CN114296283B - Electrochromic device and preparation method thereof - Google Patents
Electrochromic device and preparation method thereof Download PDFInfo
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- CN114296283B CN114296283B CN202111533903.2A CN202111533903A CN114296283B CN 114296283 B CN114296283 B CN 114296283B CN 202111533903 A CN202111533903 A CN 202111533903A CN 114296283 B CN114296283 B CN 114296283B
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- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 82
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 239000003085 diluting agent Substances 0.000 claims abstract description 21
- 239000000565 sealant Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 45
- -1 alkali metal salt Chemical class 0.000 claims description 28
- 238000002347 injection Methods 0.000 claims description 19
- 239000007924 injection Substances 0.000 claims description 19
- HYDWALOBQJFOMS-UHFFFAOYSA-N 3,6,9,12,15-pentaoxaheptadecane Chemical compound CCOCCOCCOCCOCCOCC HYDWALOBQJFOMS-UHFFFAOYSA-N 0.000 claims description 15
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 15
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 13
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000003949 imides Chemical class 0.000 claims description 7
- 229920001774 Perfluoroether Polymers 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000002093 peripheral effect Effects 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- CUNPJFGIODEJLQ-UHFFFAOYSA-M potassium;2,2,2-trifluoroacetate Chemical compound [K+].[O-]C(=O)C(F)(F)F CUNPJFGIODEJLQ-UHFFFAOYSA-M 0.000 claims description 5
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- BMWDUGHMODRTLU-UHFFFAOYSA-N azanium;trifluoromethanesulfonate Chemical compound [NH4+].[O-]S(=O)(=O)C(F)(F)F BMWDUGHMODRTLU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 claims description 3
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 3
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 2
- PWGVOCGNHYMDLS-UHFFFAOYSA-N 3-(2-methoxyethoxy)propan-1-amine Chemical compound COCCOCCCN PWGVOCGNHYMDLS-UHFFFAOYSA-N 0.000 claims description 2
- JZVUAOCDNFNSGQ-UHFFFAOYSA-N 7-methoxy-2-phenyl-1h-quinolin-4-one Chemical compound N=1C2=CC(OC)=CC=C2C(O)=CC=1C1=CC=CC=C1 JZVUAOCDNFNSGQ-UHFFFAOYSA-N 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 2
- LPIWNOOESOKGKS-UHFFFAOYSA-N FC(F)F.FC(F)F.[Na] Chemical compound FC(F)F.FC(F)F.[Na] LPIWNOOESOKGKS-UHFFFAOYSA-N 0.000 claims description 2
- RNFAKTRFMQEEQE-UHFFFAOYSA-N Tripropylene glycol butyl ether Chemical compound CCCCOC(CC)OC(C)COC(O)CC RNFAKTRFMQEEQE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- YCNIBOIOWCTRCL-UHFFFAOYSA-N azane;2,2,2-trifluoroacetic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)F YCNIBOIOWCTRCL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- QNIHZKIMYOTOTA-UHFFFAOYSA-N fluoroform;lithium Chemical compound [Li].FC(F)F.FC(F)F QNIHZKIMYOTOTA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229920001088 polycarbazole Polymers 0.000 claims description 2
- 229920000414 polyfuran Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 23
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 24
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 13
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 13
- 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 description 13
- 238000004040 coloring Methods 0.000 description 7
- 238000005562 fading Methods 0.000 description 7
- 230000004298 light response Effects 0.000 description 6
- 150000003384 small molecules Chemical group 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- SLTUFHRUEJDTKK-UHFFFAOYSA-N FC(F)F.FC(F)F.[K] Chemical compound FC(F)F.FC(F)F.[K] SLTUFHRUEJDTKK-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The application discloses an electrochromic device and a preparation method thereof. The device includes: an anode transparent conductive substrate, an organic electrochromic layer positioned on the anode transparent conductive substrate, and a cathode transparent conductive substrate positioned above the organic electrochromic layer, wherein a cavity is formed between the organic electrochromic layer and the cathode transparent conductive substrate, and the cavity is filled with a local high-concentration electrolyte; the cathode transparent conductive substrate is connected with the surface of the anode transparent conductive substrate uncovered by the organic electrochromic layer through sealant; the local high-concentration electrolyte comprises a solvent, a conductive salt and a diluent, wherein the molar ratio of the conductive salt to the solvent is 1:0.1-1:20, and the molar ratio of the conductive salt to the diluent is 1:0.1-1:40. The local high-concentration electrolyte constructed by the application is used in an organic electrochromic device, and realizes the widening of a voltage window, the increase of optical contrast and good optical and electrochemical stability.
Description
Technical Field
The application relates to the technical field of electrochromic devices, in particular to an electrochromic device and a preparation method thereof.
Background
Electrochromic refers to a phenomenon in which an electroactive material changes its color visually reversibly under an external voltage, and exhibits reversible changes in terms of optical transmittance, reflectance, absorbance, and the like. Macroscopically, the material with electrochromic phenomena undergoes a reversible state change of coloration/fading. Broadly, electrochromic materials comprise an organic electrochromic material comprising predominantly commercial WO 3 An isopmetal oxide; the latter includes conductive high molecular polymer, viologen micromolecule extremely derivative, ester micromolecule extremely derivative and the like. The organic electrochromic material has the advantages of adjustable color, high response speed, strong controllability and the like, but has the defects of poor stability, too narrow potential window and the like in practical application, and greatly limits the commercialized application of the organic electrochromic material.
A simple electrochromic device consists of a double-layer conductive substrate, an electrochromic layer and an electrolyte layer. The electrolyte layer functions to conduct ions and block electron transport. Currently, electrolytes can be classified into liquid electrolytes, gel electrolytes, and solid electrolytes by type. In commercial devices, low-concentration liquid electrolyte is mostly adopted, and although the electrolyte has good stability in devices adopting inorganic materials as electrochromic layers, the electrolyte is difficult to apply to organic electrochromic devices due to the defects of narrow potential window, side reaction of electrolyte and organic materials and the like. Therefore, it is an urgent need to find an electrolyte having high conductivity, wide voltage window, good chemical stability, and good compatibility with the organic electrochromic material.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present application aims to provide an electrochromic device and a preparation method thereof, which aims to solve the problem that the existing electrolyte is not compatible with the electrochromic material.
The technical scheme of the application is as follows:
in a first aspect of the present application, there is provided an electrochromic device, as shown in fig. 1, comprising: an anode transparent conductive substrate 1, an organic electrochromic layer 2 positioned on the anode transparent conductive substrate 1, a cathode transparent conductive substrate 4 positioned above the organic electrochromic layer 2, a cavity 3 formed between the organic electrochromic layer 2 and the cathode transparent conductive substrate 4, wherein the cavity 3 is filled with local high-concentration electrolyte; the cathode transparent conductive substrate 4 is connected with the surface of the anode transparent conductive substrate 1 uncovered by the organic electrochromic layer 2 through a sealant 5;
the local high-concentration electrolyte comprises a solvent, a conductive salt and a diluent, wherein the molar ratio of the conductive salt to the solvent is 1:0.1-1:20, and the molar ratio of the conductive salt to the diluent is 1:0.1-1:40.
The use of high concentrations of electrolyte is a promising approach to reduce electrolyte decomposition due to strong salt-solvation coordination. Although near saturation with commercial solvents such as ethers, DMSO, etc. are used in high concentration electrolytesAnd lithium salt solutions can improve the stability and reversibility of the battery, but their high viscosity, high cost and low oxygen solubility are very disadvantageous. In order to solve the problems in the high concentration electrolyte, the application designs the local high concentration electrolyte which adopts a Li + The non-coordinating co-solvent (typically polyfluoroether) is used to dilute the ultra-concentrated electrolyte such that the overall salt concentration in the electrolyte stays around the conventional 1.0M, rather than being ultra-concentrated. The essence of this strategy is to separate the bulk of the electrolyte from the responsibilities of the interface and to distribute these responsibilities to microscopically different stages.
The application adopts the local high-concentration electrolyte (belonging to organic system electrolyte) to replace the traditional organic electrolyte, effectively avoids side reaction between the traditional organic electrolyte and the organic electrochromic material, overcomes the defects of poor electrochemical stability, narrow working window, larger flammability and the like of the common organic electrolyte under the traditional low concentration, can effectively reduce the high cost caused by the concentrated salt in the high-concentration electrolyte, and effectively improves the optical contrast, the light response rate, the electrochemical stability and the device cycle life of the organic electrochromic device. The local high-concentration electrolyte has wide application prospect in the fields of electrochromic display, energy storage devices and the like.
Preferably, the mol ratio of the conductive salt to the solvent is 1:0.5-1:2, and the mol ratio of the conductive salt to the diluent is 1:0.5-1:2.
Preferably, the conductive salt is one or two of alkali metal salt, ammonium salt and the like. As an example, the conductive salt is lithium hexafluorophosphate (LiPF 6 ) Lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium triflate (LiCF) 3 SO 3 ) Lithium trifluoroacetate (CF) 3 COOLi), lithium bis (trifluoromethane) xanthimide (TFSILI), lithium trifluoromethane sulfonate (TFSLi), sodium hexafluorophosphate (NaPF) 6 ) Sodium perchlorate (NaClO) 4 ) Sodium hexafluoroarsenate (NaAsF) 6 ) Sodium tetrafluoroborate (NaBF) 4 ) Sodium triflate (NaCF) 3 SO 3 ) Sodium trifluoroacetate (CF) 3 COONa), sodium bistrifluoromethane yellow imide (TFSINa), trifluoroSodium methylsulfonate (TFSNa), potassium hexafluorophosphate (KPF) 6 ) Potassium perchlorate (KClO) 4 ) Potassium hexafluoroarsenate (KAsF) 6 ) Potassium tetrafluoroborate (KBF) 4 ) Potassium triflate (KCF) 3 SO 3 ) Potassium trifluoroacetate (CF) 3 COOK), potassium bistrifluoromethane yellow imide (TFSIK), potassium trifluoromethane sulfonate (TFSK), ammonium hexafluorophosphate (NH) 4 PF 6 ) Ammonium perchlorate (NH) 4 ClO 4 ) Ammonium hexafluoroarsenate (NH) 4 AsF 6 ) Ammonium tetrafluoroborate (NH) 4 BF 4 ) Ammonium triflate (NH) 4 CF 3 SO 3 ) Ammonium trifluoroacetate (CF) 3 COONH 4 ) Bis (trifluoromethaneyellow imide) ammonium (TFSINH) 4 ) Ammonium Triflate (TFSNH) 4 ) And the like. It should be noted that, not limited to the above-mentioned conductive salts, conductive salts commonly used in electrochromic devices are suitable for the present application.
Preferably, the solvent is an ether-type organic solvent. By way of example, the ether-type organic solvent is one or more of ethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol methyl ether, propylene glycol diethyl ether, propylene glycol butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, diethylene glycol dimethyl ether (DG), propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol butyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, diethylene glycol butyl ether acetate, and the like. The solvents listed above are merely representative solvents, and are not limited to the solvents mentioned above, and common ether-type organic solvents are suitable for use in the present application.
Preferably, the diluent is a fluoroether solvent.
By way of example, the fluoroether solvent is one or more of the structures shown below:
the above-described fluoroether solvents are representative solvents, and are not limited to the above-mentioned fluoroether solvents, and commercially available fluoroether solvents are suitable for use in the present application.
In the application, the material of the organic electrochromic layer adopts an organic polymer electrochromic material. Preferably, the material of the electrochromic layer is one or more of various electrochromic materials such as Poly (3-hexyphenyl-2, 5-diyl) (P3 HT), polyaniline electrochromic material, polypyrrole electrochromic material, polythiophene electrochromic material, polybenzazole electrochromic material, polyfuran electrochromic material, polycarbazole and derivatives electrochromic material, D-A-D type polymer, D-A type polymer and copolymers electrochromic material thereof.
Preferably, the material of the organic electrochromic layer is a small molecule electrochromic material (molecular weight is within 1000), such as one or more of various small molecule electrochromic materials such as ester electrochromic materials, viologen electrochromic materials and the like.
Further preferably, the ester electrochromic material is one or more of the following structures:
further preferably, the viologen-based small molecule organic electrochromic material is one or more of the following structures:
further preferably, the other small molecule electrochromic materials are one or more of the structures shown below:
further preferably, the polyaniline electrochromic material is one or more of the following structures:
further preferably, the polypyrrole electrochromic material is one or more of the following structures:
in a second aspect of the present application, there is provided a method for manufacturing an electrochromic device as described above, comprising the steps of:
s10, preparing an organic electrochromic layer on an anode transparent conductive substrate;
s11, coating sealant at the peripheral frame of the anode transparent conductive substrate covered by the organic electrochromic layer, and reserving an electrolyte injection port;
s12, covering a cathode transparent conductive substrate on the anode transparent conductive substrate coated with the sealant, and forming a cavity between the organic electrochromic layer and the cathode transparent conductive substrate;
s13, injecting local high-concentration electrolyte into the cavity through the electrolyte injection opening, and finally sealing the electrolyte injection opening by adopting sealant; wherein the localized high concentration electrolyte comprises a solvent, a conductive salt, and a diluent.
Preferably, step S10 specifically includes:
dissolving an organic electrochromic material in common organic solvents such as chloroform, dichloromethane, chlorobenzene, dichlorobenzene and the like to obtain an organic electrochromic material solution;
and uniformly covering the organic electrochromic material solution on the anode transparent conductive substrate by adopting a spraying method to obtain the organic electrochromic layer.
In step S13, preferably, the method for preparing the local high-concentration electrolyte includes the steps of:
injecting a solvent into the conductive salt, and uniformly stirring to obtain a conductive salt solution;
and adding a diluent into the conductive salt solution, and uniformly stirring to obtain the local high-concentration electrolyte.
Preferably, the stirring time is 0.5-10h.
In a third aspect of the present application, there is provided a method for manufacturing an electrochromic device as described above, comprising the steps of:
s20, mixing a small-molecule organic electrochromic material with a local high-concentration electrolyte to obtain a mixed solution; wherein the local high concentration electrolyte comprises a solvent, a conductive salt and a diluent;
s21, coating sealant or adhesive double-sided adhesive tape on the peripheral frame of the anode transparent conductive substrate, and reserving an electrolyte injection port;
s22, covering a cathode transparent conductive substrate on the anode transparent conductive substrate coated with the sealant or bonded with the double-sided adhesive tape, and forming a cavity between the anode transparent conductive substrate and the cathode transparent conductive substrate;
s23, injecting the mixed solution into the cavity through the electrolyte injection opening, and finally sealing the electrolyte injection opening by adopting sealant.
In step S20, preferably, the total concentration of the ionic salt of the small molecule electrochromic material and the local high concentration electrolyte in the mixed solution is 1mol/L.
The application builds a novel local high-concentration electrolyte based on the traditional organic electrolyte, is used in an organic electrochromic device, realizes the widening of a voltage window, the increase of optical contrast and good optical and electrochemical stability, effectively overcomes the instability of the organic electrochromic material, and promotes the marketization application of the organic electrochromic device.
Drawings
Fig. 1 is a schematic structural diagram of an electrochromic device provided by the application.
FIG. 2 shows the LiTFSI (TGE) content of example 1 of the present application 1.75 (BTE) 3.5 A CV curve of a P3HT electrochromic device of a locally high concentration electrolyte.
FIG. 3 shows the LiTFSI (TGE) content of example 1 of the present application 1.75 (BTE) 3.5 Ultraviolet-visible absorption spectrum of the device under different potentials of the P3HT electrochromic device of the local high-concentration electrolyte.
FIG. 4 shows the LiTFSI (TGE) content of example 1 of the present application 1.75 (BTE) 3.5 Optical contrast of P3HT electrochromic devices with locally high concentration of electrolyte.
FIG. 5 shows the embodiment of the present applicationExample 5 contains LiTFS (DME) 1 (TTE) 2 DTP electrochromic device CV curve of local high concentration electrolyte.
FIG. 6 shows LiTFS (DME) in example 5 of the application 1 (TTE) 2 Ultraviolet-visible absorption spectrum of the device under different potentials of the DTP electrochromic device of the local high-concentration electrolyte.
FIG. 7 shows LiTFS (DME) in example 5 of the application 1 (TTE) 2 Optical contrast of DTP electrochromic devices with locally high concentration of electrolyte.
FIG. 8 is LiTFSI (TGE) of comparative example 1 of the present application 4 (BTE) 4 DTP electrochromic device of electrolyte the optical contrast of the electrochromic device.
Detailed Description
The application provides an electrochromic device and a preparation method thereof, and the application is further described in detail below for the purpose, technical scheme and effect of the application to be clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
Example 1
1.1, dissolving TFSILI in tetraethylene glycol diethyl ether (TGE) solvent according to a molar ratio of 1:1.75, stirring for 2 hours at room temperature to obtain a uniform conductive salt solution, then adding a bis (2, 2-trifluoroethyl) ether (BTE) diluent into the conductive salt solution, and stirring uniformly again to obtain transparent LiTFSI (TGE) 1.75 (BTE) 3.5 Local high-concentration electrolyte;
1.2, preparing a P3HT organic electrochromic layer on an anode transparent conductive substrate;
1.3, coating sealant at the peripheral frame of the anode transparent conductive substrate covered by the P3HT organic electrochromic layer, and reserving an electrolyte injection port;
1.4, covering the anode transparent conductive substrate obtained in the step 1.3 with a cathode transparent conductive substrate, and forming a cavity between the P3HT organic electrochromic layer and the cathode transparent conductive substrate;
1.5 injection of LiTFSI (TGE) into the cavity through the electrolyte injection port 1.75 (BTE) 3.5 Local high-concentration electricityAnd (3) dissolving the electrolyte, and finally sealing the electrolyte injection opening by adopting sealant.
LiTFSI (TGE) is contained in this example 1.75 (BTE) 3.5 The P3HT electrochromic device of the locally high concentration electrolyte changed color under the applied voltage, the device was red at 0V, and when the positive voltage was applied up to 3.0V, the device turned transparent blue. FIG. 2 is a diagram containing LiTFSI (TGE) 1.75 (BTE) 3.5 CV curve of P3HT electrochromic device of locally high concentration electrolyte. FIG. 3 is an ultraviolet-visible absorption spectrum of the device at different potentials, and it can be seen from the figure that at 3.0V, the absorption peak at 520nm disappears, and the absorption intensity increases in the near infrared wavelength range (> 800 nm). FIG. 4 is a diagram containing LiTFSI (TGE) 1.75 (BTE) 3.5 The optical contrast of the P3HT electrochromic device of the localized high concentration electrolyte, as can be seen from the figure, was 94.6% at 610nm, 86.8% at 1500nm, and the photo response rate was 4.5s/4s (coloring/bleaching).
Example 2
2.1 LiBF 4 Dissolving in diethylene glycol dimethyl ether (DGE) solvent at a molar ratio of 1:0.8, stirring at room temperature for 2 hours to obtain a uniform conductive salt solution, adding 1,2, 3-hexafluoropropylethyl ether (HFE) diluent into the conductive salt solution, and stirring again uniformly to obtain transparent LiBF 4 (DGE) 0.8 (HFE) 1.6 Local high-concentration electrolyte;
2.2, preparing a P3HT organic electrochromic layer on the anode transparent conductive substrate;
2.3, coating sealant at the peripheral frame of the anode transparent conductive substrate covered by the P3HT organic electrochromic layer, and reserving an electrolyte injection port;
2.4, covering the cathode transparent conductive substrate on the anode transparent conductive substrate obtained in the step 2.3, and forming a cavity between the P3HT organic electrochromic layer and the cathode transparent conductive substrate;
2.5 injecting LiBF into the cavity through the electrolyte injection port 4 (DGE) 0.8 (HFE) 1.6 And (3) locally high-concentration electrolyte, and finally sealing the electrolyte injection port by adopting sealant.
The electrochromic device obtained in this example had substantially the same performance as in example 1, and the absorption peak at 610nm disappeared when the voltage of 3.0V was applied, and the absorption intensity in the near infrared wavelength range (> 800 nm) increased. The optical contrast at 610nm was 94%, the optical contrast at 1500nm was 85%, and the light response rate was 4.7s/4s (coloring/fading).
Example 3
The electrochromic device of this example was prepared in the same manner as in example 1, except that: the solvent is ethylene glycol monobutyl ether (BE), the diluent is 1H, 5H-octafluoropentyl 1, 2-tetrafluoro ethyl ether (OTE), and the local electrolyte is replaced by LiTFS (BE) 0.8 (OTE) 4 。
The electrochromic device obtained in this example had substantially the same performance as in example 1, and the absorption peak at 520nm disappeared when the voltage of 3.0V was applied, and the absorption intensity in the near infrared wavelength range (> 800 nm) increased. The optical contrast at 610nm was-43%, the optical contrast at 1500nm was-22%, and the light response rate was slowed to 12.6s/12.4s (coloring/fading).
Example 4
The electrochromic device of this example was prepared in the same manner as in example 1, except that: the solvent is selected from ethylene glycol Monomethyl Ether (ME), the diluent is selected from 1, 2-tetrafluoroethyl 2, 3-tetrafluoropropyl ether (TTE), and the local electrolyte is replaced by LiTFSI (ME) 0.8 (TTE) 4 。
The electrochromic device obtained in this example had substantially the same performance as in example 1, and was completely blue when a voltage of 3.0V was applied, and its absorption peak in the visible region at 520nm disappeared, and the absorption intensity in the near infrared wavelength range (> 800 nm) increased. The optical contrast at 610nm was-68%, the optical contrast at 1500nm was-86%, and the light response rate was slowed to 12.6s/12.4s (coloring/fading).
Example 5
5.1, dissolving TFSLi in a glycol dimethyl ether (DME) solvent according to a molar ratio of 1:1, stirring for 2 hours at room temperature to obtain a uniform conductive salt solution, then adding a 1, 2-tetrafluoroethyl 2, 3-tetrafluoropropyl ether (TTE) diluent into the conductive salt solution, and stirring uniformly again to obtain transparent LiTFS (DME) 1 (TTE) 2 Local high concentrationAn electrolyte;
5.2 dissolving Dimethyl Terephthalate (DTP) in LiTFS (DME) in step 5.1 at 10mM 1 (TTE) 2 Obtaining a mixed solution in the local high-concentration electrolyte;
5.3, tightly adhering the conductive side of the double-layer conductive ITO glass by using double-sided adhesive tape, reserving an electrolyte injection port, and forming a cavity between the double-layer conductive ITO glass;
and 5.4, injecting the mixed solution prepared in the step 5.2 into the cavity through the electrolyte injection opening, and finally sealing the electrolyte injection opening by adopting sealant.
LiTFS (DME) is contained in this example 1 (TTE) 2 The DTP electrochromic device of the local high-concentration electrolyte changes color under the applied voltage, the device is transparent and colorless at 0V, and the device changes into opaque red when the applied voltage reaches-4.0V. FIG. 5 is a LiTFS-containing (DME) 1 (TTE) 2 CV curve of DTP electrochromic device of local high concentration electrolyte. FIG. 6 is an ultraviolet-visible absorption spectrum of the device at various potentials, as can be seen from the figure, at-4V, the absorption peak intensity at 544nm reaches a maximum. FIG. 7 is a LiTFS-containing (DME) 1 (TTE) 2 The optical contrast of the DTP electrochromic device of the local high concentration electrolyte is 49.8% at 544nm, and the photo response rate is 9s/9s (coloring/fading).
Example 6
The electrochromic device of this example was prepared in the same manner as in example 5, except that: local electrolyte is replaced by LiBF 4 (DME) 1.75 (TFE) 3 。
The electrochromic device obtained in this example had substantially the same performance as in example 5, and the device became completely red when a voltage of-4.0V was applied, the absorption peak intensity at 544nm reached maximum, and the absorption intensity in the near infrared wavelength range (> 800 nm) increased. The optical contrast at 610nm was-68%, the optical contrast at 1500nm was-86%, and the light response rate was slowed to 9.4s/9s (coloring/fading).
Example 7
The electrochromic device of this example was prepared in the same manner as in the example5, except that: local electrolyte exchange LiTFS (ME) 1.75 (BTE) 3.5 。
The electrochromic device obtained in this example had substantially the same performance as in example 5, and the device became completely red when a voltage of-4.0V was applied, the absorption peak intensity at 544nm reached maximum, and the absorption intensity in the near infrared wavelength range (> 800 nm) increased. The optical contrast at 610nm was-68%, the optical contrast at 1500nm was-86%, and the light response rate was slowed to 8s/7.8s (coloring/fading).
Comparative example 1
The electrochromic device of this example was prepared in the same manner as in example 1, except that: electrolyte is replaced by LiTFSI (TGE) 4 (BTE) 4 As shown in fig. 8, the optical contrast of the DTP electrochromic device obtained in this example was only 8% at 520nm, and was continuously decreased.
Comparative example 2
The electrochromic device of this example was prepared in the same manner as in example 5, except that: electrolyte LiTFSI (ME) is used 1.5 (BTE) 1 The electrolyte is semi-solid at room temperature, lithium salt is not completely dissolved, the light transmittance of the device is seriously affected, and the device cannot work normally.
Comparative example 3
The electrochromic device of this example was prepared in the same manner as in example 5, except that: using electrolyte LiTFSI (TGE) 3 (BTE) 5 DTP is rapidly deactivated during the electrochromic cycle, the optical contrast drops rapidly, and the device no longer undergoes discoloration.
It is to be understood that the application is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (9)
1. An electrochromic device comprising: an anode transparent conductive substrate, an organic electrochromic layer positioned on the anode transparent conductive substrate, and a cathode transparent conductive substrate positioned above the organic electrochromic layer, wherein a cavity is formed between the organic electrochromic layer and the cathode transparent conductive substrate, and the cavity is filled with a local high-concentration electrolyte; the cathode transparent conductive substrate is connected with the surface of the anode transparent conductive substrate uncovered by the organic electrochromic layer through sealant;
the local high-concentration electrolyte comprises a solvent, a conductive salt and a diluent, wherein the molar ratio of the conductive salt to the solvent is 1:0.1-1:20, and the molar ratio of the conductive salt to the diluent is 1:0.1-1:40.
2. The electrochromic device according to claim 1, wherein the conductive salt is one or both of an alkali metal salt and an ammonium salt.
3. The electrochromic device according to claim 1, wherein the conductive salt is one or more of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium bistrifluoromethane yellow imide, lithium trifluoromethanesulfonate, sodium hexafluorophosphate, sodium perchlorate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium bistrifluoromethane yellow imide, sodium trifluoromethanesulfonate, potassium hexafluorophosphate, potassium perchlorate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, ammonium bistrifluoromethane yellow imide, ammonium hexafluoroarsenate, ammonium tetrafluoroborate, ammonium trifluoromethanesulfonate, ammonium trifluoroacetate, ammonium bistrifluoromethane yellow imide, ammonium trifluoromethanesulfonate.
4. The electrochromic device according to claim 1, wherein the solvent is an ether-type organic solvent, and the ether-type organic solvent is one or more of ethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol methyl ether, propylene glycol diethyl ether, propylene glycol butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol butyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, diethylene glycol butyl ether acetate.
5. The electrochromic device according to claim 1, wherein the diluent is a fluoroether solvent.
6. The electrochromic device according to claim 1, wherein the molar ratio of the conductive salt to the solvent is 1:0.5-1:2, and the molar ratio of the conductive salt to the diluent is 1:0.5-1:2.
7. The electrochromic device according to claim 1, wherein the material of the electrochromic layer is one or more of P3HT, polyaniline electrochromic material, polypyrrole electrochromic material, polythiophene electrochromic material, polybenzazole electrochromic material, polyfuran electrochromic material, polycarbazole and derivatives thereof electrochromic material, D-a-D type polymer, D-a type polymer and copolymers thereof electrochromic material, ester electrochromic material, viologen electrochromic material.
8. A method of manufacturing an electrochromic device according to any one of claims 1 to 7, comprising the steps of:
preparing an organic electrochromic layer on an anode transparent conductive substrate;
coating sealant at the peripheral frame of the anode transparent conductive substrate covered by the organic electrochromic layer, and reserving an electrolyte injection port;
covering a cathode transparent conductive substrate on the anode transparent conductive substrate coated with the sealant, and forming a cavity between the anode transparent conductive substrate and the cathode transparent conductive substrate;
injecting local high-concentration electrolyte into the cavity through the electrolyte injection opening, and finally sealing the electrolyte injection opening by adopting sealant;
the local high-concentration electrolyte comprises a solvent, a conductive salt and a diluent, wherein the molar ratio of the conductive salt to the solvent is 1:0.1-1:20, and the molar ratio of the conductive salt to the diluent is 1:0.1-1:40.
9. The method of manufacturing an electrochromic device according to claim 8, characterized in that the method of manufacturing a locally high concentration electrolyte comprises the steps of:
injecting a solvent into the conductive salt, and stirring to obtain a conductive salt solution;
and adding a diluent into the conductive salt solution, and stirring to obtain the local high-concentration electrolyte.
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