectrophotometer: as shown in FIG. 3, the visible light transmittance reaches over 92% in the wavelength range of 350-800nm, thereby greatly meeting the use requirement of electrochromic devices;
1.4 The electrolyte membrane was tested for conductivity by Electrochemical Impedance (EIS) method: the solid electrolyte membrane has an ionic conductivity of not less than 2.91X10 at 25deg.C -4 S·cm -1 The conductivity is high;
1.5 cyclic voltammetry test is carried out by using Zennium EL 101, the voltage scanning range is-1-6V, the scanning speed is 1mv/s, and the electrochemical window range of the solid electrolyte membrane is obtained. The experimental results show that the electrochemical window of the solid electrolyte membrane in the embodiment 1 is wider and is not lower than 4.8V.
Example 2
Example 2 the method for preparing the uv-cured 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 ℃ and rapidly stirring, sucking and dropwise adding alpha-hydroxy isobutyryl benzene equivalent to the first curing agent at room temperature after the powder is completely dissolved, slightly stirring uniformly, and standing for later use;
s2: respectively adding 10% of aliphatic polyurethane acrylate oligomer and 30% of modified epoxy acrylate resin into the mixture obtained in the step S1, and uniformly stirring to obtain a first mixture; in the embodiment, the mass ratio of the methoxy polyethylene glycol (350) monoacrylate, the aliphatic polyurethane acrylate oligomer and 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% of the total mass of the three components, namely 1% of the total system.
S3: adding LiTFSI powder accounting for 9% of the total system into organic and/or inorganic ion salt [ BMim ]]PF 6 And (3) 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, ultrasonic treating for 3-5 min, and defoaming. The ionic liquid mixed solution in this example was 49% of the total system.
S4: the preparation method of the ultraviolet curing electrolyte membrane is the same as in example 1, and the different process parameters are as follows: UV light was applied for 4min.
Preparation of solid state electrochromic device:
the PET material is sputtered with a transparent Indium Tin Oxide (ITO) conductive film coating, namely PET-ITO, 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 the device, electrochromic poly (3, 4-ethylenedioxythiophene) thiophene type conductive polymer is scraped on the transparent electrode layer, and the transparent electrode layer is added with a solid electrolyte film layer to assemble the full solid device.
Example 2 test results of solid electrolyte membrane and solid electrochromic device:
2.1 Example 2 electrolyte membrane thickness was 34 μm;
2.2 Visible light transmittance test: example 2 the electrolyte membrane has a visible light transmittance of 91.7% or more at a wavelength of 350-800 nm;
2.3 The conductivity of the solid electrolyte membrane of example 2 was tested under different temperature conditions: the graph of the change of the conductivity with the temperature is shown in fig. 4, the solid electrolyte membrane provided in the example 2 shows good ionic conductivity at different temperatures, and the ionic conductivity can reach 3.58×10 at room temperature -4 S·cm -1 ；
2.4 Example 2 the light transmittance curves of electrochromic devices in the colored and faded 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 as high as 57.98%; when a negative voltage of 2.3V was applied to the prepared electrochromic layer, the device was in a colored state, and its transmittance at 580m wavelength was 15.78%.
Example 3
The preparation method of the electrolyte membrane of example 3 comprises the following steps:
s1: adding 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide powder into methoxypolyethylene glycol (350) monoacrylate, heating to 50deg.C, rapidly stirring, sucking and dripping alpha-hydroxy isobutyryl benzene at room temperature, slightly stirring, and standing for use; the mass ratio of the two curing agents is 1:1.
S2: respectively adding aliphatic polyurethane acrylate oligomer and modified epoxy acrylate resin into the mixture obtained in the step S1, and uniformly stirring to obtain a first mixture; in the embodiment, the mass ratio of the methoxy polyethylene glycol (350) monoacrylate, the aliphatic polyurethane acrylate oligomer and 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% of the total mass of the three components, namely 2.5% of the total system.
S3: adding LiTFSI powder 10% (of the total system) into ionic liquid, i.e. selected [ BMim ]]PF 6 And (2) mixing the mixture with the premix obtained in the step (S2) after stirring, and stirring uniformly until the mixed solution is transparent. Sealing, ultrasonic treating for 3-5 min, and defoaming. The ionic liquid (ionic liquid mixed solution) in this example represents 47.5% of the total system.
S4: the preparation method of the ultraviolet-curable electrolyte membrane was the same as in example 1; the solid state electrochromic device was prepared as in example 2.
Example 3 test results of solid electrolyte membrane and solid electrochromic device:
3.1 Example 3 electrolyte membrane thickness was 35 μm;
3.2 the cut surface of the ultraviolet-cured electrolyte membrane of this example 3 was subjected to an electronic scan test, and as shown in fig. 6, the polymer-based solid electrolyte membrane was not significantly layered;
3.3 Fig. 7 is a stress-strain diagram of the uv-cured electrolyte membrane of example 3. The result shows that the tensile deformation can reach 45%, the tensile stress is 25KPa, and the electrolyte membrane has good strength;
3.4 FIG. 8 is a rheological profile of the UV-curable electrolyte raw material mixture of example 3 at a shear rate of 0.6s -1 When the viscosity of the electrolyte raw material mixed system reaches 80 Pa.s, the fluidity is lost, and the state is quite stable;
3.5 The electrochromic device of example 3 was subjected to cyclic voltammetry. The voltage scanning range is-1-6V, 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, up to 5.2V;
3.6 The results of the optical cycling stability test of the electrochromic device are shown in fig. 10, and the cycling curve shows 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 merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (8)
1. An ultraviolet curing electrolyte is characterized by comprising the following raw material components: an acrylic UV resin, an epoxy resin, a reactive diluent, a curing agent comprising a photo-curing agent, an organic and/or inorganic ionic salt, a lithium salt; the main composition of the composition in mass percent is:
10 to 25 percent of acrylic acid UV resin
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 three components of the acrylic acid UV resin, the epoxy resin and the reactive diluent;
the epoxy resin is modified epoxy acrylate resin; the acrylic acid UV resin is aliphatic polyurethane acrylate oligomer;
the organic and/or inorganic ionic salt is one or more selected from 1-butyl-3-methylimidazole dinitrile amine salt, 1-vinyl-3-ethylimidazole bistrifluoromethane Huang Xianya amine salt, 1-butyl-3-methylimidazole hexafluorophosphate and 1-butyl-3-methylimidazole tetrafluoroborate;
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 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 methacrylic acid-beta-hydroxyethyl.
2. The ultraviolet cured electrolyte according to claim 1, wherein the viscosity of the epoxy resin is 25-40 pa.s at 25 ℃ and the acid value range is 3-5 mg koh/g; and/or the viscosity range of the acrylic acid UV resin at 25 ℃ is 10-15 Pa.S.
3. The uv 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-diphenyl phosphine oxide, benzoin dimethyl ether, methyl o-benzoyl benzoate and 2-hydroxy-4' - (2-hydroxyethyl) -2-methylpropenyl acetone;
and/or the second curing agent is one or more selected from alpha-hydroxy isobutyryl benzene, 1-hydroxy cyclohexyl benzene ketone, 4- (p-tolylthio) diphenyl ketone and 4-dimethyl amino ethyl benzoate.
4. The ultraviolet curable electrolyte according to claim 3, wherein the mass of the first curing agent and the second curing agent is 0.5 to 2.5% of the sum of the mass of the three components of the acrylic UV resin, the epoxy resin and the reactive diluent, respectively.
5. A method for producing a solid electrolyte membrane, characterized by comprising the steps of:
s1: the curing agent is dissolved in the reactive diluent;
s2: sequentially adding acrylic acid UV resin and 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 ionic salt to obtain an ionic liquid mixed solution, adding the ionic liquid mixed solution into the mixed system obtained in the step S2, uniformly mixing and defoaming;
s4: and (3) coating the mixed solution obtained in the step (S3) on the surface of a substrate, and performing anaerobic UV curing and drying to obtain the solid electrolyte membrane.
6. The method for producing a solid electrolyte membrane according to claim 5, wherein the absorption wavelength in UV curing is 350nm to 400nm; the power of the lamp is 250w, and the illumination time is 30 s-300 s.
7. An electrochromic device comprising a solid electrolyte membrane made from the uv-curable electrolyte of any one of claims 1 to 4.
8. The electrochromic device according to claim 7, characterized in that 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 laminated in sequence, wherein the color-changing material of the color-changing material layer is a dioxythiophene type conductive polymer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5007718A (en) * | 1987-04-02 | 1991-04-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Electrochromic elements and methods of manufacturing and driving the same |
| US5648011A (en) * | 1995-03-15 | 1997-07-15 | Micron Communications, Inc. | Structurally stable gelled electrolytes |
| KR20030014497A (en) * | 2001-08-11 | 2003-02-19 | 삼성에스디아이 주식회사 | Polymeric electrolytes with improved adhesion and lithium battery employing the same |
| CN106252087A (en) * | 2016-09-21 | 2016-12-21 | 中山大学 | A kind of photocuring gel electrolyte and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5007718A (en) * | 1987-04-02 | 1991-04-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Electrochromic elements and methods of manufacturing and driving the same |
| US5648011A (en) * | 1995-03-15 | 1997-07-15 | Micron Communications, Inc. | Structurally stable gelled electrolytes |
| KR20030014497A (en) * | 2001-08-11 | 2003-02-19 | 삼성에스디아이 주식회사 | Polymeric electrolytes with improved adhesion and lithium battery employing the same |
| CN106252087A (en) * | 2016-09-21 | 2016-12-21 | 中山大学 | A kind of photocuring gel electrolyte and its preparation method and application |
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